Seminar Report On Hydrogen As The Future Fuel

HYDROGEN AS THE FUEL OF FUTURE DEE SBNITM.
(2012-2016)
CHAPTER -1
HYDROGEN AS THE FUEL OF THE FUTURE
1 INTRODUCTION
1.1 MOTIVATION FOR THE USE OF HYDROGEN AS A FUEL
The current energy system - based on our fossil energy resources - is not a long-lasting solution to
the problems of stationary energy supply and supply with fuel for the traffic. We are exploiting
these hydrocarbon resources about one million times faster than they can be replaced. In addition,
ecological consideration, before all, the changes in climate and environmental pollution caused by
the emission of harmful substances and the greenhouse gas carbon dioxide through the conventional
fossil-fueled energy transformation processes, are rapidly gaining importance.
At the beginning of the fast technological development of our civilization, the reserve of
combustible hydrocarbons was easily accessible and easy to use. Today, especially the traffic bases
nearly completely on the use of fossil fuel. Although, the reserves have not been totally consumed,
but only a limited time span remains in which, still relying on the well-established conventional
fuels, further development of alternatives has to be carried out.
The challenge now is the development of a new energy and fuel supply system which must be
driven by solar radiation in any form, such as direct use of solar radiation, wind, water and
geothermal energy. In sharp contrast to the present system, which consumes only long-stored
reserves, the new one must base on incoming primary energy. Additionally, the new system must
be a closed system based on non-polluting cycles. The incoming primary energy must be stored in
a secondary energy carrier. The most advantageous carrier known is hydrogen.
1.2 ADVANTAGES AND DISADVANTAGES OF HYDROGEN
Compared to fossil fuels, hydrogen offers enormous advantages. Referred to its weight, it has the
highest energy density with 35,7 kWh/kg. It is easily accessible in any amount necessary. It can be
produced pollutant-free from water with any renewable energy source. It recombines pollutant-free
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Yogesh Kumar 12ESREE039 Guide Mr. A.K. Pathak

HYDROGEN AS THE FUEL OF FUTURE DEE SBNITM. (2012-2016)
with oxygen from the air back to water. It can be used equally in adapted combustion engines and
new energy supply systems such as a fuel cell system. The technology of hydrogen-fueled
combustion engines and turbines is already developed ready to the market. The development of fuel
cells is ongoing very fast and promising. The safety aspects of hydrogen are very well-known, and
an approved safety technology is existing and developed continuously since decades.
On the other hand, hydrogen has a series of disadvantages. Referred to its specific gas volume,
hydrogen has a very low energy density with 600 kWh/m3 at 200 bar. This is, only, 5,5 % of the
energy density of gasoline. Hydrogen is a gas, which can only be stored in gaseous form or, at a
very low temperature of 20 K, as a liquid. All safety aspects are completely different from the well-
known safety technology of liquid fossil fuels. A reuse of the existing fuel supply infrastructure is
not possible, a new one has to be installed. Especially with the use of fuel cell systems in cars, they
need a complete redesign of the complete drive chain. At the current development stage of storage
methods and requiring the same operating range and load, either the cars would need much bigger
storage tanks or new light-weight cars will have to be developed. The refueling procedures and its
safety at the fuel station are completely different from the existing ones.
Nevertheless, the advantages of a closed- loop hydrogen system, basing on renewable energy
sources and operating pollutant-free as long as the sun light irradiates the earth's surface are
overwhelming.
1.3 HYDROGEN SAFETY
It has been mentioned before that the safety aspects for hydrogen are completely different from
those of the currently used combustible hydrocarbon gases or liquids. Theses differences are based
on three main aspects:
• Hydrogen is lighter than air.
• The ignition energy of hydrogen is very low.
• The ignition limits in air are very wide.
The important safety-relevant values of hydrogen are summarized in table 1 in comparison with

two other well-known hydrocarbon gases.

Nevertheless, hydrogen is widely used in the industry in very large quantities, e.g. for the production
of sugar, hardening of fat, production of metal alloys and of semiconductors. Today, the hydrogen-
consuming industry receives it mainly from three sources, thermal and catalytic splitting of natural
gas, chlorine-alkaline electrolysis and water electrolysis. Mainly water electrolysis is always used
at the consumption site if the transportation of hydrogen is too expensive. For production as well
as consumption an approved.
HYDROGEN METHANE GASOLINE

MI NOMNIMAL IGNITION ENERGY 0 2 mWs 0 9 mWs 24 mWs
SE LF IGNITION TEMPERATURE 58 5°C 5 40°C 228 - 501°C
IG CNITION LIMITS IN AIR 4- 75 Vol.-% 5,3 - 15 Vol.-% 1, 0 - 7,6 Vol.-%

2 3
2 kg TNT/m7,0 3
3 kg TNT/m44, 22 kg TNT/m3
EX PLOSION ENERGY (with gas)
LO WER HEATING VALUE 12 0 kWs/g 50 1 kWs/g 44, 5 kWs/g

FL AME TEMPERATURE 204 5°C 187 5°C 220 0°C
D IFFUSION COEFFICIENT 0, 61 cm2/s 0,1 6 cm2/s 0,0 5 cm2/s
Table 1: Revelant Safety Properties of Hydrogen, Methane and Gasoline
hydrogen safety technology including sensors, actuators, relief valves, metal and plastic materials
and handling procedures is established, available and laid down in well-defined regulations and
laws.
It has already been proven since more than 20 years by research organizations like DLR and car
OEMs like BMW and DC that the industrial safety technology can be used equally in cars. This
aspect of introduction of hydrogen as a fuel is, only, a matter of continuous adaptation of existing
technology to the specific requirements of a car and of its price.

1.4 PRODUCTION OF HYDROGEN

Besides the production from fossil resources and its role as a by-product during the chlorine
production, the emission-free production of hydrogen through water electrolysis plays today, only
a subordinate role in industry with about one per cent of the yearly total production. But i
this case, only, the availability of hydrogen as a chemical raw material is dominant. If hydrogen is
used an emission -free fuel, its role is that of a secondary energy carrier. It needs to be produced
with high efficiency from renewable energy sources, which, generally, have a much lower input
energy density and deliver its energy mostly discontinuous.
In order to fulfil the requirements of hydrogen mass production at a convenient price level, compact
production plant design and with high purity, the splitting of water with electric energy into its
constituents hydrogen and
oxygen through the so-called alkaline water electrolysis is actually best choice. In principle an
electrolysis cell consists in two electrodes, anode and cathode in a housing filled with an electrolyte
mixture of water and potassium hydroxide (KOH). Both electrodes are separated by a gas-tight but
hydrophilic membrane. If both electrodes are connected to a direct current (DC) electric energy
source ,
the water in the cell will be decomposed. At the cathode, hydrogen is evolved, at the anode pure
oxygen. The KOH makes the water conductive for OH--ions but remains unchanged in the cell. The
process takes place at a cell voltage of 1,23 V, the dissipation voltage. In a technical electrolyzer,
the cell voltage is much higher due to several ohmic losses. In industry, cell voltages between 2,2
and 2,5 V are used. Newly developed advanced and intermittently operating electrolyzers as
presented e.g. in figure 1 (10 kW DLR test electrolyzer in Stuttgart, Germany), the cell voltage
comes down to 1,6 V. Assembling several cells in series to a block - about 150 cells are technically
feasible - operating voltages between 250 and 300 V DC voltage can be reached. Since the
production rate of hydrogen is no matter of the voltage but of the current, the electrode area and the
current density play the major role. Current densities of 2 - 3 kA/m2 for commercially available and
up to 10 kA/m2 for advanced electrolyzers are used. With a maximum electrode area of 4 m 2, a
single block can take as much as 5 MW of electric energy.

Advanced electrolyzers for the dynamic operation with renewable energy sources like a
photovoltaic field are in operation over several years now at a level between 0,3 and 0,5 MW e.g.
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in the frame of the German- Saudi Arabian program HYSOLAR.
Fig. 1.1: Advanced 10 kW DLR Test Electrolyzer
Fig 1.2: 350 kW Pressurized Electrolyzer
Besides the electrolysis block, an independently operating electrolysis facility includes as a

5

minimum water supply, electrolyte circuit, cooling circuit, hydrogen/oxygen gas circuits,
gas/electrolyte separation, safety and operation sensor equipment and a control.
Atmospheric pressure as well pressurized electrolyzers up to 30 bar are available as commercial
plants and prototypes delivering the hydrogen at costs between 0,05 (low efficient chemical plant)
and 0,50 Euros (high efficient advanced prototype). The reported lifetime comes to about 30 years
before renewal of major parts. Regular maintenance intervals in industry move within 7 and 10
years.
Plates convert sunlight directly into electric energy. In figure 3, the 350 kW concentrating and two-
axis tracking photovoltaic field (PV) at the so-called Solar Village near Riyadh in the Kingdom of
Saudi Arabia is shown. Since the electric output of a photovoltaic cell directly follows the intensity
of the sunlight, and the electrolyzer is directly connected to the PV-field, both operate under very
strict boundary conditions. Electric power changes of 50 %/sec are normal.
Fig.1.3: 350 kW Photovoltaic Field

A major advantage of electrolysis facilities is its up- and down-scalability in terms of electric power
and hydrogen output. A good example is the HYSOLAR 350 kW pressurized electrolyzer in
Riyadh/ Saudi Arabia as presented in figure 2 whose technical block concept stems from the 10 kW
prototype. With the same cell/ block design and, also, operating concept, the whole input power
range between 1 kW and 1 MW can be covered.

This type of electrolyzer reaches an efficiency between 70 % (350 kW) during intermittent solar
operation and about 90 % at constant operation (10 kW). Hereby, efficiency is defined as the ratio
between hydrogen gas output (reference: higher heating value) and electric input energy. The exact
measurement of the total energy consumption of the 350 kW plant over a time period of nine months
showed additional promising results: About 91,5 % of the total input energy of the plant were used
for hydrogen production. 5,1 % were consumed for subsystem cooling and gas purification and
another 1,6 % for electrolyte cooling, only. Operation control and water treatment took another 1,2
%. For hydrogen compression, from an operating pressure of 10 bar to the bottle storage pressure
of 150 bar which is usual in Saudi Arabia, only 0,6 % of the total plant input energy were consumed.
As an input energy source for both, the 10 kW and the 350 kW electrolyzer as well, a photovoltaic
field has been used, whose semiconductor.
Since the advanced electrolyzers have been developed for the use with photovoltaic, and other
renewable energy converters show a much slower output energy change, they can be used with any
other renewable energy facility without any change in technology.
A major disadvantage of photovoltaic is its low energy conversion efficiency. It is defined as the
ratio between electric output and input energy. Yearly PV-field efficiencies between 8 and 15 %
are normal at single cell efficiencies between 15 and 25 %. Consequently, PV-fields with high
power output cover large areas. In the example of the 350 kW field, 160 two-axis trackers with 32
concentrating PV-modules of four PV-cells each cover a land area of approximately 40.000 m2.
In figure 4, the consequence of the low efficiency is shown in graphical form presenting the energy
curve shapes of a typical solar operation day of the 10 kW PV-electrolysis facility in Stuttgart.
From the 1135,6 kWh on the plain area of a 144 m2 10 kW-PV-field, it delivers only 88 kWhrs at
its mains output. So the PV efficiency is about 7,8 %, only. Through ohmic cabling and connector
losses between PV-field and electrolyzer, only 78,4 kWh are used for hydrogen production. The
efficiency comes down to 6,9 %. After electrolysis, hydrogen purification and compression, the
bottles contain compressed hydrogen with an energy content of 57,9 kWh.
Consequently, the total plant efficiency comes to 5,1 %. Nevertheless, the good news are that these
results were obtained with a PV-field of 1986. With newer technology reaching as much as 15 %
of daily efficiency, the plant efficiency increases to 9,8 %. On the other hand, photovoltaic has

some major advantages:
Fig.1.4: Typical Energy Curve Shapes during Solar Operation

