Chapter 5.

BIOFUELS (continued)

5.3. VEGETABLE OILS AND DERIVATIVES

Biodiesel is a fuel made from renewable resources such as vegetable oils or animal fats.
It is biodegradable and non-toxic, and has significantly fewer emissions than petroleum-
based diesel when burned. Biodiesel functions in current diesel engines, and is a possible
candidate to replace fossil fuels as the world's primary transport energy source.

With a flash point of 150 °C, biodiesel is classified as a non-flammable liquid making a
vehicle fueled by pure biodiesel far safer in an accident than one powered by petroleum
diesel or the explosively combustible gasoline. Precautions should be taken in very cold
climates, where biodiesel may gel at higher temperatures than petroleum diesel.

Biodiesel can be distributed using today's infrastructure, and its use and production is
increasing rapidly (especially in Europe, the United States, and Asia). Fuel stations are
beginning to make biodiesel available to consumers, and a growing number of transport
fleets use it as an additive in their fuel. Biodiesel is generally more expensive to produce
than petroleum diesel, although this differential may diminish due to economies of scale
and the rising cost of petroleum.

The use of vegetable oils as fuel in combustion engines is an old idea. Rudolph Diesel
used peanut oil to run a small diesel engine at the world exhibition in Paris in 1900. In a
1912 speech, Rudolf Diesel said, "the use of vegetable oils for engine fuels may seem
insignificant today, but such oils may become, in the course of time, as important as
petroleum and the coal-tar products of the present time."

At that time vegetable oils were cheaper than mineral oils, but a quick development of the
oil industry took over in the fuels market. With the 1973 oil crisis, a significant increase
of mineral oil prices demonstrated the vulnerability of an industrial system dependant
upon non-renewable and finite fossil energy sources.
Austria has been the pioneer of biodiesel in Europe. It was the first country that, in order
to overcome its food surplus problem, encouraged crops diversification and devoted a
part of its unemployed lands to rapeseed production for biodiesel. Furthermore, there is
an environmental interest, because its biodegradability helps to preserve some
environmentally sensitive areas which are important for tourism. In the last years a quick
development have been carried out in other European countries (France, Germany, Italy)
because of agricultural and environmental reasons.

A variety of biolipids can be used to produce biodiesel. These include:

 Virgin oil feedstock; rapeseed and soybean oils are most commonly used, though
other crops such as mustard, palm oil, hemp and even algae show promise;
 waste vegetable oil (WVO);
 Animal fats including tallow, lard, yellow grease and as a byproduct from the
production of Omega-3 fatty acids from fish oil.
As main feedstock there are sunflower and rapeseed oils and other cheaper raw material,
as they are used frying oils, animal fats and other by-products of vegetable oil industry.

For a truly renewable source of oil, crops or other similar cultivatable sources would
have to be considered. Plants utilise photosynthesis to convert solar energy into chemical
energy. It is this chemical energy that biodiesel stores and is released when it is burned.
Therefore plants can offer a sustainable oil source for biodiesel production. Different
plants produce usable oil at different rates. Some studies have shown the following
annual production:

 Soybean: 40 to 50 US gal/acre (40 to 50 m³/km²)

 Rapeseed: 110 to 145 US gal/acre (100 to 140 m³/km²)
 Mustard: 140 US gal/acre (130 m³/km²)
 Jatropha: 175 US gal/acre (160 m³/km²)
 Palm oil: 650 US gal/acre (610 m³/km²)
 Algae: 10,000 to 20,000 US gal/acre (10,000 to 20,000 m³/km²)

Soybeans are not a very efficient crop solely for the production of biodiesel, but their
common use in the United States for food products has led to soybean biodiesel
becoming the primary source for biodiesel in that country. Soybean producers have
lobbied to increase awareness of soybean biodiesel, expanding the market for their
product.

In Europe, rapeseed is the most common base oil used in biodiesel production. In India
and southeast Asia, the Jatropha tree is used as a significant fuel source, and it is also
planted for watershed protection and other environmental restoration efforts.

Malaysia and Indonesia are starting pilot-scale production from palm oil. However, the
environmental group Friends of the Earth has published a report that clearance of forests
for oil-palm plantations is threatening some of the last habitat of the orangutan.[3] Writer
George Monbiot wrote in a column for The Guardian that land clearance by cutting and
burning large forest trees frees large amounts of carbon dioxide that is never reabsorbed
by the smaller oil palms. Thus, biodiesel produced from plantation-grown palm oil may
be a net source of carbon dioxide.

Specially bred mustard varieties can produce reasonably high oil yields, and have the
added benefit that the meal leftover after the oil has been pressed out can act as a
effective and biodegradable pesticide.

The production of algae to harvest oil for biodiesel has not been undertaken on a
commercial scale, but working feasibility studies have been conducted to arrive at the
above yield estimate. In addition to a high yield, this solution does not compete with
agriculture for food, requiring neither farmland nor fresh water.

Biodiesel is a clear amber-yellow liquid with a viscosity similar to diesel, the industry
term for diesel produced from petroleum. It can be used as an additive in formulations of
diesel to increase the lubricity of pure ultra-low sulfur petrodiesel (ULSD) fuel. Much of
the world uses a system known as the "BD factor" to state the amount of biodiesel in any
fuel mix, in contrast to the "BA" system used for bioalcohol mixes. For example, 20%
biodiesel is labeled BD20,meaning a blend of 20% methylester or ethylester of a
vegetable oil or animal fat and 80% diesel fuel. Pure biodiesel, 100%, is referred to as
BD100.

In order to be used in conventional diesel engines the vegetable oils (triglycerides) are
transesterified that means they react with methanol obtaining esters of vegetable oils (or
fatty acids) whose properties are closer to diesel fuel, especially concerning viscosity.

Biodiesel can be mixed with petroleum diesel at any concentration in most modern
engines, although it has the disadvantage of degrading rubber gaskets and hoses in
vehicles manufactured before 1992. Biodiesel is a better solvent than petrodiesel and has
been known to break down deposits of residue in the fuel lines of vehicles that have
previously been run on petroleum. Fuel filters may become clogged with particulates if a
quick transition to pure biodiesel is made, but biodiesel cleans the engine in the process.

