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
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Hydrogen Production from AlgaeMaree
Description of Hydrogen
The element Hydrogen (chemical symbol H) is the lightest and most abundantelement in the universe, although relatively rare on Earth in element form. Hydrogenreadily forms compounds with most elements and is present in organic compoundsand water. Hydrogen is the third most abundant element on Earth, but mostly in theform of hydrocarbons and water.
Hydrogen Gas (H2) is colourless, odourless, non-metallic, has no taste. The gas ishighly flammable, burning in air at concentrations of 4% to 75%. Mixturesspontaneously detonate by spark, heat or sunlight with an auto-ignition temperatureof 500 degrees Celsius. Pure hydrogen and oxygen fires are invisible. Flamesascend rapidly because Hydrogen is lighter than air. Hydrogen gas reacts violentlywith chlorine and fluoride to form dangerous acids.
Because of its light weight, hydrogen gas is able to escape gravity and thus is rare inEarth'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 newchemical element.
1671 - Robert Boyle - Rediscovered and described the reaction between iron filings and dilute acidsproducing hydrogen gas.
1766 - Henry Cavendish - First to recognise hydrogen gas as a discrete substance, produced from ametal-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 andgenes for creator.
1783 - Jacques Charles - First hydrogen-filled balloon invented, an unmanned flight was tested, andthree months later Jacques himself flew in a hydrogen-filled balloon.
1800 English scientists William Nicholson and Sir Anthony Carlisle discovered that applying electriccurrent 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 andglassblowers).
1823 - Johann Wolfgang Döbereiner - Invented the Döbereiner lamp (lighter) that mixed metals andacids 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 toproduce 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 popularwork of fiction entitled The Mysterious Island.
1889 - Ludwig Mond and Charles Langer - Attempted to build the first fuel cell device using air andindustrial 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 submarinesto use hydrogen or hydrogen mixtures.
1920s - J.B.S. Haldane - Introduced the concept of renewable hydrogen in his paper Science and theFuture by proposing that “there will be great power stations where during windy weather the surpluspower 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 bythe aluminized fabric coating and static electricity. Two-thirds of the passengers died from falling orthe ensuing diesel fire rather than the hydrogen fire.
1958 - Leonard Niedrach - Devised a way of modifying existing fuel cell designs to allow platinum tobe 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, primarilyfor 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) systempowered a welding machine. He named his fuel cell design the “Bacon Cell.” Later that year, HarryKarl Ihrig, an engineer for the Allis—Chalmers Manufacturing Company, demonstrated the first fuelcell 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 famousApollo spacecraft and all subsequent space shuttle missions.
1970 - John O'M. Bockris - Coined the term “hydrogen economy” during a discussion at the GeneralMotors (GM) Technical Center in Warren, Michigan. He later published Energy: the Solar-HydrogenAlternative, describing his envisioned hydrogen economy where cities in the United States could besupplied with energy derived from the sun.
1972 - University of California's modified Gremlin wins the 1972 Urban Vehicle Design Competition forthe lowest tailpipe emissions. The vehicle was converted to run on hydrogen supplied from anonboard tank.
1973 - The development of hydrogen fuel cells for conventional commercial applications began withthe 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 theconference, the scientists and engineers who attended formed the International Association forHydrogen Energy (IAHE).
1974 - International Energy Agency (IEA) was established in response to global oil marketdisruptions. IEA activities included the research and development of hydrogen energy technologies.
1988 - The Soviet Union Tupolev Design Bureau successfully converted a 164-passenger TU-154commercial jet to operate one of the jet's three engines on liquid hydrogen. The maiden flight lasted21 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 andaerospace industries, federal, state, and local governments, and energy providers. The InternationalOrganization 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 becameoperational.
1990 - The U.S. Congress passed the Spark M. Matsunaga Hydrogen, Research, Development andDemonstration Act (PL 101-566), which prescribed the formulation of a 5-year management andimplementation plan for hydrogen research and development in the United States.
1990 - Work on a methanol-fueled 10-kilowatt (kW) Proton Exchange Membrane (PEM) fuel cellbegan 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 theHindenburg accident.
1997 - Power Systems announced a $300-million research collaboration on hydrogen fuel cells fortransportation.
1998 - Iceland unveiled a plan to create the first hydrogen economy by 2030 with Daimler-Benz andBallard Power Systems.
1999 - The Royal Dutch/Shell Company committed to a hydrogen future by forming a hydrogendivision. 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 forautomotive applications at the Detroit Auto Show.
2003 - President George W. Bush announced in his 2003 State of the Union Address a $1.2 billionhydrogen fuel initiative to develop the technology for commercially viable hydrogen-powered fuelcells, 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 hydrogenresearch and vehicle demonstration projects. This appropriation represented nearly one-third ofPresident Bush's $1.2 billion commitment to research in hydrogen and fuel cell technologies. Thefunding encompasses over 30 lead organizations and more than 100 partners selected through acompetitive review process.
