Hydrogen Production,

storage and safety

hazards

Production of hydrogen
Hydrogen is not abundant in atmosphere but it can be
synthesised from coal, oil or natural gas, or can be obtained
from water. Hydrogen is produced for a number of industrial
applications. It is an important component to produce
methanol, ammonia etc. The various methods for the
production of hydrogen are as follows
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. Thermochemical
water
decomposition
8. Photochemical

9.
Biological
hydrogen
generation by algae
10.
Decomposition
of
biomass
Nuclear fission

Catalytic steam reforming of

natural gas

1.
2.
3.
4.

The production of hydrogen by the means of

catalytic steam reforming is the most efficient,
economical, and widely used technique.
The basic process involves the conversion of a
hydrocarbon and steam to hydrogen and carbon
oxides. The process is carried out in the
following four steps.
Feed stock purification
Steam reforming of hydrocarbon to form
hydrogen and carbon oxides
Shift conversion of carbon monoxide to carbon
dioxide
Purification (removal of CO2 , CO and
hydrocarbons)

1.
2.

Feed stock purification

The sulfur content of the methane is first removed
Steam reforming of hydrocarbons to form hydrogen and
carbondioxide.
The natural gas is then mixed with process steam. The
mixture is then passed through steel tubes containing
nickel catalyst.
Cn H m + n H 2 O
n CO + (n+m/2) H2
The reaction is highly endothermic
Temperature required is 760 925 C
Pressure required 2 MPa

3.

The H2 gas produced in this step contains CO and some

unreformed methane
Shift conversion of carbon monoxide to carbon dioxide
The gas is fed to a water gas shift reactor where the
following reaction takes place
CO + H O
CO + H (water gas shift reaction)

4. Purification
The gas finally passes through a gas purifier where traces
of CO2 are removed. It also involves wet scrubbing with an
amine solution

The steam reformation is reversible and the hydrogen can

convert back to methane. Therefore an appropriate steam
to carbon ratio is maintained and high temperature is
required to favour the production of hydrogen.
The steam to carbon ratio maintained is 3:5
The temperature maintained is 815 C
Pressure up to 3.5 Mpa

Partial oxidation of heavy oil POX

Heavy oils are hydrocarbon rich fuels. These heavy oils are
oxidised to form CO and H2 . The CO produced is removed
from the mixture to form additional hydrogen. The process
is similar to the steam reforming process with an additional
step between the purification (removal of sulfur) and steam
reforming.
In the new step hydrocarbons are oxidized to provide
sufficient energy to drive the process and release additional
amount of hydrogen
The oxidation reaction proceeds as follows
CnHm + n/2 O2
n CO + m/2 H2

This reaction is exothermic and proceeds at a Temperature of

around 1150 1315 C.
The plant requires additional equipment to separate oxygen
from atmospheric air. The equilibrium conditions for POX
occurs at much higher pressures. The synthesized gas thus
exits at 6 MPa reducing the need of compression.

The other steps are similar to the catalytic

reforming of steam.
Feedstock for POX ranges from methane to coal.
Catalytic processes which occur at a
temperature of about 590 C, use feedstock
ranging from methane to naptha.
Non catalytic POX which occur at temperature
1150 1315 C uses feedstock such as methane,
heavy oil and coal
Disadvantages of heavy oil or heavy hydrocarbons
are
1. lower hydrogen to carbon ratio
2. Increased difficulties in transportation compared
to methane

Coal gasification

The POX of coal is known as coal gasification.

