Hydrogen Production from Algae

Maree

Description of Hydrogen

The element Hydrogen (chemical symbol H) is the lightest and most abundant
element in the universe, although relatively rare on Earth in element form. Hydrogen
readily forms compounds with most elements and is present in organic compounds
and water. Hydrogen is the third most abundant element on Earth, but mostly in the
form of hydrocarbons and water.

Hydrogen Gas (H2) is colourless, odourless, non-metallic, has no taste. The gas is
highly flammable, burning in air at concentrations of 4% to 75%. Mixtures
spontaneously detonate by spark, heat or sunlight with an auto-ignition temperature
of 500 degrees Celsius. Pure hydrogen and oxygen fires are invisible. Flames
ascend rapidly because Hydrogen is lighter than air. Hydrogen gas reacts violently
with chlorine and fluoride to form dangerous acids.

Because of its light weight, hydrogen gas is able to escape gravity and thus is rare in
Earth's atmosphere, at around 1 ppm.

Figure 1 - Hydrogen Gas

Figure 2 - Hydrogen gas bubbles in a demonstration bio-reactor

Hydrogen gas history

1500s - T. von Honenheim - Hydrogen gas was first artificially produced and formally described.
Metals were mixed with strong metals to form a flammable gas. He was not aware the gas was a new
chemical element.

1671 - Robert Boyle - Rediscovered and described the reaction between iron filings and dilute acids
producing hydrogen gas.

1766 - Henry Cavendish - First to recognise hydrogen gas as a discrete substance, produced from a
metal-acid reaction.

1781 - Henry Cavendish - Discovered that water is produced when the gas is burned.

1783 - Antoine Lavoisier - Gave the element the name Hydrogen from the greek hydro for water and
genes for creator.

1783 - Jacques Charles - First hydrogen-filled balloon invented, an unmanned flight was tested, and
three months later Jacques himself flew in a hydrogen-filled balloon.

1800 English scientists William Nicholson and Sir Anthony Carlisle discovered that applying electric
current to water produced hydrogen and oxygen gases. This process was later termed “electrolysis.”

1806 - Francois Isaac de Rivaz - Build first hydrogen and oxygen mix internal combustion engine.

1819 - Edward Daniel Clarke - Invented hydrogen gas blowpipe (used as a torch by jewelers and
glassblowers).

1823 - Johann Wolfgang Döbereiner - Invented the Döbereiner lamp (lighter) that mixed metals and
acids to form hydrogen gas and would ignite when a valve was opened.

1838 - Christian Friedrich Schoenbein - The fuel cell effect, combining hydrogen and oxygen gases to
produce water and an electric current, was discovered.

1845 - Sir William Grove - Demonstrated Schoenbein's discovery on a practical scale by creating a
“gas battery.” He earned the title “Father of the Fuel Cell” for his achievement

1874 - Jules Verne - Prophetically examined the potential use of hydrogen as a fuel in his popular
work of fiction entitled The Mysterious Island.

1889 - Ludwig Mond and Charles Langer - Attempted to build the first fuel cell device using air and
industrial coal gas.

1898 - James Dewer - Produced liquid hydrogen via regenerative cooling (vacuum flask).

1899 - James Dewer - Produced solid hydrogen.

1920s - Rudolf Erren - Converted the internal combustion engines of trucks, buses, and submarines
to use hydrogen or hydrogen mixtures.

1920s - J.B.S. Haldane - Introduced the concept of renewable hydrogen in his paper Science and the
Future by proposing that “there will be great power stations where during windy weather the surplus
power will be used for the electrolytic decomposition of water into oxygen and hydrogen.”

1937 - Hindenburg airship destroyed in mid-air fire over New Jersey, believed to have been ignited by
the aluminized fabric coating and static electricity. Two-thirds of the passengers died from falling or
the ensuing diesel fire rather than the hydrogen fire.
1958 - Leonard Niedrach - Devised a way of modifying existing fuel cell designs to allow platinum to
be used as catalyst for the necessary hydrogen oxidation and oxygen reduction reactions in the
'Grubb-Niedrach fuel cell'.

1958 NASA is formed. It's space program currently uses the most liquid hydrogen worldwide, primarily
for rocket propulsion and as a fuel for fuel cells.