The problems associated with the use of vegetable oils in diesel engines are basically
related to viscosity and final boiling point. The high viscosity of vegetable oils (10 times
higher than diesel fuel viscosity) is responsible of troubles in injection system and,
particularly, the combination of a high viscosity with a high final boiling point has a very
negative influence on engine deposit formation: difficulties appear in drop formation and
vaporization processes and the air-fuel mixture has not the correct ratio in all points;
because of the high temperatures, a great part of the fuel molecules will recombine to
form other different compounds that can build up carbonaceous deposits in injector
nozzles, combustion chamber, piston, valves, etc.; these deposits will deteriorate the
engine and cause it a difficult running . Furthermore, vegetable oils produce a power loss
and an emission increase: a larger quantity of particulates are created and the probability
of misfiring is greater, thus forcing a portion of unburnt fuel to go out with exhaust gases,
while other portion is remaining in combustion chamber walls and is taken out with
lubricating oil; an eventual lubricant dilution can occur. This kind of problems are more
marked in direct injection engines than in indirect injection, because in direct injection
the jet shape has a much greater influence on mix process.
Another difficulty that vegetable oils show is a really low cetane number; it could be
accepted in large and slow engines, but not in small fast automotive engines. Finally we
must denote that vegetable oils have a high Cold Filter Plugging Point (CFPP), property
that does not allow to use them at temperatures below 10ºC. To overcome all these
problems, various solutions have been studied:
-Fuel preheating.
-Use of modified engines (ej.: Elsbett engine).
-Chemical modification of fuel.
The first two solutions do not allow the use in current engines (interchangeability with
diesel fuel); the last solution, through transesterification process, is the one with a larger
development potential.

The use of methylesters (product of transesterification of a vegetable oil) in diesel

engines allows to overcome most of vegetable oils problems, since they present the
following properties:
-A very lower viscosity than vegetable oils and close to diesel fuel viscosity; this property
implies jet characteristics similar to diesel fuel in mix process.
-A lower final boiling point than vegetable oils, therefore methylesters decomposition in
other different compounds is much lesser.
-A cetane number close to diesel fuel’s or, even, higher.
-A lower CFPP than vegetable oils; thus allowing the use at colder temperatures than
vegetable oils.
Main particularities of using vegetable methylesters in diesel engines are:
1. Performance. A slight loss of power and a slight increase of fuel consumption
appears, because the heating value is smaller than that of diesel fuel; combustion
efficiency is similar in both fuels.
2. Fuel lubricity. Growing concerns about environmental problems have resulted in a
reduction in sulphur and aromatic content in diesel fuel; that involves a significant loss of
lubricity, with a great risk of deterioration of the injection pump components. Addition of
methylesters to diesel fuel, even in small proportions, involves a significant improvement
in lubricity.
3. Dilution of lubricating oil. Sometimes, a loss of viscosity has been detected in
lubricating oil, but always in quantities below 5%.
4. Cold weather limitations. Cloud point and CFPP properties of some methylesters are
higher than diesel fuel properties and may cause difficulties in vehicle operability and
startability in cold weather. These difficulties could be overcome with appropriate
antifreeze additives.
5. Incompatibility with some materials. Methylesters are more aggressive to materials
than diesel fuel and they may attack rubber and some ordinary types of paintings. To
avoid risk of chemical attacks, acrylic paintings must be used and rubber elements must
be replaced by teflon or fluoridated rubber.
6. A lesser stability and a larger tendency to form carbonaceous deposits. Because
methylester molecules have unsaturated bonds, they may present a lesser stability in long
storages than diesel fuel and they have a higher facility to oxidize and form heavier
compounds because of prereactions that happen before combustion; they may build-up
deposits on the inner elements of the engine and obstruct injector nozzles. However, this
phenomenon is not quite clear because the authors have obtained results in which the
mixtures of sunflower methylesters with diesel fuel present a smaller level of nozzle
fouling than diesel fuel alone. Methylesters would work in this case as a detergent
additive of diesel fuel .
7. Pollutant emissions. A great number of pollution tests have been made in engines
working with methylesters. The results obtained depend on the type of engine, operating
conditions, fuel quality, etc., but in general the use of vegetable oil methylesters in diesel
engines produces a more effective combustion than diesel fuel, due to the presence of
oxygen in methylester molecule. This implies a better efficiency, a significant reduction
in particulates emission (lesser opacity of smoke), and, in general, a decrease in CO and
HC emissions. NOX emissions can be increased slightly, typically with 6-15% . Some
results are summarized from different tests carried out in France, Austria and Spain on
light vehicles and urban buses; all of them were running with 100% rapeseed methylester
(RME) in different test cycles.
At global level, because the net emissions of CO2 to atmosphere of methylesters are
estimated in 1/4 of emissions produced by diesel fuel, with the consequent reduction of
greenhouse effect. At regional level, because emissions of one element responsible for
acid rain, SOX, is reduced: sulphur oxides are originated from sulphur contained in the
fuel and methylesters have, in their chemical composition, a much smaller sulphur
presence than diesel fuels.

Other source on :

Environmental benefits in comparison to petroleum based fuels include:

 Biodiesel reduces emissions of carbon monoxide (CO) by approximately 50% and

carbon dioxide by 78.45% on a net lifecycle basis because the carbon in biodiesel
emissions is recycled from carbon that was already in the atmosphere, rather than
being new carbon from petroleum that was sequestered in the earth's crust.
(Sheehan, 1998)
 Biodiesel contains fewer aromatic hydrocarbons: benzofluoranthene: 56%
reduction; Benzopyrenes: 71% reduction.
 It also eliminates sulfur emissions (SO2), because biodiesel does not include
sulfur.
 Biodiesel reduces by as much as 65% the emission of particulates, small particles
of solid combustion products.
 Biodiesel does produce more NOx emissions than petrodiesel, but these emissions
can be reduced through the use of catalytic converters. The increase in NOx
emmisions may also be due to the higher cetane rating of biodiesel. Properly
designed and tuned engines may eliminate this increase.
 Biodiesel has a higher cetane rating than petrodiesel, and therefore ignites more
rapidly when injected into the engine.