2004 - The world's first fuel cell-powered submarine undergoesdeepwater 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 naturalgas at high temperatures (700 - 1100 degrees Celsius), where it reacts with methaneto give carbon monoxide and hydrogen gas (syngas). Other means of production arepartial oxidation of hydrocarbons and coal reaction.
Hydrogen gas can also be formed through the electrolysis of water, where a lowvoltage current is passed through water. With the electrical current, water is split intohydrogen and oxygen. Oxygen bubbles are formed on the anode while hydrogenbubbles are formed at the cathode.
Some labs are in research and testing phases for using solar energy and water toproduce hydrogen, as well as many heat instead of electricity production methods ontrial.
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 hydrogento be made on site instead of transported.
There is a demonstration hydrogen from wind project at Mawson (AustralianAntarctic Division) using wind power to drive an electrolyser and an air compressorto store hydrogen for use in vehicles, to charge fuel cells for electronic devices, forcooking fuel and also for heating.
Hydrogen gas is a product of some types of anaerobic metabolism and is producedby several microorganisms. This report focuses on one example of organism groupthat 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 producingammonia for fertilizers. It is also used for welding, as a rotor cooland (due to its highthermal 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 moreenergy to create than obtained by burning it. Being an energy carrier it allows energyfrom energy sources to be stored like a battery where this energy may not be able tobe 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, oradded to fuel cells for portable or backup use to generate electricity.
Hydrogen fuel cells require hydrogen gas to produce electricity. Fuel cells are usedto store potential energy like a battery for use in various applications includingtransport 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, metalhydrides, or other means including carbon adsorption and iron oxidation.
Hydrogen transportation methods include pipelines, mobile transport or on-sitemanufacture (meaning there is reduced need to transport).
Typically, algae use sunlight to split water into protons and electrons and whencombined with carbon dioxide from the air, it produces all the starch it needs andoxygen (photosynthesis). Berkley University's Tasios Melis found that if you depletethe algae of sulphur, its photosynthetic pathway switches over to hydrogenproduction. The process is actually cyclical, with two phases. In the first phase, wateris split into protons and electrons and stored as starch. In the second phase, thestarch is converted to hydrogen. Algae has developed a survival mechanism so thatwhen sulphur is depleted, it converts starch from its cells to hydrogen allowing thealgae to stay alive and produce ATP (the universal energy carrier in cells). Theprocess is cyclical because depleting the sulphur switches the algae to hydrogenproduction and putting sulphur back allows the algae to recuperate and go back tophotosynthesis, 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, atechnology that has emerged within this decade.
The Melis Lab at Berkley University was the first to discover the alternative pathwayof photosynthesis in microalgae to generate hydrogen gas instead of oxygen,producing its first peer-reviewed paper on the subject in 2004. They are currentlyworking on genetic engineering the microalgae to increase efficiencies. They want tochange the process, diverting the organism from producing sugars and oxygen, toproducing hydrogen gas and feedstocks to the synthetic chemical industry directly,meaning the harvesting stage will be streamlined. However, they have identifiedbiological problems with sustained, high yield production that are yet to beaddressed in their research and development work.
University of Queensland's Institute for Molecular Bioscience (IMB) are using aseries of salt water ponds and square box-type bio-reactors over which the hydrogenbubbling to the surface is collected. Large plastic bag reactors are also being trialledto maximize the light that penetrates to increase efficiency. IMB's Ben Hankamer andPeter Isdale say the only inputs into the system are trace elements like most plantsneeds, water, sunlight and carbon dioxide (or other carbon sources like acetate).
They believe the first phase of hydrogen from algae use would be electricitygeneration into the grid locally, while we are waiting for hydrogen distributioninfrastructure is put in place and hydrogen vehicles are developed. IMB believe that -while most car makers have hydrogen cars in development, Boeing is developingaeroplanes 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 hydrogenbefore we drive hydrogen cars. The need for hydrogen storage facilities andpressurized 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 metalhydride 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 fuelproduction that does not compete with food because it can be located on non-arableland. 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, inAustralia at least. Melis lab believes that the use of closed bioreactor systemsminimises evaporation and thus saves on water use. Using salt-water tolerantspecies will go along way to minimise water entitlement competition. They believealgae 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 efficientsystem, Australia would only require about 1% of the continents surface to produceall our energy requirements from algae hydrogen.
According to the Melis Lab, microalgal bioreactors have already demonstrated higherbiofuel yields per hectare than conventional crops.
Melis Lab also believes it is possible to couple the production of hydrogen from algaewith CO2 sequestration from industrial waste streams. Pyrolysis on waste canproduce agrichar and also effectively sterilizes the waste biomass.
Figure 8 - IMBcom's laest success demonstrated a new strain of algae exibits up to seventimes 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 iswithin reach of commercial viability of hydrogen from algae, with engineeringsolutions and development of bio-reactors being the missing piece of the puzzle. Ifthese efficiencies are able to be achieved, the algal biofuel will be similar priced toexisting hydrogen from fossil fuels.
