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 pollutantfree 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
1
Yogesh Kumar

12ESREE039

Guide Mr. A.K. Pathak

HYDROGEN AS THE FUEL OF FUTURE

DEE SBNITM.

(2012-2016)

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 wellknown, 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/m 3 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
2
Yogesh Kumar

12ESREE039

Guide Mr. A.K. Pathak

HYDROGEN AS THE FUEL OF FUTURE

DEE SBNITM.

(2012-2016)

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.

MI NOMNIMAL IGNITION ENERGY

SE LF IGNITION TEMPERATURE

HYDROGEN
0
2 mWs
0
58
5C
5

IG
EX
LO
FL
D

42
12
204
0,

CNITION LIMITS IN AIR

PLOSION ENERGY (with gas)
WER HEATING VALUE
AME TEMPERATURE
IFFUSION COEFFICIENT

METHANE
GASOLINE
9 mWs
24 mWs
40C
228 - 501C

75 Vol.-% 5,3 - 15 Vol.-% 1,

3
3
2 kg TNT/m7,0
3 kg TNT/m44,
0 kWs/g 50
1 kWs/g 44,
5C
187 5C
220
2
2
61 cm /s
0,1 6 cm /s
0,0

0 - 7,6 Vol.-%
22 kg TNT/m3
5 kWs/g
0C
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.

3
Yogesh Kumar

12ESREE039

Guide Mr. A.K. Pathak

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
2

electrode area and the current density play the major role. Current densities of 2 - 3 kA/m for
2

commercially available and up to 10 kA/m for advanced electrolyzers are used. With a maximum
2

electrode area of 4 m , 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.

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

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
2

concentrating PV-modules of four PV-cells each cover a land area of approximately 40.000 m .
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.
2

From the 1135,6 kWh on the plain area of a 144 m 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.

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

CHAPTER-2
HYDROGEN PURIFICATION

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 (H 2 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 O 2 in H2-impurity shall always move below 1 Vol.-% in
order to guarantee a simple and safe purification. In this example, the H 2 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.
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
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 (WTRAP 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.
The compressor is an industrially available oil-free membrane compressor with integrated
3

coolers, water traps and safety valves and can take a maximum flow of 10 Nm /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
3

350 kW facility. In this case, a varying hydrogen flow up to 65 Nm /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

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 20

th

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
3

content is only 8,9 Nm corresponding to 795 g. This means, only a storage density of 1,2 wt.-%.
Far too low for mobile

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.

Fig.2.4: Liquid Hydrogen Tank of DLR

The most common storage device in cars is the cryogenic storage of liquid hydrogen in vacuumsuper-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.

The hydrogen is stored as a super-cold liquid at 20 K or -250C 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
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 -210C 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

The low temperature hydrides have a temperature range between -30 and about 70C. 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 200C. 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 200C 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 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 200C. 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 400C 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.

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 (CO 2) 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 CO 2-induced warming at
2C (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 nations 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 twothirds of the nations 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 trade deficits, to the cumulative effects of CO 2 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

in both capital and operational costs are needed to enable hydrogen production to meet the nations
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 CO 2 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 CO 2 sequestration is developed,
economic factors (the general availability and relatively 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 CO 2
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 (<130C) 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].

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).

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 (1.551.65 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.

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 nations

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

4.1.2 DYE-SENSITIZED SOLAR CELLS

A promising new technology in solar energy conversion is the dye-sensitized photoelectrochemical

cell, or Grtzel cell (Grtzel 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.

Fig Dye Sensitized Solar Cell

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 photovoltaics 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 photovoltaics, 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, dyesensitized 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
(Grtzel 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.
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 TiO 2, 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
2

(see sidebar describing hydrogen in the biosphere). Most of this hydrogen arises from anaerobic
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 CO 2 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

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 hydrogenproducing 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 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 500C or more, well within the range of solar concentrators but higher than
can be achieved by todays 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 2,000C 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 ~900C
temperatures, have not yet been commercialized, giving them a long development horizon. Lowertemperature, 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 hightemperature reactor concept, developed in the Generation IV reactor initiative, is proposed to
match hydrogen production requirements via thermal cycles with maximum temperatures of 700
950C. 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 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 550C,
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 760C. Overall efficiencies of
4549% (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 (825900C) 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 lEnergie 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 electrolysis) replaces several chemical reactions in the S-I process.

CHAPTER5
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 ~120180 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
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 earths 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 H 2 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 H 2 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.

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 H 2. 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 earths 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 H 2 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 H 2 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 H 2 releases on the long-term stability of
the ozone layer.

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 H 2 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 H 2
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 H 2
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.

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 welldesigned 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 todays 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). Hydrogens 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, 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 impurityassisted 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 hydrogens ability to diffuse through metals
readily, perhaps using grain boundaries as easy flow channels, and weakening internal metalmetal 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 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.

Improved Modeling of the Hydrodynamics of H2/Air Explosions

Hydrodynamics modeling capabilities suited to handling H 2/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 fracturesusceptible 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
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 H 2 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 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 m),
and continuum mechanics (1 mm to 10 m). Time scales range from quantum mechanical
methods (10

-15

s) to continuum methods (1 to 10 s). 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 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 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 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 hydrogenhuman 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.

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
Production

Distribution
pipelines, road, rail, ship

Hydrogen
Use

Storage
pressure & cryogenic containers

Transfer

Figure Schematic Representation of an elemental "Hydrogen Economy"

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 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
Density at NTP
Gravimetric HHV
Volumetric HHV at NTP

kg/m
MJ/kg
3
MJ/m

Methane

0.0887
142.0

0.707
55.6

12.7

40.0

6.1.3 Energy Needs of a Hydrogen Economy

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
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-cm

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

Vol[V]

2.0
1.5

Cell tage

1.0
0.5
0.0

Electrolyzer

Current Density [A/cm2]

Fuel Cell
1.76 Volt
1.23 Volt (STP)
0.70 Volt

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 nonstationary 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 (CH 4) 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 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 enduse efficiency and hence higher overall source-to-service efficiency and lower overall CO 2
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
( -1)/

W = [/( -1)] p0 Vo [(p1/p0)

- 1]

where
W

[J/kg]

specific compression work

p0
p1
V0

[Pa]
[Pa]
3
[m /kg]
[-]

initial pressure
final pressure
initial specific volume
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

= 1.41

V0 = 11.11 m3/kg

CH4

= 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 (25C) 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 counterflow 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/kgLH2 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.
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 LH 2 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.
3

However, according to [14], metal hydrides store only around 55-60 kg of hydrogen per m ,
3

whereas, ignoring the container, liquid hydrogen has a volumetric density of 70 kg/m .
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

REFRENCES

REFERENCES

[4]

[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
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 Schlsselrolle der Kryotechnik inder Wasserst off-Energiewirtschaft" H.
Quack, TU Dresden / Germany.
www.tudresden.de/mwiem/kkt/mitarbeiter/lib/wasserstoff/wassertech.html
[10]
"Flssigwasserstoff fur Europa die Linde-Anlage in Ingolstadt",
Reinhardt
Gross, Wolfgang Otto, Adolf Patzelt and Manfred Wanner, Berichte aus
Technik und Wissenschaften 71 (1994)