Ömer Utku Özdemir

18000474
 What is Hydrogen?
 Hydrogen is a chemical element with symbol H and atomic
number 1. With a standart atomic weight of 1.008, hydrogen is the
lightest element in the periodic table. Hydrogen is the most
abundant chemical substance in the Universe, constituting roughly
75% of all baryonic mass. Non-remnant stars are mainly composed
of hydrogen in the plasma state. The most common isotope of
hydrogen, termed protium (name rarely used, symbol H), has
one proton and no neutrons.
Hydrogen Production and Distribution
 Although abundant on earth
as an element, hydrogen is
almost always found as part
of another compound, such
as water (H2O), and must be
separated from the
compounds that contain it
before it can be used in
vehicles. Once separated,
hydrogen can be used along
with oxygen from the air in a
fuel cell to create electricity
through an electrochemical
process.
Hydrogen Production
 Hydrogen is the simplest
element on earth it consists
of only one proton and one
electron and it is an energy
carrier, not an energy
source. Hydrogen can store
and deliver usable energy,
but it doesn't typically exist
by itself in nature and must
be produced from
compounds that contain it.
 The major hydrogen-
producing states are
California, Louisiana, and
Texas. Today, almost all of
the hydrogen produced in
the United States is used for
refining petroleum, treating
metals, producing fertilizer,
and processing foods.
Hydrogen Production: Natural Gas Reforming

