Risø National Laboratory November 2004Risø Energy Report 3Hydrogen and itscompetitorsEdited by Hans Larsen, Robert Feidenhans’l and Leif Sønderberg PetersenRisø-R-1469(EN)ISBN 87-550-3349-0ISBN 87-550-3350-4(Internet)ISSN 0106-2840
Risø Energy Report 3Hydrogen and itscompetitorsEdited by Hans Larsen, Robert Feidenhans’l andLeif Sønderberg PetersenRisø National LaboratoryReviewed byProfessor Mildred DresselhausPhysics and Electrical Engineering, MITUSADipl.-Math. Jürgen-Friedrich HakeSystemforschung und Technologische EntwicklungForschungszentrum JülichProfessor Thorsteinn I. SigfussonScience Institute, University of IcelandConsultant Charles ButcherScience Journalist
21. Preface 32. Summary, conclusions and recommendations 53. Hydrogen in European and global energy systems 94. Hydrogen in the Danish energy system 175. Hydrogen system energy technologies in global, European and Danish perspective 235.1 Technologies for producing hydrogen 245.2 Hydrogen storage 315.3 Hydrogen conversion technologies 375.4 Hydrogen for transport 425.5 Hydrogen in portable devices 475.6 Hydrogen infrastructure 526. Hydrogen - Environmental and safety aspects 576.1 Hydrogen and the environment 586.2 Hydrogen safety 637. Index 678. References 69
Risø Energy Report 3Preface 31PrefaceHANS LARSEN, ROBERT FEIDENHANS'L AND LEIF SØNDERBERG PETERSEN, RISØ NATIONAL LABORATORYInterest in the hydrogen economy has grown rapidly inrecent years. Those countries with long traditions ofactivity in hydrogen research and development havenow been joined by a large number of newcomers. Themain reason for this surge of interest is that the hydrogeneconomy may be an answer to the two main challengesfacing the world in the years to come: climate changeand the need for security of energy supplies. Both thesechallenges require the development of new, highly-efficientenergy technologies that are either carbon-neutralor low emitting technologies.Another reason for the growing interest in hydrogen isthe strong need for alternative fuels, especially in thetransport sector. Alternative fuels could serve as linksbetween the different energy sectors, especially betweenthe power system and the transport sector, to facilitatethe uptake of emerging technologies and increase theflexibility and robustness of the energy system as awhole.This is the background for this Risø Energy Report, thethird in a series that provides a perspective on energyissues at global, regional and national levels. The followingpages provide a critical examination of the hydrogeneconomy and its alternatives. The Report explains thecurrent R&D situation, addresses the challenges facingthe large-scale use of hydrogen, and makes some predictionsfor the future.The Report explores the current and future role ofhydrogen in energy systems at Danish, European andglobal levels. It discusses the technologies for producing,storing and converting hydrogen, the role of hydrogenin the transport sector and in portable electronics,hydrogen infrastructure and distribution systems, andenvironmental and safety aspects of the hydrogeneconomy.Individual chapters of the Report have been written byRisø staff members and leading Danish and internationalexperts. The Report is based on internationally recognisedscientific material, and is fully referenced andrefereed by an international panel of independentexperts. Information on current developments is takenfrom the most up-to-date and authoritative sources available.Our target groups have colleagues, collaborating partners,customers, funding organisations, the Danishgovernment and international organisations includingthe European Union, the International Energy Agencyand the United Nations.
Risø Energy Report 3Summary, conclusions and recommendations 52Summary, conclusions and recommendationsHANS LARSEN, ROBERT FEIDENHANS'L AND LEIF SØNDERBERG PETERSEN, RISØ NATIONAL LABORATORYInterest in the hydrogen economy and in fuel cells hasincreased dramatically in recent years. The main reasonis that a hydrogen economy may be an answer to the twomajor challenges facing the future global economy:climate change and the security of energy supplies.Both these challenges call for development of new,highly-efficient technologies that are either carbonneutralor low emitting technologies. The commercialintroduction of such technologies has huge potential tocreate economic growth and new high-tech jobs.The need for new and sustainable energy technologies isparticularly urgent in the transport sector, where energydemand keeps growing, especially in China and otherdeveloping countries. It will be a major challenge for thetransport sector to convert to carbon-neutral fuels, interms of both technology and infrastructure. Hydrogencould link the power system to the transport sector,increasing the flexibility and robustness of the totalenergy system. Hydrogen could also be used to storeenergy produced from renewable, intermittent energysources, and hence open the way for their large-scalepenetration into the total energy system.Unlike coal or oil, hydrogen is not a primary energysource. Instead, it is an energy carrier comparable to theelectricity grid or a district heating network, and as suchit needs to be converted from other sources of energy.Most hydrogen produced today is used in the chemicalindustry. The dominant method of production is steamreforming of natural gas, which is currently used to makemore than 90% of all hydrogen.Alternative production methods include gasification andreforming of other fuels, electrolysis, and biologicalmethods. Biogas can be reformed directly to yield hydrogen.Solid fuels such as coal and biomass can be gasified,followed by reforming of the resulting gas. Electrolysis isa 200-year-old method, and is presently, and for theforseeable future the most straightforward way to makehydrogen from water using electricity, though it is noteconomically competitive at the moment.Biological routes to hydrogen, including biotechnologyand “bio-inspired” methods, have excellent long-termpotential as sustainable energy sources, but basic sciencebreakthroughs are needed, however, to make suchmethods commercially viable.Renewable energy sources can be used to producemethane, methanol and other hydrocarbon fuels thatdeserve careful consideration as alternatives to “renewable”hydrogen.A serious challenge, and potentially a complete obstacle,to the hydrogen economy is the need for cost-effectiveways to store hydrogen. The low energy density ofhydrogen makes it difficult to store in a cost-effectiveway smaller amounts in cars and portable devices.Possible answers are to store hydrogen in solid form, asmetal hydrides, or as synthetic hydrocarbons, but ineach case breakthroughs in basic science will be essential.Although pressurised storage of gaseous hydrogen is awell-known technology used in large scale, new lightweightstorage vessels will be needed to make thehydrogen economy practical. Very large quantities ofhydrogen could be stored in underground cavernssimilar to those now used for natural gas.Existing fuel cells can convert hydrogen efficiently intoelectric power. Emerging fuel cell technologies can dothe same for other hydrogen-rich fuels, while generatinglittle pollution. Fuel cells are already close to marketintroduction in niche areas such as portable electronicdevices and small power units, which do not require alarge hydrogen infrastructure. Applications like thiscould pave the way to a future hydrogen economy basedon hydrogen-rich fuels.If large amounts of hydrogen are to be used across theworld, a comprehensive hydrogen infrastructure willhave to be developed. Hydrogen grids could become afourth backbone in the energy supply system, alongsidethe existing electricity and natural gas grids and districtheating systems. Because hydrogen can be interconvertedbetween electricity and fuel, however, hydrogengrids could also link the other energy backbones to anextent that is not possible today.Developing robust solutions for a hydrogen infrastructurein road transport is particularly urgent. Prototypehydrogen-based fuel cell vehicles are already in operation,and hydrogen vehicles could enter the market in15-20 years' time.Hydrogen as a fuel has a low environmental impact atthe point of use, with no emissions of greenhouse gasesor of most other pollutants. The amounts of hydrogenentering and leaving the atmosphere, and the routes bywhich this happens, are still very uncertain, but ourcurrent knowledge suggests that the widespread use ofhydrogen would bring little environmental risk.Hydrogen is no more hazardous than conventional fuels,but its safety-related properties are significantly differentfrom those of conventional fuels. Thus, detailed riskassessments are needed for every element in the hydrogensupply chain.International hydrogen research and development iscomprehensive. Japan is one of the most ambitiouscountries in its hydrogen programme. The USA has
6Risø Energy Report 3Summary, conclusions and recommendations2recently launched an extensive research and developmentstrategy to develop hydrogen vehicles and ahydrogen infrastructure. Iceland plans a national hydrogeninfrastructure for transport and fishery.2003 saw the launch of the International Partnership forthe Hydrogen Economy (IPHE), the largest global effortso far aimed at harmonising progress towards a globalhydrogen infrastructure. The IPHE partners are Australia,Brazil, Canada, China, the European Commission,France, Germany, Iceland, India, Italy, Japan, Norway,Russia, South Korea, the UK and the USA.The European Commission in 2002 set up a High LevelGroup on Hydrogen and Fuel Cells.Hydrogen R&D in Denmark related to the whole valuechain of the hydrogen economy, and Danish researchcommunities have a strong position in European R&Dprojects, especially in fuel cells.The development of hydrogen systems is in line with thecurrent trend towards decentralised and distributedenergy systems. These are high on EU's agenda, and areexpanding rapidly in the USA.Driving forcesThe development of a hydrogen economy is driven byseveral forces related to the environment and security ofenergy supply. The most important of these forces are:• A hydrogen-based energy system will increase theopportunity to use renewable energy in the transportsector. This will increase the diversity of energy sourcesand reduce overall greenhouse gas emissions.• Hydrogen in the transport sector can reduce localpollution, which is a high priority in many large cities.• Government targets for reducing vehicle noise may bemet by replacing conventional engines with hydrogenpowered fuel cells.• The robustness and flexibility of the energy system willbe increased by the introduction of hydrogen as astrong new energy carrier that can interconnectdifferent parts of the energy system.• Fuel cells for battery replacement and backup powersystems are niche markets in which price and efficiencyare relatively unimportant. Sales in this market willdrive the technology forward towards the point atwhich fuel cells will become economic for the introductioninto the energy sector.• Hydrogen electrolysers/fuel cells connected directly towind turbines are a convenient way to balance outlocal fluctuations in the availability of wind power.With its strong position in wind turbines, Denmarkcould do very well in this market.• The development of fuel cells and a hydrogeneconomy will provide new market opportunities andnew jobs in Denmark as well as elsewhere.• Present knowledge indicates that hydrogen as anenergy carrier will involve little environmental risk.BarriersA hydrogen-based society will require fundamentalbreakthroughs in both basic science and technology.There is a huge performance gap between what today'stechnologies can deliver and what a market-drivenhydrogen economy will need. Most studies agree thatkey hydrogen technologies are still too inefficient andtoo expensive to meet our energy demands in the nearfuture. Most importantly:• More efficient and cheaper ways to make hydrogenmust be developed.• Better storage systems for hydrogen in the transportsector are critically important.• Fuel cell prices must fall, and their operating lifetimemust be increased.• A prerequisite for the introduction of fuel cell vehiclesis an adequate hydrogen distribution infrastructure.ConclusionsLong-term challenges such as climate change and securityof energy supply require long-term solutions. Acombination of fuel cells, which will reach commercialmaturity in 10-20 years, and a hydrogen infrastructure,could be a way forward if the technological barriers canbe overcome. This combination has the potential tocreate an efficient, clean and sustainable energy systemwithin the next 20-40 years.Present knowledge indicates that large-scale use ofhydrogen will pose no major environmental risk.Hydrogen is also no more hazardous than conventionalfuels, as long as the proper technical standards and safetyrules are used.The challenge for Danish R & D communities is todevelop critical mass in selected areas of fuel cell andhydrogen R&D, and to exploit these areas both academicallyand economically.The most pressing technical issue is to develop betterstorage systems for hydrogen, especially in the transportsector. Failure to do this could jeopardise the entirehydrogen vision.In the long term, hydrogen could be a key element inhighly diversified, robust, environmentally-benign andaffordable energy systems.RecommendationsDenmark has the potential to become a key internationalplayer in selected areas of research, innovation andproduct development related to the hydrogen economy,since Danish R&D in hydrogen and fuel cells is alreadysignificantly engaged in European research platforms inthis area. This, in turn, would allow Danish industry toplay a major role in the new market opportunities.For this potential to become reality, it is important to actquickly. Unless the right political decisions are takenwithin the next few years, Denmark will miss thehydrogen high-speed train.
Risø Energy Report 3Summary, conclusions and recommendations 72We see possibilities for Danish commercial breakthroughsin several areas of the hydrogen economy. Aswe have pointed out, Denmark is internationally recognizedfor its work in fuel cells, a key element in thehydrogen economy. Danish expertise and know-how insustainable energy technologies is unique. As a result,Danish companies could become internationally competitivein the development of new technologies, consultancyand services for the production, storage, distribution,conversion and end-use of hydrogen. And as we seeit, this market will undoubtedly grow over the next fewdecades.A prerequisite is that Danish research, both basic andapplied, focuses on carefully selected technology platforms,demonstration projects and Europe-wide projects.Danish researchers should also help to develop the internationalstandards and regulations needed to allow thesafe and widespread implementation of new hydrogentechnologies.Research areas that in particular need to be strengthenedare:• Hydrogen production by environmentally-benignroutes, including sustainable energy sources such aswind and solar power and biological/biotech methods.• Fuel cells and electrolysers as key technologies forbalancing electricity grids in conjunction withhydrogen storage and distribution systems.• The environmental effects of hydrogen.• Storage of hydrogen for use in vehicles, power plantsand electronics, including portable applications.• Infrastructure development, especially in the transportsector.• International standards and regulations.As hydrogen technologies mature, there will be a needfor large-scale demonstration projects (“lighthouse”projects).The Copenhagen-Malmö-Gothenburg Øresund metropolitanarea could be the setting for a lighthouse projecton hydrogen infrastructure involving two countries andboth land and sea transport.In conclusion, focused R&D push combined with suitableregulation and market incentives could allowDenmark to become a world leader in hydrogen and fuelcell energy systems. Delay, however, is likely to meanthat Denmark will be out-manoeuvred by the fastgrowinginternational competition.Estimated maximum potential market share for Danish industry in various hydrogen technologies and services, with a timescale for the likely commercialintroduction of each. The chart, which is purely qualitative, was drawn up by the editors in co-operation with the authors of the various chaptersof this Report.Estimated commercial potential in DenmarkHighSOFC fuel cellsPEMFC fuel cellsCentralised natural gas reformingReforming of fossil fuelsDecentralised small natural gas reformingBiomass gasificationThermochemicalHigh-temperature electrolysis (SOEC)Storage in the natural gas netPhotoelectrochemicalPhotobiologicalMediumDedicated hydrogen gridsStorage in gas cylindersStorage in chemical compoundsDistribution in the natural gas netPortable devicesPortable electronicsBusses and taxisPrivate carsKvaerner processGasification of coal using steamNuclear (thermocycles)Low2000201020202030Technology for: ■ Production ■ Storage ■ Distribution ■ Conversion ■ End use
Risø Energy Report 3Hydrogen in European and global energy systems 93Hydrogen in European and global energysystemsPOUL ERIK MORTHORST, RISØ NATIONAL LABORATORY; ULRICH BÜNGER, LUDWIG-BÖLKOW-SYSTEMTECHNIK, GERMANY; BENT SØRENSEN, RUC,DENMARKIntroductionInterest in energy systems based on hydrogen is growingrapidly. Countries including the USA, Japan andGermany have been active in this area for a number ofyears, but recently a large number of new countries haveappeared on the hydrogen scene. These includeAustralia, Romania, Greece, China and India.The main reason for this renewed interest is that a futurehydrogen society may be one of the solutions to the twomajor challenges facing the future global economy:climate change and security of energy supply. Both thesechallenges require the development of new, highly-efficientenergy technologies that are either carbon-neutralor emit only small amounts of carbon dioxide.While demand for oil is expected to keep on growing, thesupply of oil is forecasted to peak within the next 10-20years. In a longer time-perspective, there is thus a strongneed for new fuels, especially in the transport sector.Several existing and emerging low-carbon energy technologies,including photovoltaics, wind power, wavepower and nuclear plants, yield electricity as theirprimary output. If these technologies are to contributesignificantly to overall energy production, and not justto the electricity grid, we will need ways to link thedifferent energy sectors, especially electricity and transport.This will not only facilitate the adoption of newtechnologies but will also increase the flexibility androbustness of the whole energy system.Hydrogen could provide such links, and by providing away to store energy for longer periods of time, it couldalso pave the way for the large-scale use of intermittentsources of renewable energy, such as solar, wind andwave power. 1Hydrogen and energy systemsUnlike coal or oil, hydrogen is not a primary source ofenergy. Hydrogen cannot be collected by mining orharvesting; instead, it has to be manufactured, usuallyeither by electrolysis or by steam reforming of natural gas. This makes hydrogen an “energy carrier” on a parwith the electricity grid or a district heating network.In electrolysis, electrical energy is used to split watermolecules into hydrogen and oxygen. This process iswell-understood and the energy conversion efficiency isapproximately 65-75%, based on the lower heating value(LHV) of the hydrogen. Any source of electricity can beused, though electricity from renewable or nuclearsources is preferable if the hydrogen is to be used to cutcarbon dioxide emissions or reduce dependence on fossilfuels.Steam reforming of natural gas converts methane (CH 4 )to hydrogen (H 2 ), carbon monoxide (CO) and carbondioxide (CO 2 ). This process can achieve a practical efficiencyof about 80% based on LHV and is used for morethan 90% of all hydrogen manufactured today.Hydrogen can be produced in a number of other ways(Figure 1). Fossil fuels such as coal can be gasified andreformed to yield hydrogen, with the option of capturingand sequestering the resulting carbon dioxide. Biomasscan be liquefied or gasified and reformed, and biogas canbe reformed directly. Efficiencies for hydrogen productionfrom biomass, biogas and coal are similar, and lowerthan those for steam reforming.Considerable effort is being put into developing new andenvironmentally-attractive ways to make hydrogen.Approaches include photobiological, photoelectrochemicaland photochemical processes; the aim is to createhydrogen from sunlight and water more directly than ispossible from, say, a combination of solar cells and electrolysis.At the moment such processes are in theirinfancy, and much more research needs to be donebefore commercial products can be developed .Today a number of countries have quite a substantialproduction of hydrogen, among these are Germany andthe USA. In the Nordic countries most of the productionof hydrogen is related to oil refineries. In Denmark thetotal production of hydrogen is approximately 300MNm 3 per year.Storage of hydrogen will be an important part of anyhydrogen-based energy system. Hydrogen has a highenergy density: a kilogramme of hydrogen containsmore than three times as much energy as a kilogrammeof gasoline or natural gas. On a volume basis, however,hydrogen has only about one-third of the energycontent of natural gas, and this makes it difficult to storehydrogen cost-effectively in small quantities .Today, hydrogen is most commonly stored as a highpressuregas, in tanks made from composites or steel.Very large amounts of compressed hydrogen can also bestored in suitable underground caverns, such as minedcavities in salt domes; this is a well-known and relativelycheap technology. Technologies are currently under1. Especially for short-term storage other facilities like flywheels, batteries or pneumatic accumulators might be cheaper and have higher developmentstatus than hydrogen.
10Risø Energy Report 3Hydrogen in European and global energy systems3development to store hydrogen as a cryogenic liquid ininsulated tanks or within solid materials, includingmetal hydrides and nanoporous materials such as activatedcarbon or organometallic compounds.Applications for hydrogen as a fuel include portableequipment, transport, power generation (centralised ordispersed) and industrial processes. For power generationand industrial applications, hydrogen can be burned as asubstitute for natural gas. For transport, hydrogen can beused in a gasoline engine with only minor modifications.High-purity hydrogen, however, is used to best advantagein high-efficiency technologies such as fuel cells. 2 Afuel cell produces electricity, heat and water through anelectrochemical process whose inputs are oxygen fromthe air and a fuel such as hydrogen. Fuel cells have manyuseful characteristics, including modularity, good loadfollowingability, almost no noise and, when usinghydrogen, almost no emissions.Fuel cells come in many varieties. Low-temperaturedesigns such as proton exchange membrane fuel cells(PEMFCs, also known as polymer electrolyte membranefuel cells) are mostly aimed at portable and transportapplications. High-temperature designs such as solidoxide fuel cells (SOFCs) are better for stationary powerplants.At the point of use, burning hydrogen as a fuel has verylittle impact on the environment. There are no emissionsof greenhouse gases, nor of most other pollutants. If airis used as the oxygen source, nitrous oxide will bepresent in the exhaust gases and may need to becontrolled, as with any other combustion technology.The total environmental impact of hydrogen thereforedepends almost entirely on the way the hydrogen isproduced. Hydrogen energy systems based on renewableenergy sources such as wind or solar power are amongthe most environmentally-benign systems known today.The transport and distribution of hydrogen is an importantissue that does not always get the attention itdeserves. The use of large amounts of hydrogen worldwidewill require a comprehensive and very costly infrastructure,which only can be developed in a long timeperspective. To keep costs at a reasonable level, thisinfrastructure will have to be used at close to fullcapacity, making the smooth transition to hydrogen animportant challenge for society and industry .Once in place, however, a hydrogen infrastructure wouldhave several advantages. Working alongside the existinggrids for electricity, natural gas and district heating, ahydrogen grid could act as a fourth “backbone” thatwould link the other three energy sources as well asproviding energy in its own right (figure 1). Hydrogencould be distributed locally, regionally or nationally, andcould even be carried by the existing natural gas grid,with some modifications. 3 Alternatively, a proportion ofhydrogen could simply be blended with the supply ofnatural gas.Hydrogen is easy to use because of its versatility, in termsof both manufacture and end-use. Hydrogen couldprovide the link between renewable energy and thetransport sector, transforming biomass, solar and windenergy into transport fuel and reducing dependence onoil. A hydrogen economy is expected to substantiallyimprove the security of energy supply for the transportsector.Besides its potential as a fuel or energy transport mediumin the transport and power generation sectors, hydrogencould have an important role as a way to store surplusenergy. Fuel cells normally used to produce electricityfrom hydrogen can be designed to switch into reverseand produce hydrogen from electricity. At periods whenelectricity is cheap – when the wind is blowing strongly,for instance, so that wind farms are producing morepower than the grid requires – this surplus electricity canbe used to make hydrogen, which is then stored forfuture use. This “buffer” principle could be used at allscales, from centralised power stations right down tosmall fuel cells in private cars.However, especially with regard to complex energysystems, the overall efficiency from primary energy toend use has to be considered carefully and considerabledrawbacks are here identified for a hydrogen system,because of its long energy conversion chain. Whenhydrogen is produced out of electricity and then reversedback into electricity again, there are great losses andtherefore additional advantages and added values shouldbe observed to justify such a system from an energy-efficientpoint of view.One of the most important advantages of hydrogen is itspotential to replace gasoline and diesel as transport fuels,and thus to eliminate air pollution directly from vehicles.However it is produced, hydrogen cannot atpresent compete with conventional transport fuels inpurely economic terms. However, within 10-20 years thesupply of oil is expected to peak, while demand willprobably continue to grow, so in the medium to longterm the price of oil is expected to increase. Nevertheless,the introduction of a hydrogen system has to be seen asa long-term option. Although hydrogen will becomecheaper as technology improves and demand increases,hydrogen is not expected to become cost-competitive asa transport fuel in another 10-30 years time. Even if thedevelopment of a hydrogen infrastructure is given a highpriority in terms of costs and political willingness, itcannot be expected to be in place before 20-40 yearsfrom now.2. Not all the hydrogen production methods discussed here provide high-purity hydrogen. Expensive purification processes may be needed to purifyhydrogen made by reforming processes, for instance. On the other hand, some types of fuel cells do not require high-purity hydrogen.3. Most conventional natural gas pipelines are able to carry hydrogen, though compressors and valves may have to be adapted or replaced.