1959 - Francis T. Bacon - Built the first practical hydrogen-air fuel cell. The 5-kilowatt (kW) system
powered a welding machine. He named his fuel cell design the “Bacon Cell.” Later that year, Harry
Karl Ihrig, an engineer for the Allis—Chalmers Manufacturing Company, demonstrated the first fuel
cell vehicle: a 20–horsepower tractor. Hydrogen fuel cells, based upon Francis T. Bacon's design,
have been used to generate on-board electricity, heat, and water for astronauts aboard the famous
Apollo spacecraft and all subsequent space shuttle missions.

1970 - John O'M. Bockris - Coined the term “hydrogen economy” during a discussion at the General
Motors (GM) Technical Center in Warren, Michigan. He later published Energy: the Solar-Hydrogen
Alternative, describing his envisioned hydrogen economy where cities in the United States could be
supplied with energy derived from the sun.

1972 - University of California's modified Gremlin wins the 1972 Urban Vehicle Design Competition for
the lowest tailpipe emissions. The vehicle was converted to run on hydrogen supplied from an
onboard tank.

1973 - The development of hydrogen fuel cells for conventional commercial applications began with
the OPEC oil embargo.

1974 - Professor T. Nejat Veziroglu - Organized The Hydrogen Economy Miami Energy Conference
(THEME), the first international conference held to discuss hydrogen energy. Following the
conference, the scientists and engineers who attended formed the International Association for
Hydrogen Energy (IAHE).

1974 - International Energy Agency (IEA) was established in response to global oil market
disruptions. IEA activities included the research and development of hydrogen energy technologies.

1988 - The Soviet Union Tupolev Design Bureau successfully converted a 164-passenger TU-154
commercial jet to operate one of the jet's three engines on liquid hydrogen. The maiden flight lasted
21 minutes.

1989 - The National Hydrogen Association (NHA) formed in the United States with ten members.
Today, the NHA has nearly 100 members, including representatives from the automobile and
aerospace industries, federal, state, and local governments, and energy providers. The International
Organization for Standardization's Technical Committee for Hydrogen Technologies was also created.

1977 - Nickel Hydrogen (NiH2) battery used for first time in a satellite.

1990 - The world's first solar-powered hydrogen production plan in southern Germany became
operational.

1990 - The U.S. Congress passed the Spark M. Matsunaga Hydrogen, Research, Development and
Demonstration Act (PL 101-566), which prescribed the formulation of a 5-year management and
implementation plan for hydrogen research and development in the United States.

1990 - Work on a methanol-fueled 10-kilowatt (kW) Proton Exchange Membrane (PEM) fuel cell
began through a partnership including, amongst others, GM and Ballard Power Systems.

1994 - Daimler Benz demonstrated its first NECAR I (New Electric CAR) fuel cell vehicle.
1997 - Retired NASA engineer, Addison Bain, challenged the belief that hydrogen caused the
Hindenburg accident.

1997 - Power Systems announced a $300-million research collaboration on hydrogen fuel cells for
transportation.

1998 - Iceland unveiled a plan to create the first hydrogen economy by 2030 with Daimler-Benz and
Ballard Power Systems.

1999 - The Royal Dutch/Shell Company committed to a hydrogen future by forming a hydrogen
division. Europe's first hydrogen fueling stations were opened in Germany.

1999 - A consortium of Icelandic institutions formed the Icelandic Hydrogen and Fuel Cell Company,
Ltd. to further the hydrogen economy in Iceland.

2000 - Ballard Power Systems presented the world's first production-ready PEM fuel cell for
automotive applications at the Detroit Auto Show.

2003 - President George W. Bush announced in his 2003 State of the Union Address a $1.2 billion
hydrogen fuel initiative to develop the technology for commercially viable hydrogen-powered fuel
cells, such that “the first car driven by a child born today could be powered by fuel cells.”

2004 - U.S. Energy Secretary Spencer Abraham announced over $350-million devoted to hydrogen
research and vehicle demonstration projects. This appropriation represented nearly one-third of
President Bush's $1.2 billion commitment to research in hydrogen and fuel cell technologies. The
funding encompasses over 30 lead organizations and more than 100 partners selected through a
competitive review process.

2004 - The world's first fuel cell-powered submarine undergoes

deepwater trials (German navy).