 Natural gas reforming is an advanced and mature

production process that builds upon the existing natural
gas pipeline delivery infrastructure. Today, 95% of the
hydrogen produced in the United States is made by
natural gas reforming in large central plants. This is an
important technology pathway for near-term hydrogen
production. Most hydrogen produced today in the United
States is made via steam-methane reforming, a mature
production process in which high-temperature steam
(700°C–1,000°C) is used to produce hydrogen from a
methane source, such as natural gas. In steam-methane
reforming, methane reacts with steam under 3–25 bar
pressure (1 bar = 14.5 psi) in the presence of a catalyst to
produce hydrogen, carbon monoxide, and a relatively
small amount of carbon dioxide. Steam reforming is
endothermic—that is, heat must be supplied to the process
for the reaction to proceed.
 Steam-methane reforming reaction
CH4 + H2O (+ heat) → CO + 3H2
 Water-gas shift reaction
CO + H2O → CO2 + H2 (+ small amount of heat)
PARTIAL OXIDATION
 In partial oxidation, the methane
and other hydrocarbons in natural
gas react with a limited amount of
oxygen (typically from air) that is
not enough to completely oxidize
the hydrocarbons to carbon
dioxide and water. With less than
the stoichiometric amount of
oxygen available, the reaction
products contain primarily
hydrogen and carbon monoxide Partial oxidation is an exothermic process—it gives off
(and nitrogen, if the reaction is
carried out with air rather than pure heat. The process is, typically, much faster than steam
oxygen), and a relatively small reforming and requires a smaller reactor vessel. As can be
amount of carbon dioxide and seen in chemical reactions of partial oxidation, this process
other compounds. Subsequently, in initially produces less hydrogen per unit of the input fuel
a water-gas shift reaction, the than is obtained by steam reforming of the same fuel.
carbon monoxide reacts with water Partial oxidation of methane reaction
to form carbon dioxide and more
hydrogen. CH4 + ½O2 → CO + 2H2 (+ heat)
Water-gas shift reaction
CO + H2O → CO2 + H2 (+ small amount of heat)
 Hydrogen Production: Electrolysis
 Electrolysis is a promising option for hydrogen
production from renewable resources.
Electrolysis is the process of using electricity to
split water into hydrogen and oxygen. This
reaction takes place in a unit called an
electrolyzer. Electrolyzers can range in size
from small, appliance-size equipment that is
well-suited for small-scale distributed
hydrogen production to large-scale, central
production facilities that could be tied
directly to renewable or other non-
greenhouse-gas-emitting forms of electricity
production.
How Does it Work?
 Like fuel cells, electrolyzers consist of an
anode and a cathode separated by an
electrolyte. Different electrolyzers function in
slightly different ways, mainly due to the
different type of electrolyte material
involved.
Hydrogen Production:
Biomass-Derived Liquid Reforming
 Liquids derived from biomass
resources—including ethanol and bio-
oils—can be reformed to produce
hydrogen in a process similar to natural
gas reforming. Biomass-derived liquids
can be transported more easily than
their biomass feedstocks, allowing for
semi-central production or possibly
distributed hydrogen production at
fueling stations. Biomass-derived liquid
reforming is a mid-term technology
pathway.
 HOW DOES IT WORK?
 Biomass resources can be converted to
cellulosic ethanol, bio-oils, or other liquid
biofuels. Some of these liquids may be
transported at relatively low cost to a
refueling station or other point of use
and reformed to produce hydrogen.
 Hydrogen Production:
Biomass-Derived Liquid Reforming
 The process for reforming biomass-derived liquids to hydrogen is very
similar to natural gas reforming and includes the following steps:
 The liquid fuel is reacted with steam at high temperatures in the
presence of a catalyst to produce a reformate gas composed mostly
of hydrogen, carbon monoxide, and some carbon dioxide.
 Additional hydrogen and carbon dioxide are produced by reacting
