 Adiabatic flame temperature: 27560C

 Research Octane number: 130

 Auto ignition temperature: 858 K
Advantages of Hydrogen
 Renewable in nature.
 Cleanest fuel due to low emissions of NOx.
 Can be produced from variety of feed stocks.
 Is suitable for IC engines and fuel cells.
 Requires low ignition energy.
 Superior combustion characteristics.
 Adulteration free.
 High purity levels available.
Disadvantages of Hydrogen
 High flammability lends an explosive quality to the fuel‐air mixture.
Leak detection of H2 is difficult as it is odourless.
 Pre‐ignition occurs when the cylinder charge ignites before the spark.
Backfires when the flame travels back to the fuel induction system.
 Expensive as production quantity is limited.
 Lack of distribution infrastructure.
Production of Hydrogen
Currently, hydrogen is produced from a number of industrial applications. It is
an important component of the processes used to produce methanol and
ammonia and the process used to refine petroleum. It is the fuel of choice for
rocket engines. Hydrogen can be produced by several methods. Considerable
debate is going on in the industry as to which method is economically viable.
1. Electrolysis of water
2. Catalytic steam reforming of natural gas
3. Partial oxidation of heavy oil
4. Coal gasification
5. Steam iron process
6. Thermal cracking of natural gas
7. Thermo‐chemical water decomposition

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 8. Photochemical conversion
9. Biological hydrogen generation by algae
10. Decomposition of biomass
11. Nuclear fission
Electrolysis of water
This method does not depend on fossil energy. Hydrogen produced by this
method is pure in nature. Water electrolysis involves splitting the water
molecule into hydrogen and oxygen atoms by passing a direct current through
it. Water is made conductive by adding hydroxyl ions to it. The most common
electrolytes used are alkaline electrolytes such as potassium hydroxide (KOH) .
In the electrolysis process, the distilled water enters a deionizer module where
DC current is passed through it. Upon hydrolysis, the hydrogen and oxygen
atoms separate from the water molecule. The residual H2O molecules are
removed using separators. The hydrogen and oxygen produced is then
regulated and stored. The rate of H2 generation is related to current density.
The capital cost of an electrolysis plant is high. Thus, the cost of producing
hydrogen by this method is on the higher side.

Basic reaction at the negative electrode is

K + H2O ↔ K+ + H+ OH‐
H + H ↔ H2
In order to increase the rate of production of hydrogen, catalyst is applied to the
surfaces of the electrodes. Catalytic coatings have properties which allow quick
recombination of hydrogen at the electrode surfaces. Without a catalyst, atomic

2
hydrogen would build up on the electrode, reducing the current flow and
slowing the production of hydrogen gas. Nickel, coated with small quantities of
platinum metals, is the most commonly used material for cathodes. For the
anode, nickel and copper both show good activity rates for oxygen
recombination.
Catalytic Steam Reforming of Natural Gas
At present, steam reformation is the most efficient, economical and widely used
technique for the production of hydrogen. The basic process involves the
conversion of a hydrocarbon and steam to hydrogen and carbon oxides. The
modern process consists of four steps:
1. Feedstock purification (principally to remove sulfur)
2. Steam reforming of hydrocarbons to form hydrogen and carbon oxides
3. Shift conversion of carbon monoxide to carbon dioxide
4. Purification (removal of CO2, CO and hydrocarbons)

This is an economical method to produce H2. The process involves catalytic

conversion of hydrocarbons using steam to form hydrogen and carbon oxides.
The reactions taking place are as follows:

Where n = 1 and m = 4 if the feedstock is methane and N =1 and m=2.2 if the

feedstock is naphtha.
The sulphur content of the methane/naphtha feedstock is first removed and
then mixed with process steam. The mixture is then passed through steel tubes,
which contain nickel catalyst. The hydrogen gas generated in this first step
contains some methane and carbon monoxide. To remove CO and CH4, the gas
is passed through a heat recovery step. The gas is fed to water gas shift reactor
where additional hydrogen is produced. The gas finally passed through a gas
purifier where trace impurities like CO2 are removed. The purification step
involves wet scrubbing with an amine solution. The purity of H2 gas produced
by this process is 98%. Steam reformation reaction is highly endothermic,
requiring temperatures ranging from 760 – 925OC, and pressures of
approximately 2 MPa. To improve the efficiency of this reaction, catalysts are

3
used. The catalyst is usually composed of NiO mixed with Al2O3, CaO, MgO or
other oxides. After the reformer process, the gas mixture is fed through a heat
recovery step and reacted with excess steam. This reaction is exothermic and is
carried out at temperatures ranging from 200‐ 400OC in two steps called high
temperature shift (HTS) and low temperature shift converter (LTS). This step
reduces the CO content to levels of approximately 0.2‐0.4% by volume.