Risø Energy Report 3Hydrogen in European and global energy systems 113CoalBiomassFigure 1: Hydrogen could provide valuable links betweendifferent parts of the complete energy system.Wind, nuclearand solar powerGasificationNatural gasElectrolysisReformingHydrogen storageHydrogendistributionNatural gas systemPower andheat systemRest of theenergy systemTransportCurrent driving forces in hydrogendevelopmentEnvironmental issues and security of energy supplycurrently top the list of society's energy-related concerns.In both these areas, the transport sector presents thebiggest challenges. With the exception of hydrogen, it ishard to imagine any replacement transport fuel thatwould be successful. Electric vehicles are one possibility,but to date their technical performance and user-friendlinesshave not met to expectations.In terms of the environment and energy security, severalfactors work in favour of hydrogen. Among the mostimportant are:• Hydrogen will increase energy efficiency in transportand power generation, which might imply lowerprimary energy consumption and emissions of greenhousegases.• A hydrogen energy system will pave the way for the useof a variety of renewable energy sources in the transportsector. This in turn will increase the diversity ofenergy sources and reduce overall greenhouse gas emissions.• Reducing local air pollution is a priority in many cities.The use of hydrogen as a transport fuel would help.• The introduction of emerging technologies, such asfuel cells with high electrical efficiencies, will be facilitatedby a hydrogen infrastructure.• The robustness and flexibility of the energy system willbe increased by introducing hydrogen as a versatilenew energy carrier that can interconnect different partsof the energy system.• Vehicles powered by hydrogen fuel cells are quieterthan conventional vehicles, so they would assistgovernments reach their targets for noise reduction.Although the transport sector is currently the mostimportant driving force behind the development ofhydrogen, the broad scope of interactions betweenhydrogen and the rest of the energy system makeshydrogen an interesting option for the future. Hydrogencould make the existing energy system more robust, andthus improve the security of energy supply and facilitatethe introduction of new and environmentally-benignenergy sources. The trend towards decentralised energysystems, such as micro-turbines and small-scale localpower plants, would also be facilitated by the developmentof hydrogen systems.Research and development in hydrogen:selected countries and organisationsMore than 20 countries are engaged in hydrogen R&D.An increasing number of existing or prospective EUmembers, including unlikely countries such as Romania,Greece and Finland, are developing hydrogen strategiesand policies. Fewer countries are successfully developinghydrogen fuel cells and storage technologies, and atpresent the field is dominated by the USA, Canada,Germany and Japan. The following sections give moredetails on hydrogen research in each of these countries.GermanyGermany is without doubt the European leader inhydrogen and fuel cell R&D. Intensive research datesback to the mid-1980s, though the level of research hasdeclined in recent years. Much of Germany's interest inhydrogen is rooted in the transport sector, where companiesincluding BMW, DaimlerChrysler, General Motorsand Volkswagen are developing fuel cells. The automotivemanufacturers have also launched a TransportEnergy Strategy, which with government support aims atdeveloping a national policy strategy on alternativetransport fuels in the medium term. A number ofGerman companies are working on developing ahydrogen infrastructure.Current projects include:The Clean Energy Partnership (CEP). Based in Berlin, theCEP was established by the German Energy Agency in2002 with the objective of demonstrating hydrogen as a
12Risø Energy Report 3Hydrogen in European and global energy systems3viable fuel for vehicles. The four-year project will use afleet of cars to test a hydrogen infrastructure, includinghydrogen production and storage, filling stations, fuelcells and internal combustion engines running onhydrogen.Munich Airport hydrogen service station (ARGEMUC H2)is also concerned with the daily use of hydrogen as atransport fuel. The project began in 1999 and is demonstratinghydrogen refuelling facilities for buses, cars anda fork lift truck.CUTE, a project co-funded by the European Commissionbut with highly active German partners. The objective isto demonstrate hydrogen production, storage and use infuel cells. Nine European cities are involved in buildingtest facilities, including production (steam reformingand electrolysis), hydrogen filling stations and busespowered by fuel cells.JapanJapan has for a number of years been one of the mostambitious countries in developing hydrogen energytechnologies and strategies. In 2002 the JapaneseMinistry of Economy, Trade and Industry (METI)launched a comprehensive programme aiming at fullcommercialisation of fuel cells and a hydrogen infrastructureby 2020. The total budget is approximately $4billion, with $250 million set aside for the first five years.The programme has three phases. The demonstrationphase focuses on developing technology, demonstratingmobile and stationary fuel cells and establishing codesand standards. The introductory phase, which will lastfrom 2002 to 2010, concentrates on research anddemonstration. By 2010, 50,000 fuel cell vehicles and 2.1GW of stationary fuel cells are expected to be in operation.The “diffusion” phase, which will run from 2010 to2020, will concentrate on the wide implementation ofhydrogen technology. By 2020, Japan expects to have5,000,000 fuel cell vehicles, 4,000 hydrogen fillingstations and 10 GW of stationary fuel cell cogenerationplants.This ambitious programme is the latest part of an intensivehydrogen R&D effort that began in the early 1980s.The result is that Japan is a world leader in hydrogentechnology, especially in commercialisation as opposedto basic research. The work has largely been co-ordinatedby the government – METI and NEDO (New Energy andIndustrial Technology Development Organisation) – buthas also been driven by car manufacturers and otherindustries. This public-private partnership makes theJapanese hydrogen programme extremely efficient,because everybody is pulling in the same direction.Though Japan is developing a broad range of hydrogentechnologies, most of the work is on developing, demonstratingand implementing fuel cells. Japaneseresearchers are working on all four of the main types offuel cells: phosphoric acid fuel cells (PAFCs), moltencarbon fuel cells (MCFCs), solid oxide fuel cells (SOFCs)and proton exchange membrane fuel cells (PEMFCs).This year Japan will become the first country in theworld to begin mass-producing fuel cell vehicles, with 50or more vehicles planned.Japan's comprehensive commercialisation strategy forhydrogen is made up of a number of individualprogrammes. Some of the most important of these are 4 :The New Hydrogen Project. This project is a continuationof WE-NET (International Energy Network UsingHydrogen Conversion), which began in 1992. The mainobjective of the programme is to develop safety technologiesfor fuel cell vehicles and hydrogen fillingstations, but R&D on hydrogen production and storageis also carried out.Japan Hydrogen and Fuel Cell Demonstration Project. Thisproject aims to demonstrate fuel cell vehicles andhydrogen filling stations. Ten hydrogen filling stationsusing various energy sources (gasoline, naphtha,methanol, kerosene, natural gas, LPG) and technologies(reforming, electrolysis, liquid storage, high-pressure gasstorage, recovery of waste hydrogen from industrialprocesses) will be tested in seven fuel cell vehicles andone fuel cell bus. Both Japanese and foreign car manufacturersare participating.Development of regulations, codes and standards forhydrogen vehicles and filling stations are in preparationfor the use of privately-owned hydrogen vehicles onJapanese roads.USAThe USA has recently launched a comprehensive strategyfor the development of hydrogen vehicles and hydrogeninfrastructure. Over the next five years the Departmentof Energy (DOE) will spend approximately $1.5 billionon hydrogen R&D. The work will centre on developingfuel cells for automotive and stationary purposes, butwill also cover hydrogen production, storage and infrastructureas set out in the recent National HydrogenEnergy Roadmap. Basic research issues important forrealization of a hydrogen economy will also beaddressed.The programme will include research into three types offuel cells: PEMFCs, SOFCs and MCFCs. The production ofhydrogen from natural gas, clean coal, nuclear, biomassand other renewables will be investigated, as well ashydrogen storage, delivery technologies, sensors andcontrol technologies. Another important task is todevelop codes and standards in readiness for the eventualcommercialisation of hydrogen technologies.Specific projects include: 5Solid State Energy Conversion Alliance (SECA), a partner-4. The hydrogen and fuel cell development in Japan is further described in .5. More information on the development of hydrogen in USA can be found in ,  and .
Risø Energy Report 3Hydrogen in European and global energy systems 133ship between the DOE, research institutions andindustry. The main objectives of SECA are to develophigh-temperature SOFCs and MCFCs operating onnatural gas and syngas, primarily for stationary purposes.Targets for stationary fuel cell systems are a design life of40,000 operating hours and electric efficiencies of 60-70%, the higher figure to be achieved by combining fuelcells with gas turbines.The FreedomCAR partnership, an alliance between theDOE and car manufacturers including General Motors,Ford and DaimlerChrysler. The aim is to develop thePEMFCs for transport purposes. The programme setsspecific cost targets, such as $45/kW for the fuel cellsystem and $30/kW for the engine power train.International Partnership for Hydrogen Energy Economy(IPHE), a group formed in October 2003 under the leadershipof the DOE with the aim of harmonising progresstowards a global hydrogen infrastructure. The partnersare Australia, Brazil, Canada, China, the EuropeanCommission, France, Germany, Iceland, India, Italy,Japan, Norway, Russia, South Korea, the UK and the USA.CanadaFor almost two decades Canada has been highly active indeveloping hydrogen energy systems. In the mid-1980sthe Canadian government set up comprehensivenational programmes for fuel cells and hydrogen, andthis resulted in the establishment of several privatecompanies, including Ballard Power Systems (fuel cells)and Stuart Energy (electrolysis). Important Canadianprojects include:The National Hydrogen and Fuel Cell Programme coveringthree areas: R&D, hydrogen infrastructure (developedthrough the Canadian Fuel Cell Alliance), and earlymarket introduction of hydrogen and fuel cell technology.The latter is carried out through the EarlyAdopters Program, which is led by Industry Canada.The Fuel Cell Commercialisation Road Map, whose objectiveis to accelerate full-scale commercialisation of fuelcells in Canada. Published in 2003, the Road Map soughtopinions from all the relevant stakeholders in Canada.The work was led by industry and supported by thegovernment.Other countriesThe UK government recently published an Energy WhitePaper setting out a long-term strategy for sustainableenergy. One option is a hydrogen economy, especiallythe use of hydrogen fuel cells in transport. A recent documententitled A Fuel Cell Vision for UK – The First Stepsunderlines the need for more long-term investments infuel cells and hydrogen systems, with the aim of makingthe UK a world leader in the development and deploymentof fuel cells.Iceland plans to establish a national infrastructure forhydrogen for transport and fishery so as to make thecountry independent of imported oil. The country's firsthydrogen filling station was inaugurated recently.In Norway, quite an impressive number of research projectsare presently being carried out, partly driven by bigindustrial players within the oil-business such as NorskHydro and Statoil, but also research institutions anduniversities are active within the hydrogen field.Austria was one of the pioneers of fuel cells in Europe,and is still carrying out important research in fuel cellsfor both stationary and mobile applications. Althoughfairly new in the hydrogen field, interest is rapidlygrowing in countries such as Romania and Greece. InGreece the development of hydrogen systems to makesmaller islands independent of the supply of oil has ahigh priority.Korea, though still at an early stage in hydrogen development,has started an impressive number of projects,especially in relation to fuel cells.Australia is still in the process of developing a co-ordinatednational policy for hydrogen. Initiatives to dateinclude the preparation of a National Hydrogen Study.China and India are showing increasing interest inhydrogen, and policy initiatives are on the way.International research programmesAlthough most of the driving force for the developmentof hydrogen comes from individual countries, organisationsincluding the EU and the IEA are also conductingand co-ordinating hydrogen research.The development of a hydrogen economy is a longstandingresearch objective in the EU. The EuropeanCommission has supported hydrogen R&D since the1970s, mainly within its scheduled research programmes.Under the 5th Framework Programme (FP5,1999-2002) hydrogen R&D was part of the programmeson energy and the environment, rather than having itsown subject area. Nevertheless, FP5 provided funding ofapproximately €150 million for projects on fuel cells andhydrogen production, storage and infrastructure.The EU's Sixth Framework Programme (FP6) began in2003. In FP6 research into hydrogen and fuel cells fallsunder the heading “Sustainable development, globalchange and ecosystems”, which has separate sub-headingsfor fuel cells and hydrogen as an energy carrier.Around €400 million is budgeted for R&D in fuel cells,new technologies for energy carriers (hydrogen and electricity)and new concepts for renewable energy. In 2002the European Commission also established a High LevelGroup (HLG) on hydrogen and fuel cells. Its main objectiveis to provide a strategic-level policy framework topromote hydrogen and fuel cells in FP6 and subsequently.The HLG recommended starting a European Hydrogenand Fuel Cells Technology Platform (HTP). The HTPbrings together EU stakeholders in these areas to co-ordinatework on both R&D and deployment. Finally, the
14Risø Energy Report 3Hydrogen in European and global energy systems3European Commission supports the European HydrogenNetwork (HyNet), which was established in 1999 withthe main objective of bringing together Europeanhydrogen stakeholders from industry, research institutionsand governments. Thus the European Commissionis focusing more and more on the likelihood of a futurehydrogen economy.The IEA has also taken an interest in hydrogen and fuelcells, although to a lesser extent than the EU. The IEA hasset up Hydrogen Program Implementing Agreements,whose main purpose is to co-ordinate ongoing R&Dbetween IEA member countries. These are normally setup on a cost-shared basis and are open to any IEAmember, both OECD and non-OECD, who wishes toparticipate. Implementation agreements exist for bothhydrogen and fuel cells.Long-term visions for the hydrogen societyLong-term challenges, such as climate change, securityof energy supply and depletion of oil resources, requirelong-term solutions. Many politicians and scientistsbelieve that a combination of fuel cells and hydrogeninfrastructure will be a practical way to create an efficient,clean and sustainable energy system within thenext 20-40 years.One of the most ambitious recent initiatives is the InternationalPartnership for the Hydrogen Economy (IPHE,above). Its main goal is “to serve as a mechanism toorganize and implement effective, efficient and focusedinternational research, development, demonstration andcommercial utilization activities related to hydrogen andfuel cell technologies. The IPHE also provides a forum foradvancing policies, and common codes and standardsthat can accelerate the cost-effective transition to aglobal hydrogen economy to enhance energy securityand environmental protection” .The EU High Level Group for Hydrogen and Fuel Cells(HLG) has also looked into the possibilities of creating ahydrogen economy in the long term. One of the HLG'sconclusions is :“…hydrogen and electricity together represent one ofthe most promising ways to realise sustainable energy,whilst fuel cells provide the most efficient conversiondevice for converting hydrogen, and possibly other fuels,into electricity. Hydrogen and fuel cells open the way tointegrated 'open energy systems' that simultaneouslyaddress all of the major energy and environmental challenges,and have the flexibility to adapt to the diverseand intermittent renewable energy sources that will beavailable in the Europe of 2030”.Some highlights from the HLG report include:• Hydrogen opens up the possibility of using a broadrange of primary energy sources, including fossil fuels,nuclear and renewable energy.• The combination of the electricity grid and a hydrogensystem, including hydrogen storage, provides flexibilityin balancing conventional and intermittentrenewable energy sources, while hydrogen as an energycarrier makes new energy sources available to the transportsector.• Hydrogen produced from carbon-free or carbonneutralenergy sources can provide significant reductionsin carbon dioxide emissions by replacing fossilenergy sources. This is especially relevant to the transportsector.To support the development of a hydrogen economy, thepartners of the European Hydrogen Energy ThematicNetwork (HyNet) have developed a European HydrogenEnergy Roadmap. The main conclusions from this roadmapare :Hydrogen production: In the short and medium term, technologiesthat are already commercially available – steamreforming and electrolysis – will be vital for the productionof hydrogen, although at a higher cost than conventionalfuels. In the longer term, hydrogen could beproduced at costs that would make it competitive withdiesel and gasoline, based on current predictions foradvances in technology and economies of scale in manufacturing.Hydrogen infrastructure: The costs of transport, storageand refuelling facilities are key obstacles to the hydrogeneconomy. Investment costs and associated risks are high,so a hydrogen infrastructure will require significantcommitment from industry, governments and otherstakeholders. Hydrogen storage is an essential technologythat has the potential to become a bottleneck.Extensive R&D is required to develop innovative storagesolutions.Demand for hydrogen: Small portable applications forhydrogen are expected to enter the market within thenext 2-3 years, and these will help pave the way for largerhydrogen users. Stationary fuel cells, mostly based onnatural gas, are expected to be commercialised before2010. Transport applications will be the main driver forthe development of hydrogen systems, but this marketwill not take off before 2010-2015.Legal requirements, regulations and standards need to be inplace in order to facilitate hydrogen development.Socio-economic issues and government policies are important.Governments have to stimulate R&D and largescaledemonstration projects, while long-term policysupport is needed if hydrogen is to become commerciallysuccessful in a reasonable timescale.Figure 2 shows a possible timeline for the developmentof hydrogen production technologies. Short-termhydrogen development will rely mainly on conventionalfossil fuels, whilst in the very long term technologiescould include photo-biological or photo-electrochemicalconversion processes and thermonuclear conversioncycles. It is clear that a number of initiatives are underway to develop hydrogen systems. A good deal ofresearch is going on, and a number of demonstrationplants have already been established. Nevertheless, high
Risø Energy Report 3Hydrogen in European and global energy systems 153costs prohibit the large-scale use of hydrogen at present.Significant cost reductions must be made in the comingyears before hydrogen can even come close to commercialisation.But what are the perspectives for hydrogen in the longterm? Will it eventually develop into a major energycarrier and displace significant amounts of oil? Thatdepends on two further questions:• Will the necessary technologies become available inthe medium to long term, at reasonably competitiveprices and with efficiencies that make them suitablesubstitutes for existing technologies?; and• Will it be possible to build the necessary hydrogeninfrastructure, and to harvest the energy resourcesneeded to fuel a worldwide hydrogen system?Progress in fuel cells carries high expectations. Fuel cellsfor portable and stationary applications should becomecommercially available within 5-10 years. Fuel cells fortransport will take longer and are not expected to becommercialised in another 10-15 years from now.However, there are still significant uncertainties in fuelcell development. A more pressing technological issue isthe development of ways to store hydrogen. At presentthere are a number of possible technologies, but nosingle solution stands out. The lack of a really goodstorage method is likely to hinder the large-scale take-upof hydrogen.Finally, some experts are worried that although individualhydrogen technologies may be acceptably efficient,the efficiency of the complete hydrogen chainmay turn out to be too low to be useful as the core of asustainable energy economy .The development of hydrogen systems is in line with theexisting trend towards decentralised and distributedenergy systems, which are expanding rapidly, especiallyin the USA. It does not make sense to transport hydrogenover long distances, so hydrogen should be an integralpart of a distributed energy system that in the longerterm is based mostly on renewable sources. In this way,hydrogen could stimulate the expansion of renewableenergy, especially in transport, and create a faster transitionto renewables than is currently anticipated withoutthe benefit of hydrogen.The infrastructure needed for a hydrogen economy isexpected to be technically feasible, though it will requiretremendous investment and research effort. The transitiontowards a comprehensive hydrogen-based energysystem, however, will be highly risky for the pioneers.Strong policy initiatives are required from the EU and itsMember States if the change to hydrogen is to take placeat a cost that is acceptable to the societies concerned.Looking ahead to 2050, it is possible to imagine threescenarios for producing hydrogen [10,11,12]: clean fossilfuels, safe nuclear power and renewable energy. In eachcase the efficiency of energy conversion would have tobe well above today's standards, to meet future globalincreases in energy consumption.In the clean fossil fuels scenario, hydrogen would begenerated from coal or oil. The resulting carbon dioxidewould be removed from the flue gas and disposed inaquifers or at the bottom of the ocean. The environ-Figure 2: Timeline for hydrogen production technologies .PhotochemicalBiomass Gasification (w/o or with CO 2 Sequestration)Electrolysis from Renewable ElectricityNuclear (Thermocycles)Electrolysis from Nuclear ElectricityElectrolysis from Fossil Fuel derived Electricity with CO 2 SeqReforming of Fossil Fuels (NG, Oil, Coal) with CO 2 SeqElectrolysis from Fossil Fuel derived ElectricityHydrogen from CoalHydrogen from OilDecentralised Small Natural Gas ReformingCentralised Natural Gas ReformingShort term (2010)Medium term (2015)Long term (>2025)■Hydrogen vehicle fuel production EU 2020: 2.3-20.6 billion Nm/a. (Source: HyNet scenarios)
16Risø Energy Report 3Hydrogen in European and global energy systems3mental consequences of sequestering carbon dioxide inthis way are uncertain, and a cause for some concern.The “safe nuclear” scenario requires the development ofnuclear power plants that do not rely on control systemsto remain stable in the event of a malfunction. Engineerscall this “inherent safety”. It is not certain that it ispossible to develop practical inherently-safe nuclearplants. In the renewable energy scenario, hydrogenstorage would be used to compensate for variability inthe supply of energy from renewable sources, especiallysolar, wind and wave power. 6Subject to the provisos mentioned above, all threescenarios are considered to be technically feasible. Thegeneral conclusion is that enough hydrogen is availablein the very long term for hydrogen to become a significantpart of the world's energy system.The decision on whether to place hydrogen alongsideelectricity in the backbone of our energy supply needs tobe taken within the next ten years. At present it is difficultto see any practical alternatives. Hydrogen presentsbig challenges to both technology and policy, but it alsooffers huge opportunities for the European and globalenergy economies.6. There are actually four scenarios, since the renewable scenario exists in two versions, centralised and decentralised, which are rather different,especially as regards hydrogen production and infrastructure.