Since different types of coal have different sulfur and ash
content, therefore the plant used for the partial oxidation
of coal is very sophisticated and highly expensive for
hydrogen production from coal gasification.
In this process the coal fed to a gasification plant. Air is
separated into its constituents O2 and N2 by an air
separation plant. The O2 stream enters the gasification
plant along with process steam.
The reaction of coal with steam and oxygen produces raw
gas and some ash. The ash is removed and the raw gas is
passed through a desulfurization plant to reduce sulfur.
The cleaned gas is known as syngas. The syngas is then
compressed and subjected to the shift conversion process
where CO and CH4 impurities are removed from hydrogen.
Finally CO2 is removed and pure hydrogen is produced

On board storage of hydrogen

Hydrogen is stored in a vehicle in the following forms
1. A liquid in cryogenic containers
The temperature required to store liquid hydrogen is 20 K and
pressure 6 105 Pa to 350 bar. To maintain these conditions, liquid
hydrogen is stored in a double-walled, super-insulating vessel. The
hydrogen can be drawn both as a liquid or as a gas of these vessel.
An amount of energy equivalent to 40 % of heating value of the
hydrogen is lost during the liquefaction process.

Advantages
An advanced LH2 system weighs slightly more than a comparable
gasoline system.
It can be delivered to the engine cold i.e. at -80 C. With this factor
several advantages are offered
The volumetric efficiency can be increased which allows more fuel to
be inducted thus producing more energy . Secondly since the
temperature is very low Nox exhaust can be reduced.

2. Metal hydrides
Gaseous hydrogen get absorbed in metals forming a weak bond.
Metal hydrides are typically in powder form which offers large
surface area and thus large storage capacity. The gaseous
hydrogen is released by heating the hydride upto certain
temperature.
The advantage is that no cryogenic or high pressure systems are
necessary for this purpose. The disadvantage is that they have a
low energy density and thus tend to be very heavy.
The weight of hydride storage units can be 10 20 times more than
the gasoline storage plants. Complete hydride storage systems can
be large creating additional space problems.
A good hydride system should have minimal mass with satisfactory
operating characteristics.
The hydride should have a high absorption capacity, high density,
utilize minimal amount of heat to desorb and have a low cost.
Hydrides can be divided into two categories
Low temperature hydrides and high temperature hydrides
Low temperature hydrides have hydrogen desorbtion temperature
upto 373 K. Low temperature hydride eg. Ferrotitanium.

3. Compressed hydrogen
Hydrogen can be stored in compressed form in high
pressure vessels. The vessels are high typically aluminum
cylinders wrapped with fibre glass. Pressurized hydrogen
storage systems at approximately 20 MPa weigh nearly 3
times more than liq. hydrogen storage system.

Advantages and Disadvantages

Advantages

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
High flammability lends an explosive quality to the fuelair mixture
Leak detection of H2 is difficult as it is odourless
Pre-ignition occurs when the cylinder charge ignites
before the spark

Hazards of hydrogen
Leakage
Hydrogen is colourless and odourless and thus cannot be easily detected.
It can be solved by adding small amount of colourant or odourant.

Fire and explosion

Hydrogen represents the greatest fire and detonation hazard based on its
wide flammability range and low ignition energy. Hydrogen can accelerate
to its detonation velocity in a much shorter distance than other fuels.
Hydrogen can diffuse very quickly and spread to the whole room if leak
develops and form combustible mixtures. In order to minimize these
danger, hydrogen should be handled outdoors whenever possible.

Over pressure Detonation

A pressure wave caused by detonation causes the greatest structural
damage and injury. Confined over pressures are generally not more than 7
kPa, confined over pressures can exceed 800 kPa and have devastating
effects. The wider the flammability range the greater are the chances of
detonation and hydrogen has the widest combustion and detonation range.

 Asphyxiation
Any gas other than oxygen causes asphyxiation.
Even though hydrogen is non toxic, it can cause several health
hazards resulting from asphyxiation. Since H 2 has high diffusion
and buoyant velocities, this problem is negligible in unconfined
areas.

Frostbite
Cold burn or frost bite can occur if human skin is
subjected to comparatively low temperature. Cryogenic
systems, which maintain hydrogen at very low
temperatures of 20 K , can tear or freeze human skin if
there is physical contact. All pipes carrying carrying
cryogenic hydrogen must be insulated . Insulation must
also be provided to prevent the surrounding air to
condense on the pipe