2005 - Twenty-three states in the U.S. have hydrogen initiatives in place.

Hydrogen production

Hydrogen is most often produced in labs as a by-product of other reactions,

generally with metals (such as zinc) and acids.

Hydrogen gas for commercial use is usually produced by steam reforming of natural
gas at high temperatures (700 - 1100 degrees Celsius), where it reacts with methane
to give carbon monoxide and hydrogen gas (syngas). Other means of production are
partial oxidation of hydrocarbons and coal reaction.

Hydrogen gas can also be formed through the electrolysis of water, where a low
voltage current is passed through water. With the electrical current, water is split into
hydrogen and oxygen. Oxygen bubbles are formed on the anode while hydrogen
bubbles are formed at the cathode.

Some labs are in research and testing phases for using solar energy and water to
produce hydrogen, as well as many heat instead of electricity production methods on
trial.

In 2007 it was discovered that a pellet made of an alloy of aluminium and gallium,
added to water, could be used to generate hydrogen and alumina, allowing hydrogen
to be made on site instead of transported.

There is a demonstration hydrogen from wind project at Mawson (Australian

Antarctic Division) using wind power to drive an electrolyser and an air compressor
to store hydrogen for use in vehicles, to charge fuel cells for electronic devices, for
cooking fuel and also for heating.

Hydrogen gas is a product of some types of anaerobic metabolism and is produced

by several microorganisms. This report focuses on one example of organism group
that produces hydrogen gas under certain environmental conditions.
Figure 3 - Production routes for hydrogen (from Hydrogen Technology Roadmap)
Hydrogen use

Most hydrogen is used in refining, treating metals and processing foods.

The largest application of hydrogen gas at the moment is upgrading fossil fuels
(hydrodealkylation, hydrodesulphurisation and hydrocracking), as well as producing
ammonia for fertilizers. It is also used for welding, as a rotor cooland (due to its high
thermal conduction), lifting applications, and as a tracer gas for small leak detection.

Hydrogen is not an energy source but rather an energy carrier as it requires more
energy to create than obtained by burning it. Being an energy carrier it allows energy
from energy sources to be stored like a battery where this energy may not be able to
be easily stored or used in another form (such as solar or biological sources).

Hydrogen gas can be used either burned directly in stationary power or vehicles, or
added to fuel cells for portable or backup use to generate electricity.

Hydrogen fuel cells require hydrogen gas to produce electricity. Fuel cells are used
to store potential energy like a battery for use in various applications including
transport and electronic devices. Fuel cells have also been used in military field use,
to drive forklifts, and as backup power.

Hydrogen storage can be in the form of high pressure gas, liquid hydrogen, metal
hydrides, or other means including carbon adsorption and iron oxidation.

Hydrogen transportation methods include pipelines, mobile transport or on-site

manufacture (meaning there is reduced need to transport).
Figure 4 - A Proton exchange membrane fuel cell
Figure 5 - Fuel cell technologies (from Hydrogen Technology Roadmap)

Figure 6 - A fuel cell car

Description of the technology and when it began

Typically, algae use sunlight to split water into protons and electrons and when
combined with carbon dioxide from the air, it produces all the starch it needs and
oxygen (photosynthesis). Berkley University's Tasios Melis found that if you deplete
the algae of sulphur, its photosynthetic pathway switches over to hydrogen
production. The process is actually cyclical, with two phases. In the first phase, water
is split into protons and electrons and stored as starch. In the second phase, the
starch is converted to hydrogen. Algae has developed a survival mechanism so that
when sulphur is depleted, it converts starch from its cells to hydrogen allowing the
algae to stay alive and produce ATP (the universal energy carrier in cells). The
process is cyclical because depleting the sulphur switches the algae to hydrogen
production and putting sulphur back allows the algae to recuperate and go back to
photosynthesis, after which you can take the sulphur out again, and so on.

Currently there are at least two laboratory trials of hydrogen production from algae, a
technology that has emerged within this decade.

The Melis Lab at Berkley University was the first to discover the alternative pathway
of photosynthesis in microalgae to generate hydrogen gas instead of oxygen,
producing its first peer-reviewed paper on the subject in 2004. They are currently
working on genetic engineering the microalgae to increase efficiencies. They want to
change the process, diverting the organism from producing sugars and oxygen, to
producing hydrogen gas and feedstocks to the synthetic chemical industry directly,
meaning the harvesting stage will be streamlined. However, they have identified
biological problems with sustained, high yield production that are yet to be
addressed in their research and development work.