Risø Energy Report 3Hydrogen in the Danish energy system 174Hydrogen in the Danish energy systemBIRTE HOLST JØRGENSEN, RISØ NATIONAL LABORATORY; IB CHORKENDORFF, TECHNICAL UNIVERSITY OF DENMARKIntroductionHydrogen used as an energy carrier may not solve all ourenergy problems related to security of supply, climatechange and environmental degradation, but hydrogenenergy in combination with fuel cells may fit well into afuture energy system based on renewables. If Denmarkwith a small open economy wants to compete andbecome a key knowledge contributor to this technologicalfield, there is high demand for correlation ofknowledge creation and diffusion between knowledgeproducers and users. Thus the efforts must include basicresearch, access to highly qualified human resources,knowledge and technology transfer to the market, alignmentof the relations between universities and users ofknowledge and technology in the society at large, andbetter focus and prioritisation of research, technologyand innovation [8,10,11].This chapter focuses on Danish R&D in hydrogen andfuel cells, in the context of European and global R&D.The first section is an introduction to the Danish energyresearch funding system and Denmark's involvement ininternational energy research. This is followed by anaccount of Denmark's national and international R&D inthe period 1998-2003, including EU-funded projects.Finally, an assessment is given of the competitiveness ofDanish fuel cell and hydrogen research, and prospectsfor a national research strategy for hydrogen and fuelcells, including the major challenges facing Danishuniversities and industry are discussed.We conclude that “strategic intelligence” – knowledgecreation and diffusion along the whole value chain – inDanish hydrogen R&D is closely related to the involvementof stakeholders from government, the energysector, research and industry. A dialogue is needed to setgoals and decide on actions, so that once a national R&Dand demonstration programme is launched, all the keystakeholders are fully committed.Danish R&D in hydrogen and fuel celltechnologiesDanish researchers have over the years developedoutstanding competences in hydrogen R&D at national,Nordic and European levels. Their scope of work coversthe entire value chain of the hydrogen economy,including the production, storage, distribution, conversionand end-use of hydrogen in both transport andstationary applications.In the last five years, Danish energy research onhydrogen and fuel cells has been supported by theNational Energy Research Programme (EFP), the PublicService Obligation Funds for R&D relating to environmentand electricity (PSO), the Research Councils andthe short-lived Hydrogen Programme (1999-2001). Astrict division between hydrogen and fuel cell R&D isdifficult to make. The National Energy Research Programmehas historically supported R&D projects onSOFCs, but the Hydrogen Programme has supportedboth hydrogen and fuel cell R&D.A total of 34 projects with a total budget of €22.1 millionwere approved in the period 1998-2002. Some of theseare now complete, while others are still running.The Hydrogen Programme was launched in 1999 withtotal government funding of around €10 million overfour years, but with the new government in office inTable 1: Overview of Danish hydrogen and fuel cell R&D projects, 1998-2002. Including the Centre of Excellence “Towards a Hydrogen BasedSociety” covering catalysis, storage, conversion and demonstrations.Hydrogen Programme EFP; PSO; Research Councils TotalNo. of projects Million € No. of projects Million € No. of projects Million €Production 1 0.15 1 0.15Catalysis & Storage 2 0.6 31 5.62 5 6.22Distribution 1 0.27 1 0.27Conversion: combustion 1 0.23 1 0.24 2 0.47Conversion: fuel cells (SOFCs) 12 10.95 12 10.95Conversion: fuel cells (PEMFCs) 7 3.1 7 3.1Other 3 0.6 3 0.42 6 1.02Total 14 4.8 20 17.33 34 22.13
18Risø Energy Report 3Hydrogen in the Danish energy system42001 the programme was cancelled. Its goal was to studythe use of hydrogen in a future Danish sustainableenergy system. Priority was given to pre-competitiveresearch and demonstration projects in hydrogen technologies,and the development and application of PEMfuel cells for stationary and mobile applications. The programmesupported 14 projects with a total budget of€4.8 million. The abrupt cancellation of the projectcaused temporary set back in R&D activities amongapplicants, especially small and medium sized technologyproviders.Over the years the National Energy Research Programmehas given priority to R&D in SOFCs. In the period 1998-2002 it supported 12 projects with a total budget of€10.95 million, which is more than half the total spenton Danish R&D in hydrogen and fuel cells. Other projectson hydrogen storage and networks have also beensupported through the National Energy Research Programmeand the Public Service Obligation funds.In 2002 the Research Councils launched an initiative tosupport centres of excellence, with the aim of promotingresearch across institutional and disciplinary boundaries.A centre of excellence entitled “Towards a HydrogenBased Society” was among the first of these institutionsto be founded, with a budget of €3 million. Towards aHydrogen Based Society deals with R&D in catalysis andhydrogen storage, plus small demonstration projects. Ithas a strong focus on fundamental research, and representsan important opportunity to boost basic researchin Denmark. At the same time it is promoting collaborationbetween basic and applied science groups, includingDanish industry.Danish involvement in international researchDanish researchers are well represented in European fuelcell R&D. In the period 1999-2002, Danish partners wererepresented in 9 out of 43 fuel cell projects supported bythe European Commission's Fifth Framework Programme(FP5) on Energy, Environment and SustainableDevelopment (EESP), and in many other EU projects(Table 2).In the Sixth Framework Programme (FP6), Danish partnersare represented in four out of ten projects onhydrogen and six on fuel cells, including the projectsHySafe, Real-SOFC, Naturalhy and FURIM.Competitiveness of Danish researchThe competitiveness of Danish research in hydrogen andfuel cells can be measured in different ways. We can lookat both the “internal” quality of research (measuredthrough the so-called Merton values, which relate toscientific excellence, public good, universality etc.), andthe “external” quality (relevance to society and wealthcreation) . No single approach to measuring researchquality is the correct one; instead we need to takeaccount of as many factors as possible, and try to understandthe links between science and economic activities.Citations are often used as an indicator of scientificquality . Although this approach has many pitfalls,citation studies at national level give good insights intothe relative positions of nations in specific technologyareas.The success of emerging hydrogen energy technologiesdepends strongly on the scientific quality of the research,but also on the availability of development know-howand the investment needed to bring new ideas on themarket. One way to measure the practical application ofR&D is to study patent applications.An application for a patent indicates the existence ofTable 2: Overview of EU FP5 and other projects with Danish partners.Fifth Framework Programme (EESP) projectsOther EU projectsScale-up of the IP-SOFC to multi-tens of kW Level (MF-SOFC) (Risø)Component reliability in SOFC Systems for Commercial Operation (CORE-SOFC) (Risø, HaldorTopsøe A/S)Pressurized IP-SOFC (PIP-SOFC) (Risø)Integrated Researches on Materials, Technologies and Processes to Enhance MCFC (Rich Müller)50 kW PEM fuel cell generator for CHP and UPS applications (50PEM-HEAP) (IRD Fuel Cells A/S)High-temperature PEMFC Stack with Methanol Reforming (AMFC) (Technical University ofDenmark)Development of Low-cost, High-efficient PEMFC (APOLLON) (Technical University of Denmark)A 1kW DMFC Portable Power Generator (PORTAPOWER) (IRD Fuel Cells A/S)Thematic network on SOFC Technology (SOFCnet) (Risø)Advanced solid polymer fuel cells foroperation at temperatures up to200°C (Technical University ofDenmark)Ammonia Cracking (Risø)Synthesis, fabrication and characterisationof alternative anodes fordirect methane oxidation in SOFC(Risø)Advanced prediction, monitoringand controlling of anaerobic digestionprocesses behaviour towardsbiogas usage in fuel cells (Gascon)
Risø Energy Report 3Hydrogen in the Danish energy system 194Rank Country Total citations Total papers Average citations per paper1 USA 4420 713 6.22 Japan 1816 434 4.23 Germany 1420 258 5.54 England 1133 192 5.95 Canada 879 146 6.06 Italy 571 119 4.87 Denmark 393 45 8.78 Switzerland 362 44 8.29 South Korea 314 126 2.510 Sweden 299 76 3.9Table 3. Scientific papers and citations relating to fuel cell R&D, 1993-2003.Source: www.esi-topics.com/fuelcells/index.html.new knowledge that may have an economic return. Thegranting of a patent gives legal recognition to theinventor, who in return must publish the nature of theinvention. The inventor's knowledge, and ultimatelymarket share, is protected for a limited period of time –normally 20 years . The requirement to publish theinvention can be a commercial drawback, so that companiesmay prefer to rely on secrecy . And patents areoften used in a negative way, to exclude competitorsfrom large areas of research. However, patent analysis ona sufficiently large scale is a good way to learn abouttrends in R&D.Competitiveness in fuel cell technologyIn fuel cell technology Denmark scores relatively high oninternal and external research quality measured throughcitations (scientific excellence) and patents (businessdevelopment).Denmark was among the top ten nations in fuel cellresearch during the period 1993-2003, with 393 citationsto 45 scientific papers. As Table 3 shows, Denmark'saverage of 8.7 citations per paper is above the figure of6.2 for the USA, which tops the list for the total numberof citations. Note that these averages may conceal ratherlarge variations between individual papers, especiallysince the number of Danish papers is relatively low.Risø National Laboratory scored even better than theDanish average, with 270 citations from 24 papers,giving an average of 11.3 citations per paper. Thisimpressive result is down to the priority given to SOFCresearch over many years of Danish national R&Dfunding, as well as Risø's long-term collaboration withoutstanding partners abroad.The fuel cell industry being young, patents are importantin establishing market positions. The global picture offuel cell patents in the periods 1991-2000 and 2001-2003shows an exponential growth in the number of patentsfiled.The top patenting nations are Japan, the USA andGermany, but Denmark also appears on the world list. Adetailed study of Danish patents on fuel cells reveals thatDanish assignees filed 28 patents in the period 1991-2003. Table 4 compares the Danish patents with thosefrom France and the UK. It is interesting to note that theDanish assignees include universities and research andtechnology institutes as well as companies large (HaldorTopsøe, Danfoss, Vaillant), medium (Oticon) and small(IRD Fuel Cells, Danacell, Danish Power System).Although Danish research institutes and companies arewell positioned at global level in selected technologyareas, and even better when normalised to a per capitabasis, it is also obvious that the numbers of Danish citationsand patents are small when viewed in a globalcontext. This leaves the Danish R&D community with achallenge: to acquire the critical mass needed to takeadvantage of the skill and talent that undoubtedly existsin Denmark.Danish fuel cell researchers have for many years beeninvolved in larger research communities, especially inEurope and often in the context of the EU's FrameworkProgrammes for research. In industry too, both large andsmall companies have strategic alliances in fuel cell R&D.Haldor Topsøe A/S, for instance, has recently begun acollaboration with the Finnish company Wärtsilä on fuelcells with power outputs of around 200 kW fordistributed power generation and marine applications.In 2002 another Danish company, IRD Fuel Cell A/S,signed a co-operation agreement to develop and manufacturefuel cells and components for the “home energycentre”, a domestic-scale CHP system being developedby European Fuel Cell GmbH in Germany (source:www.fuelcelltoday.com).Towards a national research strategy forhydrogen technologiesDanish energy research is an example of how the interplaybetween research communities, industry andsociety at large can reach a consensus on research strate-
20Risø Energy Report 3Hydrogen in the Danish energy system4120010008006004002000JapanUSA Germany Canada UK France Korea NetherlandsSweden Australia SwitzerlandTaiwan Israel Italy Denmark■ No. patents 1991-2000 ■ No. patents 2001-2003Figure 3: Overview of fuel cell patents, 1991-2003. Source: Fuelcelltoday.com.gies and the standards by which research proposals areassessed, especially in applied research and pre-commercialactivities .The Advisory Council for Energy Research (REFU) plays acentral role in developing research strategies and settingpriorities. As a result of the budget cuts in 2001, the REFUdecided to concentrate on four areas: biomass, photovoltaics,wind energy and fuel cells. The first round ofenergy research strategies covering these four areas wasformulated in consultation with key stakeholders inscience and industry (see also www.energiforskning.dk).In 2004 it was decided to draw up a national researchstrategy for hydrogen energy technologies, coveringresearch, development and demonstration projects.Unlike its predecessors, the new strategy covers the fullspectrum of knowledge creation and diffusion in fuel celland hydrogen technologies, from basic research to precommercialactivities. The plan is to get input to thestrategy from all the key stakeholders: research communities,industry, energy companies and government.Many serious obstacles need to be overcome before ahydrogen-based society can become a reality. In principle,all the pieces of the hydrogen jigsaw are availabletoday, but most studies agree that key hydrogen technologiesare still too inefficient or too expensive tomatch the performance of the current energy network.A recent white paper on Danish hydrogen-relatedresearch, covering all the significant hydrogen and fuelcell research in Denmark, confirms that Denmark is wellplaced in terms of R&D in the most interesting andTable 4. Fuel cell patents, 1991-2003. Source for French and UK patents: fuelcelltoday.com.UK (139 patents) France (110 patents) Denmark (28 patents)Johnson Matthey Commissariat à L'Energie Atomique Haldor Topsøe A/SBritish Nuclear Fuels Ltd. Renault Risø National LaboratoryVictrex Sorapec Niels Bjerrum, DTUMorgan Crucible Alcatel Danacell Aps.Regenesys L'Air Liquide Danfoss A/SRolls Royce Centre National de la Recherche Scientifique (CNRS) Danish Power System Aps.ICI / Ineos Chlor Institut Français du Pétrole (IFP) Danish Technological InstituteBG Technology /British Gas Peugeot Citroën IRD Fuel Cells A/SQinetiq Valeo Thermique Moteur Jens Nørskov, DTUBP Compagnie Générale des Matières Nucleaires Oticon A/SCeres Power Ltd. Snecma Moteurs Vaillant A/SIntelligent Energy Ltd.
Risø Energy Report 3Hydrogen in the Danish energy system 214important hydrogen technologies . Danish R&D inhydrogen production, for instance, ranges all the wayfrom processes based on fossil fuels, through biomass, tobasic research on hydrogen-producing enzymes, biomimeticsand photo-catalysis.Of course, these different R&D areas are at very differentstages of development. Hydrogen production from fossilfuels is well established, and hydrogen from biomass isclose to commercial use. More direct methods, such ashydrogen from enzymes or photo-catalysis, still requiressubstantial fundamental research. Both the TechnicalUniversity of Denmark (DTU) and the Southern Universityof Denmark (SDU) have strong backgrounds in thesenew methods of producing hydrogen.Fuel cells probably take up even more of Denmark's R&Dresources than do hydrogen production technologies.Danish researchers have a good basic background in fuelcells, especially in the development of electrodes (bothanodes and cathodes). Both PEMFCs and SOFCs facesimilar issues when it comes to basic research on electrodes,and this work also applies to fuel cells run inreverse to produce hydrogen by electrolysis. Danishresearchers are also working hard to develop better electrolytes.Fuel cell technology has already entered the demonstrationphase, but new materials are needed before the technologycan become viable for mass production. Forexample, platinum and related metals have been used ascatalysts in demonstration PEMFCs, but the total worldproduction of platinum could only equip fuel cells for amaximum of 10-20 million cars a year. Platinum musttherefore be replaced by materials that are available ingreater quantities.Risø National Laboratory, DTU and the University ofAarhus are particularly strong in developing new electrodematerials. The same three institutions, plus theAalborg University and SDU, are active in optimising thedesign and manufacture of fuel cells and developing newmembranes.Danish researchers are also working on hydrogenstorage. Their emphasis is mainly on metal hydrides andhydrogen-carrying compounds, but they are also lookingat the problem of hydrogen embrittlement of materials.Hydrogen storage in metal hydrides is being studied inclosely related projects at the University of Aarhus, RisøNational Laboratory and DTU, and DTU is also investigatingalternative hydrogen carriers such as ammonia.Carbon-based hydrogen carriers such as methane andmethanol are well known, but practical alternatives willrequire a good deal more research. We are not aware ofany Danish research in the important area of the environmentalimpact of hydrogen.The R&D barriers to affordable and efficient hydrogenuse are too large to be overcome by incrementalimprovements of existing technology. Instead, realbreakthroughs are needed – and these will require largeinvestments. Danish companies such as Haldor Topsøe,IRD Fuel Cells and Danfoss are certainly capable ofpicking up on any such breakthroughs.We should probably not expect hydrogen technology tobe implemented through standard market mechanisms.Fossil fuels are still too cheap for this to happen atpresent. We must hope that they remain cheap for aconsiderable time to come, given the current lack oftechnically and economically competitive hydrogen andfuel cell technologies.Instead, the driving forces for a hydrogen-based societyshould be found in the ability to reduce environmentalimpact and provide a safe and sustainable energy supply,on both short and long perspectives . Focused technologypush, regulation and market incentives areneeded to bring these new technologies to market beforeour energy demands start to exceed our resources.There is, however, a growing niche market for hydrogenand fuel cells in applications such as portable powersupplies and backup systems, where cost and efficiencyare less important than weight and reliability. Suchapplications could help drive the technology forward tothe point where it is cheap enough for large-scale use andpenetration into the energy sector.Another area that may be worth exploring is the productionand consumption of hydrogen by fuel cellsconnected directly to wind turbines, since Denmarkalready has a unique market position in wind energy.ConclusionAs this chapter has shown, Denmark has a strong R&Dcommunity in hydrogen and fuel cells, whose work is ofhigh scientific quality and market relevance. Thecompetitiveness of Danish R&D is due to a continuedeffort by both research institutions and industry,supported by public funds. The emphasis is on SOFCs,but good work is also being done on basic research incatalysis, hydrogen storage, and demonstration of smallenergy conversion units. A less concerted effort has beenmade in demonstration technology for stationary andtransport applications, mainly financed through theshort-lived Hydrogen Research Programme.Over the years, Danish researchers have worked on anumber of European R&D projects, especially in fuelcells. Recently Danish partners have also been involvedin projects dealing with safety (HySafe) and distribution(Naturalhy).A big challenge is how to get the best results from R&Dinvestment in new energy technologies. Experienceshows that close collaboration across disciplinary andinstitutional boundaries is essential to progress in developingnew energy systems and to the competitiveness ofDanish industry. To work effectively with research teamsabroad and to be an attractive partner in large internationalprojects, Denmark needs a research communityon a national level. It is therefore important to have R&D
22Risø Energy Report 3Hydrogen in the Danish energy system4strategies that are comprehensive and consistent acrossdifferent programmes and institutions, backed up byfunding that is both adequate and continuous.A reasonable balance between fundamental research,applied research and demonstration projects is needed.Demonstration projects are important in proving thattechnology is viable, and in providing valuable operatingexperience, but they are expensive. Although mostdemonstrations include some research, they are notdesigned to make technological breakthroughs. Demonstrationsshould therefore be limited to projects wherethere really is something new to demonstrate. Theyshould be based on Danish research and industrialcompetences, and should be closely aligned with majorongoing and future EU demonstrations, therebyensuring that new knowledge is created.Breakthroughs created through continuous R&D effortare essential if Danish research institutions and industryare to compete in the global market for hydrogen andfuel cell technologies. This will require large resources,and in the long term it will be necessary to attract moreinvestments, both public and private. Funding should betargeted at areas in which Danish institutions and firmsare already strong, and at new areas from whichDenmark could gain particular benefits.The challenge is to get critical mass and strategic intelligenceinto R&D and demonstration projects, and thusstrengthen the overall competitiveness of Danishresearch and industry. This is the task for stakeholders asthey draw up a national research, development anddemonstration strategy for hydrogen energy.
Risø Energy Report 3Hydrogen system energy technologies 235Hydrogen system energy technologies inglobal, European and Danish perspectiveHANS LARSEN, ROBERT FEIDENHANS'L, LEIF SØNDERBERG PETERSEN, RISØ NATIONAL LABORATORYThe following chapter presents the status of R&D inprogress for essential elements in the hydrogeneconomy. Selection is based on evaluation of technologiesand systems needed to phase in the hydrogeneconomy, and characterized by requiring large researchefforts in a longer time scale. The presented technologiesand systems are assessed with respect to status, trendsand perspectives for the technology together with internationalR&D plans.