In April 2007, the Council of Australian Governments announced hydrogen to be oneof four energy technology roadmaps to be developed, the objectives of which includeassessing research capabilities and strengths as well as identifying what actionscould be taken to prepare for the possible emergence of a hydrogen economy. Itsuggests the role of governments, industry and researchers in this endeavour, withsuggested strategies and initiatives, responsibilities and timelines. The hydrogentechnology roadmap believes that European, Japanese and American developmentsare beginning to generate economic opportunities in hydrogen in stationary (powergeneration), transport and portable fuel cell makets.
Australia's hydrogen roadmap report recognises that Australia that risks significantcompetitive disadvantage in global hydrogen markets, as well as industrial growth inthe clean energy future, if it is simply left to market forces to prepare for theirintroduction locally. The report also recognises that...
large sums of money have been, and continue to be, invested overseas inhydrogen related RD&D — the International Energy Agency, for example,estimated in 2004 that public and private sector RD&D funding was $1billion and $3–4 billion per year, respectively. To date Australia has notinvested comparably to investigate the opportunities that hydrogen and fuelcells may offer for a clean energy future here — hydrogen currently ispositioned as a low priority in Australia’s energy policy. Other advanced, anddeveloping, countries are investing to prepare their economies and theirpeople for hydrogen and fuel cells as one of the components of a cleanenergy future.
The roadmap report on hydrogen also recognises that any strengths Australia has inhydrogen and fuel cells is compromised by the current energy market and innovationsystem weaknesses. In the near to medium term, the report recommends hydrogenand fuel cells are maintained as options for the future with favourable policy, buildingknowledge in consumers and policy makers, market development efforts includingpromotion, removing barriers, developing supply chains and demonstrationprograms, as well as building up a skills base. The vision for 2020 is for Australia tobe "effectively exploiting emerging hydrogen and fuel cell market and supply-chainopportunities, 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 underpinits objectives, including policy mechanisms, market support, international modellingefforts, setting up a hydrogen and fuel cell industry association, ensure adequateR&D and training, and ensuring Australian regulations and standards are developedto international best practice.
The hydrogen roadmap report goes on to identify the prime drivers for a change inAustralia's energy systems. These are climate change, energy security, air pollutionand competitiveness in the international market. In terms of hydrogen in Australia,carbon abatement and international competitiveness have been determined to be ofthe highest importance, with energy security for transport fuels also being of highimportance.
Figure 10 - Prime drivers of change to energy systems
Barriers to expansion
IMB believe that algae hydrogen production would need be seven to ten percentefficient (light to hydrogen) to make it economically viable, with current conversionefficiencies 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 todrop this to $15. Olaf Kruse and Ben Hankamer have set up the solar bio-fuelsconsortium to gather people with skills in bio-reactor building, amongst other things.Through this consortium, Clemens Posten in Germany is employed to make cheapbio-reactors. IMB also believe in the role of genetic engineering of algae, anddeveloping the best media conditions.
The Melis Lab believe genetic engineering of algae will streamline the photosyntheticpathway 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 thedevelopment of algae produced hydrogen. They need to compete with bio-diesel andLPG for investment.
Investment is currently also slow because venture capital is usually after quick turnaround projects, whereas developing the hydrogen from algae projects require somepatience. Industry speculation about what an ETS will mean to biofuels is alsodelaying investment.
IMB also believe the government investment is limited because government don'twant to influence where the market will go, wanting instead a free market to developitself.
State and federal policy also pose a barrier to expansion unless the hydrogentechnology roadmap recommendations are adopted (as described in Commerical orpolicy drivers above). It will be difficult for the hydrogen production industry todevelop with a lack of government and private investment to get it into a competitivesituation for the free market.
Non-energy impacts
Currently there few minimal jobs in research and development of hydrogenproduction in Australia. If an clean energy roadmap is adopted, possibly driven by anemissions trading scheme (international and domestic) there will likely be hundredsof jobs generated in research and development, as well as demonstration plants. Ifhydrogen is seen as a viable option for a clean energy future, job growth will be seenin hydrogen production, infrastructure projects, as well as training. The potentialnumber 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 isgood, as algal bioreactors may be placed on non-arable land to avoid foodproduction conflicts.
As described in Commercial and policy drivers, the four drivers for clean energysystems development are carbon abatement, international competitiveness, pollutionreduction and energy security (especially for the transport sector). Carbonabatement is the central issue of our times, and any contribution hydrogen mayprovide to solutions will be important. International competitiveness and energysecurity both have flow on effects for Australian society at large, both in economicsand welfare. Air pollution from energy production and transport fuels has importantimpacts on the health of the population at large, with the risk of respiratorycomplaints 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.
References
1. Hydrogen Production from Algae, Science Show on ABC Radio National from26 April 2008, presented by Robyn Williams, with Ben Hankamer and PeterIsdale, transcript: http://www.abc.net.au/rn/scienceshow/stories/2008/2224016.htm accessed 7/11/2009
