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ALTERNATIVE FUELS

ASSIGNMENT I
TOPIC : PRODUCTION, STORAGE & APPLICATION OF
HYDROGEN AS FUEL CELLS IN AUTOMOBILES
NEELESH KUMAR
15BME0406
1.Propose the methods for generation of hydrogen through hydrocarbon and
water.

Hydrogen can be produced from diverse, domestic resources including fossil fuels, biomass,
and water electrolysis with electricity. The environmental impact and energy efficiency of
hydrogen depends on how it is produced. Some projects are underway to decrease costs
associated with hydrogen production.

There are a number of ways to produce hydrogen:

Natural Gas Reforming/Gasification: Synthesis gas, a mixture of hydrogen, carbon


monoxide, and a small amount of carbon dioxide, is created by reacting natural gas
with high-temperature steam. The carbon monoxide is reacted with water to produce
additional hydrogen. This method is the cheapest, most efficient, and most common.
Natural gas reforming using steam accounts for the majority of hydrogen produced in
the United States annually.

A synthesis gas can also be created by reacting coal or biomass with high-temperature steam
and oxygen in a pressurized gasifier, which is converted into gaseous componentsa process
called gasification. The resulting synthesis gas contains hydrogen and carbon monoxide,
which is reacted with steam to separate the hydrogen.

Electrolysis: An electric current splits water into hydrogen and oxygen. If the
electricity is produced by renewable sources, such as solar or wind, the resulting
hydrogen will be considered renewable as well, and has numerous emissions benefits.
Power-to-hydrogen projects are taking off, where excess renewable electricity, when
it's available, is used to make hydrogen through electrolysis.

Renewable Liquid Reforming: Renewable liquid fuels, such as ethanol, are reacted
with high-temperature steam to produce hydrogen near the point of end use.

Fermentation: Biomass is converted into sugar-rich feedstocks that can be fermented


to produce hydrogen.

A number of hydrogen production methods are in development:

High-Temperature Water Splitting: High temperatures generated by solar


concentrators or nuclear reactors drive chemical reactions that split water to produce
hydrogen.

Photobiological Water Splitting: Microbes, such as green algae, consume water in the
presence of sunlight, producing hydrogen as a byproduct.

Photoelectrochemical Water Splitting: Photoelectrochemical systems produce


hydrogen from water using special semiconductors and energy from sunlight.
2. Suggest economical and viable methods for storage of Hydrogen. Comment
on the endothermic and exothermic reactions happening in the metal
hydrides.
Hydrogen can be stored in compressed form or liquefied form.

Compressed hydrogen is a storage form where hydrogen gas is kept under pressures
to increase the storage density. Compressed hydrogen in hydrogen tanks at 350 bar
(5,000 psi) and 700 bar (10,000 psi) is used for hydrogen tank systems in vehicles,
based on type IV carbon-composite technology. Car manufacturers have been
developing this solution, such as Honda or Nissan.

BMW has been working on liquid hydrogen tanks for cars, producing for example
the BMW Hydrogen 7.
CHEMICAL STORAGE
Apart from Metal Hydrides there are some other ways by which Hydrogen can be
chemically stored. Lets see some of the processes:

Non-metal hydrides

The Italian catalyst manufacturer Acta has proposed using hydrazine as an alternative
to hydrogen in fuel cells. As the hydrazine fuel is liquid at room temperature, it can be
handled and stored more easily than hydrogen. By storing it in a tank full of a double-
bonded carbon-oxygen carbonyl, it reacts and forms a safe solid called hydrazone. By
then flushing the tank with warm water, the liquid hydrazine hydrate is released.
Hydrazine breaks down in the cell to form nitrogen and hydrogen which bonds with
oxygen, releasing water.

Carbohydrates

Carbohydrates (polymeric C6H10O5) releases H2 in a bioreformer mediated by the


enzyme cocktailcell-free synthetic pathway biotransformation. Carbohydrate
provides high hydrogen storage densities as a liquid with mild pressurization and
cryogenic constraints: It can also be stored as a solid powder. Carbohydrate is the most
abundant renewable bioresource in the world.