Fig.1.5: Principle of a PV-Electrolysis Plant

as no maintenance costs and very high lifetime (350 kW field now 22 years and 10 kW field now
16 years without degradation).
Figure 5 shows the principle of a PV-electrolysis plant as a block diagram. Through a so-called
power conditioning unit, the PV-field is indirectly connected to the mains connectors of an
electrolysis block. The power can be a simple direct two-wire connection of the plus and minus
poles of PV-field and electrolyzer or - with the advantage of higher PV energy output during an
operating day - it can be a DC/DC-converter which operates the PV-field always at its maximum
power point (MPP) which varies with the sun insolation and PV operating temperature. Also mixed
concepts between a directly-connected PV part and a MPP-tracked part were tested successfully.
The practice of operation has shown that the energy loss of the direct connection is negligible
compared to all other concepts. The graphic also shows another fact. Through the simple electric
concept of the plant it is possible to operate the electrolyzer from any other electric energy source.
Even concepts with different sources connected in parallel to the electrolysis can be realized. Using
a controllable highly efficient AC power supply, the electrolysis facility can be operated
independently from a single power source connected to an AC-grid which is fed at different
locations from various renewable power sources.
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Fig.1.6: Curve Shapes of a PV-Electrolysis System
CHAPTER-2
HYDROGEN PURIFICATION
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2.1.1 INTRODUCTION
2.1. HYDROGEN PURIFCATION AND PRODUCTION STORAGE

The operation of an electrolyzer together with a PV-field or another dynamically operating power
source has to follow several requirements. By hands of the typical operating curve shapes in figure
6, they can be explained shortly. Specifically these are:
Start up and shut down shall not be restricted by a high startup or shutdown power level of the
electrolyzer.
In case of "solarized" electrolyzers, the minimum startup power level is smaller than 5 % compared
to about 20 % of conventional ones.
The electrolyzer must follow any changes of electric input power throughout the day without any
shutdown. The gas impurities of hydrogen in oxygen (H2 in O2) and oxygen in hydrogen (O2 in H
2) which are caused by the solubility of the gases in the electrolyte shall never exceed the shutdown
safety limit of 2 Vol.-%. The O2 in H2-impurity shall always move below 1 Vol.-% in order to
guarantee a simple and safe purification. In this example, the H2 in O2-impurity moves always
below 0,2 Vol.-%. The O2 in H2-impurity is, only, about half of this value.
Last but not least, independently of the changes of
input current, the electrolyzer cell voltage shall move between 1,6 and 1,9 V as a maximum to
guarantee a high conversion efficiency between 81 and 65 %.
From its principle of operation, electrolysis hydrogen is much purer than that produced by other
chemical processes. At the electrolysis output it, only, contains water vapor, a small amount of
oxygen and the gases which are soluble in water. The concentration of these gases moves usually
in the very low parts-per-million range (ppm) and, thus, is acceptable even for the operation of
sensitive fuel cell systems.
Consequently in this case, the main duties of a purification system are the removal of oxygen, water
vapor and liquid water, rests of potassium hydroxide in case of alkaline electrolysis and particles.
Additionally, purification and final storage system have to follow the boundary conditions of
discontinuous hydrogen production.
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Measurements with three different electrolyzer types at the DLR 10 kW PV-electrolysis test facility
have shown that the "raw” hydrogen of solar-adapted electrolyzers fulfills the requirements of
industrial hydrogen with the German quality standard 3.0 corresponding to 99,9 % purity in terms
of hydro-carbons, N2, CO and CO2.
The basic purification and storage system for electrolytic hydrogen, therefore, consists in:
• Hydrogen collection piping,
• Filter for particle removal,
• Washing bottle for KOH-removal,
• Intermediate storage vessel to de-couple discontinuous hydrogen production from

continuous gas compression,
• Compressor with gas cooling device and filling station for bottles or bottle racks. Its usual
filling pressure is 200 bar in Germany.
Fig. 7: Hydrogen Purification and Storage System
In order to update the quality 3.0 to 5.0 for the use with fuel cell systems, it is necessary to extend
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this basic system with oxygen recombination catalyst, gas cooler, water vapor dryer and liquid
water trap.
The result of the development efforts at the 10 kW facility is shown in figure 7 as a block diagram.
After collection, filtering and washing, the hydrogen is stored in the intermediate storage volume
(I-STORAGE). Since at the 10 kW facility, the hydrogen is collected at 1,1 bara, a cheap gas
balloon with inert PTFE-coating and outer conductive hull is completely sufficient. From the
balloon, a two-stage compressor sucks the hydrogen and compresses it in its first stage (COMP 1)
to a maximum of 16 bar. At its outlet, the hydrogen is cooled (COOLER 1) and passes through a
first automatically operating water trap (W-TRAP 1) into the following externally heated platinum-
rhodium catalyst (CATALYZER). Herein, the oxygen content is recombined with hydrogen to
water vapor. The catalyzer has, only, to be heated at the plant startup. During operation, the reaction
waste heat keeps the temperature constant. Since the temperature of this device depends on the
reaction rate, the oxygen content in the hydrogen shall not exceed 1 Vol.-%. Otherwise, the device
has to be cooled externally. At the a.m. impurity, 2 Vol.-% of hydrogen are necessary for complete
oxygen removal. After the catalytic device, a second water trap (W-TRAP 2) is located for final
removal of liquid water drops. The final step of purification is the surface adsorption of water vapor
in a dryer. In this case, two dryer (DRYER 1, 2) are installed for alternately purification. Whilst
one dryer is in use, the other is connected to ambient air at its outlet and unloaded from the absorbed
water with a heater and a small hydrogen flow. The outlet of the active dryer is connected to the
second compressor stage (COMP 2) which compresses the hydrogen to the final pressure of 200
bar in one of the filling stations ( FILLING STATION 1, 2). Either maximum six bottles in parallel
or one bottle rack can be filled at each line. The independent control of the purification and storage
system switches automatically between the filling stations depending on their filling pressure. If
one of the components of the system is damaged, the hydrogen production must not be shut down
but it can pass to atmosphere through an exhaust (exhaust hood) at the system inlet. This bypass
is, also, used for a short time period - about 10 minutes always at solar operation startup or shutdown
- if the hydrogen impurity exceeds 1,0 Vol.-% and must be released to atmosphere. This
startup/shutdown behavior is included in figure 6 as the H2 in O2-content. Compressor losses of
both stages from the frequent shutdowns are collected and recovered with a separate line back into
the gas balloon.
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The compressor is an industrially available oil-free membrane compressor with integrated coolers,
water traps and safety valves and can take a maximum flow of 10 Nm3/h. For inclusion of the
purification system.
The direct inter- stage piping was extended. The compressor is designed for frequent startup and
shutdown cycles. The same reliable configuration and type with an enforced motor is used at the
350 kW facility. In this case, a varying hydrogen flow up to 65 Nm3/h must be compressed to 150
bar, finally.
The purification location at the intermediate pressure level turned out to be optimal for a constant
outlet gas purity.
This kind of storage system can, also, be used to fill hydride storage vessels at a lower pressure
level or to serve as delivery system for hydrogen liquefaction.
Fig.2.2: 200 bar Hydrogen Compressor
2.1.3 STORAGE METHODS FOR MOBILE AND STATIONARY CONSUMERS
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Hydrogen is in use since the days of the first public street lighting and public house heating plants
basing on gas at the late 19 th century. It was used as a hydrogen-rich gas mixture -about 60% - of
H2, CO and CO2 known as "city gas". Enormous masses were produced from coal and water which
were stored at nearly atmospheric pressure in giant expandable steel vessels with fixed bottom and
wall and an up and down moving cover which was lifted by the content of hydrogen. These vessels
are called gas-o-meters. Also very early, it became obvious that these vessels contained an
extremely low percentage of hydrogen compared to its weight, and they were only stationary
devices. Consequently, from the piston motors a development of hydrogen compressors basing on
piston movement was derived in the very early 20th century. Today, this kind of compressor reaches
as much as 6000 bar. Nevertheless, the compressors as well as storage vessels are impractical in
public. From the development of hydrogen-safe steal alloys, a durable compromise was found at a
level of 150 - 200 bar of hydrogen. This is still the usual bottle pressure level of today.
Taking a 50 l standard bottle with a filling pressure of 200 bar and a tare weight of 65 kg, its content
is only 8,9 Nm3 corresponding to 795 g. This means, only a storage density of 1,2 wt.-%. Far too
low for mobile
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Fig.2.3: Industrial Hydrogen Storage Method
applications or even efficient gas transportation on the road. In figure 9, now, the currently used
storage methods for stationary and mobile applications with their characteristic temperature levels,
storage capacity or ranges respectively as well as areas of use are presented. They will be explained
shortly starting from left to right in this figure.
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Fig.2.4: Liquid Hydrogen Tank of DLR
The most common storage device in cars is the cryogenic storage of liquid hydrogen in vacuum-
super-isolated Dewar-tanks. Figure 10 shows a partly
cut open example of such a vessel. A 120 l tank as shown in this figure contains 8,4 kg of hydrogen
which corresponds to 277,2 kWh or about 24 l of gasoline. In terms of volume, such a tank is about
four times bigger as a gasoline tank. In terms of weight, the aluminum version is only two times
heavier than gasoline tank with the same energy content. But three main problems arise from the
use of liquid hydrogen:
• The energy amount for liquefaction is high. Although theoretically, the energy amount is,
only, 3,92 kWh/kg of liquid hydrogen, the practice delivers values between 10 and 30 kWh/kg of
primary energy amount.
• The hydrogen evaporates from the tank with a rate between 2 and 5 % of the content.
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• The hydrogen is stored as a super-cold liquid at 20 K or -250°C which makes the handling
difficult to the public.
This storage method offers acceptable ranges for cars between 180 km for conventional ones and
up to 400 km for new drive train concepts and light-weight cars. The risks of this technology have
been examined very carefully and are gradually small at the current stage of development.
The absorber storage method at low temperatures with e.g. active carbon combines the advantages
of
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2.1.4 STORAGE METHOD

