A Perspective on Its

Production and Use

ARTVILLE

HYDROGEN VISION HAS BEEN ENDORSED BY NUMEROUS WORLD

leaders and decision makers in both public and private sectors and hailed as the
key to a clean energy future. In 2003, U.S. President Bush and E.U. President
Prodi both embraced the vision of hydrogen economy. The vision calls for
transforming the global transportation energy economy from one dependent on
oil to that based on sustainable hydrogen. The rationale for this change is that
hydrocarbon-based automobiles are a significant source of air pollution, while
hydrogen powered fuel cell vehicles produce effectively zero emissions, i.e.,
no criteria pollutants and greenhouse gas emissions. In the United States,
the 2001 greenhouse gas emissions from the transportation sector
alone were more than 500 million metric tons of carbon equivalent.
Furthermore, according to the International Energy Agency (IEA),
in 2002, two-thirds of all carbon dioxide emissions from fossil fuel
combustion were generated by the transportation and energy production sectors (Figure 1). Besides the transportation area, fuel
cells can also reduce emissions in other applications, such as the
residential or commercial distributed electricity generation.

by Ali T-Raissi and David L. Block

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1540-7977/04/$20.002004 IEEE

november/december 2004

To make hydrogen vision a reality, the U.S. government has launched the hydrogen fuel initiative aimed
at developing the technologies needed to make hydrogen-powered fuel cells commercially viable by 2020.
In the United States, these actions have been supported by the automakers whose ambition is to minimize
(if not eliminate) the environmental impact of vehicle use altogether. To do that, the auto industry must
come up with a power train that generates no air emissions using battery and/or fuel cell driven electric
propulsion. Automakers prefer an electric power train in automobiles because electric motors generate higher torque and power output than that delivered by the internal combustion engines. Despite that, power train
electrification has, so far, eluded automakers mostly due to the difficulties of storing and/or generating sufficient quantities of onboard electricity. After many years of research and development, the battery technology is still unable to deliver high enough energy density to allow a reasonable vehicle range before
recharging. Therefore, automobiles remain as one of the last application areas resisting electrification. Many
believe that hydrogen fuel cells have the potential to overcome the limitations of battery power and allow
electrification of automobiles. Application of fuel cells in transportation is the key to realizing hydrogen
economy and its environmental benefits to the society.

Why Hydrogen?
Hydrogen is the perfect fuel because:
it can be produced from a variety of energy resources
it satisfies all energy needsfrom transportation to electric power generation
it is the least polluting since its use produces water
it is the perfect carrier for solar energy in that it affords solar energy a storage medium.
Likewise, hydrogen is the perfect partner for electricity, and together they create an integrated energy system based on distributed power generation and use. Hydrogen and electricity are interchangeable using a
fuel cell (to convert hydrogen to electricity) or an electrolyzer (for converting electricity to hydrogen). A
regenerative fuel cell works either way, converting hydrogen to electricity and vice versa. Hydrogen and
electricity are both energy carriers because, unlike naturally occurring hydrocarbon fuels, they must both be
produced using a primary energy source. The primary energy sources available for hydrogen and electricity
production are fossil fuels and solar and nuclear power. Solar energy encompasses all renewable resources,
including geothermal, wind, biomass, and urban waste. As far as the future transportation is concerned, timing plays a major role in determining which resource and technology is the most viable for production of
hydrogen as automotive fuel. Thus, the question of where the hydrogen is going to come from in the nearand long-term future has to be addressed first.

Where Will the Hydrogen Come from?