Synthesized hydrocarbons

An alternative to hydrides is to use regular hydrocarbon fuels as the hydrogen carrier.


Then a small hydrogen reformer would extract the hydrogen as needed by the fuel
cell. However, these reformers are slow to react to changes in demand and add a large
incremental cost to the vehicle powertrain.

Direct methanol fuel cells do not require a reformer, but provide a lower energy
density compared to conventional fuel cells, although this could be counterbalanced
with the much better energy densities of ethanol and methanol over hydrogen.
Alcohol fuel is a renewable resource.
Solid-oxide fuel cells can operate on light hydrocarbons such as propane and methane
without a reformer, or can run on higher hydrocarbons with only partial reforming,
but the high temperature and slow startup time of these fuel cells are problematic for
automotive applications.

Liquid organic hydrogen carriers (LOHC)

Reversible hydrogenation of N-Ethylcarbazole

Unsaturated organic compounds can store huge amounts of hydrogen. These Liquid
Organic Hydrogen Carriers (LOHC) are hydrogenated for storage and dehydrogenated
again when the energy/hydrogen is needed. Research on LOHC was concentrated on
cycloalkanes at an early stage, with its relatively high hydrogen capacity (6-8 wt %)
and production of COx-free hydrogen. Heterocyclic aromatic compounds (or N-
Heterocycles) are also appropriate for this task. A compound that stands in the focus
of the current LOHC research is N-ethylcarbazole (NEC) but many others do exist.
More recently dibenzyltoluene, which is already industrially used as a heat transfer
fluid in industry, was identified as potential LOHC. With a wide liquid range between -
39 C (melting point) and 390 C (boiling point) and a hydrogen storage density of 6.2
wt% dibenzyltoluene is ideally suited as LOHC material.More recently, formic acid (FA)
has been suggested as a promising hydrogen storage material with a 4.4wt% hydrogen
capacity.
PHYSICAL STORAGE
Hydrogen can also be stored in its raw form instead of converting into a chemical
hydro compound. Some of the methods are

Cryo-compressed

As of 2010, the BMW Group has started a thorough component and system level
validation of cryo-compressed vehicle storage on its way to a commercial product.

Carbon nanotubes

Hydrogen carriers based on nanostructured carbon (such as carbon buckyballs and


nanotubes) have been proposed. However, since Hydrogen usually amounts up to
~3.0-7.0 wt% at 77K which is far from the value set by US department of Energy (6
wt% at nearly ambient conditions), it makes carbon materials poor candidates for
hydrogen storage.

Clathrate hydrates

H2 caged in a clathrate hydrate was first reported in 2002, but requires very high
pressures to be stable. In 2004, researchers from Delft University of Technology and
Colorado School of Mines showed solid H2-containing hydrates could be formed at
ambient temperature and 10s of bar by adding small amounts of promoting
substances such as THF.These clathrates have a theoretical maximum hydrogen
densities of around 5 wt% and 40 kg/m3.
Glass capillary arrays

A team of Russian, Israeli and German scientists have collaboratively developed an


innovative technology based on glass capillary arrays for the safe infusion, storage and
controlled release of hydrogen in mobile applications. The C.En technology has
achieved the United States Department of Energy (DOE) 2010 targets for on-board
hydrogen storage systems. DOE 2015 targets can be achieved using flexible glass
capillaries and cryo-compressed method of hydrogen storage.

Glass microspheres

Hollow glass microspheres (HGM) can be utilized for controlled storage and release of
hydrogen.
Endothermic and Exothermic Reactions of Metal Hydrides

Hydriding Exothermic Reaction


Dehydriding Endothermic Reaction

3. Elaborate the usage of hydrogen as a fuel in SI engine and discuss the


emission characteristics of the engine using hydrogen as a fuel
Hydrogen internal combustion engine cars are different from hydrogen fuel cell cars.
The hydrogen internal combustion car is a slightly modified version of the traditional
gasoline internal combustion engine car. These hydrogen engines burn fuel in the
same manner that gasoline engines do; the main difference is the exhaust product.
Gasoline combustion results in carbon dioxide and water vapor, while the only
exhaust product of hydrogen combustion is water vapor.