24Risø Energy Report 3Technologies for producing hydrogen5.1Technologies for producing hydrogenMOGENS MOGENSEN AND ERIK STEEN JENSEN, RISØ NATIONAL LABORATORY; JENS SEHESTED AND KIM AASBERG-PETERSEN, HALDOR TOPSØE A/SIntroductionHydrogen is not an energy source but an energy carrier,and as such it requires an energy source for its manufacture.Hydrogen is already produced in very large quantities– several tens of millions of tonnes a year worldwide– for use in the process industries.Hydrogen may be produced in many different ways.Table 5 lists the main hydrogen production methods, butthere are many others.Table 5: The main methods of producing hydrogen.1 Reforming of hydrocarbons2 Partial oxidation of hydrocarbons3 Decomposition of hydrocarbons4 Coal gasification5 Biological processes6 Thermochemical cycles7 Photochemical processes8 ElectrolysisThe main uses of hydrogen are for ammonia synthesisand in the refining of crude oil. The primary means ofproduction is catalytic reforming of hydrocarbons, especiallyof natural gas. The next section discusses this inmore detail.Hydrogen can also be produced through the gasificationof coal using steam. The first step in this process createsa mixture of hydrogen and carbon monoxide (the old“town gas”), which is further processed using the shiftreaction (see below) to yield a mixture of hydrogen (H 2 )and carbon dioxide (CO 2 ) from which the hydrogen isextracted. Hydrogen from coal gasification is notcompetitive with reforming of natural gas at present.CO 2 -free production of hydrogen and carbon black fromnatural gas or heavy fuel oil and electricity is possibleusing the so-called Kvaerner process . Since the beginningof the 1980s the Norwegian firm Kvaerner Engineeringhas been developing a plasma-arc process thatseparates hydrocarbons into pure carbon and hydrogenat a temperature of 1600°C. The process itself producesno significant emissions, though it requires coolingwater and electricity as well as natural gas or oil as theprimary energy source. A pilot plant was able to produceabout 500 kg/h of pure carbon (carbon black) and 2,000Nm 3 /h of hydrogen from 1,000 Nm 3 /h of natural gasand 2.1 MW of electricity. Another by-product is 1,000kW of heat in the form of high-temperature steam.Taking into account all usable products, the plant workswith almost 100% mass efficiency: the product split is48% hydrogen, 10% steam and 40% carbon black.Biological methods, of which there are several (seebelow) seem to have great potential for hydrogenproduction, even though at the moment it is too expensivecompared to hydrogen from fossil fuels.Hydrogen can also be produced by splitting water(methods 6, 7 and 8 in Table 5). At around 2000°C watercan be decomposed directly into hydrogen and oxygen(thermochemical cycles), but it is difficult to find materialsthat can tolerate such high temperatures. Photochemicalmethods are still at the early R&D stage, so it isdifficult to assess their potential. Electrolysis, the thirdwater-splitting method, is a 200-year-old process that isstill believed to have significant potential (see below).None of the water-splitting methods are interestingunless energy from fossil fuels is significantly moreexpensive than renewable (such as wind, solar or hydro)or nuclear energy, or unless fossil fuel consumption isrestricted by political means.Instead of molecular hydrogen (H 2 ), substances knownas hydrogen carriers might be more effective as energyvectors. Potential carriers are hydrocarbons, ammonia(NH 3 ) and methanol (CH 3 OH). All these substances arealready produced and handled in large quantities, sothey have the considerable advantage that a suitableinfrastructure is already in place. Hydrocarbons are themost effective hydrogen carriers known, and they can beproduced in a CO 2 -neutral manner using water, CO 2 andenergy as the raw materials (see below).Hydrogen from fossil fuelsHydrogen is produced from fossil fuels on both small andlarge scale using industrial processes based on feedstocksincluding natural gas, LPG, liquid hydrocarbons andcoal. The choice of technology depends on the feedstockand the scale of operation. The following sectionsdescribe the main technologies currently used to makehydrogen from hydrocarbons, and briefly discussesprospects for the future. Table 6 lists the key reactionsinvolved in making hydrogen from hydrocarbons.Steam reforming of hydrocarbons is the dominantprocess for hydrogen production today . Most of thehydrogen produced is used in refineries. Natural gas isthe typical feedstock, but liquid hydrocarbon streamsincluding naphtha/gasoline are also used. Figure 4 is ablock flowsheet of a steam reforming plant. The first stepis purification of the hydrocarbon feed. Natural gas andnaphtha contain traces of sulphur, which will rapidlypoison the reforming catalyst if allowed into the
Risø Energy Report 3Technologies for producing hydrogen 255.1ProcessEnthalpy (-∆ Η ο 298 ) (kJ/mol)Steam reforming:1. CH 4 + H 2 O = CO + 3H 2 -2062. C n H m + nH 2 O = nCO + (n + ⎯ m ) H 2 2 -1175*3. CO + H 2 O = CO 2 + H 2 41CO 2 reforming:4. CH 4 + CO 2 = 2CO + 2H 2 -247Autothermal reforming (ATR):5. CH 4 + 1/2 O 2 = CO + 2H 2 O 5206. CH 4 + H 2 O = CO + 3H 2 -2067. CO + H 2 O = CO 2 + H 2 41Catalytic partial oxidation (CPO):8. CH 4 + 1/2 O 2 = CO + 2H 2 38*for n-C 7 H 16Table 6: Reactions for making hydrogen from fossil fuels.reforming unit. Purification of the feed is normally doneusing a hydrogen desulphurization (HDS) catalyst,which converts all sulphur-containing compounds tohydrogen sulphide (H 2 S). The H 2 S is then absorbed in azinc oxide (ZnO) bed, with zinc sulphide (ZnS) as theproduct. A copper-based purification catalyst may beinstalled after the ZnO reactor for final purification.After purification, steam is added to the feed and the gasis converted to synthesis gas (a mixture of hydrogen andcarbon monoxide) by steam reforming. The steamreforming reactions are strongly endothermic and causethe gas stream to expand. Pressures of 20-40 bar are typicallyused in industrial reformers. The operating pressureis a compromise: raising the pressure allows the plant'sthroughput to increase, but also reduces the fraction ofthe feed that is converted to hydrogen and increasesequipment costs.Modern steam-reforming units consist of a primaryreformer with an upstream pre-reformer (Figure 5). Theadiabatic pre-reformer converts the higher hydrocarbonsinto a mixture of carbon oxides, methane, steam andhydrogen according to reactions 1 to 3 in Table 6. Theprimary reformer contains a large number of high-alloysteel tubes filled with catalyst and placed in a furnace.The tubes are typically 100-150 mm in diameter and 10-13 m long. The inlet temperature is in the range 450-650°C and the outlet temperature is 800-950°C. A nickelcatalyst supported on a ceramic carrier is preferred industrially.Precious metals are more active and resist carbonformation better, but are too expensive for industrialhydrogen plants.The product from the reformer contains CO, CO 2 and asmall amount of unreacted methane, and these have tobe removed to obtain pure hydrogen. The water gas shiftreaction (reaction 3 in Table 6) is used to remove CO andcreate extra H 2 . This is carried out in one or two adiabaticreactors using a copper-based catalyst. After the shiftsection, the remaining CO, methane and CO 2 are generallyremoved by pressure swing adsorption (PSA) orchemical scrubbing. Removal of CO is done by methanation(the reverse of reaction 1 in Table 6). Oxidationwith molecular oxygen is also being tested as a way toproduce CO-free hydrogen as a feedstock for PEM fuelcells.Partial oxidation (Table 6) is an alternative to steamreforming. It can be carried out in three ways. Noncatalyticpartial oxidation (POX) requires high temperaturesto ensure complete conversion of methane and toNGSteamHDS Reforming Shift CO 2 removalFigure 4: Block flowsheet of a typicalhydrogen plant based on steam reforming.Natural gas (NG) and steam are the feeds,and hydrogen is the final product.H 2
26Risø Energy Report 3Technologies for producing hydrogen5.1CO 2 (optional)Figure 5: Flowsheet of a typical reforming unit.Tubular reformerPrereformerWaste heat channelFeed from HDSProcess steamreduce soot formation. This method is mostly used forheavy feeds. Some soot is formed and is removed in aseparate scrubber system downstream of the partialoxidation reactor . As with other thermal methods,this process typically produces a gas containinghydrogen and CO in the ratio 1.7-1.8:1. Downstream COremoval is therefore needed to produce pure hydrogen.The auto-thermal reforming (ATR) process  is a hybridof partial oxidation and steam reforming, using a burnerand a fixed catalyst bed to allow the gas to reach equilibrium.ATR is the preferred technology for the large-scaleproduction of synthesis gas for methanol or syntheticdiesel plants based on Fisher-Tropsch synthesis. Forhydrogen plants, ATR using oxygen is only economic atvery large scales because of the capital cost of the oxygenplant.In catalytic partial oxidation (CPO) the reactants arepremixed, and all the chemical conversions take place ina catalytic reactor without a burner [5,6]. The direct CPOreaction (Table 6) yields a hydrogen/CO molar ratio of 2and has a low heat of reaction (38 kJ/mol). In practice,the reaction is accompanied by the reforming and watergas shift reactions, and at high conversions the productgas will be close to thermodynamic equilibrium . COremoval is necessary to produce pure hydrogen.Table 7: Comparison of CPO and steam reforming for producing hydrogento supply low-temperature fuel cells .CPOCompactHigher combined(heat + power) efficiencyNo steam addedShort start-up timeFewer heat exchangersAutothermalSteam reformingHigher electrical efficiencyHigher cell voltageNo noble metal catalystHigher hydrogen yield atreformer outletNo need for air compressionFor automotive applications [7,8], the choice of hydrogengeneration technology for small fuel cells (5-50 kW)is dictated by criteria such as simplicity of design andrapid response to transients (Table 7). Steam reforming islikely to be the most energy-efficient process for theseapplications, but catalytic partial oxidation or autothermalreforming with air may be preferred because theequipment is more compact .Hydrogen from biomass and microorganismsGeneral aspectsBiomass and biomass-derived fuels are renewable energysources that can be used to produce hydrogen sustainably.Using biomass instead of fossil fuels to producehydrogen reduces the net amount of carbon dioxidereleased to the atmosphere, since the carbon dioxidereleased when the biomass is gasified was previouslyabsorbed from the atmosphere and fixed by photosynthesisin the growing plants.Most regions of the world have enough suitable biomass– agricultural crops, crop residues, wood, agro-industrialwaste, household waste, animal manure, sewage sludgeand so on – to provide significant economic and environmentalbenefits. The eventual aim should be to coproducehydrogen alongside other value-added by-products.A wide range of technologies exists for transformingbiomass into hydrogen (Figure 6). The conversion maytake place either directly or via storable intermediates.Processes can be grouped into thermochemical andbiological (fermentation) routes, both of which are relevantin the near- and mid-term. In the long term it mayalso be possible to produce hydrogen using photobiologicalprocesses, such as photosynthesis in cyanobacteriaand algae.Hydrogen or hydrogen-rich gas derived from biomasscan readily be used in most hydrogen energy conversiondevices and fuel cells. However, no technology forproducing hydrogen from biomass or microbes is yet
Risø Energy Report 3Technologies for producing hydrogen 275.10BioResourceBiologicalThermochemicalAnaerobicDigestionFermentationMetabolicProcessingGasificationHigh PressureAqueousPyrolysisSevereCH 4 /CO 2CH 3 CH 2 OH/CO 2H 2 /CO CH 4 /CO 2CH 4 /CO 2CH 1.4 O 6ReformingShiftPyrolysisReformingShiftPhotobiologyBio-shiftSynthesisCH 3 OH/CO 2ReformingShiftReformingShiftShiftReformingShiftH 2 /CO 2 H 2 /C H 2 /CO 2 H 2 /O 2 H 2 /CO 2H 2 /CO 2 H 2 /CO 2H 2 /CO 2H 2 /CH 2 /CO 2Figure 6: Pathways from biomass to hydrogen. Storable intermediates are shown in boxes. .economically competitive or commercially available. Inparticular, biomass cannot currently compete with steamreforming of natural gas as a source of hydrogen.Biological productionHydrogen can be produced via purely biological routesthrough the fermentation of biomass using micro-organisms,or directly from cyanobacteria and micro-algae.Algae, and some microbial fermentations, use photosynthesisto produce hydrogen. Other fermentationprocesses, and direct production of hydrogen fromcyanobacteria, can take place in the absence of light.All biological hydrogen production processes depend onthe presence of a hydrogen-producing enzyme. Nitrogenase,Fe-hydrogenase and NiFe hydrogenase are threesuch enzymes currently known to exist in micro-organisms.Research on fermentation of biomass for hydrogen isincreasing rapidly, especially on thermophilic bacteriaand hydrogenases. Photobiological processes appearpromising, but are not likely to become commerciallyavailable for some years .Photobiological hydrogen production is based on photosynthesisin bacteria and green algae. The organism'sphotosynthetic apparatus captures light, and theresulting energy is used to couple water splitting to thegeneration of a reducing agent which is used to reduce ahydrogenase enzyme within the organism. Thus photosynthesisuses solar energy to convert water to oxygenand hydrogen.Hydrogen production in photobiological systems ispresently limited by low energy conversion efficiencies.Solar conversion efficiencies are normally less than 1%in cultures of micro-algae, and a tenfold increase isrequired before hydrogen production from micro-algaecan become practical.Another difficulty is the fact that hydrogenase enzymesare inhibited by oxygen at concentrations above 0.1%.This has been a key problem during 30 years of researchon hydrogen-producing micro-organisms , butstrains of algae that can overcome oxygen intoleranceare now being developed .Another serious barrier is the “light saturation effect”, inwhich cells near the outside of the culture mediumabsorb all the available sunlight. In the laboratory this isnot a problem, but in large-scale plants it seriouslyreduces the yield of hydrogen. Photosynthetic bacteriaalso tend to absorb much more light than they can effectivelyconvert into hydrogen, resulting in wasted energy.Research in these areas is aimed at distributing the availablelight more evenly – by stirring the culture mediumor by using reflecting devices to transfer light into thedepths of the culture – and developing algal strains thatcapture light less efficiently .In photofermentation, photosynthetic bacteria producehydrogen from organic acids, food processing and agriculturalwastes, or high-starch biomass produced in turnby micro-algae grown in open ponds or photobioreactors.There are some reports of high hydrogen yields, butthese systems have several drawbacks: the nitrogenase
28Risø Energy Report 3Technologies for producing hydrogen5.1BiomassH 2 CO 2AgriculturalproductsPretreatmentGasseparationOrganicwasteFermentation(Metabolicallyengineeredorganisms)Figure 7: Hydrogen production based on fermentation .enzymes used have high energy demands, solar energyconversion efficiencies are low, and huge areas of photobioreactorsare needed .It is often argued that it is simpler and more efficient toextract the hydrogen from organic substrates using adark fermentation process.Dark fermentation under aerobic conditions usesbiomass such as plant materials and organic wastestreams (Figure 7). Most of the hydrogen is actuallyproduced during anaerobic metabolism of pyruvateformed during the catabolism of carbohydrates andother substrates. There is scope for metabolic engineeringof the micro-organisms to redirect electrons so asto increase the hydrogen yields .Thermochemical conversionBiomass consists of carbon, hydrogen, oxygen, andnutrients such as nitrogen and sulphur. Figure 8compares the composition of wood with that of hydrocarbonfuels. Wood consists mainly of cellulose, whichcontains 6.2% hydrogen. As a result, the total hydrogencontent of wood is close to 6% and biomass is a reasonablefeed for hydrogen production.A large number of thermochemical processes to producehydrogen from biomass are under development ([11,14];see also other references to reviews of processes andexperimental technologies).In thermal gasification, solid biomass is first convertedthermochemically into a gas. In the case of steam gasificationand other indirectly-heated gasification processes,the result is a synthesis gas which can then be convertedto hydrogen.The first step in gasification is pyrolysis, in which thedissociated and volatile components of the biomass (70-85% of the dry weight) are vaporised at temperatures oftypically around 600°C. The resulting gas, whichcontains H 2 , CO, CO 2 , tar and water vapour, is firstcleaned to remove impurities and then optionallyupgraded using the water gas shift reaction to yield CO 2and hydrogen. The final step is to purify the hydrogen.The residue from pyrolysis is a mixture of char (fixedcarbon) and ash. The char is subsequently gasified byreacting it with oxygen, steam and/or hydrogen, and thisprovides the heat needed to run the gasifier.Many gasification systems have been developed .Among the more unusual of these are the use of solarenergy to provide the heat for gasification  and theaqueous conversion of biomass to hydrogen undersupercritical conditions (374°C and 22 MPa) .Fast pyrolysis processes can convert biomass into twooxygenated oils. These can be stored as intermediates,and later steam reformed to yield hydrogen and CO.Biomass-derived methanol and ethanol may also besteam reformed in the presence of a catalyst to producehydrogen. Methane derived from anaerobic digestioncan yield hydrogen through pyrolysis as well asreforming .Research needsTechnologies must be developed and sized according tothe availability and quality of locally-available biomass.Biomass is assessed in terms of price (including transportcosts), distribution, mass, and physical and chemicalproperties. Future research should also assess whetherthermochemical and biological processes could becombined. Biological processes are in general less energyintensiveand more environment-friendly than thermochemicalprocesses.Biological routes• Development of crops with compositions optimised forbiological hydrogen production.
Risø Energy Report 3Technologies for producing hydrogen 295.1Wt %90Figure 8: Composition of common fuels.80706050403020100CoalOilFuelMethaneWood■ C ■ H ■ O• Pretreatment of feedstock to increase accessibility.• Systems for fermentable biomass, including light-darkfermentation systems for hydrogen.• New thermophilic micro-organisms for hydrogenproduction.• Effects of culture conditions on hydrogen production.• Co-production: for instance, the effluent from afermentation process for hydrogen can be used togenerate methane.Thermochemical routes• Biomass feedstock typically has a low bulk density andis fibrous in nature. These properties create challengesin developing feed transport and preparation systems,such as pelletising, that are suitable for reactors operatingat high temperatures and pressures.• Research to improve product selectivity so that onlyhydrogen, carbon dioxide and water are produced.• New technologies for gas separation, cleaning andprocessing so that hydrogen from biomass gasificationcan be used, for example, in fuel cells.• Discover new opportunities for technology developmentby understanding and optimising feedstockconversion technology and market opportunities.• Develop high-pressure aqueous processing technologyto produce hydrogen from biomass.• Technology for CO 2 capture (hydrogen production/decarbonisation accompanied by the capture andsequestration of carbon).• Biomass and micro-organisms have the potential toaccelerate the development of hydrogen into a majorfuel of the future. This will require significant R&D,however, since hydrogen made from biomass, evenwith reasonably efficient technologies, cannot yetcompete with hydrogen from natural gas.Hydrogen from electrolysisThough it has been known for 200 years, electrolysis isstill the only practical way to make hydrogen from water– and this situation is not likely to change in the foreseeablefuture. The largest source of electrolytichydrogen is in fact the chlor-alkali industry, which hasbeen operating for around 100 years. In chlor-alkalimanufacture the main products are chlorine and sodium(or potassium) hydroxide, and hydrogen is regarded as aby-product.Only a vanishingly small proportion (of the order of0.1%) of the world's hydrogen is produced directly bywater electrolysis. Even this small quantity has declinedin recent years as energy prices have fallen to the pointwhere hydrogen produced electrolytically for fertilisermanufacture can no longer compete with hydrogenfrom natural gas. Because electrolytic hydrogen iscreated indirectly, using electricity as an energy carrier, itis only economic if electricity is extremely cheap. Thismay be the case in countries that have large hydroelectricsystems, such as Egypt, Brazil, Iceland, Canada,Norway and Zaire, or a large nuclear component in thegenerating mix, such as France, Belgium and Switzerland.PrincipleThe decomposition of water by electrolysis involves twopartial reactions that take place at the two electrodes.The electron-conducting electrodes are separated by anelectrolyte that conduct ions but not electrons.Hydrogen is produced at the negative electrode(cathode) and oxygen at the positive electrode (anode).Energy to split the water molecules is supplied as electricityto the two electrodes, and the necessary exchangeof charge occurs as ions flow through the electrolyte.The following sections describe electrolysis processes asoptimised for hydrogen production: the well-tested lowpressureelectrolysis method, and two processes – highpressureand high-temperature electrolysis – that are stillunder development. Chlor-alkali electrolysis is notdiscussed further here.
30Risø Energy Report 3Technologies for producing hydrogen5.1Conventional water electrolysisConventional water electrolysis uses an alkaline aqueouselectrolyte. The cathode and anode areas are separatedby a microporous diaphragm to prevent mixing of theproduct gases. At output pressures of 2-5 bar the processcan reach efficiencies of around 65%. Instead of the alkalineelectrolyte with an inert diaphragm, a solid acidproton conductor of the Nafion type (as used in PEMFCs)can also be used as a combined electrolyte anddiaphragm .Electrolysers are commercially available in capacities of 1kW e -125 MW e . The Electrolyser Corporation Ltd.(Canada), Norsk Hydro Electrolysers AS (Norway) andDeNora (Italy) are well-established manufacturers ofelectrolysers for hydrogen, though much of their businessis in the chlor-alkali market. Electrolyser manufacturerswith a more specialized background in hydrogeninclude Ammonia Casale and Stuart Energy.High-pressure electrolysisAs the volumetric energy density of gaseous hydrogen israther low, it is an advantage to produce pressurisedhydrogen directly. High-pressure water electrolysers nowbeing developed can generate hydrogen at pressures upto 120 bar from an alkaline electrolyte. A 5 kW e prototypewas tested at Forschungszentrum Jülich in Germany. Another advantage of the high-pressure electrolyseris that its internal electrical resistance is lower, so theoverall energy efficiency increases.High-temperature electrolysisHigh-temperature electrolysers started as an interestingalternative during the 1980s. If part of the energyrequired to split the water molecules is supplied in theform of high-temperature heat, less electricity is needed.High temperatures also speed up the reaction kinetics,decreasing the internal resistance of the cell andincreasing the energy efficiency.High-temperature solid oxide electrolyser cells (SOECs)have the advantage that they can also split CO 2 into COand O 2 . A mixture of steam and CO 2 can be electrolysedto give a mixture of H 2 and CO – synthesis gas – fromwhich hydrogen carriers such as methane (CH 4 ) andmethanol (CH 3 OH) may be easily produced. Note thatsuch artificial CH 4 will be a CO 2 neutral hydrogen carrier[20,21].The original idea was to use heat from solar concentratorsor waste heat from power stations for high-temperatureelectrolysis . Low energy prices halted this workaround 1990, but the current emphasis on hydrogen hasbrought renewed interest. If fossil fuels become scarce,high-temperature electrolysis may have a future as a wayto use heat from renewable or nuclear energy sources.Several R&D projects on SOECs are in progress in Europeand the USA.Research needsA massive R&D effort is necessary in order to obtain inexpensiveelectrolysers with high durability and efficiency.Mainly the following research areas are important in thiscontext: 1) Materials research in order to identifyimproved materials and fabricate effective structures, 2)Surface science in order to understand the nature of theinterfaces between the electrodes and electrolyte, and 3)Solid state electrochemistry in order to understand theprocesses and the losses involved. It is of major importancethat these areas are researched in a close interplay.Conclusions and recommendationsAt present hydrogen from fossil fuels are by far cheaperthan hydrogen from other sources. A massive researcheffort in the technologies of harvesting the renewableenergy as well as in the conversion technologies is necessaryin order to decrease the cost of "renewable"hydrogen. Synthetic CO 2 neutral hydrocarbons have thepotential of being competitors to "renewable" hydrogen,and therefore this option should also be carefully consideredthrough serious research programmes.