Some visionaries of hydrogen economy believe that, in the distant future, petroleum use as a transportation
fuel will be forbidden to save the remaining resources for production of high-value products such as drugs,
building materials, and petrochemicals. Likewise, coal use will be banned for environmental reasons.
Remaining primary energy sources, mostly renewables and nuclear power, will then be used to generate
electricity and hydrogen. According to David Scott of the Institute for Integrated Energy Systems at the
University of Victoria in Canada, nearly all energy uses late in this century will be met by the intertwined
electricity and hydrogen energy carriers. Electricity will be converted into hydrogen when supply exceeds
demand and energy needs to be stored. Hydrogen will be converted back into electricity when required by a
fuel cell vehicle.
The near-term hydrogen vision, i.e., during the transition period, is to use fossil fuels (primarily natural
gas and coal) to produce electricity and hydrogen energy carriers with concurrent carbon dioxide (CO2 )
sequestration. At present, CO2 cant be sequestered effectively at the fueling stations or onboard automobiles when carbogenic fuels such as gasoline or natural gas are used. Consequently, the requirement that no
CO2 be emitted by the vehicle implies that only hydrogen or electricity should be used as automotive fuel.
The manner in which electricity and hydrogen are created is dependent on the way they are used as vehicular fuel subject to environmental and other constraints. In the following, we will discuss various scenarios
by which hydrogen can be produced, transported, and used in the fueling stations to power future fuel cell
vehicles without greenhouse gas emission. The hydrogen production mode for each scenario depends on
whether the vehicle fueling station is simply a hydrogen dispensing (or pumping) station or a complex facility incorporating both hydrogen production and dispensing functions, combined.

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Others (Commerce, etc.)

Residential
Use
5.8%
8.0%
Transport
43.6%
24.0%
(Road 17.7%)
Energy Production

Alternatively, hydrogen can be

shipped, on the highway via tanker
trailers, in liquid state, either as liquid
hydrogen or in the form of a liquid or
solid chemical hydride that librates
hydrogen onboard through thermolysis
(e.g., methylcyclohexane) or reaction
with water (e.g., sodium or lithium
borohydride). The preferred mode of
hydrogen transport (i.e., via pipeline or
tanker trailers) is dictated by the economic and other considerations (e.g.,
safety).

18.5%

Long Term
In the long term, hydrogen would
have to be produced using renewable
resources (solar, biomass, wind)
IEA CO2 Emissions
and/or nuclear energy that do not proManufacturing
from Fuel Combustion
Industries and
duce or require carbon dioxide seques(2002 Edition)
Construction
tration. Again, renewable and/or
nuclear-based hydrogen production
can occur in large-scale facilities that
figure 1. IEA carbon dioxide emissions from the combustion of fossil fuels.
can use the economy of scale to boost
efficiency and cut costs. ThermoFuel Stations as Dispensing Stations
chemical water splitting cycles present one such hydrogen
production technology in this category. As before, hydrogen
Near Term
can then be transported to fueling stations via pipeline or on
During the transition period, hydrogen would be made in the highway via tanker trailers, in liquid state. Again, the prelarge-scale central facilities using fossil fuels, such as coal or ferred mode of hydrogen transport is dictated by the economgas, wherein carbon dioxide can be sequestered efficiently and ic, safety, and other considerations.
cost effectively. Steam methane reformation (SMR) of natural
gas is the benchmark technology for hydrogen production in Fuel Stations as Production
this category. Another prospective near-term technology for and Dispensing Stations
production of hydrogen is an integrated coal gasification combined cycle process (Figure 2). Hydrogen can then be trans- Short Term
ported to fueling stations, in gaseous state, via pipeline. In the short term (during transition period), hydrogen would
be made, in a distributed manner, using grid electricity produced in large power plants from fossil energy sources such
as coal and/or natural gas with concurrent CO2 sequestration
or noncarbogenic energy sources (nuclear and hydroelectric
power). Hydrogen is produced and stored on site by grid
electrolysis of water at the fueling stations. This will be a
plausible scenario for hydrogen production only if the future
automobiles require pure gaseous hydrogen. In other words,
production and simultaneous liquefaction of hydrogen at
fueling stations are unlikely to occur until cost-effective and
energy-efficient, small-scale hydrogen liquefiers are available. Similarly, it is not going to be practical to produce
hydrogen via grid electrolysis onsite and then synthesize
from it (i.e., regenerate) chemical hydrides at small scale
figure 2. Coal and natural gas can be converted cleanly
from spent fuel collected at the fueling stations. Another
for production of either electricity or hydrogen gas using
impractical method for forecourt hydrogen production,
new technologies such as this 180 MW natural gas fueled
already experimented with in the United States (in Las Vegas,
peaking unit at TECOs Polk Power Station in Tampa,
Florida (courtesy of Tampa Electric Co.).
Nevada); Stuttgart, Germany; Madrid, Spain; and elsewhere,
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IEEE power & energy magazine

november/december 2004

table 1. Cost and performance characteristics of various hydrogen production processes.