Pure biodiesel (BD100 or B100) can be used in any petroleum diesel engine, though it is
more commonly used in lower concentrations,usually 20-25%. Some areas have
mandated ultra-low sulfur petrodiesel, which reduces the natural viscosity and lubricity of
the fuel due to the removal of sulfur and certain other materials. Additives are required to
make Ultra Low Sulphur Diesel fuel properly flow in engines, making biodiesel one
popular alternative. Ranges as low as 2% (BD2 or B2) have been shown to restore
lubricity. The European diesel fuel standard EN590 allows to have 7% FAME (Fatty
Acid Methyl Ester) which is the chemical name of biodiesel. Since biodiesel is more
often used in a blend with petroleum diesel, there are fewer formal studies about the
effects on pure biodiesel in unmodified engines and vehicles in day-to-day use. Fuel
meeting the standards and engine parts that can withstand the greater solvent properties
of biodiesel is expected to--and in reported cases does--run without any additional
problems than the use of petroleum diesel. The flash point of biodiesel (150 °C) is
significantly higher than that of petroleum diesel (64 °C) or gasoline (−45 °C).

Many advocates suggest that waste vegetable oil (WVO) is the best source of oil to
produce biodiesel. However, the available supply is drastically less than the amount of
petroleum-based fuel that is burned for transportation and home heating in the world.
According to the United States Environmental Protection Agency (EPA), restaurants in
the US produce about 300 million US gallons (1,000,000 m³) of waste cooking oil
annually.[1] Although it is economically profitable to use WVO to produce biodiesel, it is
even more profitable to convert WVO into other products such as soap. Hence, most
WVO that is not dumped into landfills is used for these other purposes. Animal fats are
similarly limited in supply, and it would not be efficient to raise animals simply for their
fat. However, producing biodiesel with animal fat that would have otherwise been
discarded could replace a small percentage of petroleum diesel usage.

The composition of pure biodiesel (B100), the fatty acid metyl ester (FAME), is
standardized in EN 14214.

The European standard of diesel fuel, EN 590, allows a maximum content of 7% FAME.
This requirement is included also in Romanian product standards.

Supplementary SVO Straight Vegetable Oil (SVO) is a fuel for diesel engines that can be
either pure new vegetable oil or Waste vegetable oil that has been cleaned.

SVO burns well in many diesel engines but, due to its relatively high viscosity, using
SVO with unmodified engines can lead to poor atomisation of the fuel, incomplete
combustion, coking in the injectors, ring carbonisation, and accumulation of fuel in the
lubricating oil. The proportion of SVO in diesel fuel is low, 5-10%.

Most diesel car engines are suitable for the use of SVO with some modifications. One
common solution is to add an additional fuel tank, one for SVO and a separate tank of
diesel (petrodiesel or biodiesel) and an electric valve to switch between them. The
viscosity of the SVO is reduced by preheating it using heat from the engine; the engine is
started on diesel, switched over to SVO as soon as it is warmed up and switched back to
diesel shortly before being switched off to ensure it has no SVO in it when it is started
from cold again. In colder climates it is often necessary to heat the SVO’s fuel lines and
tank as it can become very viscous. Another common solution (the one-tank system) is to
add electric pre-heating of the fuel and if necessary upgrade the injection pumps and
glow-plugs to allow SVO fuel use with one tank.
With unmodified engines the unfavourable effects can be reduced by mixing, or
“cutting”, the SVO with diesel fuel. For normal use, without either mixing or a second
tank and associated modifications in a petrodiesel engine, vegetable oil must be
transesterified to biodiesel.

Chapter 6. HYDROGEN

6.1. INTRODUCTION

Nowadays as transportation sector is fueled almost exclusively by petroleum products

like gasoline and diesel and power plants run mainly on oil, natural gas and coal, it may
be said that most of world economy is a fossil fuel economy.

The use of fossil fuels made possible the development of the human society to the
actual level, but created two important problems : environmental pollution and economic
dependency.

Environmental pollution means greenhouse effect which generates global warming and
climate changes, air pollution with the products combustion ( carbon monoxide, CO,
gaseous hydrocarbons, HC, nitrogen oxides , NOx, and particulate matter Pt) and other
water, land pollution from the processes of manufacturing, transporting, storing,
distributing of the fuels.

A way to solve the present day problem and to cope with the fossil fuel depletion is to
gradually pass to hydrogen economy.

As for the moment hydrogen can be produced by water electrolysis ( consuming

electricity produced usually through fossil fuel burning ) or by fossil fuel reformulation
(hydrocarbons decomposes generating hydrogen and other carbon based compounds ) it
is needed to use renewable energy sources rather than fossil fuels to produce hydrogen
and to have a pure hydrogen economy. The advantages of hydrogen economy are the
reduction of pollution caused by fossil fuels, mainly the elimination of greenhouse gases,
the limitation of economic dependence and ubiquity of hydrogen production.

In transport sector hydrogen is as primary source of power through one of two methods:
combustion or fuel-cell conversion. In combustion, the hydrogen is burned in engines in
the same way as conventional engines. In fuel-cell conversion, the hydrogen is turned
into electricity through fuel cells which then powers electric motors.