Risø Energy Report 3Hydrogen storage 315.2Hydrogen storageLOUIS SCHLAPBACH, EMPA MATERIALS SCIENCE AND TECHNOLOGY INSTITUTION OF THE ETH DOMAIN AND UNIVERSITY OF FRIBOURG; ANDREASZÜTTEL, UNIVERSITY OF FRIBOURG; ALLAN SCHRØDER PEDERSEN, RISØ NATIONAL LABORATORYHydrogen is a gas at ambient temperatures and pressures,but it can be stored as a gas, a liquid or a solid. In the caseof solid storage, the hydrogen exists as a chemicalcompound, and not as a pure substance.None of the existing methods for storing hydrogen areefficient in terms of energy density, neither on a volumenor a mass basis, and release rate at the same time.Compared to fossil fuels such as gasoline, hydrogen hasa very obvious shortfall in the amount of energy it canstore in a given volume or a given weight. The US Departmentof Energy has set up a target of 6.5% hydrogen byweight or 62 kg H 2 /m 3 and several storage techniques areable to meet these requirements (magnesium being anexample, se later). These techniques do not, however,show other needed features like release or filling rate atproper temperature or even reversibility.This is a critical barrier to the wider use of hydrogen inthe transport sector (Figure 9). In stationary applicationsthe problem is less severe.Storing hydrogen as a gasHydrogen is the smallest and lightest molecule known.As a result, hydrogen in the gaseous state has anextremely high ability to diffuse through solid materialsand to escape from even the smallest openings in jointsand seals.Storage of hydrogen as a gas dates back more than acentury. Today the most widely used technology forcommercial distribution of hydrogen is steel oraluminium cylinders pressurised to 200-250 bar. Suchcylinders are heavy and the energy density is relativelylow (Table 8). High-pressure cylinders are available involumes up to about 50 litres; larger volumes are storedat much lower pressures, and the largest compressedw-%h g H/l kJ/ml Kj/gHydrogen at 200 bar 100.0 17 2.4 141.0Magnesium Hydride 7.6 101 14.4 10.9Hydride of Fe-Ti 1.8 96 13.7 2.7Hydrie of La-Ni 1.4 89 12.7 1.9Liquid Hydrogen 100.0 70 10.0 141.0Methanol 12.5 99 19.0 22.7Gasoline 33.4 47.6Lead/Acid Battery 0.2Advanced battery 0.5Liquid Methane 25.0 106 25.0 55.7Liquid Ammonia 17.6 120 17.9 25.2Fly Wheel 0.5Table 8. Physical and chemical properties of hydrogen, methane andgasolinehydrogen tanks in the world (about 15,000 m 3 ) use pressuresof only 12-16 bar . Pressurised gas is still thepreferred technology for storing and distributinghydrogen because it is well established and has an extensiveinfrastructure.If gaseous hydrogen is to replace stores of liquid fossilfuels, the technology needs to be improved significantly.Intensive development taking place at present includesefforts to create lighter storage cylinders made fromfibre-reinforced composites. The Canadian companyDynetek Industries Ltd., for example, claims weightsavings of 20-50% for its composite cylinders operatingat 200-350 bar. Dynetek has also developed hydrogencylinders that can operate at 825 bar for stationary useand 700 bar in transport applications .Figure 9: The volume of 4 kg of hydrogenstored in different ways, relative to thesize of a car.Mg 2 NiH 4 LaNi 5 H 6 H 2 (liquid) H 2 (200 bar)
32Risø Energy Report 3Hydrogen storage5.2In contrast to liquefaction (see below), compressinghydrogen requires relatively small amounts of energy.Compressing hydrogen from atmospheric pressure to450 bar requires 25 kJ/mol, for instance, which is 9% ofthe higher heating value of hydrogen (285 kJ/mol).Underground storage of gaseous hydrogenA special case of gaseous hydrogen storage is the use oflarge underground cavities similar to those now used tostore natural gas. In both cases the quantities of energyinvolved have the potential to meet the needs of largecommunities for extended periods, such as might beneeded to ensure security of supply or to meet seasonalvariations in energy production. This gives undergroundstorage a special importance.Two methods of underground storage that are suitablefor both hydrogen and natural gas are the use of cavitiesleft after the mining of salt, and in empty aquifers. In theTees Valley, UK, a salt dome beneath an urban area isused to store 1,000 tonnes of hydrogen for industrial use.Associated with the storage cavity is 30 km of hydrogendistribution pipeline .Liquid hydrogenLiquid hydrogen can exist only at temperatures below33K (-240°C) – the “critical temperature” of hydrogen. In practice, liquid hydrogen is usually stored at thelower temperature of 20K (-253°C) because at 20K it canbe stored at atmospheric pressure, whereas liquidhydrogen at 33K requires pressurised storage at 13 bar.Hydrogen molecules exist in two different forms, distinguishedby the alignment of the nuclear spins in each oftheir two atoms. In ortho hydrogen the nuclear spins arein the same direction, whereas in para hydrogen thespins are in opposite directions. Note that this hasnothing to do with isotopes; ortho and para hydrogenhave exactly the same molecular weight.At ambient temperatures hydrogen contains 25% of thepara form and 75% ortho. At low temperatures parahydrogen is by far the more stable form, and at 20Kalmost all the ortho molecules eventually transform intothe para form. The conversion is accompanied by therelease of around 1 kJ/mol of heat, which is larger thanthe heat of vaporization of hydrogen (approximately 0.9kJ/mol).This means that until the transformation to the paraform is complete, liquid hydrogen has a built-in sourceFigure 10: The amount of hydrogen, on a mass and volume basis, stored by metal hydrides, carbon nanotubes, gasoline and other hydrocarbons.160140BaReH 9520 K500 200MgH 2620 K, 5 barKBH 4dec. 580 KH 2 physisorbedon carbon120NaBH 4dec. 680 KLiAIH 4dec. 400 K80LiHdec. 650 K50C 8 H 18liq.NH liq. 3b.p. 239.7 KC 4 H liq. 10b.p. 272 KLiBH 4dec. 553 KH liq. 220.3 KCH 4liq.b.p. 112 K20002013pres. H Gas 2(steel)p [MPa]520131015Gravimetric H 2 density [mass%]pressurized H Gas 2(composit material)p [MPa]20
Risø Energy Report 3Hydrogen storage 335.2H 2 gas Metalhydride ElectrolyteMetaladsorbed hydrogenSolid solutionα-phaseHydride phaseβ-phaseFigure 11: A metal lattice with hydrogen atoms in the interstitial spaces and hydrogen molecules at the surface. The hydrogen atoms come fromphysisorbed hydrogen molecules (left) and dissociation of water molecules (right).of heat that is always present, regardless of the amountof insulation, and is sufficient to boil the liquid. It istherefore important to make sure that as much conversionas possible takes place during the liquefactionprocess, when heat removal is easier . Suppliers ofliquid hydrogen are typically able to guarantee that up to98% exists in the para form.The density of liquid hydrogen is 70 kg/m 3 . Though thisis remarkably low for a liquid, it is still higher than thedensity of gaseous hydrogen at 200 bar (Figure 10).Liquid hydrogen's greater density and the fact that it canbe handled at atmospheric pressure means that theliquid hydrogen is preferred in many large industrialdistribution networks.On the other hand, liquefaction is energy-intensive ;the process consumes 30-40% of the total energy contentof the hydrogen. Though the heat of vaporization is onlyaround 1 kJ/mol, as we saw above, operating the liquefactionplant at temperatures down to 20K requiresaround 90 kJ/mol.A typical modern liquid hydrogen storage tank wasdeveloped by industrial gas supplier Linde in Germanyfor a hydrogen-powered bus. The cylindrical tank has anoutside diameter of 500 mm and an overall length of 5.5m. Its capacity is 540 l of liquid hydrogen, based on anullage of 10%. It is designed to work at pressures from fullvacuum up to 8 bar, and at temperatures in the range 20-353K .Solid-state storageThis section is based on reference .Hydrogen adsorption on solids with large surface areasSolid surfaces adsorb hydrogen to an extent that dependson the pressure, temperature and the nature of thesurface. The mechanisms include both Van der Waalstypeweak physisorption of molecular hydrogen, andchemisorption of atomic hydrogen following dissociation.Adsorption as a way to store hydrogen has been studiedmainly on surfaces based on carbon. A monolayer ofhydrogen on a surface contains about 1.3 x 10 -5 mol/m 2 .A graphene sheet with a specific surface area of 1,315m 2 /g has been shown to adsorb a maximum of 0.4hydrogen atoms for each carbon atom on the surface,giving a total of 3.3% hydrogen by weight for adsorptionon one side of the sheet only.On activated carbon with the same specific surface area,at a temperature of 77K, hydrogen is reversibly sorbed toa maximum of 2% by weight. Nanostructured graphite,produced by ball milling for 80 hours in an atmosphereof hydrogen at 10 bar, adsorbs up to 0.95 hydrogenatoms per carbon atom, or 7.4 wt%. 80% of this hydrogencould be desorbed again by heating to 600 K .Carbon nanotubes may be a promising material forhydrogen storage, but experimental results to date havebeen controversial [10,11] – probably because the carboncompounds actually used were of different kinds and notwell characterised. One group of researchers  concludedthat at both 77K and ambient temperature,physisorption is the mechanism for hydrogen storage oncarbon nanotubes. The maximum amount of hydrogenadsorbed depends on the specific surface area, and isaround 1.5 wt% for a specific surface area of 1,000 m 2 /g.Hydrogen storage in metal hydridesMany metals and alloys can reversibly absorb largeamounts of hydrogen. The hydrogen can be introduced
34Risø Energy Report 3Hydrogen storage5.2T cß-Phase8010060P eq [bar]10α-Phaseα+ß-Phase4020E 0 [mV]10-200.10.00.20.4 0.6 0.8 1.02.8 3.2 3.6C H [H/M] T –1 [10 –3 K –1 ]Figure 12: Pressure-concentration-temperature (pcT) plot and Van't Hoff curve (logarithm of the equilibrium pressure vs. the reciprocal temperature)for LaNi 5 . The vertical axis indicates the corresponding hydrogen pressure or the equivalent electrochemical potential.to the metal either as molecules, in the gas phase, or asatoms from an electrolyte (Figure 11). In the former case,hydrogen molecules dissociate at the surface beforeabsorption; desorption releases hydrogen atoms, whichrecombine to form H 2 .The thermodynamics of hydride formation from gaseoushydrogen are described by pressure-compositionisotherms or pcT curves (Figure 12). The host metaldissolves some hydrogen as a Sieverts-type solid solutionphase. As the hydrogen pressure increases, so does theconcentration of hydrogen atoms in the metal (c H ). Atsome point, H-H interactions become locally importantand a hydride phase starts to nucleate and grow.While the solid solution and the hydride coexist, theisotherms show a plateau whose length determines howmuch hydrogen can be stored and recovered by means ofsmall pressure changes. In the pure hydride phase, thehydrogen pressure rises steeply with concentration.The plateau or equilibrium pressure p eq (T) dependsstrongly on temperature. The enthalpy of hydride formation(∆H) can be found from the slope of a Van't Hoffplot of the logarithm of the plateau pressure against 1/T.For an equilibrium pressure of 1 bar at 300K, ∆H shouldbe 19.6 kJ/mol hydrogen. The operating temperature ofa metal hydride system is fixed by the plateau pressure inthermodynamic equilibrium and by the overall reactionkinetics [13,14].Hydrogen is stored in the interstices of the host metallattice as atoms, never as molecules. As hydrogen isabsorbed, the lattice expands and often loses some of itssymmetry. The co-existence of the non-expanded solidsolution phase and the anisotropically expanded hydridephase gives rise to lattice defects and internal strainfields, ultimately causing the decrepitation of brittle hostmetals such as intermetallics. The hydrogen atomsvibrate about their equilibrium position, move locallyand also undergo long-range diffusion.In terms of electronic structure, the hydrogen atom'snuclear proton attracts the electrons of the host metal.As a result, the metal's electron bands are lowered inenergy and hybridise with the hydrogen band to formlow-lying bands 6-8 eV below the Fermi level. The Fermilevel itself is shifted, and various phase transitions(metal-semiconductor, magnetic-nonmagnetic, reflecting-transparent,order-disorder) may occur.The metal-hydrogen bond has the advantages ofproviding very high hydrogen storage density atmoderate pressure, and desorption of all the storedhydrogen at the same pressure.Which metallic systems are appropriate for hydrogenstorage? Hydrides can be formed from many metals,including palladium (PdH 0.6 ), the rare earth metals(REH 2 and REH 3 ) and magnesium (MgH 2 ). However,none of these are in the pressure-temperature rangeattractive for mobile storage: 1-10 bar and 0-100°C,corresponding to ∆H in the range 15-24 kJ/mol hydrogen.The discovery of hydrogen sorption by intermetalliccompounds created a flurry of R&D effort worldwide, inthe hope that some of these compounds would be suitablefor practical hydrogen storage systems (Table 9).Alloys based on LaNi 5 have some very promising properties,including fast and reversible sorption with littlehysteresis, a plateau pressure of just a few bars at roomtemperature, and good cycling life. The volumetric (crystallographic)density of hydrogen in LaNi 5 H 6.5 at 2 bar isequal to that of gaseous molecular hydrogen at 1,800 bar,and all this hydrogen is desorbed at only 2 bar. In prac-
Risø Energy Report 3Hydrogen storage 355.2Type metal hydride Struc. m% Peq, TTable 9: AB 5 , AB 2 , AB, A 2 B and bbc intermetallics and their hydrogen storageproperties .A Pd PdH0.6 Fm3m 0.56 0.02 bar, 298 KAB 5 LaNi 5 LaNi 5 H 6 P6/mmm 1.37 2 bar, 298 KAB 2 ZrV 2 ZrV 2 H5.5 Fd3m 3.01 10 -8 bar, 323 KAB FeTi FeTiH 2 Pm3m 1.89 5 bar, 303 KA 2 B Mg 2 Ni Mg 2 NiH 4 P6222 3.59 1 bar, 555 Kbcc TiV 2 TiV 2 H 4 bcc 2.6 10 bar, 313 Ktice, the packing fraction of LaNi 5 powder reduces theamount of hydrogen that can be stored, but thehydrogen density is still above that of liquid hydrogen(Figure 10). Intermetallic compounds such as LaNi 5 arealso a very safe way to store hydrogen.As La and Ni have high molecular weights, the amountof hydrogen in LaNi 5 H 6.5 is less than 2 wt%. This is anattractive material for electrochemical hydrogen storagein rechargeable metal hydride electrodes, such as electrodesfor commercially-available AB 5 type metalhydride batteries that have capacities of up to 330mAh/g.For mobile hydrogen storage applications, however, lowmass density is a general weakness of all known metalhydrides working around room temperature. Practicalapplications require hydrogen storage densities of 4-5wt%, short term US DOE target is even higher, at 6.5%hydrogen by weight or 62 kg H 2 /m 3 . Many intermetalliccompounds and alloys form hydrides with up to 9%hydrogen by weight (Li 3 Be 2 H 7 ) and 4.5 hydrogenatoms per metal atom (BaReH 9 ), but they are notreversible within the required range of temperature andpressure.When hydride formation and decomposition are limitedby reaction kinetics instead of thermodynamic equilibrium,various physical and chemical pre-treatments canbe used to improve performance. Ball milling, forinstance, has beneficial effects on the grain size anddefect concentration, and shortens the diffusion path.Fluorination has been shown to render surfaces active, apparently to a greater extent than the use ofsurface nickel precipitates, whose role in the hydrogendissociation process is well known.New families of Laves-phase-related BCC solid solutionalloys are being studied in several Japanese laboratories. These are based on vanadium, zirconium and titaniumas the more electropositive components,combined with 3d and 4d transition metals. Reversiblehydrogen storage capacities approaching 3 wt% aroundroom temperature have been reported.Higher mass density can only be reached using lightelements such as calcium and magnesium. In fact,magnesium forms an ionic, transparent hydride (MgH 2 )containing 7.6 wt% hydrogen, but its formation frombulk magnesium and gaseous hydrogen is extremelyslow. Once the hydride does reach equilibrium, a plateaupressure of 1 bar requires a temperature of 300°C.Various micro- and nano-structuring processes havebeen used to treat magnesium with the aim of improvingthe kinetics of MgH 2 formation. Precipitation frommetal-organic solutions or high-energy ball millingyielded good storage and discharge kinetics, even at150°C, and the equilibrium was evidently not affected[14,19]. Alloying is another approach: Mg 2 Ni, forinstance, forms a ternary complex hydride Mg 2 NiH 4 thatcan hold 3.6 wt% of hydrogen. The hydride forms quiterapidly, probably due to the action of nickel as a catalystfor the dissociation of molecular hydrogen, but the thermodynamicsstill dictate a temperature of 280°C tooperate at 1 bar. Magnesium does not form a binaryintermetallic compound with iron, but the presence ofhydrogen allows the formation of the rather stableternary hydride Mg 2 FeH 6 , which contains 5.5 wt%hydrogen .Another approach is to make composite materialscontaining two or more distinct components, in aneffort to compensate for the weaknesses of each. Magnesium,for instance, can be ball-milled with graphiticcarbon or mixed with hydrides such as LaNi 5 or Mg 2 Ni,which have fast kinetics. Not surprisingly, the hydrogencapacities of these materials fall between those of theirindividual constituents.Alanates and other light hydridesSome of the lightest elements in the periodic table –including lithium, boron, sodium, aluminium and theircompounds – form stable ionic hydrides. One of these,LiBH 4 , has the highest hydrogen density known: 18 wt%hydrogen at room temperature . However, the lighthydrides desorb their hydrogen only at temperatures inthe range 80-600°C, and it is not yet known to whatextent all of them are reversible.One group showed in 1996 that the decompositiontemperature of NaAlH 4 can be lowered by doping withTiO 2 . Recently, the same group showed that hydrideformation was reversible for several cycles of absorptionand desorption. This highlights the potential of suchhydrides, which were discovered more than 50 years ago,but several points need to be clarified. First, is the highdesorption temperature reported earlier due to poor
36Risø Energy Report 3Hydrogen storage5.2kinetics or the thermodynamic stability of the hydride?If the process is rate-limited, the kinetics can beimproved by incorporating a catalyst , or by ballmilling and the introduction of defects.Second, what are the conditions for a reversible reaction?The reversible formation of LiBH 4 and most of the otherhydrides in this potentially very attractive group is achallenge. Desorption of hydrogen requires the formationand stabilisation of clusters of an intermetalliccompound containing the remaining metals. SiO 2 isknown to play a catalytic role, but these light-metalhydrides need much more research.Heat Management in Hydride OperationAs discussed above, a considerable absorption or releaseof heat is involved in metal hydriding/hydriding process.In several cases the reaction heat amounts to about 25%of the combustion energy of the stored hydrogen andthis fact calls for clever, dedicated solutions for exchangingheat with the hydride material. One example of suchheat management could be a hydride store, whichshould feed a fuel cell with hydrogen. In this case theheat produced by the fuel cell may be used to dissociatethe metal hydride and the systems may be tailored for anoptimal thermal match. Large Danish companies havelong experience in handling and exchanging heat, andfor such companies the topic of thermal management ofhydride stores could be of commercial interest.Other hydrogen-rich compoundsSimilarly to storing hydrogen in metal hydrides also theformation of other types of hydrogen-rich compoundscould be attractive for hydrogen storage. For instance itis possible to form methane by direct electrolysis of waterin the presence of carbon dioxide and indeed it ispossible to form liquid compounds like methanol byproperly reacting hydrogen and carbon dioxide. Bothreactions may be done in an environmentally friendlyway by taking the carbon dioxide from the atmosphere.The attractive features of such carbon based compoundsis that we have a long handling experience and that aninfrastructure is existing or at least well-known.Visions for the futureIt is reasonable to hope that improvements in theperformance of hydrogen storage materials will one daymatch those of high-temperature superconductors andpermanent magnets. In developing sustainable energypolicies, however, we must look at society, economicsand the way we think about energy, as well as the scientificand technical challenges.As mobility continues to increase, we must decidewhether prestige, size and power should remain importantin vehicle design. And do vehicles really needstrong, heavy structures to protect their occupants, or areelectronic control and collision-avoidance systems abetter approach? They could certainly make it possiblefor much lighter and more energy-efficient vehicles to bebuilt in those countries that do not consider energyavailability to be unlimited. Europe and Japan alreadyhave small, light cars whose engines consume as little as3 l of gasoline per 100 km. A single kilogramme ofhydrogen can fuel an engine-driven car for 100 km; witha hydrogen fuel cell the range is 200 km.