Compressed gas with its low energy amount for storage and liquefication with the high specific energy
density. In this case, a pressure vessel contains an active carbon powder or carbon nanotubes with high
inert surface and reactivity to absorb hydrogen at the surface. A storage pressure of 50 bar and a
temperature -130 and -210°C give storage densities between 2 and 6 wt.-%. This kind of storage does not
have the difficulties of the high hydride storage weight and does not need a high temperature level of
thermal power for hydrogen de-sorption from the storage material surface. Nevertheless, this technology
is still under development in the laboratories and, only , in small volumes available to the market.
Metal hydrides are alloys of two up to five alloy components having a highly porous, ceramic-like
consistency. The hydrides store hydrogen in gaseous form adsorbed within the material. The alloy group
of hydrides can be divided into three main groups which are classified by its temperature level for a
hydrogen dissociation pressure ≥ 1 bar.
Fig.2.5 : Metal Hydride Storage of Daimler Benz
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The low temperature hydrides have a temperature range between -30 and about 70°C. Fe-Ti or Ti-Cr
systems are typical examples. Reversible storage densities between 1,5 and 2,3 wt.-% were measured with
storage tanks. The disadvantages of these alloys are the low storage density and the loading pressure level
between 10 and 50 bar. These devices may be used for highly efficient energy converters such as fuel cells
in combination with a low car weight to reach convenient ranges.
Middle temperature hydrides work between 100 and 200°C. La-Ni or Fe-Ni are typical representatives.
Since the storage density of maximum 2,5 wt.-% is, only, gradually higher than the a.m. one, they may be
interesting because of the low loading pressure level of ≤ 5 bar, only. The practical relevance for cars is
very small. The main market area may be the storage of heat for household purposes.
For combustion engines, the high temperature hydrides with its temperature above 200°C and the high
storage density of up to 8 wt.-% were a matter of intensive research. Typical alloy examples are Mg-Cu
and Mg-Ni systems. An additional advantage of this hydride family is the loading pressure around or below
1 bar. Nevertheless, the operation of these hydrides is difficult in cars due to the necessity of thermal energy
at a high temperature level for hydrogen de-sorption especially at startup. This kind of storage system
needs a highly efficient thermal management system. Figure 11 shows a technical storage vessel from
Daimler-Benz which was used in combustion engine cars.
All hydride storage devices have the disadvantages of high weight, necessity of cooling during the loading
procedure and heating during operation.
On the other hand, its operation risk is very low and well known. At a leakage, the hydrides freeze very
soon after release of small amounts of gas and deliver afterwards only small flows.
The storage of compressed gas has been described at the beginning of this chapter for the level of 200 bar.
Today, also stationary and mobile vessels for 300 up 350 bar are usual. The latest development goes as
high as 700 bar. So, storage densities up to 8 wt.-% can be achieved. Even the weight of these high-pressure
tanks is reduced by the usage of composite materials such as aluminum- carbon fiber. But the energy
amount for high pressure is high and the filling pressure can go as high as 1000 bar. This is a technology
which needs new developments, ideas and time.
The risk of pressure storage is very high. Additionally to the risk of burning and detonation of big amount
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of gaseous hydrogen, the risk of vessel detonation has to be considered before all.
Other storage methods of high interest are graphite nanofibers – currently of high scientific interest – with
a loading pressure up to 120 bar, sponge iron inoculated with a catalytic noble metal to reach operating
temperatures between 80 and 200°C. The viability of this method has not yet been seriously investigated.
Glass microspheres with a storage density of about 10 wt.-% but for loading conditions of 200 – 400°C
and pressures up to 630 bar are necessary and, finally, aerogels as a type of open-cell foam with ultra-fine
pores and a high surface area. A storage density of 3,7 wt.-% at 83 bar was reported so far.
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CHAPTER -3
HYDROGEN PRODUCTION
3.1 THE NEED FOR HYDROGEN PRODUCTION
Current U.S. energy systems are not sustainable. They primarily exploit limited resources and will soon
accumulate unacceptable environmental impacts. Carbon dioxide (CO2) from energy production now
contributes 82% (weighted by global warming potential) of the greenhouse gas emissions in the U.S.
Because the effect of CO2 release is cumulative, the need to find alternative means of energy production
is becoming increasingly compelling. Recent estimates call for the generation of more than 30% of
primary power from non-carbogenic sources by 2020 in order to stabilize the global mean temperature
increase due to CO2-induced warming at 2°C (Caldeira et al. 2003). Although hydrogen is not an energy
resource itself (because no natural hydrogen reserves exist), it has the potential to serve as an energy
carrier at the core of a carbon-neutral system of energy production and use. Cost-effective production
of hydrogen in sufficient quantities to meet growing energy demands, however, is a challenge that
cannot be resolved without intensive effort in both basic research and engineering. The U.S. requires an
enormous amount of energy, making this a daunting challenge. Because of the short timeline for
development of large-scale hydrogen production capacity, the need to address the underlying basic
science questions is immediate.
The need to develop alternative energy technology is also driven by the limited petroleum reserves in
the U.S. At this time, petroleum is the major contributor to energy production. Fossil fuels currently
provide 85% of the nation’s energy supply, with oil accounting for 39% of that total; natural gas, 24%;
and coal, 22%. By 2020, the use of fossil fuels, which totaled approximately 3.3 terawatts (TW) in 2000,
is projected to increase by 32%, maintaining roughly the same proportions of oil, natural gas, and coal.1
Transportation consumes about two- thirds of the nation’s oil, and this figure is expected to remain
essentially constant through 2020. In 2000, the U.S. imported 52% (net) of its oil supply; by 2020, this
percentage is expected to increase to 65%. Oil imports accounted for about one-fourth of the U.S. trade
deficit in goods in 2000. Clearly, as long as oil continues to be the most significant component of U.S.
energy use (especially for transportation, as illustrated in Figure 1a), it will be a large contributor to
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trade deficits, to the cumulative effects of CO2 emissions (Figure 1b), and possibly to geopolitical
instability.
Carbon-neutral hydrogen production technologies (including technologies that use and reuse carbon but
are not net producers of CO2) could exploit many resources in sufficient supply to meet the needs of a
hydrogen economy. These resources include sun-energized resources (solar, biomass, wind) and nuclear
energy. Geothermal and geochemical resources could also play a role. In each case, development is
needed. Substantial improvements in efficiency and reductions
Fig3.1: Hydrogen versus Vehicle barrels curve
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in both capital and operational costs are needed to enable hydrogen production to meet the
nation’s future energy needs. Each technology faces a different set of technically diverse
scientific challenges, although some of these challenges (improved chemical processes,
catalysis, materials, and separations) are common to all.
3.1.2 HYDROGEN PRODUCTION FROM FOSSIL FUELS
Hydrogen is currently produced on an industrial scale (9 Mtons/yr in the U.S.) through steam
reforming of natural gas. At present, most of the hydrogen made from fossil fuels is used in
the fertilizer, petroleum, and chemical industries. Natural gas resources will be sufficient for
several decades to expand this capacity to support the FreedomCAR and Fuel Initiative. By
2040, it is anticipated that the use of hydrogen in fuel cell powered cars and light trucks
could replace consumption of 18.3 MB per day of petroleum. Assuming that hydrogen
powered vehicles have 2.5 times the energy efficiency of improved gasoline vehicles, this
reduction in petroleum use would require the annual production of approximately 150 Mtons
of hydrogen by 2040. If all of this hydrogen were produced by petroleum reforming, the net
savings in petroleum use would be 11 MB per day (U.S. Department of Energy [DOE] 2003).
The total energy used for transportation in the U.S., however, includes a substantial
component of other kinds of vehicles (Figure 1a), and meeting that need poses a greater
challenge to hydrogen production.
Other fixed carbon reserves, such as coal or biomass feedstocks, could be used to generate
hydrogen via reforming processes. Relative to natural gas, however, these resources generate
approximately twice as much CO2 per amount of hydrogen produced. This factor puts
additional pressure on the development and economics of carbon sequestration (storing the
CO2 produced, rather than releasing it into the atmosphere). These feedstocks also contain
variable amounts of water, sulfur, nitrogen, and nonvolatile minerals that substantially
complicate reforming process engineering. Nevertheless, if an economic and safe method
for CO2 sequestration is developed, economic factors (the general availability and relatively
25

low cost of coal) may enable coal to play a significant mid-term role in hydrogen generation.
Reliance on coal as a sole source of energy for generating hydrogen for FreedomCAR
transportation needs would require doubling of current domestic coal production and
consumption. Two technically effective strategies for hydrogen production from coal or
biomass are under development: (1) reforming under partial oxidation and (2) a combined-
cycle method that uses Ca(OH)2 to force the reforming reaction by adsorbing CO2 as it is
produced (Lin et al. 2002).
Although the technology is available for generating hydrogen in quantity via reforming of
natural gas or possibly other carbon reserves, the hydrogen produced is not of sufficient
purity for direct use in the low-temperature (<130°C) fuel cells under development for
transportation applications. The last stage in current reforming processes, the water-gas shift
reaction, leaves enough carbon monoxide (CO) in the product stream to poison the fuel cell
anode. Current methods for removing this residual CO include pressure-swing adsorption,
preferential oxidation, or catalytic methanation, all of which add cost and complexity to the
fuel processing system. Basic research can supply alternative solutions to this problem,
which could come in the form of more active catalysts for the low- temperature water-gas
shift reaction, better gas stream separation processes and membranes, or CO-tolerant
catalysts at the fuel cell anode [see section on fuel cells].
26

3.1.3 WATER ELECTROLYSIS: PROTON REDUCTION AND WATER OXIDATION
Electrolysis is a process for breaking water (H2O) into its constituent elements (hydrogen, H2, and
oxygen, O2) by supplying electrical energy. The advantage of this process is that it supplies a very
clean hydrogen fuel that is free from carbon and sulfur impurities. The disadvantage is that the process
is expensive, relative to steam reforming of natural gas, because of the cost of the electrical energy
needed to drive the process.
Chemically, the electrolysis of water is simply the reverse of the electricity-generating reaction that
occurs in a fuel cell. Physically, an electrolyzer is designed very much like a fuel cell, with two
electrodes immersed in a common aqueous electrolyte solution. The reaction can be thought of as
occurring in two “half-cells” separated by a gas-impermeable
Electrolyte membrane (the figure provides aschematic drawing of the electrolysis process).In the
cathode half-cell, hydrogen ions (protons) are reduced to hydrogen:
2 H+(aq) + 2e− = H2(g).

27

On the anode side, water is oxidized to oxygen and protons:
2 H2O(liq) = O2(g) + 4 H+(aq) + 4e−.
By multiplying the first half-reaction by two and adding the two half-reactions together, we obtain the
overall reaction:
2 H2O(liq) = O2(g) + 2 H2(g).
Because water is a very stable molecule relative to oxygen and hydrogen, this reaction requires input
of energy. In principle, the reaction can be driven by an applied voltage of 1.23 V, which translates to
a free energy input of 237 kJ/mole of hydrogen. In practice, somewhat larger driving voltages (1.55–
1.65 V) are used because of slow kinetics in the two half-cells. The energy efficiency of the cell can
be calculated simply as the theoretical voltage (1.23 V) divided by the applied voltage; for example,
a cell operating at 1.60 V would have an efficiency of 1.23/1.60 × 100% = 77%. The process of
oxidizing water in the oxygen-evolving half-cell is mechanistically and kinetically more complex than
the hydrogen-evolving process because it requires four electrons and proceeds through a series of
distinct oxidation intermediates. In an uncatalyzed reaction, some of these intermediate electron
transfer steps require more energy than others, and some are slower than others. As a consequence,
extra voltage is needed to drive the cell, primarily at the oxygen-evolving electrode, and efficiency is reduced.
An ideal catalyst for water oxidation would equalize the energy required at each step in addition to
equalizing the rates of each electron transfer, thus maximizing efficiency. The water oxidation
complex that supports oxygen evolution in photosynthesis is one catalyst that comes close to meeting
this ideal and provides a tantalizing model for building catalysts for electrolyzer anodes and fuel cell
cathodes.
28

CHAPTER-4
SOLAR HYDROGEN
4.1 INTRODUCTION
Solar hydrogen, which is produced by driving water electrolysis with solar cells, by direct photocatalytic
water splitting into hydrogen and oxygen, by photobiological water splitting, or by solar thermal
processes, represents a highly desirable, clean, and abundant source of hydrogen. Hydrogen made this
way is suitable for use, without further purification, in low-temperature fuel cells and even in alkaline
fuel cells, which are more efficient but more carbon-intolerant. While solar-to-electric energy
conversion is an established technology, current solar cells are either too expensive or too inefficient
for widespread application. However, the potential capacity for solar hydrogen is quite large. The
estimated power output from 10% efficient solar cells covering 1.7% of the land area of the U.S. (an
area comparable to the land devoted to the nation’s
Figure 4.1: (Left) Scanning Tunneling Microscopy Image of a Ni Surface Alloyed with Au (The
Au atoms are shown in black; the neighboring Ni atoms have a distinct electronic structure
29