Mazda has developed Wankel engines burning hydrogen. The advantage of using an
internal combustion engine, like Wankel and piston engines, is the lower cost of
retooling for production.
4. Schematically explain the construction of fuel cell and explain the types of
fuel cells.

Fuel Cells consist of an anode, a cathode, and an electrolyte that allows positively charged
hydrogen ions (protons) to move between the two sides of the fuel cell. At the anode a
catalyst causes the fuel to undergo oxidation reactions that generate protons (positively
charged hydrogen ions) and electrons. The protons flow from the anode to the cathode
through the electrolyte after the reaction. At the same time, electrons are drawn from the
anode to the cathode through an external circuit, producing direct current electricity. At the
cathode, another catalyst causes hydrogen ions, electrons, and oxygen to react, forming
water.
SOFC
Solid oxide fuel cells (SOFCs) use a solid material, most commonly a ceramic material called
yttria-stabilized zirconia (YSZ), as the electrolyte. Because SOFCs are made entirely of solid
materials, they are not limited to the flat plane configuration of other types of fuel cells and
are often designed as rolled tubes. They require high operating temperatures (8001000 C)
and can be run on a variety of fuels including natural gas.
SOFCs are unique since in those, negatively charged oxygen ions travel from the cathode
(positive side of the fuel cell) to the anode (negative side of the fuel cell) instead of positively
charged hydrogen ions travelling from the anode to the cathode, as is the case in all other
types of fuel cells. Oxygen gas is fed through the cathode, where it absorbs electrons to create
oxygen ions. The oxygen ions then travel through the electrolyte to react with hydrogen gas
at the anode. The reaction at the anode produces electricity and water as by-products. Carbon
dioxide may also be a by-product depending on the fuel, but the carbon emissions from an
SOFC system are less than those from a fossil fuel combustion plant. The chemical reactions
for the SOFC system can be expressed as follows:
Anode Reaction: 2H2 + 2O2 2H2O + 4e
Cathode Reaction: O2 + 4e 2O2
Overall Cell Reaction: 2H2 + O2 2H2O
MCFC
Molten carbonate fuel cells (MCFCs) require a high operating temperature, 650 C (1,200 F),
similar to SOFCs. MCFCs use lithium potassium carbonate salt as an electrolyte, and this salt
liquefies at high temperatures, allowing for the movement of charge within the cell in this
case, negative carbonate ions.
Like SOFCs, MCFCs are capable of converting fossil fuel to a hydrogen-rich gas in the anode,
eliminating the need to produce hydrogen externally. The reforming process creates CO2
emissions. MCFC-compatible fuels include natural gas, biogas and gas produced from coal.
The hydrogen in the gas reacts with carbonate ions from the electrolyte to produce water,
carbon dioxide, electrons and small amounts of other chemicals. The electrons travel through
an external circuit creating electricity and return to the cathode. There, oxygen from the air
and carbon dioxide recycled from the anode react with the electrons to form carbonate ions
that replenish the electrolyte, completing the circuit. The chemical reactions for an MCFC
system can be expressed as follows:
Anode Reaction: CO32 + H2 H2O + CO2 + 2e
Cathode Reaction: CO2 + O2 + 2e CO32
Overall Cell Reaction: H2 + O2 H2O
5. Comment on the application of fuel cell in automobiles
Fuel cell cost

Hydrogen fuel cells are relatively expensive to produce, as their designs require rare
substances such as platinum as a catalyst, In 2014, Toyota said it would introduce its
Toyota Mirai in Japan for less than $70,000 in 2015. Former European Parliament
President Pat Cox estimates that Toyota will initially lose about $100,000 on each
Mirai sold.

Freezing conditions

The problems in early fuel cell designs at low temperatures concerning range and cold
start capabilities have been addressed so that they "cannot be seen as show-stoppers
anymore". Users in 2014 said that their fuel cell vehicles perform flawlessly in
temperatures below zero, even with the heaters blasting, without significantly
reducing range.

Service life

The service life of fuel cells is comparable to that of other vehicles. PEM service life is
7,300 hours under cycling conditions