Risø Energy Report 3Hydrogen conversion technologies 375.3Hydrogen conversion technologiesSØREN LINDEROTH, RISØ NATIONAL LABORATORY; JOHN BØGILD HANSEN, HALDOR TOPSØE A/S; DR. MOHSEN ASSADI AND PROFESSOR BENGTJOHANSSON, LUND INSTITUTE OF TECHNOLOGY.IntroductionHydrogen needs to be converted into power and heatwith high efficiency and little or no pollution from NOx,particles and noise. Emerging technologies can make thispossible. Most of these technologies can also converthydrogen-rich fuels with high efficiency and little pollution.For fuels such as natural gas, methanol, bioethanoland biogas, technologies that are either already existingor will be available in the near future provide clean andefficient conversion to power and heat, thus paving theway for a hydrogen society based on hydrogen-rich fuels.These technologies can also be combined in hybridcycles to reach electrical efficiencies of up to around70%. This chapter outlines the technologies, their status,advantages and areas for improvement, and shows howthey can be combined.Fuel cellsFuel cells are likely to play an important role in futureenergy supply as sources of both power and heat. Fuelcells of the future will be highly efficient, clean, quiet,scalable, reliable and potentially cheap.Various kinds of fuel cells are being developed worldwidefor commercial use in portable, transport and stationaryapplications (Table 10).Low-temperature fuel cells, notably PEMFCs, are mostuseful for converting high-purity hydrogen into electricityand heat. Electrical efficiencies reach nearly 50%using hydrogen.With other fuels the electrical efficiency decreases, sothat the efficiency for natural gas is expected to bearound 35%. This is because the feedstock must first be“reformed” into a mixture of hydrogen, carbonTable 10: Types of fuel cells and their properties. Fuel cells fall into two types: low-temperature, which operate at temperatures below 450°C, andhigh-temperature. This chapter deals mainly with PEMFCs and PAFCs (50-200°C) and SOFCs (550-1,000°C).Fuel cell type Solid polymer or Phosphoric acid Molten carbonate Solid oxideProton exchangemembranePEMFC PAFC MCFC SOFCElectrolyte Proton-conducting polymer H 3 PO 4 K-Li-CO 3 Y-Zr 2 O 3Operating temperature ~80°C ~200°C ~650°C ~600-1000°CAdvantages Works at ambient Reliability Internal reforming Internal reformingtemperature Tolerates above Fuel flexibility Fuel flexibilityHigh power density ~1% of CO High-temperature High-temperatureQuick to start up waste heat waste heatSolid electrolyte No noble metals Solid electrolyteVery durableNo noble metalsDisadvantages Very sensitive to CO Relatively low efficiency Requires expensive Sealing problemsWater management Limited durability alloys Thermal cyclingLimited durability Loss of phosphoric Corrosive liquid Slow to start upLow-temperature waste acid electrolyte electrolyteheatCO 2 needed in the airto the cathodeLow power density
38Risø Energy Report 3Hydrogen conversion technologies5.3Indirect fuel cellDesulphurizationPrereformer(450-500°)“Tubular”reformer(600-900°)GascleaningFuelcellDirect fuel cellDesulphurizationPrereformerFuelcellFigure 13: SOFC system design. Fuel Processing Schemesmonoxide and carbon dioxide, which is then treated toremove carbon monoxide (CO). Allowable CO contentsare around 10 ppm for PEMFCs operating at 80°C andaround 1% for PAFCs operating at 150-200°C.Methanol may also be used directly as a fuel, in whichcase PEMFCs are sometimes referred to as DMFCs (directmethanol fuel cells). NEC and Toshiba expect tocommercialise DMFCs in 2005, primarily for portableapplications such as laptop computers and personaldigital assistants (PDAs). Although their efficiency israther low, at around 30%, DMFCs are ideal replacementsfor batteries in portable equipment. Their energydensity is 4-5 times that of batteries, and they can berefuelled easily.High-temperature fuel cells (SOFCs) can run on fuelssuch as natural gas, biogas and methanol, thanks to theirability to reform hydrocarbons within the cell itself.Reforming is an endothermic process, meaning that itabsorbs heat, and thus it can use waste heat createdduring the electricity generation process. Direct fuellingwith methane or methanol therefore increases both theelectrical efficiency and the total efficiency of the fuelcell compared to using hydrogen as the fuel.High-temperature fuel cells typically operate at about1,000°C, and the materials needed to withstand suchhigh temperatures make these fuel cells rather expensive.More recently, intermediate-temperature fuel cells operatingbelow 750°C promise to be more competitivebecause they are more durable as well as cheaper to build.Current R&D aims at developing SOFCs that can operateat 550-600°C.Direct SOFCs have the advantage that it is easy to removecarbon dioxide from the exhaust, because the gasstreams leaving the anode and cathode remain separate.The anode gas contains water, carbon dioxide andunburned hydrogen. One approach to exhaust cleanupuses a membrane to remove the hydrogen, which is thenrecycled to the inlet of the fuel cell. An alternative is tooxidise the hydrogen, using oxygen extracted fromatmospheric air by another type of membrane. In eachcase the result is a gas stream containing only water andcarbon dioxide. The carbon dioxide can then be separatedby cooling to condense out the water.SOFC systemsIn a complete SOFC system (Figure 14), natural gas is firstpre-heated and desulphurised. It is then mixed with recycledanode off-gases, which provide steam and heat,before passing through an adiabatic pre-reformer. Thepre-reformer yields a mixture of methane, hydrogen,carbon monoxide and carbon dioxide. After passingthrough a final heat exchanger which increases itstemperature to around 650°C, the fuel gas enters theanode compartment of the SOFC.Off-gas from the anode first heats the incoming fuel gas.Part of the off-gas stream is then mixed with the fuelentering the pre-reformer, while the rest goes to acatalytic incinerator. Heat from the incinerator exhaustis recovered in a further series of heat exchangers.On the cathode side, air is compressed in a blower andpre-heated in a heat exchanger, also to around 650°C.Off-gas from the cathode, consisting of depleted air, isfirst cooled against the incoming cathode air. Some ofthe off-gas then goes directly to heat recovery, while therest passes through the incinerator.Such a system has an electrical efficiency of nearly 56%and a total efficiency of 88%.PEMFC and PAFC systemsPEMFCs and PAFCs have attracted a lot of research effortin the last decade, especially for mobile applications,where they have the advantages of operating at temperaturesclose to ambient and fast start-up. PEMFCs will bethe preferred choice for devices such as uninterruptiblepower supplies (UPSs). The main disadvantage ofPEMFCs is their need for very pure hydrogen: state-ofthe-artPEMFCs cannot tolerate much more than 50 ppmof carbon monoxide in the anode feed without seriousdeterioration in performance. Water managementaround PEMFCs is complicated, and waste heat is onlyavailable at moderate temperatures.
Risø Energy Report 3Hydrogen conversion technologies 395.3Flue gasE5Natural gas E1 Desulphurisation PrereformerWater for start upE6E2SOFCFlue GasE7CatalyticBurnerAnoderecycleAnodeCathodeE3AirBlowerFigure 14: Basic layout of an SOFC-based CHP system.In a complete PEMFC system (Figure 15) the feed ispreheated and desulphurised before steam is added.Steam reforming is carried out in a heat exchangereformer, using heat supplied by a gas-fired heater andalso recovered from the reformer exhaust stream.The carbon monoxide content in the reformed gas is firstlowered to a few thousand ppm in a shift reactor, andthen reduced to below 50 ppm in a preferential oxidation(PROX) reactor, which uses air to selectively oxidisecarbon monoxide to carbon dioxide. The exit gas fromthe PROX unit is cooled to 80°C before entering theFigure 15: Basic layout of a PEMFC-based CHP system.Natural gasDesulphurisationBFWHeat ExchangeReformerPROXFlue gasShiftBurnerAirBlowerPEMFCBFWAnodeCathodeCoolingWaterBFW
40Risø Energy Report 3Hydrogen conversion technologies5.3anode compartment of the PEMFC. The PEMFC itself iscooled by water, from which heat is recovered.Off-gas from both the anode and the cathode is firstcooled to condense out pure water (boiler feed water,BFW) for re-use. The offgas, which contains unburnedhydrogen, is then burned in the reformer heater.Such a system has an electrical efficiency of 37% and atotal efficiency of 82%.Homogeneous charge compression ignitionHomogeneous charge compression ignition (HCCI) is anemerging technology for internal combustion enginesthat can provide high efficiency (up to 43%) usingvarious fuels, including hydrogen. HCCI creates verylittle pollution, with almost no NOx or particulates. Thetechnology is of interest for both transport and electricitygeneration, and is being followed closely by automotivemanufacturers. The basic advantage of HCCI is tocombine the very low emissions of an SI engine using athree-way catalyst and the very high efficiency of a diesel(CI) engine.HCCI combines the characteristics of spark-ignition (SI,or Otto) engines, such as standard gasoline engines, andcompression-ignition (CI or diesel) engines. Fuel and airare mixed before combustion, as in a conventional SIengine. As in a diesel engine, however, there is no sparkplug, and combustion is started by autoignition instead.To ensure that the autoignition temperature is reachedjust as the piston reaches top dead centre, HCCI enginescontrol the inlet temperature, the compression ratio, orboth.Because the fuel/air mixture is close to homogeneouswhen the charge is ignited, there is no differencesbetween local and global combustion rates, in contrast tothe situation in a SI or CI engine. This means that toprevent excessive combustion rates, the mixture must bevery lean. A too rich mixture will burn the entire chargein a small fraction of the power stroke, producing veryhigh combustion pressures, high stresses and high noiselevels. A too lean mixture produces slow and incompletecombustion.Lean burning means that the HCCI engine cannot createparticulates, and the low combustion temperature limitsthermal NOx to 0.1-2 ppm. On the other hand, aproblem with current HCCI engines running on hydrocarbonfuels is higher levels of unburned hydrocarbonsand carbon monoxide in the exhaust.An HCCI engine running on hydrogen, however, cannotform carbon monoxide or emit unburned hydrocarbons– in fact its only exhaust product is steam. Researchers atLund Institute of Technology in Sweden are developinghydrogen-fuelled HCCI engines.The main problem with HCCI is to control the combustionprocess, balancing the inlet conditions to getcombustion at the correct point in the cycle. Changingthe inlet temperature by just a few degrees, for instance,can be enough to stop the engine. This degree of controlcannot be achieved with a direct link between the acceleratorpedal and the throttle. Modern electronic enginemanagement systems, however, are capable of theclosed-loop control that HCCI requires.Gas turbinesHydrogen as a fuel for gas turbines (GTs) has been investigatedfor several decades. Producing exhaust gasescontaining only water vapour, oxygen, nitrogen andsome unburned hydrogen, gas turbines running onhydrogen offer the prospect of environment-friendlyand CO 2 -free electricity generation.Burning hydrogen in gas turbines raises issues including:• high flame speed can cause the flame to move upstreamand stabilise on the fuel injector, resulting indamage to the burner;• increased risk of flashback in premix mode;• high flame temperatures increase NOx emissions; and• hydrogen can cause embrittlement of metal componentsin the fuel system.Hybrid cycles with fuel cells and HCCI/GTBecause of their high electrical conversion efficiencies,SOFCs will probably form the basis of the best futureCHP plants. Adding a heat engine such as a HCCI or a gasturbine can improve the operation of a SOFC plant evenfurther.A stand-alone atmospheric-pressure SOFC plant uses acatalytic incinerator with waste heat recovery to destroyunburned fuel in the anode exhaust gas. Replacing theincinerator with an HCCI engine improves overall efficiency,increases the proportion of shaft power availablefrom the plant, reduces exhaust gas volumes andprovides greater flexibility during load following, startupand shutdown.Running the SOFC under pressure reduces the volume ofthe fuel cell stack and improves performance by allowingthe electrochemical reactions to operate more effectively.If we use a gas turbine instead of an HCCI engine toreplace the incinerator, there is the further advantagethat compressed air from the gas turbine's compressorcan be used to supply the SOFC.Calculations show that small hybrid SOFC/GT plants ofaround 350 kW e could achieve electrical efficiencies of60-70%, which is considerably better than competingtechnologies of this size. Burning hydrogen instead ofnatural gas would further increase the efficiency by a fewpercentage points.Disadvantages of hybrid systems include:• the need to develop new gas turbines specifically forSOFC/GT hybrid systems. Off-the-shelf GTs would notbe suitable;• lack of operating flexibility, especially at part load,because of the strong interdependency between theSOFC and the GT; and• complications during start-up, shutdown and loadchange, because of the risk of compressor surge.
Risø Energy Report 3Hydrogen conversion technologies 415.3Electricalefficiency (%)Commerciallyavailable inAtmospheric SOFC (CHP) 50-55 About 5 yearsAtmospheric hybrid (HCCI) 40-50 About 5 yearsPressurised SOFC 50-60 >10 yearsPressurised hybrid (GT) 60-70 >15 yearsTable 11: Emerging SOFC hydrogen technologies and their time to market.Conclusions and recommendationsSOFC systems is the most interesting and prospectivesystems for the Danish and Global energy systems. Thisstems from the high electrical efficiency of such systems,the high quality steam produced, the possibility to separatethe CO 2 exhaust gas (in case of C-containing fuels)for possible sequestration and the high degree of fuelflexibility. Fuels, such as natural gas, will be most importantin Denmark due to the natural gas grid already availablein Denmark, but also biogas, biodiesel, methanol,ethanol, gasified coal gas, as well as hydrogen (pure orless pure) can be utilised directly or after pre-reforming.The possibility for module building of systems and theintegration with other systems like gas turbinesenhances the benefit of SOFCs.Both SOFC and PEMFC fuel cells can be used in verymany applications (portable, APUs, transport, singlehouses, UPS, medium size CHPs and large powerstations) and can be integrated with the electricity andgas grids and wind power-and-electrolysis systems thusproviding the most flexible and efficient overall system.The strength and competences already existing inDenmark both at research institutions and in industryprovide a strong basis for Denmark to play a major rolein the commercialization and use of fuel cell systems andhence an important entry in the hydrogen economy.Risø together with industrial partners in Denmark andNordic countries (especially Sweden) could form thebasis in a lighthouse project for the demonstration offuel cell systems for different use, e.g. an Örestad Ligthhouseproject, much in line with projects proposed bythe European Hydrogen and Fuel Cell Technology Platform.Table 11 compares expected efficiencies and commercialavailability market for the various stand-alone andhybrid SOFC technologies.Figure 16 shows the range of plant size and electrical efficiencyexpected for a range of energy conversion technologies.It is clear that, from today's perspective at least,the eventual winners will be SOFCs as either stand-aloneunits or in combination with gas turbines.Figure 16: Expected plant size and electrical efficiency for a range ofenergy conversion technologies.Electrical Efficiency (%)Operation with natural gas706050403020100101001.000 10.000Plant Power (kW)100.0001.000.000■ Gas Turbine ■ Steam Turbine ■ Combined Cycle■ PEM Fuel Cell ■ SOFC Fuel Cell ■ SOFC Gas Turbine Hybrid
42Risø Energy Report 3Hydrogen for transport5.4Hydrogen for transportANTONIO FUGANTI AND EMANUELE BELLERATE, CENTRO RICERCHE FIAT; ALLAN SCHRØDER PEDERSEN, RISØ NATIONAL LABORATORYIntroductionOne reason to look seriously at hydrogen as an energycarrier is that it can readily be used to power road vehicles,locomotives, ships and aircrafts. The most advanceduse of hydrogen in the transport sector is for motor vehicles,especially cars. This is why automotive manufacturersall over the world are putting a lot of money intohydrogen R&D.Hydrogen can be used to power vehicles by means ofinternal combustion engines (ICEs), fuel cells or gasturbines. Since fuel cells have higher useful energyconversion efficiencies than simple ICEs, they are veryattractive in automotive applications (see below and alsoChapter 5.3).ICEs, however, are a well-established technology that isfairly easy to convert from conventional liquid fuels tohydrogen. For these reasons, some car manufacturers arealso working on ICEs specifically for hydrogen.Most gas turbines today are much too large to be used inroad vehicles. However, R&D in countries includingGermany and the USA aims to develop small hydrogenfuelledgas turbines suitable for road vehicles. When usedwith other energy conversion technologies in hybridcycles, gas turbines should be able to match the efficiencyof fuel cells. For this reason, some people believethat gas turbines may be the winning technology inhydrogen for transport applications.Hydrogen has been applied for transport purposes inaviation (Russian and American aeroplanes) as well as inseveral areas of surface transport (buses, cars and trucks).As mentioned, however, the most intense and advanceddevelopments have been done in the automobile sectorand therefore a detailed description hereof is given in thefollowing section.Hydrogen from the car manufacturers' pointof viewDrivers and technologyEnergy consumption associated with transport isexpected to grow around 2% per year in Europe over thenext few years, and much faster in developing countriessuch as China and India. Oil is the source of 96% of theenergy currently used in transport.Within this context, automakers face increasingly tightlegal restrictions on polluting emissions. There is alsogrowing public pressure to decrease emissions of carbondioxide and other greenhouse gases (GHGs), which areparticularly associated with transport. In Europe, avoluntary agreement by all the car manufacturers has setcarbon dioxide emissions targets of 140 g CO 2 /km for2008 and 120 g CO 2 /km for 2012.CO 2 g/km190Refinements in conventional engine technology willprobably be able to keep pace with legislative requirementsfor pollutants such as NOx and hydrocarbons. Thetargets for CO 2 , however, require improvements in fueleconomy that conventional engines will probably not beable to meet (because with conventional fuels, a givenamount of energy is always associated with a fixed quantityof CO 2 ).The answer may be to use hydrogen-fuelled internalcombustion engines (ICEs) or fuel cells. ICEs running onhydrogen emit NOx, but since their fuel contains nocarbon, their exhaust contains no CO 2 or hydrocarbons.Fuel cells are more efficient than ICEs, and have nomoving parts. When fuelled by hydrogen, they produceonly water. For these reasons, most of the hydrogen R&Dcarried out by automotive manufacturers in recent yearshas focused on fuel cells, particularly proton exchangemembrane fuel cells (PEMFCs). Among the favourablecharacteristics of PEMFCs for transport applications arelow operating temperatures and short start-up times.Figure 18 shows the power train of a simple fuel cellvehicle. The fuel cell generates electricity, which drivesan electric motor. Although the fuel cell vehicle has twoseparate energy conversion steps, compared to one in aconventional ICE vehicle, its overall efficiency can behigher because the fuel cell and especially the electricmotor have very high individual conversion efficiencies.Fuel cells can overcome the problems of range, performanceand refuelling time associated with traditional electricvehicles, which use accumulators to store electricity.Because chemical energy storage media such as hydrogenhave a higher energy density than accumulators, fuel cellvehicles have better range and performance than tradi-165-1701401201995Figure 17: Targets for CO 2 emissions.CEC – ACEA Agreement -26%CEC Review-14%2003 2008 2012 Year
Risø Energy Report 3Hydrogen for transport 435.4Number of prototypes16HydrogenFuel CellDC powerInverterMech power1412AUX F.C.AirElectricMotor108Fuel CellSystem64Figure 18: The power train of a simple fuel cell vehicle.20199719981999200020012002Figure 20: Figures for prototype fuel cell vehicles show that althoughmethanol was a popular choice some years ago, the consensus is now touse pure hydrogen.■ Methanol ■ Hydrogen ■ Gasolinetional electric vehicles. They can also be “recharged” in afew minutes, compared to the hours needed to charge abattery-powered vehicle.Fuels for fuel cell vehiclesThe range of a fuel cell vehicle depends on the amountof hydrogen it can carry. Weight for weight, hydrogencontains more energy than any other chemical energystorage medium, but its low density is a problem in boththe liquid and gas phases. Gasoline, for example, has avolumetric energy content of around 32 MJ/l, but liquidhydrogen is only around 8.4 MJ/l.The low volumetric energy content of hydrogen, and thelack of infrastructure for hydrogen refuelling, hasencouraged car manufacturers to study the use of moreconventional liquid fuels that can be converted tohydrogen-rich gas mixtures by a “fuel processor” in theFigure 19: Car manufacturers have in the past had differing ideas aboutthe use of liquid hydrogen and alternative liquid fuels that can be convertedto hydrogen on board the vehicle.Compressed Liquid Gasoline Methanolhydrogen hydrogen reformer reformerBMW■DC ■ ■ ■Ford■GM ■ ■ ■Hyundai ■Honda ■ ■Nissan■Opel■Renault ■ ■Toyota ■ ■VW ■ ■Fiat■vehicle. Gasoline and methanol are two obvious choices(Figure 19).An example of parallel development in different fueltechnologies is that of DaimlerChrysler. Different prototypesof NECAR (a prototype fuel cell vehicle based on aMercedes-Benz A-Class) used both methanol reforming(NECAR III and V) and pure hydrogen (NECAR II and IV).Today, however, there is a clear consensus among the carmanufacturers on the use of direct hydrogen fuel cells(Figure 20). In most cases, high-pressure gaseoushydrogen is preferred over liquid hydrogen.The reason is that on-board reforming has not lived upto its original promise. It implies additional complexityand cost, and has seriously hindered vehicle performancesbecause of time lags in the reformer. It reducesoverall efficiency and eliminates the “zero emission”benefit of fuel cell vehicles, to the extent that a fuel cellvehicle with an onboard fuel processor has no environmentaladvantages over ICE vehicles. Figure 21 shows,for example, that overall (“well to wheel”) CO 2 emissionsfor a fuel cell vehicle with a gasoline fuel processorare the same as those for an ordinary diesel vehicle.Technology barriers to the development of fuel cells intransportPEMFCs and related components have shown stunningprogress in the last decade, notably in power density andspecific power (Figure 22).Nevertheless, serious technology barriers remain at thecomponent level. Laboratory tests cannot prove thatPEMFCs will be commercially viable in mass-producedvehicles. The main challenges now are to:• reduce the cost of the fuel cell stack itself;• reduce cost of other devices required by the fuel cellsystem;• improve performance at temperatures below freezing;• increase tolerance to carbon monoxide and othercontaminants in the hydrogen;
44Risø Energy Report 3Hydrogen for transport5.4135Power densitites1,8100901,6801,4706050403020100Current PFIAdvancedHybridICE-GasolineCurrentAdvancedHybridICE-DieselCurrentAdvancedHybridICE-CNGLH2 from NGICE-H2Battery (electricity from the net)FC (CH 2 from NG)FC (LH 2 from NG)FC (gasoline reforming)ElectricFC (H from Renewables)1,21,00,80,60,40,20,019971998199920002001■ WTT ■ TTW■ kW/l ■ kW/kgFigure 21: Overall CO 2 emissions from different fuels and engine types.WTT=well to tank, i.e. emissions incurred in extracting, refining anddistributing the fuel. TTW=tank to wheel, i.e. emissions created by thevehicle itself. CNG=compressed natural gas.Figure 22: Technical progress in power density and specific power forPEMFCs over the last decade.• demonstrate the durability of individual componentsand the complete system;• develop high-efficiency thermal, water, and airmanagement subsystems;• develop and put in place a suitable fuel infrastructure;and• solve the problem of hydrogen storage.The last point, storage, is the biggest research problemremaining in the development of hydrogen-poweredvehicles. Hydrogen's low density makes it difficult tostore sufficient amounts on board a vehicle to achieve auseful range without the container being too large or tooheavy.Currently, hydrogen must be either pressurised to severalhundred atmospheres or stored as a liquid at cryogenictemperatures. Neither of these options are appropriatefor normal road vehicles. There has therefore been muchresearch into new storage technologies such as carbonnanotubes and metal hydrides, both of which can theoreticallyhold large amounts of hydrogen safely in a relativelysmall space (see also Chapter 5.2). The difficulty ofthis research, however, is shown by the extremely lowlevel of patenting in this area.Market projections and cost targetsIt is difficult to predict the market share of fuel cells infuture transport applications, since a significant marketfor fuel cell vehicles cannot emerge until the currenttechnical and infrastructure challenges have beensolved. Fuel cells also have to compete with gasoline anddiesel ICE technologies, which also are improved continuously.Figure 23 combines the results of several studies to give aqualitative view of how fuel cell vehicle sales may grow.It is important to remember that estimates of the potentialmarket for fuel cells in the transport sector vary enormouslyin terms of both value and number. Uncertaintiesassociated with fuel cell technology are probablyresponsible for the fact that no such market studies havebeen published since 2002.A study by Allied Business Intelligence (ABI), not shownin Figure 23, predicts a market in the range $608,000-$1.2 million for fuel cell vehicles in the USA by 2010, anda global market of $1.5 million by 2011, accounting for2.7% of all new road vehicles. New regulatory incentivesor unexpected technical progress could increase theglobal market to $2.4 million, or 4.3% of all vehicles,according to ABI. The study suggests that the number ofvehicles produced could reach 800,000 by 2012.It is highly significant that METI, the Japanese Ministryof Economy, Trade and Industry, at the end of 2003announced that it forecasts an eventual total of 50,000fuel cell vehicles on Japanese roads. Also important is thefact that electric vehicles are already available for leasingfrom car manufacturers including Toyota, Honda,Nissan, DaimlerChrysler and Opel. 7Notwithstanding the different forecasts for growth rateand eventual market size, most experts believe that fuelcells will not enter the vehicle market in commercialnumbers until after 2015. The reason is because of thetime needed for testing, first in niche areas and then insmall fleets.Fuel cell vehicles also need to be supported by a distributioninfrastructure for hydrogen. At the start, with veryfew hydrogen vehicles on the market, refuelling stations7. Toyota, for example, leases its FCHV4 vehicle at $10,000 per month.