It is still difficult to store hydrogen in sufficient quantity for motor fuel use. Hydrogen
fuel cells were promoted as mobile power sources with lower emissions than hydrogen-
burning internal combustion engines. The low emissions of hydrogen in internal
combustion engines and fuel cells are currently offset by the pollution created by
hydrogen production. This may change if the substantial amounts of electricity required
for water electrolysis can be generated primarily from low pollution sources such as
nuclear energy or wind.
6.2 PRODUCTION OF HYDROGEN
Hydrogen is the simplest element on earth. An atom of hydrogen has only one proton
and one electron. It is a colorless, odorless, nonmetallic, univalent, tasteless, highly
flammable diatomic gas. Hydrogen is the lightest (density 0.08988 g/l) and most
abundant element. Hydrogen has a very high specific energy (120.0 MJ/kg), making it
very desirable as a transportation fuel.It is present in water, all organic compounds and in
all living organisms. Hydrogen is able to react chemically with most other elements.
There are no hydrogen reserves such wells or mines for oil or coal, so hydrogen cannot
be considered a primary energy source like fossil fuels or uranium. Hydrogen has a great
potential as an energy carrier in the future. An energy carrier is a substance or system
that moves energy in a usable form from one place to another. The typical energy carrier
is electricity which moves from coal, uranium, oil, waterfalls.
Hydrogen can be produced in thermal, electrolytic and photolytic processes:
Thermal processes use the heat and catalysts to release hydrogen from different energy
sure sources: natural gas, coal, or biomass; the processes are steam reformation and
partial oxidation.
Steam reformation uses a high-temperature steam (700 - 1000°C) to produce hydrogen
from a hydrocarbon. Typical reactions for producing hydrogen from methane and
gasoline are as follows;
Methane: CH4 + H2O (+heat) → CO + 3H2
Gasoline: C8H18 + 8H2O (+heat) → 8CO + 17H2
Additional hydrogen can be recovered from the carbon monoxide through the water-gas
shift reaction:
CO + H2O → CO2 + H2
The reformation of fossil fuel (mainly methane and methanol) is produced in a device
called reformer.
In partial oxidation, hydrocarbons combines with a limited amount of oxygen
Methane: CH4 + ½O2 → CO + 2H2 (+heat)
Gasoline: C8H18 + 4O2 → 8CO + 9H2 (+heat)
Other reaction is coal, biomass or alcohol gaseification through which heated
hydrocarbon in the presence of oxigen is converted under pressure into a gaseous mixture
of hydrogen, carbon monoxide and carbon dioxide.
CH + O2 + H2O → CO + CO2 + H2
Electrolytic processes use electricity to split water into hydrogen and oxygen, a process
that takes place in an electrolyzer. Electrolyzers consist of an anode and a cathode
separated by an electrolyte. Their types are similar to fuel cell types polymer electrolyte
membrane (PEM) electrolyzer, alkaline electrolyzers, solid oxide electrolyzers.
Photolytic processes use light energy to split water into hydrogen and oxygen using
sunlight and specialized microorganisms, such as green algae and cyanobacteria which
consume water and produce hydrogen as a byproduct of their natural metabolism.
Another version produces hydrogen from water using sunlight and semiconductors
(photoelectrochemical materials) which dissociate water into hydrogen and oxygen.
From the abovementioned processes steam reforming, mainly from natural gas-methane,
is the most spread and least expensive method of producing hydrogen (95% of production
volume).As natural gas is a fossil fuel, the process still generates greenhouse gas
emissions.

6.3. STORAGE OF HYDROGEN

One of the most challenging problems in the development of hydrogen-powered vehicles

is the on-board storage as the hydrogen density is very small so also the energy density,
requiring specific techniques in order to guarantee an acceptable driving range (400-500
km).
Current on-board hydrogen storage techniques are: compressed hydrogen gas tanks,
liquid hydrogen tanks, metal hydrides, carbon-based materials/high surface area sorbents,
and chemical hydrogen storage.
Among the requirements imposed to storage systems are gravimetric capacity (of 2
kWh/kg system or 6 wt.% hydrogen) and volumetric capacity (of 1.5 kWh/l or 0.045 kg
hydrogen/l), low cost, safety devices, low operation time and maintenance periods.

6.3.1. Tanks for compressed gas

Driving range of fuel cell vehicles carrying compressed hydrogen tanks depends on
vehicle design and on the quantity and pressure of stored hydrogen. Increasing the
amount and the pressure of hydrogen, an increased driving extent could be accomplished,
but with extra costs and diminishing the useful space of the vehicle. Key benchmarks of
compressed hydrogen tanks are then maximal pressure and volumetric capacity.
Time for refueling, costs of compression energy and heat control during compression
need also to be considered.
Energy density of gaseous hydrogen can be improved by it at higher pressures ; in order
to provide tank integrity, improved design and materials are needed. Carbon fiber-
reinforced 350 bar to 700 bar compressed hydrogen gas tanks are produced. The inner
liner of the tank is a high molecular weight polymer that serves as a hydrogen gas
permeation barrier. A carbon fiber-epoxy resin composite shell is placed over the liner
and constitutes the gas pressure load-bearing component of the tank. Finally, an outer
shell is placed on the tank for impact and damage resistance. The pressure regulator for
the 700 bar tank is located in the interior of the tank. There is also an in-tank gas
temperature sensor to monitor the tank temperature during the gas filling process when
heating of the tank occurs.
Two approaches are being pursued to increase the gravimetric and volumetric storage
capacities of compressed gas tanks from their current levels. The first approach involves
cryo-compressed tanks. This is based on the fact that, at fixed pressure and volume, gas
tank volumetric capacity increases as the tank temperature decreases. Thus, by cooling a
tank from room temperature to liquid nitrogen temperature (77 K), its volumetric
capacity will increase by a factor of four, although system volumetric capacity will be
less than this due to the increased volume required for the cooling system.
The second approach involves the development of conformable tanks. Present liquid
gasoline tanks in vehicles are highly conformable in order to take maximum advantage of
available vehicle space. Concepts for conformable tank structures are based on the
location of structural supporting walls. Internal cellular-type load bearing structures may
also be a possibility for greater degrees of conformability.
Compressed hydrogen tanks for 350 bar and 700 bar have been certified worldwide
according to ISO 11439 (Europe), NGV-2 (U.S.), and Reijikijun Betten (Iceland)
standards and approved by TUV (Germany) and The High-Pressure Gas Safety Institute
of Japan (KHK). Some tanks - implemented in several fuel cell prototype vehicles - are
available commercially. Composite tanks of 700 bar have proven a 2.35 safety factor
(2.35 x 700 bar burst pressure) as required by the European Integrated Hydrogen Project
specifications.
6.3.2. Liquid hydrogen ( LH2 ) tanks
The energy density of hydrogen can be improved [36] by storing hydrogen in a liquid
state, at 20 K (-253°C). Nevertheless, specific issues with LH 2 (liquefied hydrogen) tanks
are, besides size, weight and cost, the energy required for hydrogen liquefaction and the
boil-off of hydrogen.
Energy requirements for liquefaction are high: 30% of the heating value of hydrogen is
normally required for liquefaction ( ! ). Insulation is compulsory for LH 2 tanks and this
diminishes the volumetric and gravimetric capacity.
LH2 tanks can obviously store more hydrogen in a given volume than compressed gas
tanks. Volumetric capacity of LH2 is 0.070 kg/l, compared to 0.030 kg/l for 700 bar gas
tanks.
LH2 tanks were tested in hydrogen-powered vehicles. Hybrid tanks (that combine both
high-pressure gaseous and cryogenic storage) are investigated. These "cryo-compressed"
tanks with insulated pressure vessels are lighter than liquefied and more compact than
high pressure vessels at ambient-temperatures. As required temperatures are not as low as
for LH2, less energy is needed for liquefaction and evaporative losses are lower.
 Fig.6.1. Linde liquid hydrogen storage system [37]