4.1.2 DYE-SENSITIZED SOLAR CELLS
A promising new technology in solar energy conversion is the dye-sensitized photoelectrochemical

cell, or Grätzel cell (Grätzel 2001).
This cell consists of a highly porous, thin layer (~15 m) of titanium dioxide nanocrystal aggregates
(~20 nm in diameter; see scanning electron micrograph), the same material used as the pigment in
white paint. The nano crystals are coated with a dye and a liquid electrolyte that contains reactive
iodide ions or other diffusible oxidation/reduction mediator, sandwiched between two conducting
glass or plastic plates sealed together (schematic drawing shows the mediator cycle and electron
injection). When excited by light (S0 to S* transition in the figure), the dye becomes oxidized (S+
state), injecting electrons into the titanium dioxide. In the figure, oxidation/reduction potentials of the
various reactants are depicted relative to the normal hydrogen electrode (left axis). The titanium
dioxide layer then transmits electrons to the conducting glass electrode, which is connected to an
external circuit. The reduced reduction/oxidation mediator transfers electrons to re-reduce the dye,
and the oxidized form diffuses away in the electrolyte. The return path for the electrons is through the
other electrode to the oxidized mediator in the solution, which completes the cycle by diffusing back
to the film layer.
30

Fig Dye Sensitized Solar Cell
31

3.3 TW, equivalent to the total U.S. fossil fuel use in 2000. To place this capacity in perspective, 3,300
new 1-GW nuclear power plants would need to be built — roughly 1 for every 10 miles of coastline or
major waterway — to supply the same 3.3 TW of power. This capacity is more than 30 times greater
than that provided by the 103 nuclear plants now in the U.S. Such growth in nuclear power is not feasible
today because of the severe constraints in cost, nuclear fuel supply, site availability, safety, public
acceptance, and waste disposal. Nevertheless, thermo chemical cycles that use the heat from nuclear
reactors to produce hydrogen by water splitting are being developed and could, in principle, play a role
in the hydrogen economy on a smaller scale (see below).
The most efficient and also the most costly sources of solar electricity for water electrolysis are solid-
state photovoltaic (PV) devices. Commercially available photovoltaic’s include single-crystal silicon
and GaAs, amorphous silicon, and polycrystalline thin film materials, such as CdTe and CuIn1-xGaxSe2,
which have solar-to-electric power conversion efficiencies ranging between 12% and 25% under full
sunlight. Tandem photovoltaic’s, which are two-bandgap devices (for example, GaAs and GaInP2 )
utilizing a greater fraction of the solar spectrum, are more efficient, but also more expensive, and are
envisioned for special use in solar concentrator systems and space applications.
Current water electrolysis systems (see sidebar on water electrolysis) that produce hydrogen gas operate
at about 75% energy efficiency (free energy content of hydrogen relative to input electrical energy),
giving an integrated efficiency of hydrogen production from solar energy via PV/electrolysis of ~15%.
This sets an efficiency standard for other technologies to meet using less costly and more abundant
resources for materials. Lower-cost alternatives include photoelectrochemical cells based on
polycrystalline and nanocrystalline semiconductors, dye-sensitized titanium dioxide (see sidebar on
dye-sensitized solar cells), the Texas Instruments silicon microsphere system, and thin film devices
based on organic liquid crystals and/or polymers (Grätzel 2001). The lower efficiency of hydrogen
generation in each case arises from energy losses in electrolysis, where the most significant problem is
catalysis of the water oxidation reaction. The water oxidation reaction is particularly kinetically
demanding because it is a four-electron, four-proton process.
32

The efficiencies of different kinds of PV devices have followed similar time -efficiency development
curves, which began in the 1950s for single crystal silicon; in the 1970s for amorphous silicon, CdTe,
and copper-indium-diselenide and related thin film devices (CIS/CGIS); and in the 1990s for dye-
sensitized nanoparticle TiO2, organic, and photocatalytic systems. This trend is illustrated in Figure 2
(Kazmerski 2001). The newest of these systems are the least developed and offer the greatest
opportunities for contributions from basic research.
4.1.3 HYDROGEN FROM BIOLOGICAL AND BIOMIMETIC SYSTEMS
Solar energy capture based on photosynthesis can follow one of two routes: (1) storage of energy by
CO2 fixation (biomass) followed by hydrogen production via reforming or fermentation, or
(2) direct water splitting to hydrogen and oxygen (e.g., using blue-green or green algae [biophotolysis])
. Biological energy conversion systems use readily available materials for conversion and catalysis, and
these systems are also self-maintaining. For these reasons, they might be able to compete on a cost basis
with other hydrogen production systems. Biomass is currently a substantial component of global energy
consumption. Of the 13 TW of global energy used in 1998, approximately 1.2 TW can be attributed to
biomass. This amount, however, represents unsustainably burned, as opposed to renewably farmed,
biomass. The solar- to-chemical energy conversion efficiency of current biomass crops (switchgrass
and poplar) is in the range of 0.4% of total solar irradiance, and further losses would be incurred in the
conversion to hydrogen. It is plausible that genetic research could improve this yield two- to three-fold,
but fundamental limitations would prevent it from rising above the range of a few percent, thereby
requiring use of large arable land areas to contribute significantly to the hydrogen economy.
In contrast, biophotolysis in natural populations of algae currently has peak yields of hydrogen in the
range of 5% solar conversion efficiency, although this is only at low light intensities, about 10% of
typical solar intensity in the U.S.; lower efficiency is found at higher light levels. Thus, research is
needed to make these yields sustainable and to find new organisms or engineer the photo systems of
existing organisms that will give similar efficiencies in full sun.
Globally, biological processes produce at a minimum of more than 250 Months/year of hydrogen (see
sidebar describing hydrogen in the biosphere).2 Most of this hydrogen arises from anaerobic
33

fermentation of carbon previously fixed by photosynthesis. Six to 17 Months/year of hydrogen is

produced as a by-product of terrestrial biological nitrogen fixation. This biological hydrogen is
completely used as an energy carrier that fuels the growth of organisms and the maintenance of essential
life processes. Much of it is consumed in CO2 or organic acid reduction by methanogenic archaebacteria
that give off methane as a by-product. On the oceanic continental shelves and in permafrost regions,
this methane has accumulated in the form of extensive methane hydrate deposits, the extent of which
exceeds all known petroleum, coal, and natural gas deposits. In other locales, methane is released to the
environment, and a portion enters the atmosphere.
Fig.4.3: Hydrogen Efficiency Curve
34

If methane hydrates could be used, either by reforming them to make hydrogen or using them directly
in fuel cells that generate electricity, they could have a large impact on the global energy economy.
However, utilization of methane hydrates presents daunting technical challenges because of the depth
at which they are found, because of their dispersion as ice-like crystals in ocean sediments, and because
of their decomposition (to methane gas and liquid water) at ordinary pressures.
In some specific cases, details of the biological processes linked to hydrogen metabolism and of the
enzymes involved as essential catalysts have been investigated and are reasonably well known.
However, efforts to understand the variety of organisms and the diversity of biochemical mechanisms
that participate in this extensive biological hydrogen energy economy are still at an early stage. The
emergence of highly capable tools for genomic analysis of microorganisms and for dissecting the
interlocking metabolic functions of microbial communities presents an opportunity for extremely rapid
progress in this promising area of research (Reysenbach and Shock 2002). It is possible that exploiting
and mimicking components of these natural hydrogen-producing systems, once they are better
understood, will enable key improvements in efficiency and reduction in the cost of solar hydrogen
production.
4.1.4 THERMAL ENERGY FOR HYDROGEN PRODUCTION
Production of hydrogen from thermal energy sources is a conventional technology via the multistep
route of thermal energy to electricity, and electricity to hydrogen and oxygen by electrolysis of water.
The heat can be delivered from a conventional fossil energy source, a nuclear reactor, or a solar
concentrator/receiver. The net efficiency (heat energy to hydrogen) is about 26%. Current hydrogen
production costs, not including storage and delivery costs or the long-term costs of nuclear waste
management, are $ 4–$5/kg (nuclear thermal) and $15/kg (solar thermal). Experience with solar thermal
generators is not as extensive as with nuclear plants; hence, costs for solar thermal systems are expected
to drop more quickly as development proceeds.
In principle, hydrogen can also be produced by using thermal energy from solar concentrators or from
35

nuclear reactors to drive thermochemical water-splitting cycles, the overall output of which is water
splitting to hydrogen and oxygen without intervening electricity generation. These cycles need
temperatures of 500°C or more, well within the range of solar concentrators but higher than can be
achieved by today’s light-water reactors. These temperatures are also within the range of present-day,
gas-cooled reactors and designs for future nuclear power plants (Marcus and Levin 2002). The reactor
operating temperature is a key factor because higher temperatures enable faster chemical reactions and
higher efficiencies, at the expense of a harsh thermal and chemical materials environment. Because of
the technical challenges that they raise, high- temperature reactors will also take longer to reach
commercialization. High-temperature solar collector/receivers have been demonstrated and could
potentially drive very efficient cycles. For example, the National Renewable Energy Laboratory has
demonstrated 51% thermal collection efficiency in a 2,000°C process fluid. The potential advantages of
higher operating temperatures, sitting in desert locations, and lower capital cost of solar concentrators
must be offset against the lower duty cycle (8 h/day) of solar power relative to nuclear reactor power.
Nuclear reactors, such as the helium gas-cooled reactor which has demonstrated ~900C temperatures,
have not yet been commercialized, giving them a long development horizon. Lower-temperature, gas-
cooled reactors may offer nearer-term implementation of hydrogen production and a materials-friendly
environment at the expense of lower production rates. The advanced high-temperature reactor concept,
developed in the Generation IV reactor initiative, is proposed to match hydrogen production
requirements via thermal cycles with maximum temperatures of 700–950°C. It is a more advanced
reactor that would use a low-pressure molten salt coolant rather than high-pressure helium as a coolant.
Further out in time, fusion energy might become an important source of high-temperature heat for
driving thermochemical hydrogen production.
A related technology is the electrolysis of water assisted by heat from a nuclear reactor. By performing
electrolysis at elevated temperatures using heat from a high-temperature reactor, the overall efficiency of
the process can be increased relative to low -temperature electrolysis. In both cases, the energy source is
noncarbogenic. A third (carbogenic) way in which nuclear energy can be used to augment hydrogen
production is in nuclear-assisted steam reforming of natural gas. Here, nuclear energy replaces fossil fuel
36

combustion as the means of driving the endothermic steam reforming reaction. Thus, less natural gas
would be used to produce the same amount of hydrogen.
More than 100 different thermochemical cycles have been proposed for performing the overall water
splitting reaction in high-temperature reactors (Brown et al. 2002). At present, the most promising high-
temperature cycles appear to be the calcium bromide-iron oxide cycle, the sulfuric acid-hydrogen iodide
(sulfur-iodine or S-I) cycle, and the Westinghouse cycle. Also, an important lower-temperature cycle,
(copper -chloride [Cu-Cl]), can produce hydrogen using heat from current and near-future reactors. The
Cu-Cl cycle, originally proposed in the 1970s, has recently been proven in the laboratory, and several
commercially appealing variants are being evaluated. This cycle has an estimated efficiency of ~40%
at its envisioned operating temperature of 550°C, not including cogeneration of electricity. A key
challenge for the Cu-Cl cycle is effective catalysis of the low-temperature reactions. The calcium
bromide cycle has four fixed-bed reactors, each of which performs one step of the cycle at temperatures
around 760°C. Overall efficiencies of 45− 49% (including cogeneration of electricity from waste heat)
are projected. In this process, hydrogen and oxygen are produced at subatmospheric pressures and
removed via membranes; hence, there is a major challenge for membrane technology and for
compression/storage of hydrogen. In the S-I cycle, which uses all fluid reagents, a higher temperature
(825–900°C) is used for the oxygen-evolving reaction, and higher efficiencies (~50% and ideally 60%
with cogeneration of electricity) are possible. The individual reactions in the S-I cycle have been
demonstrated, although not in a continuous process, nor at the temperatures envisioned for
implementation of the technology. This cycle is being actively researched in several laboratories,
including the Japan Atomic Energy Research Institute (Japan), Commisariat à l’Energie Atomique
(CEA) (France), and Department of Energy laboratories (Sandia National Laboratories, Idaho National
Engineering and Environmental Laboratory) and General Atomics in the U.S. Among the key
challenges with this approach is the verification of durable high-temperature, chemically inert materials
for fabrication of the chemical reactors needed to withstand the thermo chemical cycle over
economically useful lifetimes (Trester and Staley 1981). The Westinghouse cycle is a variant of the S-
I process where a low-temperature, low-voltage electrolysis step (a fraction of that required for water
37