Thermal Cracking of Natural Gas

The thermal decomposition of natural gas was carried out earlier to obtain
carbon black. The decomposition requires a lot of energy some of which comes
from the produced hydrogen.
CH4 + Heat → C + 2H2
The process is carried out in a furnace at near atmospheric pressure. A methane
air flame at 14000C is used to heat the furnace. The methane decomposition
produces carbon particles that are collected in filter bags. Catalysts are used to
achieve faster decomposition. This is a very common method of producing
hydrogen as prices of natural gas are low as compared to other fuels.
On‐Board Storage of Hydrogen
One of the greatest challenges in developing a hydrogen‐fuelled vehicle is
designing a satisfactory on‐board storage system for the fuel. The principal
problem with storing hydrogen is that it has such a low density. Thus, most
hydrogen storage systems are considerably bulkier and/or heavier than those
used for conventional gasoline or diesel fuels. Hydrogen is typically stored on a
vehicle in the following forms:

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 1. A liquid in cryogenic containers
2. A gas bound to certain metals (hydride)
3. A high pressure compressed gas
4. Activated carbon storage

5. Glass microspheres.

Liquid Hydrogen
Liquid hydrogen (LH2) storage has been subject of considerable development
in Japan, Germany and the United States. The conditions necessary to store
liquid hydrogen are fairly severe; however, they require a temperature of 20 K
at 2 x 105 Pa. To maintain these conditions, liquid hydrogen is typically stored
in a double‐walled, super insulating vessel. Hydrogen can be drawn from either
the liquid or gas phase of these vessels and delivered to the engine. These
vessels help to minimize the transfer of heat from the outside world, thus
reducing the boil‐off hydrogen. Evaporative rates with these vessels are
typically in the order of 2% per day or less. It is significant to note that an
amount of energy equivalent to 40% of the heating value of the hydrogen is
lost during the energy intensive liquefaction process.
One of the advantages of LH2 as opposed to other on‐hydrogen systems is its
weight. As shown in table 2.1 an advanced LH2 system weighs slightly more
than comparable gasoline system. However, LH2 is considerably more bulky
than gasoline. Complete LH2 systems can be 6 to 10 times larger than gasoline
tank holding the equivalent amount of energy, thereby reducing storage and/or
passenger space. This ratio is slightly less on an equal distance basis, as
hydrogen can be used more efficiently in an engine than gasoline. Another
advantage of using LH2 is that allows hydrogen to be delivered to the engine
cold, that is ‐80O C. This offers several performance advantages. The volumetric
efficiency of the engine can be increased, for example, as cold hydrogen occupies
less volume than an equivalent amount of warmer hydrogen. This, in essence
allows more of the fuel‐air mixture to be inducted into the cylinder, producing a
higher energy charge mixture. Secondly, the level of NOx in the exhaust can be
reduced since cryogenic hydrogen acts like a heat sink, and reduces the
temperatures in the combustion chamber.

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Metal Hydrides
Metal hydride storage systems are based on the idea that gaseous hydrogen
readily absorbs in metals, forming a weak chemical bond. Metal hydrides are
typically in a granular or powder form and thus, have a large surface area and
large capacity for storage. To release gaseous hydrogen from the metal, the
hydride is heated to a certain temperature. Exhaust heat from the engine,
carried by cooling water or exhaust gases, is commonly used for this purpose.
There are several advantages to using hydride system. The metal hydride
system is easier to deal with than other on‐board storage systems, since neither
high pressures nor cryogenic temperatures are necessary for operation.
Hydrogen obtained from a hydride storage system is insufficiently pressured for
the use in high‐pressure injection applications; however, a metal hydride
system is also one of the safest alternatives for storing hydrogen.
The biggest disadvantage of hydride systems is that they have a low m ass
energy density, and thus tend to be very heavy. In fact, hydride storage units,
including the hydride and cooling system can range from 120‐485 kg,
containing only 0.5% to 2% hydrogen by weight. The weight of hydride storage
units is about 10 to 20 times greater than that of gasoline tanks for the same
energy content. Besides affecting performance, the high storage weight limits
the range of the car to 150 ‐300 km. the capacity of the hydride system can be
reduced due to contamination. Oxygen and water contamination was the
primary cause of the loss in storage capacity. The hydrides can be divided into
two categories: low temperature hydrides, with hydrogen desorption
temperatures up to 373K, and high temperature hydrides. Among the low
temperature hydride, ferrotitanium is one of the most promising candidates.
One problem with these hydrides is that the bulk density of Fe‐Ti is high
making these systems heavy.
Compressed Gas
Probably the most straight forward way to store hydrogen is as a compressed
gas in a high‐ pressure vessel. These vessels are typically aluminum cylinders
wrapped with fiber glass. Other designs being tested include aluminum
cylinders wrapped with Kevlar or graphite, plastic liners wrapped with