6.3.3. Storing hydrogen in materials

There are three generic mechanisms known for storing hydrogen in materials.
These mechanisms are: absorption, adsorption, and chemical reaction.
 Absorption. In absorptive hydrogen storage, hydrogen is absorbed directly into the
bulk of the material. The typical structure is simple crystalline metal hydrides (with
absorption by incorporation of atomic hydrogen into interstitial sites in the
crystallographic lattice) but there are also intensive R&D efforts on carbon-based
materials.
 Adsorption (storage on the surface) may be subdivided into physisorption and
chemisorption, based on the energetics of the adsorption mechanism. Physisorbed
hydrogen is weaker energetically bound to the material than is chemisorbed
hydrogen. Sorptive processes require materials with high porosity in order to
maximize the surface available for hydrogen sorption, and to allow the easy uptake
and release of hydrogen.
 Chemical reaction. The hydrogen storage chemical route involves displacive
chemical reactions both for hydrogen generation and for storage. Hydrogen is
released via chemical reaction (usually with water or alcohol); the 'spent fuel' (e.g.
sodium borohydride) or byproduct is usually regenerated off-board.
Metal hydrides are reversible solid-state materials that can be regenerated usually on-
board as result of little changes in the temperature and pressure.A simple metal hydride
such as LaNi5H6, that is incorporating hydrogen in its structure, can function, but has an
insufficient gravimetric capacity (~1.3 wt.%) and is too expensive to be applied at
vehicles.
Complex metal hydrides such as the above-mentioned alanate materials (AlH 4) have
higher gravimetric hydrogen capacities in the operational window than simple metal
hydrides. AlH4 can reversibly store and release hydrogen when doped with titanium
catalyst – see the following two-step reaction for NaAlH4 (sodium alanate):
NaAlH4 = 1/3 Na3AlH6 +2/3Al+H2
Na3AlH6 = 3 NaH + Al + 3/2H2
At 1 atm, the 1st reaction is thermodynamically favored for temperatures above 33°C and
can release 3.7 wt.% hydrogen, while the 2 nd reaction takes place above 110°C and can
release 1.8 wt.% hydrogen. The amount of hydrogen that a material can release (more
important in this case than the amount the material can hold), is the main parameter that
determines system (net) gravimetric and volumetric capacities.
Problems of complex metal hydrides include, beside costs, the low hydrogen capacity as
well as slow uptake and release. The maximum gravimetric capacity (of material, not of
the system), 5.5 wt.% hydrogen for NaAlH4 is below the target of 6 wt.% set for the
system in 2010. For the moment, 4 wt.% reversible hydrogen content has been proven
with alanates. Hydrogen release kinetics are still slow for vehicles. The packing density
of these powders is not more than 50% and affects the volumetric capacity of the system.
Even if sodium alanates aren't expected to meet the targets set for 2010, their study
facilitate the R&D of improved complex metal hydrides.
The state-of-the-art is a new complex hydride system based on lithium amide, with the
reversible reaction at 285°C and 1 atm:
Li2NH + H2 = LiNH2 + LiH
Actual 6.5 wt.% hydrogen can be reversibly stored and this could be improved up to 10
wt.%. The current operating temperature is unfortunately outside of the vehicular
operating window. By magnesium substitution, the temperature of this reaction can be
lowered to 220°C, although at higher pressure. More R&D on this system might improve
the operating conditions with increased capacity.
Thermal control during refueling is another problem of complex metal hydrides, due to
reaction enthalpies. Depending on the amount of stored hydrogen and on refueling time
required, megawatts up to half gigawatt must be managed during recharging on-board
systems based on metal hydrides. Reversibility has also to be tested for more than 1000
cycles.
 Fig.6.2. Metal hydrides characteristics [36]
Carbon-based materials are other reversible solid-state materials that can be
regenerated on-board. They include carbon nanotubes, aerogels, nanofibers (including
metal doped hybrids), as well as metal-organic frameworks, conducting polymers and
clathrates. Provided the structures can be tailored at nano-scale, the hydrogen storage
could be enhanced.
Single-walled carbon nanotubes have hydrogen gravimetric capacities of 3-10 wt.% at
room's temperature. These values are also below the target of 6.0 wt.% set for 2010 and
further R&D is needed. Costs should be lowered for high-volume production in order to
make single-walled carbon nanotubes attractive for vehicular applications.

6.3.4. Challenges for the hydrogen storage

In transportation, it is needed to store enough hydrogen for a 4-500 km driving range in
vehicles' restricted volume, with limited weight and price, with maximum of efficiency
and in very safe conditions. Durability must also be tested and validated over the
expected systems' lifetime, with acceptable refueling times must be achieved. So, the
main challenges are:
 Weight and Volume. Present hydrogen storage systems are still bulky and heavy
(thus indirectly reducing the driving range) compared to conventional fueled vehicles.
New materials are needed for light and compact storage systems that should allow the
above-mentioned 4-500 km driving range in light-duty vehicles.
 Energy efficiency. The energy required to store and release hydrogen is essential for
reversible solid-state materials. Life-cycle energy efficiency is essential for chemical
hydride storage with off-board by-product regeneration. The energy needed for
compression and liquefaction has to be considered for the other two technologies.
 Durability. Materials and components should resist to 1500 cycles of hydrogen
storage/release.
 Refueling Time. It should stay under 3 minutes (a value not yet practically
available), for the life of the system.
 Cost. It is still too high compared with conventional petrol fuel storage. Materials and
components for hydrogen storage systems are still expensive. Manufacturing costs are
expected to decrease in mass production.
 Codes & Standards – for storage and interfacing/operating, are still needed in order
to facilitate safe implementation, sales and acceptance.
 Life-Cycle and Efficiency Analyses – for hydrogen storage systems.
The state-of-the-art of the main benchmarks (weight, volume and cost) of hydrogen
storage types is shown in fig.6.3. The values are estimates from storage system R&D.