Energy Required
[kWh/Nm3 of H2 ]
Hydrogen Production Process

Ideal

Practical

Steam methane reforming

0.78

22.5

Methane/NG pyrolysis
H2 S methane reforming

Efficiency
[%]

Costs Relative % of Total

to SMR
Production

mature

7080

R&D to
mature

7254

0.9

50

<1

R&D
R&D

4758

~1

0.94

4.9

mature

70

1.8

30

mature

Steam reforming of waste oils

R&D

75

<1
1.42.6

mature

60

Partial oxidation of coal

mature

55

Steam-iron process

R&D

46

Chloralkali electrolysis

mature

Grid electrolysis of water

Y
N

Naphta reforming
Coal gasification (TEXACO)

48

Need for CO2

Sequestration

1.5

Landfill gas dry reformation

Partial oxidation of heavy oil

Status of
Technology

1.01

3.54

8.6

4.9

Y
18

1.9
by-product

R&D

27

310

Solar & PV-electrolysis of water

R&D to
mature

10

>3

High-temperature electrolysis
of water

R&D

48

2.2

Thermochemical water
splitting cycles

early R&D

3545

Biomass gasification

R&D

4550

2.02.4

Photobiological

early R&D

<1

Photolysis of water

early R&D

<10

Photoelectrochemical
decomposition of water

early R&D

Photocatalytic decomposition
of water

early R&D

N
N
N

is to reform natural gas pipelined to the site. This technique is

not viable because there are no cost-effective methods for
small-scale sequestration of CO2 generated at the fueling stations. However, if methane at the fueling station is biogenically generated, the SMR process could be used for its
conversion to hydrogen. Examples of biogenically generated
methane include landfill gas and that from biomass fermentation or gasification processes. Another exception to this rule
is a process under development at the Florida Solar Energy
Center for thermocatalytic conversion of natural gas (and
other hydrocarbons) to hydrogen and carbonaceous products
(solid residue that can be readily sequestered).
Long Term
In the long term, energy carriers (electricity and hydrogen)
will have to be generated from sustainable (e.g., solar, wind
and geothermal) resources. Under this scenario, electricity
would be generated and fed into the grid at large-scale central
facilities such as solar power towers that use economy-ofscale for efficient and cost-effective production of electricity
(Figure 3). Again, hydrogen would be generated and stored
onsite using grid electrolysis of water at the fueling station.
november/december 2004

figure 3. Central power-mounted receivers such as this

solar plant in Barstow, California, can be used for generating either electricity or hydrogen.
IEEE power & energy magazine

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figure 4. This solar powered water electrolysis hydrogen

production and fueling station at Honda R&D Americas,
Inc., Los Angeles Center in Torrance, California, is an
example of PV-based hydrogen production for vehicle use
(courtesy of Honda R&D Co., Ltd.).

As discussed previously, this will not be a practical method

for hydrogen production if the future automobiles run on liquid hydrogen or chemical hydrides (that need regeneration
from spent fuel) instead of pure gaseous hydrogen. However,
it is quite plausible that hydrogen production can take place
at the fueling station via photovoltaic (PV) electrolysis of
water (Figure 4). Although, PV electrolysis may become
practical (since the efficiency of PV devices continues to
improve and costs come down), in most cases, the electricity
generated by PV is much too valuable to be used for hydrogen production. This is so because PV power readily matches
the air conditioning peak load of the utilities.

Cost of Hydrogen Production

Today, almost 95% of the hydrogen used in the United States
is produced by steam reformation of natural gas and other fossil fuels. It is also interesting to note that 95% of the hydrogen
has captive use. In other words, the hydrogen is produced but
then immediately consumed as a feedstock in another chemical process. Production of fertilizer is a case in point where
hydrogen is produced by steam reformation of natural gas and
used to make ammonia for fertilizer production.
Hydrogen produced by steam reformation of natural gas
costs about three times the cost of feedstock. This means that
if natural gas costs US$4/million BTU, then hydrogen will
cost about US$12/million BTU. Hydrogen produced from
electrolysis of water using grid electricity at US$0.05/kWh
will cost about US$28/million BTUabout two to three times
the cost of hydrogen generated from natural gas. Furthermore,
we note that the cost of hydrogen produced by electrolysis of
water is a linear function of power input and electricity costs,
so electricity at US$0.10/kWh will give hydrogen at a cost of
about US$56/million BTU. Now a days PV power costs
about US$0.15/kWh. Therefore, using PV electrolysis will
generate hydrogen at a cost of about US$84/million BTU or
about seven times that produced from natural gas.
In most places, the PV power output readily matches the
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IEEE power & energy magazine