Risø Energy Report 3Hydrogen for transport 455.4Test Phase 2000-2010Niche Production2010-2015Market Penetration2015-2020Consolidation2020-2025MITI-2003-50.000F. & S.-2001-5000FROST &SULLIVAN-2001900.000-1.000.000F. & S.-2001-500NOMURA-20002.500-5.000NOMURA-200010.000-100.000TEXACO-2000150.000-700.000TEXACO-20007.500-40.000Honda &Toyota fleets2000 2003 20052010 2015 2020 2025■Hydrogen Infrastructure options■ Centralized NG reforming and pipeline distributions ■ Delivery with LH, truck ■ Small NG on site reforming + Small electrolyzerFigure 23: Many studies have tried to predict the growth of fuel cell vehicles, but uncertainty surrounding the technological problems still to be solvedhas yielded a wide range of answers - and no new market studies since 2002.generating their own hydrogen from natural gasreforming or electrolysis would be the best option. As thenumber of hydrogen vehicles increases, liquid hydrogenmay be distributed to filling stations by road tanker.Eventually, when the market matures some time after2020, centralised steam reforming of natural gas anddistribution by pipeline may become economic.Turning to costs, the US Department of Energy has estimatedthat light-duty fuel cell vehicles will be commerciallyviable by 2015-2020 provided that:• advances in technology allow hydrogen vehicles to bemanufactured in volumes of over 500,000 units a year;• fuel cell costs fall to $45/kW for a 50-kW unit (i.e. aunit cost of $2,250);Figure 24: Fiat Seicentohydrogen fuel cell car(phase 2).Dynamic air compressor 2.5kWFuel Cell StackPEM Nuvera 20kWCompressedHydrogen Tank68 l @ 350 barHeatExchangersPanasonic batteryNi-Meh 144v-900WhMain characteristics:• Hybrid configuration (FC-Battery): Load Follower• Payload:4 persons• Acceleration 0-50 km/h:8 s• Max velocity:120 km/h• Grade ability fully loaded: 20%• Refuelling time:
46Risø Energy Report 3Hydrogen for transport5.4• vehicles can maintain full performance over 5,000operating hours; and• hydrogen costs fall to $1.50-$2.10 per gallon gasolineequivalent.The Fuel Cell Commercialization Conference of Japan(FCCJ) arrived at a similar estimate for the threshold costof fuel cells: ¥5,000 ($42)/kW, including auxiliary equipment.CRF prototypesIn projects funded by the Italian Ministry of the Environment,Fiat's CRF research centre developed twoconcepts for PEMFC city cars (Figure 24).Conclusions and recommendationsEstimations of the size of a future market for hydrogenpropelledcars have shown dramatic divergences andthere is still no consensus concerning the near future.Although direct hydrogen fuel cells and pressurisedonboard hydrogen storage currently seem to have aleading position in the competition between hydrogentechnologies for transport purposes, it is still uncertainwhat the winning technology will be.The problem of cost effective and energy effectivehydrogen storage onboard vehicles is persistent andneeds considerable scientific and technical attention ifwe want hydrogen vehicles to be comparable to conventionalvehicles concerning operation range.
Risø Energy Report 3Hydrogen in portable devices 475.5Hydrogen in portable devicesJUERGEN GARCHE, ZSW – ELECTROCHEMICAL ENERGY STORAGE AND ENERGY CONVERSION DIVISION; ULRICH STIMMING, TECHNISCHE UNIVER-SITÄT MÜNCHEN; ANDREAS KASPER FRIEDRICH, ZAE BAYERN; ROBERT FEIDENHANS'L, RISØ NATIONAL LABORATORYIntroductionFuel cells were originally intended for use in powerplants and vehicles. More recently, developers realisedthat it is possible to build much smaller units and forlower prices per kilowatt than their larger relatives. Thishas led to strong interest in developing small fuel cells.Small fuel cells could replace batteries in portable electronicequipment (up to 100 W) and internal combustionengines in portable generators. The upper limit forportable generators is about 5 kW, mainly because of theweight of the fuel cell.The International Electrotechnical Commission IEC saysof fuel cells for hand-held or portable devices: “The fuelcell power unit may be intended for mounting in a dedicatedcavity in the device for easy removal, or maybe astand-alone electrical power source system intended forconnecting to one or more devices with a wiring andconnector means”.The main applications for low-power fuel cells aremobile phones, personal digital assistants (PDAs), laptopand notebook computers, cameras, medical equipment,military applications and other portable electronicdevices. In comparison to batteries, fuel cells can supplymuch more power per unit volume or weight, thoughthey have lower output voltages and are slower torespond to transients.Applications for fuel cells up to 5 kW include portablegenerators, uninterruptible power supplies (UPSs), auxiliarypower units, power tools, light vehicles such as electrictrolleys, lawn mowers and roadside equipment.Fuel cell types that are suitable for portable applicationsinclude:• proton exchange membrane fuel cells (PEMFCs) usingpure hydrogen (H 2 -PEMFCs);• PEMFCs using hydrogen-rich gases from hydrocarbonor alcohol reforming (Ref-PEMFCs);• direct methanol fuel cells (DMFCs); and• high-temperature fuel cells such as solid oxide fuel cells(SOFCs) and molten carbonate fuel cells (MCFCs) usinghydrocarbons directly.cations. However, PEMFCs that are to be integrated intosmall electronic devices, need to be specially designed forminiaturisation.Fuel cells for portable applications have the advantagethat the cost per kW is much less important than forstationary and transport applications. They are usuallyonly required to have relatively short lifetimes, typicallyof the order 2,000 hours. This makes them suitable forrapid market introduction.Fuel cells do not create new applications for portableequipment, but they can improve the practical value ofexisting devices. As battery replacements, for instance,fuel cells can increase the operating time of electronicand electrical equipment. In portable generators theyeliminate the noise and emission characteristics ofinternal combustion engines.These advantages will only be taken up if the costs of fuelcells are comparable with those of the technologies theyreplace. As shown in Figure 25 this is already close to bethe case for portable equipment. In this marked sector itis therefore only necessary to solve the remaining problemsassociated with reliability, lifetime, volume andweight.ApplicationsLow-power applications in electronic devices(up to 20 W)Fuel cells for small electronic devices such as mobile andcordless phones, pagers, radios, portable CD players, taperecorders and battery chargers are known as “device-integrated”because the requirements set limits on the fuelFigure 25: Costs at which fuel cells will become competitive in differentapplications (“4C” = camcorders, cellular phones, computers, cordlesstools).Cost/€/kW5.0004CPortableDMFCs are mostly used for small units and devices inintegrated systems because they use a liquid fuel with ahigh energy density that is easy to distribute. PEMFCs arebetter for high-power systems because of their higherpower density. Applications of small high-temperaturefuel cells are limited to auxiliary power units that are infrequent use, and therefore they will not be dealt withfurther in this chapter.PEMFCs for portable generators do not differ much fromthe large PEMFCs used in stationary and transport appli-5005005StationaryCar50 power/kW
48Risø Energy Report 3Hydrogen in portable devices5.5Cellular PhoneCellular PhoneFigure 26: This “power holster” for a mobilephone uses DMFCs to charge the phone battery(source: Manhattan Scientifics).Micro-Fuel Cell TMPower Holster TMSMicro-Fuel Cell TMPower Holster TMFuel Ampulecell system volume. For device-integrated fuel cellsystems, volume is clearly even more important thanreliability, lifetime and costs.It is therefore important to reduce the size of the fuel cellstack, the fuel storage system and auxiliary componentssuch as valves, sensors, control units and liquid/gas separators.For this reason, air or oxygen should be suppliedto the fuel cell without the need for active air movementssuch as fans. Water management is perhaps themost complicated problem for miniature PEMFCs andDMFCs, because it includes fuel concentration control,membrane humidification, water recovery and recirculation.Whereas it is possible to operate a fuel cell passivelywithout any peripheral device, substantial improvementsare expected from engineering modeling.In principle there are two ways to construct small fuelcells. One is to take a standard fuel cell and miniaturiseit; the other is to use micro-fabrication techniques, inwhich the various components – membranes, electrodesand catalyst – are “printed” directly onto ceramic orsilicon wafers, or more recently flexible polymer sheets.The power conditioning for the low-power device-integratedapplications is unlike analog equipment thatdraws a steady current; the mobile phone, for instance,requires short, large current spikes. Therefore, a hybridconfiguration of fuel cells with a small battery or a supercapacitor may be necessary.The following examples show a device-integrated fuelcell and a methanol micro-reformer.Figure 26 shows a “power holster” fitted with DMFCswhich charge the phone when it is in the holster. Thearray contains ten fuel cells in a package measuring 120x 46 x 0.5 mm and generating around 1 W. The cells areformed from paper-thin plastic sheets intended for rollfedmass production. They are mounted side by side, butare connected in series to provide the necessary voltage.Initial tests achieved a specific energy of 356 Wh/kg froma single fuel ampoule, and 28 g of fuel was enough tosupply more than twice the energy contained in a 900-mAh Li-ion battery.The relatively low specific power available from DMFCsat ambient temperature and the difficulty of storingFigure 27: Integrated methanol micro-reformer and chemical heater(Motorola)Reformer Cavity Packed Catalyst BedChemical Heater Outlet CavityChemical Heater (microchannels)Reformer Fuel Vaporizer CavityChemical Heater Fuel Inlet
Risø Energy Report 3Hydrogen in portable devices 495.5Fuel cell stack Switching micro valveHydrogen cartridgesFansElectronics/control unit (white area)Figure 28: A notebook computer (LG CiNOTE 7400) with an integrated H 2 -PEMFC system (LG; ISE Freiburg).hydrogen have led to work on “micro-reformers” thatcan produce hydrogen to feed conventional PEMFCs.One such methanol micro-reformer developed byMotorola measures just 35 x 15 x 4 mm. Its methanolconversion efficiency is greater than 95%. The operatingtemperature of around 230°C is achieved by oxidisingliquid methanol over a bed of activated platinum catalyst.Device-integrated systems for higher powers(20-100 W)Devices such as notebook computers, power tools,camcorders, digital cameras and toys may consume morethan 20 W, and power requirements are increasing all thetime as manufacturers add new functions. These applicationstoo require special miniaturised fuel cells.Fuel cells have lower electrical efficiencies (around 50%)than the batteries they replace (around 80%). Since anyenergy that is not converted to electricity ends up asheat, fuel cells in this power range can suffer from overheating.Overcoming the problem of excess heat requires intelligentthermal design. Metal hydrides require heat torelease their stored hydrogen, so this may be a way to usesurplus heat from the fuel cell. Also, compact and efficientthermal barriers are required.Other important R&D issues in fuel cell systems forconsumer electronics are safety and effluent management.Fuels such as methanol, which is toxic andflammable, need to be contained safely. Exhaust componentsincluding methanol, formic acid (from DMFCs)and carbon monoxide (from PEMFCs) must be eliminated.Replacement fuel cartridges will need to be standardised.Having to buy different refuelling systems for eachdevice will seriously hinder market introduction.The first of two example applications of higher-powereddevice-integrated fuel cells is a notebook computerpowered by a PEMFC with metal hydride hydrogenstorage .This state-of-the-art system provides about 55 W/l or 95W/kg , with an energy density of about 120-140 Wh/l.The fuel cell system measures 275 x 62 x 22 mm andweighs 170 g. The operating voltage of the 27-cell stackis in the range 10-20 V and needs a DC/DC converter toincrease it to the computer's operating voltage of 24 V.Portable power generators (500 W-5 kW)Back-up power generators and auxiliary power units(APUs) in the range 500 W-5 kW could reach the marketrelatively quickly, because cost and lifetime for theseunits are less important than for other high-volumeapplications. Reliability and rapid start-up at ambientconditions are critical, especially for uninterruptiblepower supplies (UPSs), which need to be on-line within20 ms. Fuel cells for these applications also need totolerate highly dynamic electrical loads.Low-power units will use mainly DMFCs, while PEMFCswill cover the high end of the power range. For APUswith high load systems and long operating times,reformers will be essential. The fuel could be LPG,methanol, diesel, kerosene or gasoline.Prototype back-up power generator systems based onfuel cells are already available for around €10/W, but thetarget for mass-produced compact units is €2/W. Systemlifetime is currently below 1,000 h and needs to beincreased to 2,000 h or more. Power densities are in therange 10-100 W/l. The units can operate at temperaturesfrom -20°C to 50°C, and at high relative humidities.Most existing systems incorporate a small battery toprovide power for start-up. Hybrid systems incorporatinga larger battery alongside the fuel cell could help toreduce size and costs.The following section shows an example of a high-powerfuel cell module.The NEXA from Ballard Power Systems is the firstcommercially-available H 2 -PEMFC power module. Table12 shows its technical specifications.Future opportunities for fuel cell systems in this powerrange include military applications, unattended marinesystems and light traction. The military application isespecially interesting because in this area an early market
50Risø Energy Report 3Hydrogen in portable devices5.5Figure 29: NEXA 1.2-kW H 2 -PEMFC module (Ballard Power Systems).Performance Rated net output 1200 WCurrent46 ADC voltage26 VOperating lifetime 1500 hoursFuel Composition 99.99% dry H2Operating Ambient temperature 3-30°Cenvironment Relative humidity 0-95% RHPhysical Length x width x height 56 x 25 x 33 cmWeight13 kgTable 12: Operating data for the Ballard NEXA.entrance even at today's costs is probable. For militaryuse a power supply is necessary that emits a minimum ofheat and noise.Fuel cells are also an excellent replacement for batterieswherever access for charging is difficult, such as marinebuoys, lighthouses and remote weather stations. In somecases the fuel cells could act as a backup for solar panelsin seasonal systems. In this way the PV module areacould be strongly reduced and therefore the costs canbecome acceptable. Light traction comprises fuel cells forbikes, scooters, internal transporters, wheelchairs, maintenancerobots, golf cars, etc. The power range isdependent on the application 100 W – 5 kW. The advantageof the FC driven light traction is the higher cruisingrange in relation to battery driven vehicles.R&D tasksThe R&D tasks for portable applications are relativelybroad, covering PEMFCs, DMFCs, hydrogen storagesystems and fuel processors.PEMFCsThe following points cover PEMFCs not just for portableapplications but also for transport and stationary uses.Catalysts need higher reactivity and lower platinumcontent. The oxygen electrode is a particular challengehere. Especially for REF-PEMFCs, the focus is on catalystswith high CO tolerance and on high-temperature technologythat allows the development of CO-tolerant fuelcell systems.Membrane costs need to be reduced, and there is scopefor developing new types of membranes. Membranesrequiring less or no humidification would make thesystem simpler, lighter and cheaper. Low-cost non-fluorinatedmembranes, for instance, offer the potential toachieve the target operating life of 2,000 hours for fuelcells in portable applications.The need to increase the operating life of fuel cells is notconfined to portable units. R&D in this area concentrateson membrane materials, catalyst stability and the choiceof optimal operating conditions.DMFCsThe need to reduce the platinum loading of catalysts isespecially important for DMFCs. Today's figures of 4 mgPt/cm 3 and 0.05 W/cm 3 result in a platinum cost aloneof €1,600 per kW of capacity.The activity of anode catalysts must increase, and themethanol sensitivity of cathode catalysts must bereduced in order to exclude mix potential formation ofthe oxygen reduction and the methanol oxidation.Methanol crossover from one side of the membrane tothe other reduces the efficiency of the system. Newmembranes with low methanol crossover need to bedeveloped, although it is already possible to circumventthe problem by varying the methanol injection ratedepending on the load.Water management presents serious problems inDMFCs. The system could be simplified. Membranesshould be developed which allow e.g. a water recyclingthrough the membrane from the cathode to the anodeside in order to simplify the system. The development ofa passive system is a main target.Concerns have also been expressed about the toxicity ofmethanol as a fuel. This has prompted some developmentwork on direct ethanol fuel cells.H 2 -PEMFCs and DMFCsH 2 -PEMFCs and DMFCs require the development of catalystswith high activity at ambient temperatures, becausehigh temperatures are not an option for most deviceintegratedfuel cells.System development is very important, with greaterfunctional integration used for reducing system complexity.Components such as mass flow controllers,sensors, pumps, blowers, gas/liquid separators, watermanagement systems, temperature controllers and low-
Risø Energy Report 3Hydrogen in portable devices 515.5cost power conditioners need to be further developed,and miniaturised for portable applications.The “manufacturability” of fuel cells needs to beimproved, especially with regard to sealing methods.The traditional bipolar construction of fuel cells creates ageometric form that is often inconvenient for deviceintegration. Alternative designs such as monopolar cellsor serially-connected cells in a planar configuration aretherefore being developed.FuelsFuel supply for fuel cells is a problem generally, but especiallyso for portable applications. The state of the art forportable units is to use cartridges containing hydrogen,as metal hydrides or compressed gas, or methanol. Ineach case the cartridges must be certified as safe undercurrent chemical and transport regulations.Intensive scientific effort is needed to develop existinghydride storage systems and discover new ones. Fuelcartridges for small portable applications may beregarded as disposable, so reversible storage is not absolutelynecessary.To extend the operating times of high-power portablefuel cells, compact reformers with simple gas purificationsystems are needed to run on a wide variety of fuels,including propane, butane and methanol.ConclusionsFuel cells for portable devices is becoming a niche, highvaluemarket area which has good opportunities for a fastintroduction of fuel cell technology and the firstconsumer products in the electronic market can beexpected within the coming year and is believed to growrapidly thereafter. Danish industry is involved in thedevelopment of SOFC, PEMFC and DMFC fuel cells andthe industry has in particular a strong position in systemcomponents and complete systems. This gives goodopportunities for Danish companies for developing newproducts like for instance UPS, APU's and other portabledevices. When combining the industry with theexpertise existing in the Danish research institutes andUniversities, it will be able to meet some of the R&D tasksmentioned above, which will give the industry a competitiveedge.An important area for Danish Industry is system integration,where fuel cells and hydrogen technologies areimplemented in electrical powered products. This is anarea which is particular suited for small and mediumsized enterprises and for start-ups. One example is in themedical sector – electrical wheelchairs with fuel cell technologyas replacement for batteries giving longer drivingrange and faster re-charging. System integration is anarea where Danish industry traditionally has a strongposition and where innovative new applications of fuelcell technology can lead to new products.