Fig.6.3 Hydrogen storage status [35]

6.3.5. Hazards
Several unique properties of hydrogen make it more hazardous than most other
flammable gases. Hydrogen cannot be easily detected as it is a colorless, odorless, and
tasteless gas. It burns with a flame that is extremely hot but doesn't light, so the burning
of hydrogen has few warning signs and the extent of hydrogen fires are difficult to
accomplish. Hydrogen can form ignitable mixtures between 4 and 75 % of volume in air.
The range for explosive mixtures is also incredibly broad: 18 to 59 % of volume in air.
The energy content per weight of a stoichiometric mixture of hydrogen and air is about
the same as that for the explosives, although much less energy is converted to pressure
waves during detonation. Hydrogen needs extremely low ignition-energy: a 20 µJ spark
can ignite a stoichiometric hydrogen/air mixture (10 times less than the energy required
to ignite a gasoline/air mixture.) Unfortunately, such sparks can be generated by most
types of electrical equipment as well as by any static charges (e.g. on clothes). Hydrogen
auto-ignition temperature is 585°C.
Factors to be considered in the design of hydrogen systems:
 Embrittlement – underwent by many metals exposed to hydrogen. It is then
important to select suitable materials to safeguard against this condition. Austenitic
stainless steel, monel, copper, and aluminum are generally satisfactory for hydrogen
use. Cast iron pipe and fittings are not suitable and shall not be used.
 Flammable Mixtures. Confined hydrogen/air mixtures can detonate instead of burn.
Hence, it is imperative to prevent the formation of flammable hydrogen/air mixtures
in the system. When air or other oxidizing gases connect to a hydrogen system, a
check valve on the oxidizer supply must be installed and flash arrestors on the
hydrogen supply.
 Ventilation. Hydrogen shall be used only in well-ventilated areas. The amount of
ventilation required will vary in each case depending on the total supply of hydrogen,
the rate of use or generation, and the venting arrangement from the process or
hydrogen system. For all hydrogen gas systems, it may be necessary to vent normal
effluent and pressure-relief devices outdoors or into a suitable exhaust duct, to avoid
or carefully locate spark-producing motors and make-or-break electric contacts and to
place the system in a ventilated enclosure.
Hydrogen supplies should be located outside buildings, and the gas should be piped to the
laboratory at the lowest usable pressure. The extra hydrogen cylinders must be stored in
well-ventilated outdoor locations, away from flammable and combustible materials.
Hydrogen cylinders shall be stored at least 60 m ft from all oxidizing gases or be
separated by a noncombustible, fire-resistant barrier.
6.3.6. Fuel stations
Since the turn of the millenium, filling stations offering hydrogen have been opening
worldwide. Among them around 50 units in USA, most of them in California opened by
the California Fuel Cell Partnership and under hydrogen highway program: In Europe the
leader is Germany with 24 stations, 4 in France and Italy, and in many other European
cities as part of the Clean Urban Transport for Europe program. There are 19 stations in
Japan, 7 in Canada, 2 in China and another 20 units are in different stages of construction
all over the world.

6.4. FUEL CELLS

Today, fuel cells are being developed to power passenger vehicles, commercial buildings,
homes, and even small devices such as laptop computers.
Fuel cell systems can be extremely efficient over a large range of sizes (from 1 kW to
hundred of megawatts). Some systems can achieve overall efficiencies of 80% or more
when heat production is combined with power generation. Fuel cell systems integrated
with hydrogen production and storage can provide fuel for vehicles, energy for heating
and cooling, and electricity.
6.4.1 Fuel cell configuration
The most obvious step in the hydrogen development will be the marketing of fuel-cell-
powered vehicles. Although they will be powered initially by gasoline and reformers,
fuel cells embody two major improvements over the internal combustion engine:
 They are about twice as efficient.
 They can significantly reduce air pollution in cities.
A history of fuel cell can be highlighted with the events:
 William Grove is consider to be the inventor of the fuel cell, in 1839 he built a device
using H2 as fuel, O2 as oxidizing agent and H2SO4 solution as electrolyte.
 In 1870 Jules Verne in his novel The Mysterious Island anticipated the solution:
“Water will be the coal of the future”.
 Francis T. Bacon developed the fuel cell H2/O2 using Ni electrodes showing higher
efficiencies than conventional combustion engine.
 It was Sadi Carnot in his book “Reflexions sur la puissance motrice du feu” who
demonstrated the thermal cycle efficiencies of 35%.
 At the beginning of XX century electric energy was obtained in power plant with low
efficiency (2.6%) from coal burning. W. Jacques used in fuel cells carbon as fuel with
efficiency of 80%.
The basic difference and advantage of fuel cell is that internal process are
electrochemical which are not limited by the Second Law of Thermodynamics, thus
leading, at least in theory, at efficiencies twice or even more higher than of conventional
heat engines.
Fuel cells are galvanic cells which convert chemical energy to electrical energy by means
of electrochemical process. The device is similar to a battery, but differing from the latter
in that it is designed for continuous replenishment of the reactants consumed; i.e. it
produces electricity from an external fuel supply of hydrogen and oxygen as opposed to
the limited internal energy storage capacity of a battery. Additionally, the electrodes
within a battery react and change as a battery is charged or discharged, whereas a fuel
cell's electrodes are catalytic and relatively stable.
In a fuel cell it is forced an electron transfer to take place through an external pathway
rather than directly, between reactants. A fuel and an oxidant (O2 or air) which are placed
at separate electrodes and the excess chemical energy is converted into DC electricity the
fuel source is usually H2 or a H2 carrier (natural gas or methanol). Outside fuel is turned
into electrical energy and fuel cell doesn’t require to be discarded or to be recharged.
It consists of two porous electrodes where the energy conversion takes place and the solid
or liquid electrolyte conducts ions to form a closed circuit.

load The electrons are drawn to the

cathode forming the negative
charged ions. The electrons move
Cathode Anode to the external circuit connecting
(oxidant (fuel the cathode and anode and it is
electrode) electrode)
created the electric energy as a
source of power.
The electrolyte provides a path for
O2 H2 H2 ions (protons) to pass from the
anode to the cathode (oxygen) side
of the cell.