air conditioning peak load of the utilities. In such cases, the

PV electricity would be too valuable to be used for hydrogen
production instead of air conditioning peak load. There are
obvious exceptions to this rule. For example, the off peak
electricity from nuclear power plants is a good option for producing hydrogen. As noted previously, any time excess electric power is availablei.e., when generated off-peak, in the
remote areas, from seasonal resources such as wind, hydrogen provides a perfect method for its storage. Likewise,
hydrogen can be generated from renewable sources such as
wind, hydro or geothermal when the resource does not readily match the electric load profile.
Among other solar-based water splitting schemes, various
photoelectrochemical and photocatalytic approaches have so
far failed to meet the cost and efficiency goals required to
make them viable hydrogen production processes. However,
in the long term, the only plausible hydrogen production
schemes compatible with the long-term scenarios discussed
previously are photobiological and high-temperature thermochemical processes. These direct solar-to-hydrogen processes
have been under development for many years, and all have
major challenges to overcome. Photobiological processes suffer from very low system level efficiencies (presently, less
than about 1%).
On the other hand, thermochemical water splitting cycles
(TCWSCs) have been shown to deliver very high overall
thermal to hydrogen energy system efficiencies (as high as
50% in some cases). TCWSCs split water via a series of
chemical reactions. All chemical intermediates are recycled
internally in the course of the cycle so that the net effect is
the decomposition of water input to the cycleforming
hydrogen and oxygen gases only. TCWSCs, however, suffer
from cost impediments of requiring a high-temperature (in
excess of 750 C) heat source. Research is underway in the
United States, Japan, and Europe to develop TCWSCs for
cost-effective production of hydrogen. Over the years, many
thermochemical cycles have been devised and some evaluated, experimentally. The following TCWSCs have received
most attention: JRC Mark 1 and 15, General Atomics sulfuriodine, UT-3, ZnO/Zn, and Fe 3 O 4 /FeO cycles. A great
majority of TCWSCs have been devised originally for
nuclear power interface (i.e., coupling to the high temperature gas-cooled reactors). TCWSCs are now being developed
for interface with the high flux, high temperature heat
sources from central receiver solar thermal power systems
(Figure 3).
Finally, other renewable energy-based processes such as
the biomass gasification are also important hydrogen production schemes. Examples include: thermochemical and enzymatic processes that convert biomass (municipal waste,
agricultural waste, energy crops, food processing residues,
etc.) to a hydrogen rich synthetic gas from which pure hydrogen can be recovered. Table 1 provides a summary of cost
and performance characteristics of various hydrogen production processes discussed in this article.
november/december 2004

Conclusions
Techniques for generating electricity and hydrogen energy carriers in the future depend on the scheme of onboard utilization at
the hydrogen fueling stations. Plausible near- and long-term production scenarios for forecourt hydrogen delivery when the fueling station functions as a dispensing unit only are the following:
In the near term, hydrogen is made in large-scale central facilities using fossil fuels such as natural gas or
coal with concurrent CO2 sequestration. Steam reformation of natural gas is the benchmark technology for
hydrogen production in the near future.
In the long term, hydrogen would be produced using
renewable and nuclear resources that do not require
CO2 sequestration. Hydrogen production will be carried out in large-scale facilities that take advantage of
the economy of scale. For now, thermochemical water
splitting cycles appear to be the most practical method
for hydrogen production in the future.
Plausible near- and long-term production scenarios for the
forecourt hydrogen delivery when the fueling station functions
as both the hydrogen production and dispensing facility are:
In the short term, hydrogen would be made using grid
electricity produced in large power plants using fossil
fuels with concurrent CO2 sequestration or noncarbogenic energy sources such as nuclear. Hydrogen is produced and stored onsite by grid electrolysis of water
located at the fueling stations. It is impractical to produce
hydrogen via steam reformation of natural gas pipelined
to the site. This technique is not viable because there are
no cost-effective methods for small-scale sequestration of
CO2 . However, if biogenic methane is available at the
fueling station, a steam-methane reformation process
could be used to produce hydrogen, onsite.
In the long term, hydrogen will have to be generated
from sustainable resources. Electricity will be generated
and fed into the grid at large-scale central facilities that
enjoy the economy of scale. Again, hydrogen will be
made and stored onsite using grid electrolysis of water
at the fueling stations. It is possible that hydrogen production can take place at the fueling station using PV
electrolysis of water. Although plausible (since the efficiency of PV devices continues to improve and costs
come down), it is highly unlikely to occur. In most
cases, the PV-based electricity will be too valuable to be
used for hydrogen production in this manner.