University of Queensland's Institute for Molecular Bioscience (IMB) are using a

series of salt water ponds and square box-type bio-reactors over which the hydrogen
bubbling to the surface is collected. Large plastic bag reactors are also being trialled
to maximize the light that penetrates to increase efficiency. IMB's Ben Hankamer and
Peter Isdale say the only inputs into the system are trace elements like most plants
needs, water, sunlight and carbon dioxide (or other carbon sources like acetate).

They believe the first phase of hydrogen from algae use would be electricity
generation into the grid locally, while we are waiting for hydrogen distribution
infrastructure is put in place and hydrogen vehicles are developed. IMB believe that -
while most car makers have hydrogen cars in development, Boeing is developing
aeroplanes that run on hydrogen, and even the space shuttle is running on hydrogen
- we will likely see people running laptops and other electronics running on hydrogen
before we drive hydrogen cars. The need for hydrogen storage facilities and
pressurized systems to deliver the hydrogen to cars means this may be a while off.
Ways of storing hydrogen so far involve pressurization into a liquid form, or metal
hydride storage units.
Figure 7- IMB research lab developing hydrogen from algae
What benefits does hydrogen production from algae provide?

Hydrogen from algae proponents propose that one benefit is that it will be fuel
production that does not compete with food because it can be located on non-arable
land. However, whether it is a water intensive industry is not able to be determined.
Water entitlements would be something that would compete with food production, in
Australia at least. Melis lab believes that the use of closed bioreactor systems
minimises evaporation and thus saves on water use. Using salt-water tolerant
species will go along way to minimise water entitlement competition. They believe
algae biofuels open up new opportunities for arid, drought affected and saline areas.
IMB believes when you consider the amount of land in Australia that is classed non-
arable land in Australia, there is huge potential.

Ben Hankamer from IMB believes that if they are able to achieve a 7 percent efficient
system, Australia would only require about 1% of the continents surface to produce
all our energy requirements from algae hydrogen.

According to the Melis Lab, microalgal bioreactors have already demonstrated higher
biofuel yields per hectare than conventional crops.

Melis Lab also believes it is possible to couple the production of hydrogen from algae
with CO2 sequestration from industrial waste streams. Pyrolysis on waste can
produce agrichar and also effectively sterilizes the waste biomass.

Figure 8 - IMBcom's laest success demonstrated a new strain of algae exibits up to seven
times the efficiency of hydrogen production over the wild strain of algae
Commercial or policy drivers

Studies by IMB in conjunction with a large engineering company show that IMB is
within reach of commercial viability of hydrogen from algae, with engineering
solutions and development of bio-reactors being the missing piece of the puzzle. If
these efficiencies are able to be achieved, the algal biofuel will be similar priced to
existing hydrogen from fossil fuels.

In April 2007, the Council of Australian Governments announced hydrogen to be one

of four energy technology roadmaps to be developed, the objectives of which include
assessing research capabilities and strengths as well as identifying what actions
could be taken to prepare for the possible emergence of a hydrogen economy. It
suggests the role of governments, industry and researchers in this endeavour, with
suggested strategies and initiatives, responsibilities and timelines. The hydrogen
technology roadmap believes that European, Japanese and American developments
are beginning to generate economic opportunities in hydrogen in stationary (power
generation), transport and portable fuel cell makets.

Australia's hydrogen roadmap report recognises that Australia that risks significant
competitive disadvantage in global hydrogen markets, as well as industrial growth in
the clean energy future, if it is simply left to market forces to prepare for their
introduction locally. The report also recognises that...

large sums of money have been, and continue to be, invested overseas in
hydrogen related RD&D — the International Energy Agency, for example,
estimated in 2004 that public and private sector RD&D funding was $1
billion and $3–4 billion per year, respectively. To date Australia has not
invested comparably to investigate the opportunities that hydrogen and fuel
cells may offer for a clean energy future here — hydrogen currently is
positioned as a low priority in Australia’s energy policy. Other advanced, and
developing, countries are investing to prepare their economies and their
people for hydrogen and fuel cells as one of the components of a clean
energy future.