water

electrolyte
 H2 ions combine catalytically with O2 and electrons will form water:

Fig.6.4. Fuel cell scheme The overall reaction:

The ideal efficiency of fuel cell is 80-90%, in reality there are losses leading to
efficiencies in the range 45…65%.
Typical reactants used in a fuel cell are hydrogen on the anode side and oxygen on the
cathode side (a hydrogen cell). Typically in fuel cells, reactants flow in and reaction
products flow out, and continuous long-term operation is feasible virtually as long as
these flows are maintained.
Most fuel cell systems consist of four basic components:
 Fuel cell stack
 Fuel processor
 Current converter
 Heat recovery system
Most fuel cell systems also include other components and subsystems to control fuel cell
humidity, temperature, gas pressure, and wastewater.
The fuel cell stack is the heart of a fuel cell power system. It generates electricity in the
form of direct current (DC) from chemical reactions that take place in the fuel cell. A
single fuel cell produces enough electricity for only the smallest applications. Therefore,
individual fuel cells are typically combined in series into a fuel cell stack. A typical fuel
cell stack may consist of hundreds of fuel cells. The amount of power produced by a fuel
cell depends upon several factors, such as fuel cell type, cell size, the temperature at
which it operates, and the pressure at which the gases are supplied to the cell.
The fuel processor converts fuel into a form useable by the fuel cell. If hydrogen is fed to
the system, a processor may not be required or it may only be needed to filter impurities
out of the hydrogen gas. If the system is powered by a hydrogen-rich conventional fuel
such as methanol, gasoline, diesel, or gasified coal, a reformer is typically used to convert
hydrocarbons into a gas mixture of hydrogen and carbon compounds called "reformate."
In many cases, the reformate is then sent to another reactor to remove impurities, such as
carbon oxides or sulfur, before it is sent to the fuel cell stack. This prevents impurities in
the gas from binding with the fuel cell catalysts. This binding process is also called
"poisoning" since it reduces the efficiency and life expectancy of the fuel cell. Some fuel
cells, such as molten carbonate and solid oxide fuel cells, operate at temperatures high
enough that the fuel can be reformed in the fuel cell itself. This is called internal
reforming. Fuel cells that use internal reforming still need traps to remove impurities
from the unreformed fuel before it reaches the fuel cell. Both internal and external
reforming release carbon dioxide, but less than the amount emitted by internal
combustion engines, such as those used in gasoline-powered vehicles.
Current inverters and conditioners adapt the electrical current from the fuel cell to suit
the electrical needs of the application, whether it is a simple electrical motor or a complex
utility power grid. Fuel cells produce electricity in the form of direct current (DC). In a
direct current circuit, electricity flows in only one direction. The electricity in your home
and work place is in the form of alternating current (AC), which flows in both directions
on alternating cycles. If the fuel cell is used to power equipment using AC, the direct
current will have to be converted to alternating current. Both AC and DC power must be
conditioned. Power conditioning includes controlling current flow (amperes), voltage,
frequency, and other characteristics of the electrical current to meet the needs of the
application. Conversion and conditioning reduce system efficiency only slightly, around
2 to 6 percent.
Heat recovery. Fuel cell systems are not primarily used to generate heat. However, since
significant amounts of heat are generated by some fuel cell systems—especially those
that operate at high temperatures such as solid oxide and molten carbonate systems—this
excess energy can be used to produce steam or hot water or converted to electricity via a
gas turbine or other technology. This increases the overall energy efficiency of the
systems.
6.4.2. Fuel cell types
There are several types of fuel cells currently developed, each with its own advantages,
limitations, and potential applications:
 Polymer Electrolyte Membrane (PEM) Fuel Cells –this is used for automotive
 Direct Methanol Fuel Cells
 Alkaline Fuel Cells
 Phosphoric Acid Fuel Cells
 Molten Carbonate Fuel Cells
 Solid Oxide Fuel Cells
 Regenerative Fuel Cells

Polymer Electrolyte Membrane (PEM) Fuel Cells

Fig. 6.5. PEM cell

Polymer electrolyte membrane (PEM) fuel cells—also called proton exchange membrane
fuel cells—deliver high power density and offer the advantages of low weight and
volume, compared to other fuel cells.
PEM fuel cells use a solid polymer as an electrolyte and porous carbon electrodes
containing a platinum catalyst. They need only hydrogen, oxygen from the air, and water
to operate and do not require corrosive fluids like some fuel cells. They are typically
fueled with pure hydrogen supplied from storage tanks or onboard reformers.
Polymer electrolyte membrane fuel cells operate at relatively low temperatures, around
80°C (176°F). Low temperature operation allows them to start quickly (less warm-up
time) and results in less wear on system components, resulting in better durability.
However, it requires that a noble-metal catalyst (typically platinum) be used to separate
the hydrogen's electrons and protons, adding to system cost. The platinum catalyst is also
extremely sensitive to CO poisoning, making it necessary to employ an additional reactor
to reduce CO in the fuel gas if the hydrogen is derived from an alcohol or hydrocarbon
fuel. This also adds cost. Developers are currently exploring platinum/ruthenium catalysts
that are more resistant to CO.
PEM fuel cells are used primarily for transportation applications and some stationary
applications. Due to their fast startup time, low sensitivity to orientation, and favorable
power-to-weight ratio, PEM fuel cells are particularly suitable for use in passenger
vehicles, such as cars and buses. PEM fuel cells are made from several layers of different
materials The three key layers in a PEM fuel cell include: membrane electrode assembly,
catalyst and hardware.
The electrodes (anode and cathode), catalyst, and polymer electrolyte membrane together
form the membrane electrode assembly (MEA) of a PEM fuel cell.
 Anode. The anode, the negative side of the fuel cell, has several jobs. It conducts the
electrons that are freed from the hydrogen molecules so that they can be used in an
external circuit. Channels etched into the anode disperse the hydrogen gas equally
over the surface of the catalyst.
 Cathode. The cathode, the positive side of the fuel cell, also contains channels that
distribute the oxygen to the surface of the catalyst. It conducts the electrons back from
the external circuit to the catalyst, where they can recombine with the hydrogen ions
and oxygen to form water.
 Polymer electrolyte membrane. The polymer electrolyte membrane (PEM)—a
specially treated material that looks something like ordinary kitchen plastic wrap—
conducts only positively charged ions and blocks the electrons. The PEM is the key to
the fuel cell technology; it must permit only the necessary ions to pass between the
anode and cathode. Other substances passing through the electrolyte would disrupt
the chemical reaction.
The thickness of the membrane in a membrane electrode assembly can vary with the type
of membrane. The thickness of the catalyst layers depends upon how much platinum (Pt)
is used in each electrode.