electrolysis) replaces several chemical reactions in the S-I process.
38

CHAPTER-5
5.1 IMPACT OF THE HYDROGEN ECONOMY ON THE ENVIRONMENT
5.1.2 SCIENTIFIC CHALLENGES
The development of a large-scale hydrogen economy is motivated in part by its beneficial effects on
the environment, including a reduction of the anthropogenic emission of carbon dioxide and other
greenhouse gases and of atmospheric pollutants associated with the present fossil fuel economy.
These beneficial effects are easy to foresee; however, our ability to anticipate the potential of
harmful environmental effects from increased emissions of hydrogen itself to the atmosphere is
more restricted. Although hydrogen is neither a greenhouse gas nor a toxic substance, it influences
the dynamics of atmospheric methane, water vapor, and ozone, and it actively interacts with the
biosystem of the soil. The transition to a hydrogen economy may lead to a substantial increase in
the amount of hydrogen entering the atmosphere — from a current ~75 Months/year (Novelliet al.
1999) to as much as ~120–180 Months/year, based on estimates of the possible rates of leakage from
hydrogen generation, storage, and transport sites (Tromp et al. 2003). In the current steady state, it
is hypothesized that the bulk of the hydrogen entering the atmosphere is taken up by microbiological
hydrogen metabolism in subsurface soils (Novelliet al. 1999). It is unknown whether this biological
sink has the capacity to accommodate the expected increased hydrogen flux, or if the net
concentration of hydrogen in the atmosphere will increase. Preliminary modeling indicates that an
increased atmospheric concentration has the potential to:
• Affect the oxidizing capacity of the atmosphere,
• Impact the stratospheric ozone layer by moistening the stratosphere,
• Alter the pace of climate change by indirectly increasing the lifetime of methane, and
• Change the balance of hydrogen-consuming microbial ecosystems in subsurface soils.
To reliably quantify the potential impacts of large-scale increases of hydrogen releases to the
39

atmosphere, we need to improve our understanding of the global biogeochemical cycles of

atmospheric hydrogen. This research would also provide an engineering constraint on the
environmentally acceptable amount of ‘leakage’ from a large-scale hydrogen infrastructure —
information that is urgently needed by those industries seeking to develop a safe and efficient
hydrogen infrastructure.
Hydrogen is a naturally occurring atmospheric trace gas. The National Oceanic and Atmospheric
Administration Climate Modeling Diagnostics Laboratory has collected observations of hydrogen
as an atmospheric trace gas at sites around the world on a regular basis. The global average
tropospheric concentration is ~500 parts per billion. The two main sinks for H2 are believed to be
reaction with OH radicals and deposition at the earth’s surface through the activities of terrestrial
microbes, with the latter sink predominating. The primary sources of H2 to the atmosphere are from
oxidation of methane, oxidation of nonmethane hydrocarbons, fossil fuel combustion, and biomass
burning. Our understanding of the processes governing the sources and sinks of atmospheric H2 is
limited, and the magnitudes of the fluxes are poorly constrained.
5.1.3 RESEARCH DIRECTIONS
The goal is to develop a fundamental understanding of the processes involved in the global
biogeochemical cycling of atmospheric H2. This knowledge will make it possible to perform a
comprehensive assessment of the environmental impact of the release of H2 to the atmosphere from
a developing global H2 economy.
5.2 New Modeling and Simulation Tools
Models of the sources and sinks of atmospheric hydrogen need to be developed and incorporated
into global three-dimensional coupled chemistry-climate models. Long time series of observations
of atmospheric H2 are available for testing and comparing models.
40

5.2.1 BIOLOGICAL AND TECHNOLOGICAL SOURCES AND SINKS OF H2
The H2 inventory is biologically mediated both as a source and as a potentially major sink. At least
two routes lead to the release of H2. One route to H2 production is through wetlands fermentation
of photosynthetically produced biomass (Schlesinger 1997). Mats of photosynthetic cyanobacteria

also generate molecular hydrogen as a by-product of nitrogen fixation at concentrations well above
atmospheric (Hoehler et al. 2001). A modest fraction of this biogenic H2 probably escapes utilization
by other microbes and enters the atmosphere. Biogenic hydrogen emanating in one way or another
from biological solar energy conversion is thought to have had a profound effect on the evolution
of the earth’s atmosphere (Hoehler et al. 2001) . Much of this impact arises from the role of hydrogen
as a source or reductant in the synthesis of methane from carbon dioxide by methanogenic
archaebacteria in subsurface soils. Our understanding of the spatial and temporal distribution,
magnitude, and intensity of the soil sink for atmospheric H2, as well as of the fates of the reductant
once the hydrogen is consumed, needs to be expanded. The possible effect of increased atmospheric
H2 on soil uptake, fertilization, warrants study.
5.2.2 Importance of H2 in Determining the Oxidative Capacity of the Atmosphere
Atmospheric H2 is reactive and first affects the lower atmospheric layer, called the troposphere. It
reacts with the trace OH radicals to form water. The trace OH radical inventory is critical to the
cleansing of the atmosphere. Hence, any additional stress on OH radicals is a problem. Prinn et al.
(2001) recently reported a potentially dramatic variation in the atmospheric inventory. Increasing
the stress on the OH radical concentration through the deployment of a hydrogen economy that is
leaky would have to be viewed as deleterious. Global atmospheric chemistry models can be used to
study the impact of H2 releases on the oxidizing capacity of the atmosphere.
5.2.3 Role of H2 Releases on the Stratospheric Ozone Layer
H2 releases significantly impact the chemistry of the troposphere and the stratosphere, particularly
with regard to the long-term stability of the stratospheric ozone layer. Stratospheric chemistry
models can be used to study the impact of H2 releases on the long-term stability of the ozone layer.
41

5.3 Likely Source of H2 to the Atmosphere from a Hydrogen Economy
It is almost certain that international agreements will be developed that limit the emissions of H2 to
the atmosphere at an environmentally sustainable level as we go forward with the development of a

hydrogen economy. The OH radical inventory in the troposphere and ozone depletion in the
stratosphere provide constraints on how “tight” the hydrogen economy must be. Estimates show that
a 1% leak rate from a hydrogen economy would double current anthropogenic H2 emissions.
Leakage rates much greater than 1% are likely if no action is taken to engineer systems in advance
to minimize hydrogen leakage. To quantify the potential impacts of large-scale releases of hydrogen
to the atmosphere, we need to develop precise systems-based engineering models of the likely H2
release arising from a developing global hydrogen economy infrastructure.

5.3.1 COMPREHENSIVE IMPACT ASSESSMENT
Ultimately, we must perform a series of simulations to quantify the effects of an increasing H2
release as a consequence of the large-scale development of a hydrogen economy. Such simulations

must be able to assess the impact of these releases on the oxidative capacity of the atmosphere, the
long-term stability of the ozone layer, the impact on climate, the impact on microbial ecosystems
involved in hydrogen uptake, and the role of those biological impacts in causing indirect effects on
the atmosphere and climate. This information can be used to provide a reliable estimate of the
maximum leak rate that can be tolerated from an environmental standpoint from large-scale H2
systems that might be deployed in the future.

5.3.2 POTENTIAL IMPACTS
Improvements in our understanding of the global biogeochemical cycles of atmospheric H2 will
provide essential anticipatory guidance in developing hydrogen energy technologies that minimize
environmental impacts. Large-scale implementation of hydrogen energy systems does not seem
prudent in the absence of these critical assessments.
• Improving our understanding of the global biogeochemical cycles of atmospheric

hydrogen would lead to a reliable quantification of the potential environmental impacts
of large-scale releases of hydrogen to the atmosphere.
42

• This research would also provide an engineering constraint on the environmentally

acceptable amount of leakage from a large-scale hydrogen
5.3.3 SAFETY IN THE HYDROGEN ECONOMY
5.3.4 SCIENTIFIC CHALLENGES
The large-scale use of hydrogen as an energy carrier for stationary, automotive, and portable power
generation will result in close contact between hydrogen and the public. In a well-designed hydrogen
infrastructure, gaseous hydrogen would remain confined in storage devices and delivery lines as it
moved from production to use. The everyday presence of large quantities of hydrogen, however,
demands that we understand fully its behavior and danger if significant quantities were to leak into
the open environment or into enclosed spaces. Hydrogen is significantly different from today’s
common fuels because of its tendency to embrittle metals and other containment materials, its rapid
leaking behavior, its fast diffusion through the atmosphere, its high buoyancy, and its combustion
behavior. These differences in properties and behavior require that special research be done in order
to understand and control the safety hazards that a hydrogen economy would pose.
Hydrogen can leak through tiny orifices 2.8 times faster than methane and 3.3 times faster than air
because of its small molecular size (Larminie and Dicks 2003). It is flammable over a wider range
of compositions in air than is methane, propane or gasoline, and its detonation range is similarly
broad (Larminie and Dicks 2003; Ogden 2002). Hydrogen’s unusually high diffusion and buoyant
velocities in air, however, somewhat compensate for the danger posed by its fast leak rate and wide
range of combustible compositions. In the open environment, hydrogen quickly disperses up and
away from the source of a leak, rather than concentrating in low-lying areas, as do propane and
gasoline vapors. If hydrogen does catch fire, it burns with a nearly invisible flame that is hard to
detect. Its ignition energy is lower than methane or propane at most compositions, enabling self-
ignition of high-pressure leaks.
Because the combustion behavior of hydrogen differs from that of other fuels, it presents another
set of hazards and requires diverse safety precautions. In the open air, for example, the high
buoyancy and diffusivity of pure hydrogen make it very unlikely to accumulate to its threshold of
flammability, which gives hydrogen an intrinsic safety feature. In enclosed spaces, however,
43

combustible compositions can build up, and precautions such as ventilation and careful monitoring
are needed.
The basic kinetics and explosion limits of hydrogen/air are well known (Lewis and von Elbe 1987)
because very few chemical species are involved. The ignition step in pure hydrogen/air mixtures
(i.e., H2 + O2 → H + HO2), however, is essentially never involved in accidental explosions. Rather,
an external heat source (e.g., a spark from static electricity) or an impurity-assisted lower energy
dissociation reaction (e.g., the thermal dissociation of a lubricant or organic film) in the presence of
hydrogen initiates the production of radicals and triggers a subsequent runaway chain reaction.
Beyond kinetics, the hydrodynamics of hydrogen mixtures in oxygen and nitrogen are complex
because of the very different masses and the broad range of transport properties (e.g., diffusivities,
viscosities, and buoyancies) of the constituent gases. When chemical combustion is added to the
picture, modeling and predicting flame and explosion behavior become more complex, because the
relatively unknown transport properties of the airborne neutral radicals (e.g., H and OH) are
important in modeling the turbulent characteristics of the explosion. Nevertheless, a thorough
understanding of the hydrodynamics and combustion of hydrogen in the open atmosphere and in
enclosed spaces as a function of mixing ratio, wind speed, and ventilation rate is needed if we are
to recognize and control the safety hazards presented by the hydrogen economy.
An obvious precaution against fire is the prevention of leaks in the hydrogen infrastructure through
careful construction, sensing, and maintenance. Hydrogen presents special difficulties, however,
because of its tendency to embrittle metallic container materials like stainless steel and its welded
joints. Embrittlement arises from hydrogen’s ability to diffuse through metals readily, perhaps using
grain boundaries as easy flow channels, and weakening internal metal-metal bonds by combining
locally with host atoms. Because embrittlement occurs slowly and can cause catastrophic failures of
hydrogen storage containers, it creates a basic materials science challenge that must be overcome if
the hydrogen economy is to be successful.
The safety hazards of hydrogen in everyday life can be significantly mitigated by simple knowledge
of its presence. Hydrogen is largely invisible to human senses, such as sight and smell. Sensors that
selectively reveal the presence of hydrogen are needed to provide early warning of leaks before the
flammability threshold is reached. Beyond human safety, such sensors would be useful for
monitoring, optimizing, and controlling the technical operation of the hydrogen economy, such as
44