the carbon monoxide (created in the first step) with high-temperature
steam in the "water-gas shift reaction."
 Steam reforming reaction (ethanol)
C2H5OH + H2O (+ heat) → 2CO + 4H2
 Water-gas shift reaction
CO + H2O → CO2 + H2 (+ small amount of heat)
 Biomass-derived liquids, such as ethanol and bio-oils, can be
produced at large, central facilities located near the biomass source
to take advantage of economies of scale and reduce the cost of
transporting the solid biomass feedstock. The liquids have a high
energy density and with some upgrading can be transported with
minimal new delivery infrastructure and at relatively low cost to
distributed refueling stations, semi-central production facilities, or
stationary power sites for reforming to hydrogen.
Hydrogen Production: Microbial
Biomass Conversion(Fermantation)
 Microbial biomass conversion
processes take advantage of the
ability of microorganisms to
consume and digest biomass and
release hydrogen. Depending on
the pathway, this research could
result in commercial-scale systems
in the mid- to long-term
timeframe that could be suitable
for distributed, semi-central, or
central hydrogen
production scales, depending on
the feedstock used.
Hydrogen Production: Microbial
Biomass Conversion(Fermantation)
 HOW DOES IT WORK?
 In fermentation-based systems, microorganisms, such as bacteria, break down
organic matter to produce hydrogen. The organic matter can be refined
sugars, raw biomass sources such as corn stover, and even wastewater.
Because no light is required, these methods are sometimes called "dark
fermentation" methods.
 In direct hydrogen fermentation, the microbes produce the hydrogen
themselves. These microbes can break down complex molecules through
many different pathways, and the byproducts of some of the pathways can be
combined by enzymes to produce hydrogen. Researchers are studying how to
make fermentation systems produce hydrogen faster (improving the rate) and
produce more hydrogen from the same amount of organic matter (increasing
the yield).
 Microbial electrolysis cells (MECs) are devices that harness the energy and
protons produced by microbes breaking down organic matter, combined with
an additional small electric current, to produce hydrogen. This technology is
very new, and researchers are working on improving many aspects of the In microbial electrolysis cells, microbes (tan ovals)
system, from finding lower-cost materials to identifying the most effective type consume organic matter such as acetic acid,
of microbes to use. producing electrons (e-) and protons (hydrogen ions,
H+). The electrons are passed to an electrode and
travel through a wire to the electrode in the cathode
section of the MEC. Here, with the help a small
added voltage, the protons are combined with the
electrons to produce hydrogen gas.
Hydrogen Production
 A number of hydrogen production methods are in development.
 High-Temperature Water Splitting: High temperatures generated by
solar concentrators or nuclear reactors drive chemical reactions
that split water to produce hydrogen.
 Photobiological Water Splitting: Microbes, such as green algae,
consume water in the presence of sunlight, producing hydrogen as
a byproduct.
 Photoelectrochemical Water Splitting: Photoelectrochemical
systems produce hydrogen from water using special
semiconductors and energy from sunlight.
 Hydrogen Production:
Thermochemical Water Splitting
 HOW DOES IT WORK?
 Thermochemical water splitting processes use high-temperature heat (500°–2,000°C) to drive a series of chemical reactions that
produce hydrogen. The chemicals used in the process are reused within each cycle, creating a closed loop that consumes only
water and produces hydrogen and oxygen. The necessary high temperatures can be generated in the following ways:
 Concentrating sunlight onto a reactor tower using a field of mirror "heliostats," as illustrated in Figure 1. For more information, see
Chapter 5 of the SunShot Vision Study.
 Using waste heat from advanced nuclear reactors. For more information, see the U.S. Department of Energy’s Nuclear Hydrogen R&D
Plan.