Supplementary reading
6.4.4. Fuel cell -Facing problems

Cost and durability are the major challenges to fuel cell commercialization. However,
hurdles vary according to the application in which the technology is employed. Size,
weight, and thermal and water management are barriers to the commercialization of fuel
cell technology. In transportation applications, these technologies face more stringent
cost and durability hurdles. In stationary power applications, where cogeneration of heat
and power is desired, use of PEM fuel cells would benefit from raising operating
temperatures to increase performance.
The key challenges include:
 Cost. The cost of fuel cell power systems must be reduced before they can be
competitive with conventional technologies. Currently the costs for automotive
internal combustion engine power plants are about $25-$35/kW; for transportation
applications, a fuel cell system needs to cost $30/kW for the technology to be
competitive. For stationary systems, the acceptable price point is considerably higher
($400-$750/kW for widespread commercial-lization and as much as $1000/kW for
initial applications.
 Durability and Reliability. The durability of fuel cell systems has not been
established. For transportation applications, fuel cell power systems will be required
to achieve the same level of durability and reliability of current automotive engines,
i.e., 5,000 hour lifespan (150,000 miles equivalent), and the ability to function over
the full range of vehicle operating conditions (40°C to 80°C). For stationary
applications, more than 40,000 hours of reliable operation in a temperature at -35°C
to 40°C will be required for market acceptance.
 System Size. The size and weight of current fuel cell systems must be further reduced
to meet the packaging requirements for automobiles.
This applies not only to the fuel cell stack, but also to the ancillary components and
major subsystems (e.g., fuel processor, compressor/expander, and sensors) making up
the balance of power system.
 Air, Thermal, and Water Management. Air management for fuel cell systems is a
challenge because today's compressor technologies are not suitable for automotive
fuel cell applications. In addition, thermal and water management for fuel cells are
issues because the small difference between the operating and ambient temperatures
necessitates large heat exchangers.
 Improved Heat Recovery Systems. The low operating temperature of PEM fuel
cells limits the amount of heat that can be effectively utilized in combined heat and
power (CHP) applications. Technologies need to be developed that will allow higher
operating temperatures and/or more effective heat recovery systems and improved
system designs that will enable CHP efficiencies exceeding 80%. Technologies that
allow cooling to be provided from the low heat rejected from stationary fuel cell
systems (such as through regenerating dessiccants in a desiccant cooling cycle) also
need to be evaluated.

The typical fuel cells parameters for a passenger car are:

Net continuous power 20 kW
Net peak power 60 kW
Specific power 0.9 W/cm2
 Current density (peak) 1.8 A/cm2
Current density (continuous) 0.4 A/cm2
Volume 0.072 m3
Mass 100 kg
Number of cells 133

A block diagram of a fuel cell electric vehicle propulsion system is illustrated in fig.6.10.

Electronics Power system

Fuel Cell Stack
Air compressor
System Controller

Water recovery s.

Fuel Cell Controller

Cooling system

Power conditioning
Vaporizer

Motor Controller Fuel pump Fuel Tank

Fuel Processor

Motor Transmission Wheels

Fig.6.10. Fuel cell power-train configuration

6.5. HYDROGEN ENGINES

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. Hydrogen internal combustion cars burn hydrogen
directly, with no other fuels and produce pure water vapor exhaust.
Hydrogen has a very high specific energy (120.0 MJ/kg), making it very desirable as a
transportation fuel. Hydrogen has a very high flame speed (3.24 - 4.40 m/s), wide
flammability limits (4.0 - 75 vol%), low ignition energy (0.017 mJ), high autoignition
temperature (520C), and flame temperature of 2050 C.
The use of hydrogen as a fuel in motor vehicles offers several advantages over traditional
fossil fuels:
 There exists an unlimited supply of hydrogen -- hydrogen is the most abundant
element in the universe and the tenth most abundant element on Earth.
 Hydrogen is renewable -- When hydrogen reacts with oxygen, the by-product is
water (H2O), which can then be hydrolyzed (broken up into its component parts) to
yield more hydrogen.
 Hydrogen is clean burning -- Unlike the burning of fossil fuels, hydrogen
combustion has less destructive environmental pollutants.
 Hydrogen weighs less and generates more power than hydrocarbon-based fuels.
 Hydrogen burns faster (and at a lower temperature) than conventional gasoline.
 The specific properties regarding combustion are as follows:H2 is an extremely light
gas, 14.5 times lighter than air, with a very good diffusivity (ability to disperse in the
air),which have large range of flammability (4…75%) comparing with gasoline
(2….5%).It can be burned “lean” requiring less energy to ignite (10 times smaller
than energy used in gasoline) and there is the risk of premature ignition and flashback
leading to inefficient and rough engine running.
Octane number is low, (ON= 60), meaning the ease of abnormal combustion, knock can
appear at low compression ratios (ε = 5).The flame speed is 10 times higher than in
gasoline mixture.
As the density is extremely flow, the fuel requires large volume to store enough to give
the vehicle an appropriate driving range and the power output at the same displacement is
lower. Considering the combustion emission as the reaction is :

there will be no carbon or sulfur pollutants, meaning no CO, CO 2, HC, SOx, black smoke.
Unfortunately the flame temperature is sufficiently high to dissociate atmospheric
nitrogen which was introduced in combustion chamber with the air and to form
undesirable NOx emissions. So acid rain and ozone formation (low level) are still
generated with hydrogen combustion.
There are several companies convinced that internal combustion engine using hydrogen
as a a fuel which demonstrated the competitiveness of the solution. A specification of an
internal combustion hydrogen race car could show the state of the art:
 6.0-liter, V-12 liquid-hydrogen-powered engine
 232 HP
 Top speed 300 kph
 Aluminum space-frame chassis, carbon-fiber-reinforced
 0 to 62 mph (100 kph) in 6 seconds
 1,560 kg with full tank and driver