fuel cell operation, the charge/discharge cycle of hydrogen storage devices, and hydrogen
production by the water splitting or hydrocarbon reforming routes.
Education and training in safe hydrogen practices are important factors in reducing the hazards of a
hydrogen economy. Hydrogen-powered cars would expose the public to hydrogen during the
refueling process and would release hydrogen to enclosed spaces during maintenance and repair
operations. Repair technicians, professional drivers, and the driving public should receive
instructions in the safe handling of hydrogen and in emergency procedures, should an accidental
release of hydrogen occur. The institutional training and safety procedures for handling hydrogen in
the fertilizer and petroleum industries provide one set of models for establishing an appropriate
culture of safety as part of a hydrogen economy.
5.4 RESEARCH DIRECTIONS
The goal of research on safety in the hydrogen economy is to (1) develop predictive models of the
hydrodynamic behavior of hydrogen/air mixtures in open environments and in enclosed spaces; (2)
develop predictive models of the combustion and detonation of hydrogen in open and enclosed
spaces in the presence of other gases and other materials; (3) develop a basic understanding at the
atomic level of hydrogen embrittlement of materials; and (4) identify, discover, and develop
inexpensive and effective sensors that selectively and sensitively monitor the presence and
concentration of hydrogen. Promising research directions are discussed in the following sections.
 Improved Understanding of Ignition Sources for H2/Air Explosions

Experimental and theoretical studies can help to identify low-energy heterogeneous and
homogeneous sources of radicals that can initiate chain branching and consequent explosions in
H2/air mixtures. Resonance-weakened bonds in certain organic lubricants, oils, and films or metal-
catalyzed chemical transformations at imperfections or ruptures in metallic containers can be a

potential source for generating radicals under external conditions of heat, shock, or stress. Ignition
of mixtures of hydrogen with gases other than air needs to be studied. The risk of ignition of
commonly occurring mixtures of hydrogen with methane, gasoline, benzene, and other volatile
liquids is not well understood.
45

 Improved Modeling of the Hydrodynamics of H2/Air Explosions
Hydrodynamics modeling capabilities suited to handling H2/air turbulence explosions in confined
spaces need to be developed. Such developments would include a more secure experimental and/or
theoretical database of the transport properties of airborne neutral radicals such as H and OH under
explosive conditions.
5.4.1 Understanding of the Basic Physics of Hydrogen Transport in Metals and Hydrogen-
assisted Damage Mechanisms
Corrosion and hydrogen embrittlement of materials are closely connected to details of their
microstructure, and, in particular, to the segregation and diffusion processes that occur at internal
interfaces and associated defects, such as dislocations. Although it is well known that the segregation
of common solute impurities, such as sulfur and phosphorus, to grain boundaries can promote
decohesion of these boundaries, the suspected synergistic role of hydrogen in this process is not well
understood. The dependence of interfacial segregation on the nature of the grain boundary is also
unclear. Filling this gap would help in designing an optimal microstructure that might, for example,
minimize the connectivity of fracture-susceptible boundaries. We need to improve our
understanding of the mechanisms and activation barriers for intergranular diffusion, in particular
because grain boundaries can act as fast diffusion pathways. Diffusion and bonding of hydrogen in
the microstructure of bulk materials are key factors that control hydrogen embrittlement and
corrosion. An integrated approach uniting experimental studies with sophisticated theory and
modeling is required.
Preventing hydrogen embrittlement by coating exposed surfaces with a self-sealing barrier should
be explored. Such a barrier can be created by surface segregation of a dissolved element that reacts
with hydrogen to form a protective layer. Breaches of the surface layer are automatically sealed by
reaction of hydrogen with freshly exposed surface. Research is needed to identify suitable alloys
with components that surface-segregate and form barriers upon reaction with hydrogen.
5.4.2 Sensors for Hydrogen
46

New concepts for hydrogen sensors are needed to detect the presence of dangerous levels of
hydrogen in refueling stations, repair garages, passenger cabins in hydrogen-powered cars, and other
situations where the public is exposed to hydrogen. These sensors need to be reliable, highly
specific, and low cost, and they need to have low power requirements. For example, resistive sensors
could be developed from nanowires or ultra-thin films, where a thin layer of hydride forming at the
surface significantly alters the bulk resistivity. Adsorption of hydrogen on carbon nanotubes
produces a distinctive signature in the transport properties, especially in the thermopower. Highly
selective detection of H2 can also be achieved with various spectroscopic approaches. For instance,
the high reactivity of hydrogen enables chemical sensing, where a hydride forming on the surface
of a reactive film can be detected spectroscopically or through its optical reflectivity.
5.4.3 POTENTIAL IMPACTS

Safety is a prime requirement for the success of the hydrogen economy. The development of
predictive models for the dynamics of free H2 in air in open and enclosed spaces would allow the
assessment of risk and establishment of safety procedures for specific activities of the hydrogen
economy, such as hydrogen vehicle refueling, driving in partially enclosed tunnels, indoor parking,
and vehicle repair. Models of hydrogen ignition and detonation in the presence of vapors from
common volatile liquids would enable new standards for their use in proximity to hydrogen.
Fundamental knowledge of hydrogen embrittlement of metals and welded joints would enable the
setting of standards for the materials used in building a hydrogen infrastructure. Sensitive, selective
sensors for detecting hydrogen would warn against the danger of fire or explosion in sheltered or
enclosed areas.
5.4.4 THEORY, MODELING, AND SIMULATION OF HYDROGEN
Overview
Theoretical modeling, including computational simulation and analysis, will impact all research
47

areas essential for the development of effective hydrogen energy systems. A strong, synergistic
relationship between theory and experiments on well-defined systems will provide insight into
mechanisms, predict trends, identify promising new materials and reaction processes, and guide new
experiments. Successful efforts in these areas will significantly enhance our ability to meet the key
technical challenges of the hydrogen economy in hydrogen production, storage, and use.
 Research Needs
New computational approaches are needed to integrate across disparate time and length scales that
are important for hydrogen production, storage, and use. For example, modeling has traditionally
been carried out separately for increments of length scales using quantum mechanics (0.1 to 10 nm),
statistical mechanics (1 to 1,000 nm), mesoscale (0.1 to 100 µm), and continuum mechanics (1 mm
to 10 m). Time scales range from quantum mechanical methods (10-15 s) to continuum methods (1
to 105s). There is a critical need for theoretical modeling and simulation to span all these length and
time scales seamlessly to meet the needs of hydrogen research. New first-principle algorithms are
required to simulate and model condensed-phase phenomena with higher accuracy. This will enable
experimental measurements to be assessed for the identification of trends that will aid in the
development of new materials and processes for specific applications. For example, computational
tools could aid in the identification of elements or compounds that could be added to nanostructured
hydrogen storage materials to help improve the rate of hydrogen release. Simulations could then be
used to understand the molecular-level processes responsible for the observed improvements.
Computational methods can be used in the design of novel biologically inspired components for
catalysis, for example, and to predict the structure and mechanisms of these processes.
Computational methods are also needed to understand the structure of materials and interfacial
regions, interactions in composites, and ionic and electronic transport within and across phase
boundaries. Predictive modeling will be required to provide an atomic-scale understanding of
catalytic sites and of the mechanisms involved in catalysis to allow tailored design of catalysts on
the nano scale. For hydrogen storage, computational methods are needed to understand how
hydrogen reacts with the surface, interface, grain boundaries, and bulk defects of a particular storage
material. In fuel cell research, fundamental understanding of ionic transport properties of
48

electrolytes used in membranes and the detailed reduction processes of oxygen at the cathode
electrocatalyst-electrolyte interface, for example, are needed to develop improved electrode and
electrolyte materials. Understanding electron transfer processes at interfaces is needed to enhance
photocatalysis and electrocatalysis processes involved in fuel cells and hydrogen production.
 Impact
Coupled with new characterization techniques that will yield unprecedented amounts of detailed
information about atomic and molecular processes, new computational methods for theory,
modeling, and simulation have the potential to revolutionize the design of materials at the nano scale
and to expedite the discovery of molecular-level processes critical for hydrogen energy systems.
Development of these novel materials and processes is critical for attaining the full suite of
technologies necessary for a hydrogen economy. The time horizon for the development of practical
hydrogen energy systems is short and cannot be met without a strong investment in theory and
modeling in parallel with a significant investment in basic experimental research.
 SAFETY AND ENVIRONMENTAL ISSUES
 Overview
Safety and environmental issues impact all aspects of hydrogen utilization. Moving toward a
hydrogen economy will require production, storage, and utilization of large quantities of hydrogen
under various operating conditions. The accidental release of hydrogen poses significant risks that
differ from those associated with fossil fuels. Hydrogen ignites more readily than propane, and a
high-pressure leak can be self-igniting, burning with an invisible flame. Its high diffusivity and
buoyancy normally prevent the buildup of flammable concentrations in the open air, but in enclosed
spaces, the risk of fire or explosion can be serious. With large quantities of hydrogen in everyday
use, we must be able to predict the behavior of hydrogen under many conditions, including enclosed
garages, covered parking structures, enclosed or partially ventilated cars, and windless or windy
open air. In each case, we should understand the hydrodynamics well enough to predict the threshold
of flammable or explosive concentrations, and understand the combustion dynamics well enough to
49

predict the magnitude of the released heat and blast. Of paramount importance to the safe handling
of hydrogen is the training of skilled personnel and extensive public education. In addition,
improved materials are needed that address issues related to hydrogen exposure, such as
embrittlement, weld failures, and general materials compatibility. Developed technologies must also
incorporate safeguards and processes that protect the environment from hydrogen leaks and
potentially hazardous by-products of hydrogen production, storage, and use.
A large part of the interest in adopting hydrogen for use as an energy carrier arises from its potential
for reducing the negative environmental impacts of our energy systems. However, in planning the
development of any technology system that is intended to be implemented on a large scale, it is
prudent to anticipate potential deleterious environmental impacts as well. If hydrogen were to
become established as the primary carrier in the worldwide energy economy, the additional amount
of hydrogen cycled each year would exceed the known amount cycled by all present-day
geochemical, biological and atmospheric processes. If 10% of the hydrogen in use were to escape
to the atmosphere, the amount of hydrogen entering the atmosphere from all sources would more
than double. Hydrogen is rapidly mixed into the atmosphere and has a relatively short turnover time
(~2 yr), being consumed in atmospheric processes and by soil microorganisms. The potential
consequences of doubling the annual inputs into these processes need careful scientific study.
 Research Needs
The need to understand the behavior of hydrogen under a wide variety of conditions demands better
theory and modeling of its hydrodynamics and combustion dynamics. Such models would allow
predictive capability for assessing the risk of fire or explosion under the many possible leak and
failure scenarios that would be found in the hydrogen economy. These predictive models of
hydrogen accumulation, ignition, and combustion will form the basis for establishing
comprehensive safety standards and procedures. The fundamentals of the interactions of hydrogen
with specific materials need to be understood, as well as the mechanisms involved in materials
failure. Embrittlement in metals, the role of grain boundaries and other microstructure in promoting
or retarding materials degradation, and the effect of hydrogen in weakening welds and joints need
to be examined to anticipate catastrophic failures in the hydrogen infrastructure. Studies are needed
to fully assess requirements for materials compatibility. Sensors are needed to detect trace amounts
of hydrogen escaping into public places and to warn of potential flammable accumulations in
50