6
graphite, and high‐strength aluminum cylinders. However, volume and mass

7
are both issues with storing hydrogen as a compressed gas. Pressurized
hydrogen systems at approximately 20 MPa weigh nearly three times more
than what a comparable liquid hydrogen system does, and they occupy more
than twice the volume. This volume can be reduced by increasing the pressure
of the compressed gas, potentially up to as high as 55Mpa (8000 psi). For such
high‐pressure vessels, cost and safety will be crucial issues.
Activated Carbon Storage
Another technique of storing hydrogen is by adsorbing it onto a carbon
surface. With this technique, the amount of adsorption can be increased as the
temperature is lowered, but cryogenic temperatures are not needed. Super‐
treated carbon has been developed which can absorb a large amount of carbon
molecules at 123OC and 55 MPa.
Glass Microspheres
Hydrogen can also be stored under high pressure in glass spheres. The basis of
this storage method is that hydrogen can be released by heating the
microcapsules, which increases the rate of diffusion of hydrogen through the
glass. At room temperature, the diffusivity of hydrogen through the glass
capsule is sufficiently small that the hydrogen will not diffuse. Micro spheres
have not been developed for commercial applications
Material Compatibility for Hydrogen
Aluminum, copper and alloys like bronze and brass are compatible with
hydrogen. This gas is also compatible with all elastomers and does not pose
material or compatibility concerns. Hoses for hydrogen should be non‐porous
to prevent leakage.
Due to hydrogen`s unique molecular properties, it is capable of diffusing into
materials, which are impermeable to most fluids or gases. Diatomic H2 is the
most stable form of hydrogen. However, when provided with enough energy,
diatomic hydrogen can dissociate into hydrogen atoms, which are small
enough to penetrate a container surface. This penetration can cause structural
damage to the container, especially when using metal containers. This
phenomenon is known as “hydrogen embrittlement”.

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Hazards of Hydrogen
1. Leakage: Similar to methane, hydrogen is invisible and odourless and
thus cannot be easily detected. This problem can be alleviated by adding
small amounts of a colorant or odorant to the gas as is done for natural
gas.
2. Fire and Explosion: Probably the greatest hazards in dealing with
hydrogen are fire and detonation. For any fire to occur the proper mix of
hydrogen and oxygen must be present and the minimum ignition energy
must be supplied. Hydrogen represents the greatest fire and detonation
hazard based on its wide flammability range and low ignition energy. One
consequence of hydrogen`s high burning velocity is that hydrogen has a
higher probability of undergoing a deflagration to detonation (DDT), that
is translation from simple combustion to an explosion. Hydrogen has
much higher burning velocity compared to other fuels and can accelerate
to its detonation velocity in a much shorter distance than other fuels.
Hydrogen has the highest diffusion velocity and the highest buoyant
velocity. Thus, in unconfined areas, hydrogen leaks will rise and diffuse
rapidly to non‐combustible proportions. However, in enclosed areas,
hydrogen can quickly spread to the whole of the room of leak develops,
forming a combustion mixture. In order to prevent this danger, hydrogen
should be handled outdoors whenever possible, and in confined area only
when adequate ventilation is possible.
3. Overpressure Detonation: A detonation hazard consists of several key
components: fire, a pressure wave resulting from a dramatic increase in
pressure and shrapnel. Of these components, pressure wave causes the
greatest structural damage. In general, the wider is the flammability
limits, the greater are the chances of a detonation that can cause
extensive damage and injury. Since hydrogen has the widest combustion
and detonation range, it has the greatest danger of detonating.
4. Asphyxiation: Hydrogen is non‐toxic, and it emits non‐toxic combustion
products when it is burned with oxygen. However, as with any other than