For Further Reading

D. Sperling and J.S. Cannon, Eds., The Hydrogen Energy
Transition: Moving Toward the Post Petroleum age in Transportation, New York: ElsevierAcademic, 2004.
Hydrogen as an Energy Carrier and Its Production by
Nuclear Power, Publication of International Atomic Energy
Agency, Tech. Rep. IAEA-TECDOC-1085, 1999.
C. Huang and A.T. Raissi, Analyses of sulfur-iodine thermochemical cyclePart I: Decomposition of sulfuric acid,
november/december 2004

Solar Energy J., to be published.

N.Z. Muradov, A.T. Raissi, F. Smith, and M. Elbaccouch,
Hydrogen production via catalytic reformation of landfill gas and biogas, in Proc. 15th World Hydrogen
Energy Conf., Yokohama, Japan, 2004.
N.Z. Muradov, A.T. Raissi, and T. Robertson, Hydrogen
production via catalytic reformation of low-quality
methane containing feedstocks, in Proc. Hydrogen
Power Theoretical and Engineering Solutions Int. Symp.
(HYPOTHESIS), Porte Conte, Italy, 2003, pp. 191199.
N.Z. Muradov, C. Huang, A.T. Raissi, and F. Smith,
Hydrogen production from natural gas with reduced
CO2 emissions, in Proc. 15th World Hydrogen Energy
Conf., Yokohama, Japan, 2004.
S. Lin, M. Harada, Y. Suzuki, and H. Hatano, Hydrogen
production from coal by separating carbon dioxide during
gasification, Fuel, vol. 81, no. 16, pp. 20792085, 2002.
M.K. Mann and P.L. Spath, The economic feasibility of
producing hydrogen from sunlight, wind, and biomass
energy, in Proc. Renewable and Advanced Energy Systems 21st Century, Maui, HI, Apr. 1115, 1999, pp. 405417.
J.E. Funk, Thermochemical hydrogen production: Past
and present, Int. J. Hydrogen Energy, vol. 26, no. 3, pp.
185190, 2001.
M.L. Wald, Questions about a hydrogen economy, Scientific Amer., vol. 290, no. 5, pp. 6673, 2004.
D.R. Simbeck, CO2 capture and storagethe essential
bridge to the hydrogen economy, Energy, vol. 29, no. 9-10,
pp. 16331641, 2004.

Biographies
Ali T-Raissi is the director of the Hydrogen R&D Division
at the Florida Solar Energy Center (FSEC) of the University
of Central Florida (UCF) and 20-year veteran of hydrogen
research. He has a Ph.D. in engineering from the University
of California at Berkeley. He is well published in the areas
related to hydrogen production and storage technologies
and photocatalysis. His research is focused on hydrogen and
solar energy technologies, biomass energy conversion, environmental photocatalysis and electrochemical processes. He
received UCFs I&C Distinguished Researcher Award in
1993 and in 2003. He has been granted 12 patents in the
United States and Canada.
David L. Block is Director Emeritus at the Florida Solar
Energy Center (FSEC). He was FSEC Director from
19772002. He was responsible for FSECs programs and
activities, which included photovoltaics, cooling and dehumidification, solar heating, energy-efficient buildings, hydrogen energy technologies, pollutant detoxification, solar
equipment testing, and education. He was also a professor of
engineering at the University of Central Florida. He worked
for the federal government at NASA and for private industry
at Martin Marietta Corporation. He is a registered professional engineer. He received his M.S. and Ph.D. degrees in engip&e
neering mechanics from Virginia Polytechnic Institute.
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