enclosed spaces. Such sensors should be highly selective and highly sensitive to hydrogen, providing
quantitative as well as qualitative information.
The fate of hydrogen that escapes to the atmosphere needs to be studied in greater detail so that the
consequences of increased releases can be accurately modeled and projected. The capacity of soil
and various aqueous microbial ecosystems to take up the increased hydrogen flux must be assessed.
To make an accurate assessment, the properties of hydrogen-metabolizing organisms and microbial
consortia need to be much better understood. The impact of any increased microbial uptake on the
diversity and stability of their ecosystems and of increased accumulation of their metabolic by-
products, such as methane, must also be assessed. These data are needed for projecting whether or
not the net content of hydrogen in the atmosphere would rise. The consequences of increasing
atmospheric hydrogen must be carefully studied, including an assessment of its impact on other
atmospheric processes.
 Impact
The ability to model the hydrodynamics and combustion dynamics of hydrogen in the open air and
in enclosed spaces will enable reliable risk assessment of the many potential hydrogen-human
contact situations that would occur in a hydrogen economy. Understanding the causes and evolution
of hydrogen embrittlement of metals and weld joints at the atomic level will enable prediction and
prevention of mechanical failures within the hydrogen infrastructure and the accidental release of
hydrogen to the environment. Development of inexpensive and effective sensors for the presence
and concentration of hydrogen will provide early warning of dangerous hydrogen concentrations
before they reach the ignition point.
51

CHAPTER-6
FUTURE OF THE HYDROGEN ECONOMY BRIGHT OR BLACK

6.1.1 INTRODUCTION
Hydrogen has fascinated generations of people for centuries, including visionaries like Jules
Verne. A "Hydrogen Economy" is often advocated as the ultimate solution for energy and
environment. Hydrogen societies have been formed for the promotion of this goal by
publications, meetings and exhibitions.
Hydrogen can be produced from electricity and water. Its conversion to heat or power is
simple and clean. When burnt with oxygen, hydrogen generates no pollutants, but only
water, which can return to nature. However, hydrogen, the most common chemical element
on the planet, does not exist in nature in its elemental form. It has to be separated from
chemical compounds, by electrolysis from water or by chemical processes from
hydrocarbons or other hydrogen carriers. The electricity for the electrolysis may come
eventually from clean renewable sources such as solar radiation, kinetic energy of wind and
water or geothermal heat. Therefore, hydrogen may become an important link between
renewable physical energy and chemical energy carriers.
But have the physics and chemistry been properly considered? Most attention has been
given to the apparent benefits of hydrogen in use, while the upstream aspects of a hydrogen
economy are rarely addressed, Figure 1.
Hydrogen Economy
Packaging
compression, liquefaction, hydrides
Hydrogen Distribution Hydrogen
Production pipelines, road, rail, ship Use
Storage
pressure & cryogenic containers
Transfer
Figure Schematic Representation of an elemental "Hydrogen Economy"
52

Like any other product, hydrogen must be packaged, transported, stored and transferred, to
bring it from production to final use. These standard product processes require energy. In
today's fossil energy economy, the energy lost between the well and the consumer is about
12% for oil and about 5% for gas.
“Hydrogen Economy”. Our analysis should be of particular interest for the assessment of
fuel options for transport applications.
Without question, technology for a hydrogen economy exists or can be developed.
In fact, considerable amounts of hydrogen are generated, handled, transported and used in
the chemical industry today. However, this hydrogen is a chemical substance, not an energy
commodity. Hydrogen production and transportation costs are absorbed in the price of the
synthesized chemicals. The cost of hydrogen is irrelevant as long as the final products find
markets. Today, the use of hydrogen is governed by economic arguments and not by
energetic considerations.
However, if hydrogen is to be used as an energy carrier, energetic issues must also be

considered. How much high-grade energy is required to make, to package, to handle, to
store and to transport hydrogen? It would be difficult to establish a sustainable energy future
if much of the energy harvested from nature is wasted before it reaches the energy consumer.
We have examined the key stages by physical and chemical reasoning and conclude that the
future energy economy is unlikely to be based on elemental hydrogen. Hydrogen may be
the main link between renewable physical and chemical energy, but most likely it will reach
the consumer chemically packaged in the form of one or more consumer-friendly natural or
synthetic liquid hydrocarbons
 Preliminary results of our study have already been presented at THE FUEL CELL
WORLD conference in July 2002 [1].
6.1.2 Properties of Hydrogen
The physical properties of hydrogen are well known [2, 3]. It is the smallest of all atoms.
Consequently, hydrogen is the lightest gas, about eight times lighter than methane
(representing natural gas). Promoters praise the energy content of hydrogen. However, for
most practical applications, the heating value per unit mass of any gaseous energy carrier is
53

of little relevance [4]. Most storage tanks are limited by volume, especially in automotive
applications. Also, the capacity of pipelines depends on the square of their diameter, and the
flow velocity.
Therefore, in most cases, it is more meaningful to consider the energy content per unit
volume.
For this energy analysis, it is proper to use the heat of formation or higher heating value
(HHV), which is the true energy content of the fuel, based on the energy conservation
principle (i.e. the 1st Law of Thermodynamics). Unfortunately, in many countries, when
expressing the efficiency of heat engines and other energy converters, the lower heating
value (LHV) is used. However, when referred to the physically correct HHV, the
efficiencies would be lowered according to the ratio of LHV to HHV, i.e. by factor 0.940
for gasoline, 0.903 for natural gas and 0.845 for hydrogen [5]. Hence, efficiencies and fuel
economies on the LHV basis are 6.4%,
10.7% and 18.3% higher than those on the HHV basis. In particular, hydrogen energy
converters look much less attractive if their output is related to the physically correct energy
input. Also, LHV-efficiencies may exceed 100% - as with some condensing boilers - which
violates the energy conservation principle.
Therefore the use of the LHV should be abandoned for all energy engineering applications.
Since the production of hydrogen is governed by the heat of formation or the higher heating
value, its use should also be related to the HHV energy content. Our analysis is based on
physical and chemical reasoning and therefore uses the higher heating value (HHV)
throughout. The reference density and heating values of hydrogen and methane used in this
study are shown in Table 1.
Table Density and heating values of hydrogen and methane
Units Hydrogen Methane
Density at NTP kg/m3 0.0887 0.707

Gravimetric HHV MJ/kg 142.0 55.6
Volumetric HHV at NTP MJ/m3 12.7 40.0
6.1.3 Energy Needs of a Hydrogen Economy
54

Hydrogen is not a natural fuel, but a synthetic energy carrier. It only carries energy generated
by other processes. For example, hydrogen may be produced from electricity by electrolysis
of water. However, high-grade electrical energy is also required to compress or liquefy it,
and to transport, transfer and store it. Moreover, in many cases, hydrogen offers little or no
end-use advantage over the source energy. For example, in all stationary applications,
hydrogen would compete with grid electricity, which could be distributed directly to the end
user with much lower energy losses.
Clearly the cost of hydrogen should be as low as possible. However, a hydrogen economy
could establish itself only if it makes sense energetically. Otherwise, better solutions will
conquer the market. Also, the present infrastructure could handle almost any synthetic liquid
hydrocarbon, while hydrogen requires a totally new distribution network. A transition to an
elemental hydrogen economy would affect the entire energy supply and distribution system.
Therefore, all aspects of a hydrogen economy should be discussed and understood before
making any investments - including those for research and development.
The fundamental question: "How much energy is needed to operate a hydrogen economy?"
is analyzed here in some detail. We consider the key stages of a hydrogen economy -
production, packaging, transport, storage and transfer of elemental hydrogen - and relate the
energy consumed for these functions to the energy content of the delivered hydrogen. All
the process analyses are based on either ideal physics and chemistry or actual data from the
gases industry. Hence they are most unlikely to be bettered significantly in future.
6.1.4 Production of Hydrogen
Hydrogen does not exist in nature in its elemental state, but has to be produced from sources
like water and natural gas, with the expenditure of energy. Ideally, the energy input would
equal the energy content of the synthesized gas. However, hydrogen production by any
process, such as electrolysis or reforming, involves the transformation of energy. The
electrical energy or chemical energy of hydrocarbons is transferred to the chemical energy
of hydrogen. Unfortunately, energy transformations are always associated with energy
losses.
Making hydrogen from water by electrolysis is one of the more energy-intensive methods.
As long as the electricity comes from a clean source, electrolysis is a clean process, but it is
associated with considerable losses. Electrolysis is the reverse of the hydrogen oxidation
55

reaction in a fuel cell, the standard potential of which is about 1.23 Volts at NTP conditions.
However, electrolyzers need a higher voltage to separate water into hydrogen and oxygen.
Under operational conditions, an over-voltage is needed to overcome polarization and
resistive losses. For solid polymer or alkaline systems, the polarization losses are typically
0.28 Volt. Assuming that the same electrolyte and catalysts are used, the open circuit
voltages for fuel cell and electrolyzer become 1.23 V +/- 0.28 V = 0.95 V and 1.51 V
respectively. Assuming also for both cases an area-specific resistance of 0.2 Ohm-cm2 gives
the characteristics of a low temperature fuel cell (dashed line) and a corresponding
electrolyzer (solid line) in Figure 3.
Figure 3 Voltage-current characteristics of hydrogen
2.5
2.0
Cell Voltage [V]
Electrolyzer
Fuel Cell
1.5 1.76 Volt
1.23 Volt (STP)
0.70 Volt
1.0
0.5
0.0
0 1 2 3 4
Current Density [A/cm2]
56