9
 oxygen, it can act as a simple asphyxiant. Asphyxiation should not be
taken lightly, as it can cause dizziness, vomiting, unconsciousness and
even death. In enclosed areas, this can be a problem if large leaks develop
in a hydrogen containment vessel. This problem can be solved by using
proper ventilation system. If an asphyxiation danger does exist, self‐
contained breathing apparatus should be kept in hand.
5. Frostbite: When dealing with LH2, frostbite is another hazards of
concern. Human skin can easily be frozen or torn if it is exposed to
cryogenic surfaces, which maintain hydrogen at its liquefaction
temperature of 20 K. all pipes containing cryogenic hydrogen must be
insulated and operators must insulate body parts, which may be exposed
to these cold surfaces. Insulation of pipes is also necessary to prevent the
surrounding air from condensing on the pipes as an explosion hazard
can develop if air condenses on the pipes and then drips onto nearby
combustibles. Asphalt pavement, for example is composed of
combustible petroleum products, which can ignite in the presence of
liquid air. Thus areas where LH2 is used should be paved with concrete
instead of asphalt.
Safety Systems for Hydrogen
1. Leak Detection systems: Hydrogen is a colorless and odorless gas;
hence it will require leak detection systems. Hydrogen detectors are
required to be placed strategically over the refueling area at the
appropriate locations. The hydrogen detectors should produce an audible
alarm when the concentration of hydrogen reaches 1% by volume in air,
which is 25% of the lower flammability limit for hydrogen. If H2
concentration continues to rise further, the detectors should have the
capability to shut down the refueling systems until the ambient H2
concentration is reduced. Due to its size, hydrogen can diffuse readily
through joints or connections, even the ones that are considered “air
tight”. In order to reduce the potential of forming leaks, the number of
joints and connections in a system should be reduced and welded joints
should be used wherever possible.

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2. Fire Suppression Systems: All refueling systems of significant size
should incorporate a fire suppression system. The standard system using
dry chemical powder is effective for extinguishing hydrogen flames. If it is
safe to do so, the fuel flow should also be disconnected. Other hydrogen
containers should be removed from the area because if these containers
become too hot, that is above 52OC, pressure in the system can build to a
point where the gas will be vented by the relief system. Water can be used
to cool nearby flammable objects. This will reduce the possibility if
explosive re‐ignition, which can occur after the hydrogen flame is
extinguished if nearby surfaces were not sufficiently cooled by water.
3. Electrical Protection Systems: Since leaks will occur, it is necessary to
eliminate ignition sources wherever possible. All electrical equipment’s
must be securely grounded to eliminate electrostatic sparks. Equipment
should also be kept at safe distance from hydrogen sources as friction or
mechanical sparks can occur during normal operation of the equipment.
Of course, smoking or striking of matches should never be permitted in
area where hydrogen is present. Even precautions such as lightning rods,
to protect against lightning strikes should be used.
4. Purging Systems: To remove air from the system so that combustible
mixtures cannot develop within a hydrogen containment vessel, the
system must be purged with an inert gas, such as nitrogen. The purging
procedure is important and must be done properly. In fact, it was found
that approximately 8% of hydrogen accidents are a result of inadequate
purging. After purging, the system must be tested for residual oxygen
before hydrogen is allowed to enter the system. Gas chromatography is an
accurate method of testing for trace amounts of oxygen.
5. Pressure Relief Devices: Pressure relief devices are designed to vent
excess gas when the pressure in a vessel exceeds a certain design value.
Two of the most common pressure relief devices are spring‐loaded safety
valves and rupture discs.
6. Detonation and Shrapnel Protection: The geometry of the
containment vessel can affect the probability for a transition from

11
 deflagration to detonation. One way to minimize the probability of this
transition is to decrease the length of the pipe and increase the diameter.
Pipes with a high length to diameter ratio (L/D) are more likely to
propagate a DDT than enclosures with a low L/D ratio. Another way of
inhibiting explosions is by using a “lean” mixture of hydrogen and air or
a mixture towards the lower end of the flammability range. This lowers
the burning velocity substantially bringing the flame into laminar flow
regions.
Detonations can send shrapnel fragments flying for several hundred
meters, thus minimum safety distances are necessary to protect personnel
from shrapnel. In addition, shrapnel protection shields should be used
whenever possible. Shrapnel protection shields are difficult to design
because it is hard to predict the volume, mass or velocity of the
fragments, as these quantities vary with the strength of the detonation.
Materials such as structural steel, high‐strength/low alloy steel, and
stainless steel, are effective as shrapnel shields.
Methods of using Hydrogen in SI Engines:
1. Carburetion: The simplest way of delivering fuel to a hydrogen engine is
via a carburetor. Although carburetor is no longer a variable technology
for modern vehicles, there were several advantages to using a carburetor
for early hydrogen engine developments. This system is similar to that
used for carbureted gasoline engines, which made it easy to convert a
standard gasoline engine into a dual‐fueled gasoline/hydrogen or a simple
hydrogen engine. This system does not require a sophisticated high‐
pressure injector. The disadvantage of this technique is that engines that use
carburetors are more susceptible to irregular combustion due to pre‐
ignition and back fire problems. Additionally, the power output of an ideal
hydrogen engine with a carburetor is about 15% lower than that of a
comparable gasoline engine

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