Two mirror-based approaches for focusing

sunlight on a thermochemical reactor to
produce temperatures up to 2,000°C are
illustrated: (a) a field of heliostat mirrors
concentrates sunlight onto a central
reactor tower; and (b) dish mirrors focus
sunlight onto an attached reactor module.
The solar-generated high-temperature heat
can be used to drive thermochemical
reactions that produce hydrogen.
 Hydrogen Production:
Thermochemical Water Splitting
 Numerous solar thermochemical water-splitting cycles have been investigated for hydrogen production, each
with different sets of operating conditions, engineering challenges, and hydrogen production opportunities. In
fact, more than 300 water-splitting cycles are described in the literature. For more information, see Solar
Thermochemical Hydrogen Production Research: Thermochemical Cycle Selection and Investment Priority.
 Two examples of thermochemical water splitting cycles, the "direct" two-step cerium oxide thermal cycle and
the "hybrid" copper chloride cycle, are illustrated in Figure 2. Typically direct cycles are less complex with fewer
steps, but they require higher operating temperatures compared with the more complicated hybrid cycles.

This illustration shows two example water-

splitting cycles: (left) a two-step "direct"
thermochemical cycle based on oxidation
and reduction of cerium oxide particles; and
(right) a multi-step "hybrid"
thermochemical cycle based on copper
chloride thermochemistry, which includes
an electrolysis step that needs some
electricity input.
Hydrogen Production:
Thermochemical Water Splitting
 WHY IS THIS PATHWAY BEING CONSIDERED?
 Solar- and nuclear-driven high-temperature thermochemical water-splitting cycles
produce hydrogen with near-zero greenhouse gas emissions using water and either
sunlight or nuclear energy.
 RESEARCH FOCUSES ON OVERCOMING CHALLENGES
 Challenges remain, however, in the research, development, and demonstration of
commercially viable thermochemical cycles and reactors:
 The efficiency and durability of reactant materials for thermochemical cycling need
to be improved.
 Efficient and robust reactor designs compatible with high temperatures and heat
cycling need to be developed.
 For solar thermochemical systems, the cost of the concentrating mirror systems needs
to be reduced.
 Exciting progress continues in this field, leveraging synergies with concentrated solar
power technologies, and with emerging solar-fuel production technologies.
 Hydrogen Production:
Photobiological
 HOW DOES IT WORK?
 In photolytic biological systems, microorganisms—such as green microalgae
or cyanobacteria—use sunlight to split water into oxygen and hydrogen ions.
The hydrogen ions can be combined through direct or indirect routes and
released as hydrogen gas. Challenges for this pathway include low rates of
hydrogen production and the fact that splitting water also produces oxygen,
which quickly inhibits the hydrogen production reaction and can be a safety
issue when mixed with hydrogen in certain concentrations. Researchers are
working to develop methods to allow the microbes to produce hydrogen for
longer periods of time and to increase the rate of hydrogen production.
 Some photosynthetic microbes use sunlight as the driver to break down
organic matter, releasing hydrogen. This is known as photofermentative
hydrogen production. Some of the major challenges of this pathway include
a very low hydrogen production rate and low solar-to-hydrogen efficiency,
making it a commercially unviable pathway for hydrogen production at this
time.
 Researchers are looking at ways to make the microbes better at collecting
and using energy to make more available for hydrogen production, and to
change their normal biological pathways to increase the rate of hydrogen
production.
Hydrogen Production:
Photobiological
 WHY IS THIS PATHWAY BEING CONSIDERED?
 In the long term, photobiological production technologies may provide economical hydrogen
production from sunlight with low- to net-zero carbon emissions. The algae and bacteria could be
grown in water that cannot be used for drinking or for agriculture, and could potentially even use
wastewater.
 RESEARCH FOCUSES ON OVERCOMING CHALLENGES
 Research in photobiological hydrogen has progressed in recent years, though it is still in the early
stages. There are a number of common challenges to both photolytic and photofermentative biological
hydrogen production. Many of these challenges require further research into basic, fundamental
questions, such as that being done in the U.S. Department of Energy’s Office of Science, including:
 Improving the activity of the enzymes that produce the hydrogen, as well as the metabolic
pathways needed for the reactions, to increase the hydrogen production rates.
 Developing strains that can efficiently use the sunlight and other inputs to increase the hydrogen
yields.
 Developing strains and reactor configurations that can ultimately be used at large scales for
commercial hydrogen production.
Hydrogen Production:
Photoelectrochemical Water Splitting
 In photoelectrochemical
(PEC) water splitting,
hydrogen is produced
from water using sunlight
and specialized
semiconductors called
photoelectrochemical PEC reactor approaches
materials, which use light It shows two different
energy to directly approaches to PEC solar
dissociate water hydrogen production reactors:
molecules into hydrogen (a) electrode systems similar to
and oxygen. This is a flat-plate photovoltaic panels;
and (b) particle systems
long-term technology comprised of slurries of PEC
pathway, with the semiconductor particles.
potential for low or no
greenhouse gas
emissions.
Hydrogen Production:
Photoelectrochemical Water Splitting
 HOW DOES IT WORK?
 The PEC water splitting process uses semiconductor materials to convert
solar energy directly to chemical energy in the form of hydrogen. The
semiconductor materials used in the PEC process are similar to those
used in photovoltaic solar electricity generation, but for PEC
applications the semiconductor is immersed in a water-based
electrolyte, where sunlight energizes the water-splitting process. Watch
a laboratory-scale demonstration of this process performed at the
National Renewable Energy Laboratory.
 PEC reactors can be constructed in panel form (similar to photovoltaic
panels) as electrode systems or as slurry-based particle systems, each
approach with its own advantages and challenges. To date, panel
systems have been the most widely studied, owing to the similarities with
established photovoltaic panel technologies. Click on each figure title
to see some different possible implementations of both the panel and
slurry reactor concepts.
PEC Reactor Design Schemes

It shows possible PEC

reactor design schemes
for (a) electrode
systems, including a flat
plate and a tubular
reactor (providing
moderate solar
concentration onto one
electrode strip); and (b)
a plastic "baggie"
covered dual bed
particle reactor with
wide-by-side
photocatalyst slurries.
Hydrogen Production:
Photoelectrochemical Water Splitting
 WHY IS THIS PATHWAY BEING CONSIDERED?
 PEC water splitting is a promising solar-to-hydrogen pathway for hydrogen production
at semi-central and central scales, offering the potential for high conversion
efficiency at low operating temperatures using cost-effective thin-film and/or particle
semiconductor materials.
 RESEARCH FOCUSES ON OVERCOMING CHALLENGES
 Continued improvements in efficiency, durability, and cost are still needed for market
viability. Ongoing research and development of PEC materials, devices, and systems
is making important strides, benefiting from strong synergies with contemporary
research efforts in photovoltaics, nano-technologies, and computational materials.
 Efficiencies are being improved through enhanced sunlight absorption and better
surface catalysis.
 Durability and lifetime are being improved with more rugged materials and
protective surface coatings.
 Hydrogen production costs are being lowered through reduced materials and
materials processing costs.