Under open circuit conditions, the standard electrochemical potential of the hydrogen-oxygen pair is
1.23 Volts at NTP. To optimize the system efficiency, fuel cells are normally operated at about 0.7
Volt – i.e. at about 1.2 A/cm2. We assume the same optimization requirements also hold for an
electrolyzer. In this case, the corresponding voltage of operation is 1.76 Volts - as indicated by the
horizontal dash-dot line in Figure 3. The standard potential of 1.23 Volts corresponds to the higher
heating value HHV of hydrogen. Consequently, the over-voltage is a measure of the electrical losses
of the functioning electrolyzer. The losses relative to the HHV of hydrogen depend on the hydrogen
production rate – i.e. the current density.
Compared with the standard potential of 1.23 Volts, an operating potential of 1.76 Volts implies that
1.43 energy units must be supplied to generate 1 HHV unit of hydrogen, giving a stage efficiency of
1/1.43 = 70%. At higher specific hydrogen production rates, i.e. higher current densities, this
efficiency is even lower. Also, this analysis takes no account of the losses in converting the high
voltage AC electricity from the grid to the high current DC electricity used in electrolyzers.
Nevertheless, electrolysis may be the only practical link between physical renewable energy (kinetic
energy from wind, water and waves, radiation from the sun, geothermal heat) and non-stationary fuel
cells needed for transportation.
Also, electrolytic production of hydrogen offers one method of storing electricity from intermittent
sources. Other - and proven – methods include hydro-electricity, pumped storage, flywheels and
batteries.
6.2 Reforming
Hydrogen can also be extracted from hydrocarbons by reforming. This chemical process is, in
principle, an energy transformation process. The HHV energy contained in the original substance can
be transferred to the HHV energy of hydrogen. Theoretically, no external energy is needed to convert
a hydrogen- rich energy carrier like methane (CH4) or methanol (CH3OH) into hydrogen by an
autothermal reforming process.
However in reality, thermal losses cannot be avoided and the HHV energy contained in the generated
hydrogen is always less than that in the original hydrocarbon fuel. The efficiency of hydrogen
57

production by autothermal reforming is about 90%, but may be less, especially for compact, mobile
plant. Thus at least 1.1 units of energy must be invested to obtain 1 HHV unit of hydrogen. Also, more
CO2 is released by this indirect process than by direct use of the hydrocarbon precursors. Hence this
reduces the overall well-to-wheel efficiency and increases the overall CO2 emissions.
For most practical applications, natural gas can do what hydrogen does. There is no need for a
conversion of natural gas into hydrogen which, as shown in this study, is more difficult to package
and distribute than the natural energy carrier. For all stationary applications, the source energy
(electricity or hydrocarbons) could be used directly by the consumer at comparable end-use efficiency
and hence higher overall source-to-service efficiency and lower overall CO2 emission. Therefore,
transforming electricity or natural gas to hydrogen offers no universal solution to the energy future.
At today's energy prices, it is considerably more expensive to produce hydrogen by water electrolysis
than by reforming of fossil fuels. According to [6], it costs around $5.60 for every GJ of hydrogen
energy produced from natural gas, $10.30 per GJ from coal, and $20.10 per GJ to produce hydrogen
by electrolysis of water.
Before taxes, gasoline costs about $3.00 per GJ.
6.2.1 Packaging of Hydrogen
6.2.2 Compression of Hydrogen
Compressing gas requires energy, and the compression work depends on the thermodynamic
compression process. Ideal isothermal compression, which is impossible in practice, follows a simple
equation:
W = p0 V0 ln(p1/p0)
For ideal gases, and real gases far above their boiling temperature, the actual thermodynamic process
is more closely described by the adiabatic compression equation
W = [γ/(γ -1)] p0 Vo [(p1/p0)(γ -1)/γ - 1]

where
W [J/kg] specific compression work
p0 [Pa] initial pressure
p1 [Pa] final pressure
58

V0 [m3/kg] initial specific volume

γ [-] ratio of specific heats, adiabatic coefficient
In both isothermal and adiabatic compression, the compression work is the difference between the
final and the initial energy states of the gas. The difference between the two compression processes is
shown by the final temperature of the compressed medium. In the ideal isothermal case, the
temperature would remain constant, while under adiabatic conditions, it rises considerably. Moreover,
the magnitude of the compression work depends on the nature of the gas.
For example, for hydrogen and methane, the adiabatic coefficients and initial specific volumes are:
H2 γ = 1.41 V0 = 11.11 m3/kg
CH4 γ = 1.31 V0 = 1.39 m3/kg
For adiabatic compression of diatomic hydrogen and five-atomic methane from atmospheric
conditions to higher pressures, the energy consumed.Clearly, much more energy per kg is required to
compress hydrogen than methane.
6.2.3 Liquefaction of Hydrogen
Even more energy is needed to compact hydrogen by liquefaction. Theoretically, only about 14.2
MJ/kgLH2 have to be removed to cool hydrogen gas from 298 K (25°C) to 20.3 K and to condense the
gas at 20.3 K and atmospheric pressure [9]. This energy analysis includes the energy needed for the
removal of heat released by the para-ortho conversion of electron spin orientations at low
temperatures. In the interests of energy efficiency, hydrogen is liquefied by complex processes.
The cooling is accomplished by multi-stage compression and expansion coupled with counter-flow
heat exchange and energy recovery by expansion turbines. Generally, a three-stage vapor compression
propane refrigeration system is used for cooling from ambient temperature to 73K, followed by multi-
stage nitrogen expansion to obtain 77K, and a multi-stage helium compression-expansion to obtain
the liquefaction of hydrogen at 20.3K and atmospheric pressure [10]. However, the 14.2 MJ/kg LH2
obtained by an exergetic analysis does not include any electrical, mechanical, thermal, or flow-related
losses. Therefore, we present published operating data of representative hydrogen liquefaction plants.
59

The medium size liquefaction plant of Linde Gas AG at Ingolstadt in Germany produces 182
kgLH2/hour [11] at a specific energy consumption of about 54 MJ/kgLH2 [9], while the best large plants
in the US require 36 MJ/kgLH2 to liquefy hydrogen [9]. The authors of a Japanese feasibility study of
a hydrogen liquefaction plant of 300 metric tons LH2 per day or 12,500 kgLH2/h capacity conclude that
in the best case at least 105.2 MW are required to operate the plant [12]. This corresponds to 30.3
MJ/kgLH2 for a plant about 6 times larger than any existing facility. The use a helium-neon mixture for
the low temperature cycle has been suggested to reduce the energy consumption to, perhaps, 25.2
MJ/kgLH2 (= 7 kWh/kgLH2) for a plant producing 7,200 kgLH2 per hour, or 173 metric tons LH2 per day
[9], but experimental results are not yet available.
The variation of energy consumption with capacity for existing hydrogen liquefaction plants.
6.3 Physical Metal Hydrides
Hydrogen may be stored physically, e.g. by adsorption in spongy matrices of special alloys as physical
metal hydrides. The hydrogen forms a very close, but not perfect, bond with alloys like LaNi5 or
ZrCr2.
Rather than considering specific hydrides, the energy balance will be described in general terms.
Again, energy is needed to produce and compress hydrogen. Some of this energy input is lost in form
of waste heat. When a metal hydride storage container is filled with hydrogen, heat is released and
usually lost.
Conversely, when the process is reversed to liberate the stored hydrogen, heat must be added. The
release of hydrogen at pressures below the filling pressure requires a heat inflow proportional to the
hydrogen release rate. For small release rates and for containers designed for efficient heat exchange
with the environment, no additional heat may be required. Also the hydrogen storage container may
be heated with waste heat from the fuel cell. Thus the energy needed to package hydrogen in physical
metal hydrides may be more or less limited to the energy needed to produce and compress hydrogen
to a pressure of
3 MPa [15]. This is significantly less than for hydrogen stored as compressed gas at 20 MPa, and far
less than for hydrogen stored at 80 MPa, or as a liquid.
60

However, according to [14], metal hydrides store only around 55-60 kg of hydrogen per m3, whereas,
ignoring the container, liquid hydrogen has a volumetric density of 70 kg/m3. Moreover, metal hydride
cartridges are very heavy. A small metal hydride container holding less than 2 g of hydrogen weighs
230 g [16]. Hence it might require a hydride store weighing up to 200 kg to contain 2 kg of hydrogen.
Since this is equivalent to only about 8 liters or 2 U.S. gallons of gasoline, this type of hydrogen
packaging is quite impractical for automotive applications.
CONCLUSION
61

REFRENCES
62

REFERENCES
[1] "The Future of the Hydrogen Economy: Bright or Bleak?", Baldur Eliasson and Ulf
Bossel, Proceedings, THE FUEL CELL WORLD, Lucerne / Switzerland, July 2002
[2] “Handbook of Chemistry and Physics”, recent editions
[3] G. H. Aylward, T. J. V. Findlay, “Datensammlung Chemie in SI-Einheiten”, 3. Auflage
(German Edition), WILEY-VCH, 1999
[4] “Synthetic Fuels”, R. F. Probstein and R. E. Hicks, Mc-Graw Hill,1982
[5] Properties of Fuels. http://www.afdc.doe.gov/pdfs/fueltable.pdf
[6] H. Audus, Olav Karlstad and Mark Kowal, “Decarbonisation of Fossil
Fuels: Hydrogen as an Energy Carrier”, CO2 Conference, Boston/Cambridge
1997, published in Energy Conversion Management,
Vol. 38, Suppl., pp. 431-436.
[7] E. Schmidt, “Technische Thermodynamic”. 11th Edition, Vol.1, p287 (1975)
[8] Burckhardt Compression AG, Winterthur / Switzerland (private
communication)
[9] "Die Schlüsselrolle der Kryotechnik inder Wasserst off-Energiewirtschaft" H. Quack,
TU Dresden / Germany.
www.tudresden.de/mwiem/kkt/mitarbeiter/lib/wasserstoff/wassertech.html
[10] "Flüssigwasserstoff fur Europa – die Linde-Anlage in Ingolstadt", Reinhardt
Gross, Wolfgang Otto, Adolf Patzelt and Manfred Wanner, Berichte aus
Technik und Wissenschaften 71 (1994)
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Seminar Report On Hydrogen As The Future Fuel

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HYDROGEN AS THE FUEL OF FUTURE DEE SBNITM.

1.2 ADVANTAGES AND DISADVANTAGES OF HYDROGEN

Yogesh Kumar 12ESREE039 Guide Mr. A.K. Pathak

1.3 HYDROGEN SAFETY

• The ignition energy of hydrogen is very low.

• The ignition limits in air are very wide.

Yogesh Kumar 12ESREE039 Guide Mr. A.K. Pathak

two other well-known hydrocarbon gases.

HYDROGEN METHANE GASOLINE

IG CNITION LIMITS IN AIR 4- 75 Vol.-% 5,3 - 15 Vol.-% 1, 0 - 7,6 Vol.-%

LO WER HEATING VALUE 12 0 kWs/g 50 1 kWs/g 44, 5 kWs/g

Table 1: Revelant Safety Properties of Hydrogen, Methane and Gasoline

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1.4 PRODUCTION OF HYDROGEN

single block can take as much as 5 MW of electric energy.

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in the frame of the German- Saudi Arabian program HYSOLAR.

Fig. 1.1: Advanced 10 kW DLR Test Electrolyzer

Fig 1.2: 350 kW Pressurized Electrolyzer

Besides the electrolysis block, an independently operating electrolysis facility includes as a

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Fig.1.3: 350 kW Photovoltaic Field

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Yogesh Kumar 12ESREE039 Guide Mr. A.K. Pathak

some major advantages:

Fig.1.4: Typical Energy Curve Shapes during Solar Operation

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Fig.1.5: Principle of a PV-Electrolysis Plant

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Yogesh Kumar 12ESREE039 Guide Mr. A.K. Pathak

Fig.1.6: Curve Shapes of a PV-Electrolysis System

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2.1. HYDROGEN PURIFCATION AND PRODUCTION STORAGE

Last but not least, independently of the changes of

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of hydro-carbons, N2, CO and CO2.

• Filter for particle removal,

• Washing bottle for KOH-removal,

• Intermediate storage vessel to de-couple discontinuous hydrogen production from

Fig. 7: Hydrogen Purification and Storage System

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startup/shutdown behavior is included in figure 6 as the H2 in O2-content. Compressor losses of

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Fig.2.2: 200 bar Hydrogen Compressor

2.1.3 STORAGE METHODS FOR MOBILE AND STATIONARY CONSUMERS

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low for mobile

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Fig.2.3: Industrial Hydrogen Storage Method

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Fig.2.4: Liquid Hydrogen Tank of DLR

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Yogesh Kumar 12ESREE039 Guide Mr. A.K. Pathak

2.1.4 STORAGE METHOD

Fig.2.5 : Metal Hydride Storage of Daimler Benz

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Yogesh Kumar 12ESREE039 Guide Mr. A.K. Pathak

Yogesh Kumar 12ESREE039 Guide Mr. A.K. Pathak

3.1 THE NEED FOR HYDROGEN PRODUCTION

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Yogesh Kumar 12ESREE039 Guide Mr. A.K. Pathak

3.1.2 HYDROGEN PRODUCTION FROM FOSSIL FUELS

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