The roadmap report on hydrogen also recognises that any strengths Australia has in
hydrogen and fuel cells is compromised by the current energy market and innovation
system weaknesses. In the near to medium term, the report recommends hydrogen
and fuel cells are maintained as options for the future with favourable policy, building
knowledge in consumers and policy makers, market development efforts including
promotion, removing barriers, developing supply chains and demonstration
programs, as well as building up a skills base. The vision for 2020 is for Australia to
be "effectively exploiting emerging hydrogen and fuel cell market and supply-chain
opportunities, locally and globally".
Figure 9 - The five-pointed star of the Hydrogen technology roadmap's 2020 vision

The roadmap report includes a summary of key strategies and activities to underpin
its objectives, including policy mechanisms, market support, international modelling
efforts, setting up a hydrogen and fuel cell industry association, ensure adequate
R&D and training, and ensuring Australian regulations and standards are developed
to international best practice.

The hydrogen roadmap report goes on to identify the prime drivers for a change in
Australia's energy systems. These are climate change, energy security, air pollution
and competitiveness in the international market. In terms of hydrogen in Australia,
carbon abatement and international competitiveness have been determined to be of
the highest importance, with energy security for transport fuels also being of high
importance.
Figure 10 - Prime drivers of change to energy systems
Barriers to expansion

IMB believe that algae hydrogen production would need be seven to ten percent
efficient (light to hydrogen) to make it economically viable, with current conversion
efficiencies only about one percent.

IMB also believe this hydrogen from algae viability is achievable with cheaper bio-
reactors. Currently bio-reactors cost about $150 per square metre, and they need to
drop this to $15. Olaf Kruse and Ben Hankamer have set up the solar bio-fuels
consortium to gather people with skills in bio-reactor building, amongst other things.
Through this consortium, Clemens Posten in Germany is employed to make cheap
bio-reactors. IMB also believe in the role of genetic engineering of algae, and
developing the best media conditions.

The Melis Lab believe genetic engineering of algae will streamline the photosynthetic
pathway towards hydrogen production, and are concentrating their efforts on this.

IMB believe market speculation about what the next big fuel will be is holding up the
development of algae produced hydrogen. They need to compete with bio-diesel and
LPG for investment.

Investment is currently also slow because venture capital is usually after quick turn
around projects, whereas developing the hydrogen from algae projects require some
patience. Industry speculation about what an ETS will mean to biofuels is also
delaying investment.

IMB also believe the government investment is limited because government don't
want to influence where the market will go, wanting instead a free market to develop
itself.

State and federal policy also pose a barrier to expansion unless the hydrogen
technology roadmap recommendations are adopted (as described in Commerical or
policy drivers above). It will be difficult for the hydrogen production industry to
develop with a lack of government and private investment to get it into a competitive
situation for the free market.
Non-energy impacts

Currently there few minimal jobs in research and development of hydrogen

production in Australia. If an clean energy roadmap is adopted, possibly driven by an
emissions trading scheme (international and domestic) there will likely be hundreds
of jobs generated in research and development, as well as demonstration plants. If
hydrogen is seen as a viable option for a clean energy future, job growth will be seen
in hydrogen production, infrastructure projects, as well as training. The potential
number of jobs for the hydrogen production industry would run into the thousands.
The potential for economic benefits and job creation in rural and regional areas is
good, as algal bioreactors may be placed on non-arable land to avoid food
production conflicts.

As described in Commercial and policy drivers, the four drivers for clean energy
systems development are carbon abatement, international competitiveness, pollution
reduction and energy security (especially for the transport sector). Carbon
abatement is the central issue of our times, and any contribution hydrogen may
provide to solutions will be important. International competitiveness and energy
security both have flow on effects for Australian society at large, both in economics
and welfare. Air pollution from energy production and transport fuels has important
impacts on the health of the population at large, with the risk of respiratory
complaints and cancer reducing with any reduction of air, land or water pollution.
This in turn has impacts on health care and welfare systems for society.

Figure 11 - A vertical bioreactor with algae.

Figure 12 - The latest generation of vertical bioreactors with algae.

Figure 13 - An artist rendering of a algae biofuel plant.

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