52Risø Energy Report 3Hydrogen infrastructure5.6Hydrogen infrastructureLARS HENRIK NIELSEN AND HANS LARSEN, RISØ NATIONAL LABORATORY; JAN JENSEN, DANISH GAS TECHNOLOGY CENTRE; AKSEL HAUGE PETER-SEN, DONG.Introduction“Hydrogen infrastructure” refers to the physical linksbetween sites where hydrogen is produced and where itis consumed. Infrastructure includes long-distancepipelines, transport by road, rail and water, largehydrogen storage facilities and filling stations.Hydrogen as an energy carrier has the potential toreplace almost all of the fuels in use today. Largedemands for hydrogen are expected to emerge first in thetransport sector, especially in road transport. Significantdemand may also emerge in areas such as portable electronics,portable generators and uninterruptible powersupplies (UPSs). Small-scale distributed CHP based onfuel cells may become a new source, as well as a user, ofhydrogen.Geographically these demands are dispersed. The infrastructureoptions may though be different according tothe type, scale and quality requirements of the particulardemands, and according to the specific hydrogen supplyoptions. Generally, the supply side options may be bothcentralised large-scale and distributed or smaller-scalesolutions.This chapter describes the options for developinghydrogen supply infrastructures for road transport andother emerging technology areas. A central issue is theneed for strategies to create hydrogen infrastructuresthat can grow gradually as demand increases. Hydrogenvehicles are expected to enter the market in 15-20 years.Drivers and visionsAn important driver for the introduction of hydrogen inthe transport sector is serious concern about air pollutionfrom road transport, especially in cities, and the healthproblems this generates. Direct hydrogen vehicles offer asolution, since hydrogen fuel cells produce virtually noemissions apart from water.Another driver of growing importance is the security offuture energy supplies for transport. At present thissector relies almost solely on oil. Hydrogen can beproduced from virtually any energy resource, and thus isa good way to diversify energy production and increasesecurity of supply.But the hydrogen vision goes beyond transport.Hydrogen technology may penetrate into almost anyenergy cycle applied in society and provide sustainability,diversity, high efficiency and flexibility. Futureenergy supply systems based on hydrogen as an energycarrier could be configured for combined production ofelectricity, heat and hydrogen as a transport fuel. SuchFigure 30: Hydrogen infrastructure. Solar cellsTransducerTransformerWaterChange-over switchElectrolysisAuxiliary powerLocal networkLarge powersupplynetworkO 2O 2H 2H 2StorageStorageFuel cell bus
Risø Energy Report 3Hydrogen infrastructure 535.6systems can achieve very high overall efficiencies, anddue to the modular nature of fuel cell technologies theycan be configured to be distributed, centralised oranywhere in between.Robust hydrogen supply infrastructure solutions for roadtransport are needed urgently. Prototype hydrogenbasedfuel cell vehicles are already being tested anddemonstrated in Europe, Japan and the USA, and somemajor automotive manufacturers have announced thatthey will market fuel cell vehicles already by 2005.Large numbers of hydrogen vehicles, however, are notexpected before 2015-20. Considerable efforts are beingmade to develop infrastructure solutions to supportthese vehicles, both through national R&D and demonstrationprogrammes and by the car industry. Theaccelerating development of hydrogen vehicles brings anurgent need for common codes, standards and regulations.Filling stations for pressurised hydrogen gas are expectedto be an essential part of an initial infrastructure.Hydrogen stored as a compressed gas at up to 700 baralready gives today's vehicles a range comparable to thatof conventional vehicles, whereas infrastructures tosupport liquid hydrogen, metal hydride and otherstorage methods are not seen as viable at the moment.Road maps presenting the shorter-term aims and strategiesfor introduction of hydrogen for transport generallyagree on the steps towards an extended hydrogen infrastructure.First, hydrogen filling stations will be built inlarge cities to supply bus fleets and other vehicles inregular operation within a limited area. A single fillingstation in a densely-populated area can serve a largenumber of users and maximize the environmental andhealth benefits of hydrogen. This is an optimal way toincrease public awareness and acceptance of hydrogentechnology.Step two is to build filling stations on major roadslinking cities and large towns that already have theirown hydrogen filling stations. This allows existing fleetsof hydrogen vehicles to increase their range, and willhelp to increase the size of the hydrogen vehicle market.Hydrogen infrastructure and future supplyoptionsThe relevant hydrogen production options to supply thenetwork of filling stations much depend on the local orregional conditions. In an initial stage the hydrogenproduction and supply may take advantage of theexisting infrastructure for electricity and natural gas.Via electrolytic production hydrogen may be generatedand supplied at almost any location. The modularity ofthe electrolysis technologies means that both large andsmall-scale plants may be relevant. The individualhydrogen filling stations may be equipped with electrolysisunits, e.g. for high-pressure electrolysis, compressorand storage facilities, and dispensers for high-pressurehydrogen. Even very small-scale residential dispenserunits may be a future option based on electrolysis.Producing hydrogen via electrolysis means that attributesof the power production system in question e.g.primary energy inputs and CO 2 characteristics, partly aretransmitted to the transport sector. Fuel flexibility andsystem development options for the overall powersystem become options for transport as well.Where natural gas is available, reforming is anothersupply option for hydrogen. Reformer plants could besituated near, or in, hydrogen filling stations. Economiesof scale, however, may favour larger reformer plants,which in turn would require local pipelines to supply thefilling stations.Beyond the very initial stages of a hydrogen supplyinfrastructure build-up another option may be todistribute hydrogen mixed into the NG-grid in quantitiesup to about 15% volume, depending on pipelinematerial, pipeline pressure and end user technology.Hydrogen supplied from numerous sources may bedistributed via mixed gas grid lines.Hydrogen filling stations would be able to separate thehydrogen from the natural gas, purify and pressurise itfor use in vehicles. Most other users would simply be ableto burn the natural gas/hydrogen mixture without problems.The only difficulties would be with internalcombustion engines running on natural gas. Denmarkhas many such engines in small CHP stations, and it hasbeen shown that hydrogen levels above 1-2% in the gascan cause operational problems or reduced output. Newengines developed for natural gas/hydrogen blendsshould not suffer from these problems.Various other factors also limit the proportion ofhydrogen than can be added to natural gas pipelines. Theneed to preserve the combustion quality of the gas(Wobbe index) would limit the hydrogen content to 25%by volume, while restrictions on density would allow amaximum of 17% hydrogen. The most stringent limit isset by leakage and material compatibility. Above about15% hydrogen, problems of leakage, corrosion, degradationof polyethylene pipe and embrittlement of steels areexpected . Tests and analyses of using the Danish NGgridfor transporting medium-pressure pure hydrogenhas been carried out during 2003 . Results of this testcarried out during one year indicate that materialchanges may take place in the 4 bar distribution grid.Leakage measurements show that connections and sealingsmust be checked more frequently than for naturalgas.The energy content of hydrogen is only around onethirdthat of the same volume of natural gas. As a consequence,pipelines and underground storage caverns forhydrogen would have to be three times the size of theirnatural gas equivalents, at the same pressure, to coverthe same energy demand. For safety reasons, hydrogenpipelines will also operate at lower pressures than natural
54Risø Energy Report 3Hydrogen infrastructure5.6gas pipelines (Chapter 6.2). Add in the fact thathydrogen is more demanding than natural gas in termsof materials of construction, and it is clear that pipelinesfor pure hydrogen will be more expensive than fornatural gas.Storage of gaseous hydrogen at high pressures is wellknowntechnology (Chapter 5.2). Hydrogen fillingstations would require pressurised storage tanks holdinghydrogen equivalent to roughly one day's sales. On amuch larger scale, hydrogen can be stored undergroundin aquifers and cavities, in the same way as natural gas.Current hydrogen use and infrastructureCurrent world hydrogen production represents less than1% of world energy production, or 73 Mtoe (2001) .The industrial gas companies currently supply hydrogenfor refineries and the industry in general as well as forspace flight and hydrogen vehicle demonstrations .With 50 large hydrogen plants and 2,500 km of pipelinecarrying high-purity hydrogen in the USA and Europe,the gas companies have expertise covering the entirehydrogen chain from production to industrial consumers.Current hydrogen storage facilities include small- andmedium-scale storage of liquid and gaseous hydrogen inindustry, large-scale underground storage of gaseoushydrogen, and large-scale liquid hydrogen storage byNASA in the USA.Hydrogen infrastructure can evolve gradually with conversionand production technologies, since most of theinfrastructure developed for fossil-fuel-based hydrogenwill also work with hydrogen from renewable andnuclear sources. Infrastructure development will beginwith pilot projects and expand to local, regional, andultimately national and international projects. The maininfrastructure investment period is expected to be 2015-2035 .Hydrogen infrastructure and demonstrationinitiatives in the USA, Japan and Europe The USA has recently been an outspoken advocate of thetransition to hydrogen as a replacement for fossil fuelson the grounds of energy security and the environment.The US government has pledged $1.7 billion over thenext five years to develop hydrogen-powered fuel cells,hydrogen infrastructure and advanced automotive technologies.The US hydrogen vision envisages a transportsystem powered by hydrogen derived from a variety ofdomestic sources, as well as stationary fuel cell applications.Japan's hydrogen effort focuses on R&D to commercialiseand popularise fuel cells, fuel cell vehicles andhydrogen infrastructure. The Japanese government hasset ambitious targets for the penetration of hydrogenfuel cells, including 50,000 hydrogen vehicles by 2010, 5million vehicles by 2020 and 15 million vehicles by2030. The 2030 target also includes a nationwidehydrogen infrastructure with 8,500 filling stations. Aprogramme covering 2003-2007 with a budget of about¥31 billion (€230 million) has been planned.EU countries are among the most active worldwide indeveloping the technologies and concepts that wouldunderlie the transition to a hydrogen economy. The EUis seeking to promote greater co-operation, pooling ofresources and harmonisation of efforts in this area, withthe goals of reducing the negative environmental effectsof energy use and improving the security of energysupply. The EU's long-term vision is to have an energysupply system based on renewable energy and fuel cellsin place within 20-30 years, with hydrogen and electricityas prominent energy carriers.In 2002 the European Commission established a HighLevel Group on Hydrogen and Fuel Cells (HLG),involving European stakeholders. The HLG aims to facilitatehigh-level strategic discussions for developing aEuropean consensus on the introduction of hydrogenenergy. In January 2004 the Commission launched theEuropean Hydrogen and Fuel Cells Technology Platform.A third European initiative, a network called HyNet (theEuropean Hydrogen Energy Thematic Network), was setup in 1999 by about 40 leading companies from a broadspectrum of industries and technologies. In May 2004HyNet published a European Hydrogen Roadmap as partof the EU-funded HyWays project.Other European hydrogen projects are CUTE andECTOS, which will develop and operate 30 Daimler-Chrysler Citaro fuel cell buses in ten European citiesfrom 2003 onwards, with pressurised hydrogen as fuel.The EU has contributed €21 million to the projects.Germany has been at the forefront of hydrogen fuel celltechnology development and implementation worldwide,with various federal and numerous regional initiatives.There has been strong co-operation between publicand private enterprises, with involvement from Daimler-Chrysler, Opel, Ford, BMW and Ballard Power Systemsamong others. Particularly well known is the NEBUSpassenger bus demonstration project. Another is thehydrogen service station at Munich airport. Furthermorean interesting initiative is the public/private TransportEnergy Strategy (TES), which supports R&D onhydrogen, methanol and natural gas as alternative fuels.Total public finance for hydrogen in Germany is approximately€100 million a year.The government of Iceland has the vision to create theworld's first hydrogen economy. Because most of thecountry's energy is derived from renewable (>70%) andenvironment-friendly sources, the initial focus ofIceland's efforts is the transport sector. The plan to createa hydrogen economy involves co-operative R&Dthrough various public/private partnerships. The mostsignificant, Icelandic New Energy (INE), was establishedas a joint venture to promote the use of hydrogen as atransport fuel. INE's main work is demonstration projectsfor buses, cars and fishing vessels. A demonstration
Risø Energy Report 3Hydrogen infrastructure 555.6project for passenger buses is already in progress (theECTOS project, 2001-2005).The long-term vision for a hydrogen infrastructureThe long-term vision is energy systems that are highlydiversified, robust, environmentally benign and affordable.Fuel cells and electrolysers or reversible fuels cells,plus hydrogen grids and storage systems, are likely to bekey technologies for balancing electricity grids.Hydrogen has the potential for being a link between thetransport sector and the heat and power sectors. The flexibilityof such system configurations can compensate forfluctuating power inputs, such as from wind power andsolar cells, and thus promote the use of renewable energyfor transport, heating and electricity.Barriers to this vision include the need to improve theperformance of hydrogen and hydrogen-related technologiesto the point where they can compete ineconomic terms with existing energy technologies. Inparticular, this means improving the performance of fuelcells and mobile hydrogen storage technologies. Thevision for getting started would involve the transportsector in particular and the build-up of a limited numberof filling stations primarily for serving car fleets liketaxies and buses in urban areas. In following stages ofbuilding up a hydrogen infrastructure, pipelines withhydrogen or natural gas mixed with hydrogen may bemade available e.g. to selected blocks with flats andpublic buildings like schools, hospitals etc. According to the share of hydrogen as a vehicle fuel in Europewould be 2% by 2015 and 5% by 2020, and this woulddemand 10000 hydrogen filling stations in 2020. Thetechnology to produce hydrogen from on site SMR(Steam Methane Reforming) is ready. The same appliesfor electrolytic hydrogen production.The vision for the next 20-40 years is to make hydrogenfully competitive with conventional energy sources forboth vehicles and individual dwellings. This will requireextensive hydrogen distribution grids and a densenetwork of urban filling stations.
Risø Energy Report 3Hydrogen - Environmental and safety aspects 576Hydrogen – Environmental and safetyaspectsOn the face of it hydrogen seems to have low impact onthe environment, but there are a number of uncertaintiesconcerning the consequences of a large-scale shifttowards a hydrogen economy.Likewise hydrogen is probably no more hazardous thanconventional fuels, but because of the many propertiesthat make hydrogen distinct from conventional fuels, itis necessary to deal with the risk assessments for all theelements in the use and supply chain of hydrogen.These fields are discussed in this chapter.
58Risø Energy Report 3Hydrogen and the environment6.1Hydrogen and the environmentMARTIN SCHULTZ, MAX-PLANCK-INSTITUT FÜR METEOROLOGIE, GERMANY; FRANK MARKERT AND KIM PILEGAARD, RISØ NATIONAL LABORATORYIntroductionHydrogen (H 2 ) is widely regarded as a key component infuture energy systems because it is a sustainable, clean,and transportable energy carrier. It can be generatedfrom pure water, and burned to produce nothing butwater. Thus if hydrogen generated using clean andsustainable processes replaces fossil fuels as our mainenergy carrier, we will have significantly lower emissionsof greenhouse gases, especially carbon dioxide (CO 2 ),and air pollutants, notably nitrogen oxides and volatileorganic compounds.This view is somewhat idealistic, however, as the technologyfor the clean and sustainable production ofhydrogen is still in the pioneering phase. A great deal ofeffort will have to be made to build up sufficienthydrogen production capacity from sustainable energysources such as wind power and solar cells.The production and distribution of hydrogen inevitablyinvolves energy losses. If the energy source is a fossil fuel,the energy losses and pollution involved in producingand distributing hydrogen may turn out to be greaterthan those from direct use of the fuel via conventionaltechnology. When considering the use of hydrogen inany application, it is therefore important to check theoverall environmental balance and to compare this withalternatives such as the direct use of electricity fromwindmills or solar cells.Initially at least, the production of hydrogen as describedin Chapter 5.1 will be based largely on the chemicalconversion of fossil fuels such as natural gas and coal.Such processes generate carbon dioxide emissions whichmay exceed those from the direct use of the fossil fuel inan internal combustion engine. When hydrogen isproduced at a large centralised plant, however, it may bepossible to capture the carbon dioxide and end up witha net reduction in greenhouse gas emissions. In terms ofother air pollutants, reforming would almost certainly bepreferable to the present situation.The use of hydrogen as such is regarded as sustainableand would improve air quality in urban areas. Nevertheless,it is important to assess the overall impact ofhydrogen on the environment. The environment is acomplex, highly coupled, non-linear system which mayreact in unforeseen ways to changes in the status quo.Emissions of man-made compounds including CFCs,which destroy ozone and act as greenhouse gases, otherhalogenated compounds and of course carbon dioxidehave already caused environmental problems. We do notwant to repeat the same mistakes with hydrogen.This chapter gives an overview, based on the scientificliterature, of current knowledge of the consequences ofhydrogen in the soil and in the atmosphere.Sources, sinks and concentrations ofatmospheric hydrogenThe (incomplete) combustion of fossil fuel and biomassin boilers and internal combustion engines generateshydrogen along with carbon monoxide and carbondioxide. At present, this source accounts for about 40%of all the hydrogen released into the atmosphere.Another important source, accounting for an estimated50% of atmospheric hydrogen emissions, is the atmosphericphotochemical oxidation of methane (CH 4 ) andnon-methane hydrocarbons (NMHCs). Emissions fromvolcanoes, oceans and nitrogen-fixing legumes accountfor the remaining 10% [10,4]. These estimates are stillvery uncertain.Movement of hydrogen into the upper atmosphere andthen to space is negligible in terms of the global hydrogenbudget. Instead, hydrogen is removed from theatmosphere largely through dry deposition at the surfaceand subsequent microbiological uptake in soils. The rateof uptake depends on microbial activity, soil texture andmoisture content. This sink is largest in the northernhemisphere because of its larger landmass, and it isthought to account for about 75% of all hydrogenremoval.The remaining 25% of hydrogen is removed throughoxidation by hydroxyl free radicals (OH) in the atmosphere:(R1)(R2)H 2 + OH → H + H 2 OH + O 2 + M → HO 2 + MThe hydrogen peroxy radical (HO 2 ) produced in reaction(R2) continues to react with nitrogen oxide (NO), a keystep in photochemical ozone formation (see R6 below),or it reacts with itself or other peroxy radicals, therebyterminating the photochemical oxidation chain.Hydroxyl radicals are also the main initiating reactant inthe atmospheric degradation of volatile organic compounds(VOCs), greenhouse gases such as methane(CH 4 ), and carbon monoxide:(R3) CO + OH + O 2 → HO 2 + CO 2Hydroxyl radicals are produced mainly through thephotolysis of an ozone molecule (O 3 ) to produce anoxygen molecule (O 2 ) and an electronically excited“singlet” oxygen atom (O), which then reacts with a
Risø Energy Report 3Hydrogen and the environment 596.1molecule of water vapour (H 2 O) to produce twohydroxyl radicals:(R4)(R5)O 3 + hν →O 2 + OO + H 2 O → 2 OHOzone is produced mainly by the photolysis of nitrogendioxide to yield low-energy triplet oxygen atoms (O( 3 P)),which then react with oxygen to produce ozone:(R6) NO + HO 2 → OH + NO 2(R7) NO 2 + hν →NO+O( 3 P)(R8) O( 3 P) + O 2 + M → O 3 + M“hν” denotes a photon of ultraviolet light. Ozone in thetroposphere is also an important component of summersmog.These atmospheric reactions, which are closely linked,are important because they determine the capacity of theatmosphere to neutralise pollutants. The concentrationof hydroxyl radicals is particularly important, since it isthese radicals that begin the whole oxidative degradationprocess, and the reactions involved (R1 and R3) arethe slowest in the whole sequence. More hydrogen in theatmosphere will tend to lower the concentration ofhydroxyl radicals and so inhibit the capacity of theatmosphere to oxidise greenhouse gases and other pollutants.On the other hand, in a hydrogen economy, emissionsof other compounds (e.g. CO, NMHC, and NO x ),which affect the hydroxyl radical concentration moreeffectively, will be reduced. The resulting effect isdiscussed in more detail below (section on oxidizingcapacity).Measurements from ground stations, balloons andresearch aircrafts typically find about 0.5 ppmv (parts permillion by volume) of hydrogen in the troposphere (thepart of the atmosphere extending from the earth'ssurface up to about 10 km), and 0.4-0.5 ppmv in thestratosphere (10-60 km altitude) . No significant trendcan be deduced from observations made after 1990,although earlier observations did indicate a positivetrend.The tropospheric hydrogen concentration exhibits aclear yearly cycle. In the northern hemisphere the amplitudeof the variation is 0.04-0.08 ppmv, with a maximumin the spring. In the southern hemisphere the amplitudeis 0.02-0.04 ppmv, with a maximum during summer inthe northern hemisphere. These seasonal variations arecaused largely by the build-up of CH 4 and NMHC in thewinter, followed by increased oxidation rates in thesummer. Seasonal variations in the rate of dry depositionmay also contribute to the cycle.Estimates of future emissionsThe future environmental consequences of a large-scalehydrogen economy will depend on how much hydrogenwe use, how it is produced, how fast our use increases,the amount of fossil fuel emissions that can be saved,and the steps we take to control hydrogen emissions. Thepresent atmospheric hydrogen concentration of 0.5ppmv implies a total mass of about 175 million tonnes ofhydrogen, of which around 20% is thought to be fromthe combustion of fossil fuels.There has been considerable recent controversy in thescientific literature over how much hydrogen a globalscalehydrogen economy would release into the atmosphere.Estimates range from less than 0.1% of hydrogenconsumption, for tightly-controlled industrial applications,to 10-20% for evaporation from liquid hydrogentanks in poorly-designed automobiles. 3% would be amore realistic upper limit, however, simply becausehigher leakage rates would be neither economic nor safe.Assuming the complete replacement of today's energysystem with a hydrogen chain, about 1400-1800 milliontons H 2 /year would be required. 8 Correcting for thepresent emissions of 42-54 million tons H 2 /year andFigure 31: Sources and sinks for hydrogen inCH 4 VOC40H 219reaction with OHthe atmosphere (million tonnes/year). Thenumbers are uncertain, especially for trafficand industry emissions (±10 million1615Biomassburning656tonnes/year) and soil deposition (±15 milliontonnes/year).TrafficindustrySoil uptakeSoils, ocean8. Energy consumption 2001 = 404·10 18 J (EIA, 2003), energy density of hydrogen = 1.2·10 8 J/kg. Thus, an upper limit for the 1:1 replacement oftoday's energy demand would be given by 3340 million ton/year. However, one must factor in the efficiency gain when replacing an old technologywith a new one (e.g. factor 2 for fuel cells over internal combustion engines), and conversion efficiency changes (e.g. coal to electricity versus steamreformation for hydrogen production). The value of 1400-1800 million ton/year given in the text is a conservative estimate based on different sources.
60Risø Energy Report 3Hydrogen and the environment6.1assuming a 3% loss of 42-54 million tons H 2 /year the H 2emissions would increase by 17-49 million tons H 2 /year(or 22%-64%), it is worthwhile to note that lower leakrates than 3% could even lead to a net reduction ofhydrogen emissions.Of course, a simple 1:1 replacement scenario of thepresent-day energy demand is overly simplistic, andconsiderable future efforts are needed to develop morereliable emission scenarios for hydrogen applications.Our view is that these hydrogen emissions are probablymuch less important than the overall atmospheric emissionsof CO 2 , CO, and NOx from reformers and otherhydrogen plants, and emissions of these gases will bereduced as conventional technologies are replaced bytheir hydrogen equivalents . Of particular interesthere are emissions of carbon dioxide and NO x . Carbondioxide is important because it is the biggest contributorto climate change. NOx levels drive the oxidisingcapacity of the atmosphere (essentially the OH concentration),and so regulate the lifetime of the greenhousegas methane, and they control the amount of photochemicalozone formed in the troposphere. Table 13 listscurrent estimates of NO x sources .Table 13: Global tropospheric NO x emissions estimates for 2000 .NO x sourceFossil fuel combustion 30-36Aircraft 0.5-0.8Biomass combustion 4-12Soils 4-7Ammonia oxidation 0.5-3.0Lightning 2-12Transport from the stratosphere
Risø Energy Report 3Hydrogen and the environment 616.1Temperature change (K)0,0-0,5-1,0Our estimateTromp et alassumption0-5-10-15-20O 2 depletion (%)Figure 32: Relative temperature changes in the lower stratosphere at74°N (solid line) and the resulting maximum ozone depletion in thenorthern polar vortex (dashed line) as a function of increased atmospherichydrogen concentrations relative to the today's actual hydrogenconcentration of about 0.5 ppmv. The cause of the temperature changeis the stratospheric water vapour resulting from the oxidation of hydrogen.The graph is taken from Tromp et al. , with additions.-1,5123 4 5H 2 Increase (fold)6-257OH concentration has probably remained stable in about10% over this time.Significant future changes in either NO x or carbonmonoxide emissions could have a much larger effect onOH levels. Such changes could happen in a hydrogeneconomy, but equally they could happen in a world offossil fuels as a result of tightening emission controls.More research is clearly needed to produce reliable estimatesbased on probable emission scenarios.2. Changes in atmospheric water vapourThe oxidation of hydrogen produces water vapour,which could have different consequences depending onwhere in the atmosphere it is released. One recent articlesuggests that increasing atmospheric hydrogen concentrationsby a factor of four would increase the amount ofwater vapour in the stratosphere by up to 30% .According to these researchers, this could decrease thelower stratospheric temperature at the polar vortex byabout 0.2°C, which in turn could trigger additional polarozone losses of up to 8% (polar ozone depletion is verysensitive to small temperature changes ). Anothermodel, however, showed a much weaker effect on stratospherictemperatures and ozone loss .As discussed above, hydrogen levels are more likely toincrease by 20% than by 400% in the coming decades.Even when we use the more pessimistic model , theconsequences for stratospheric temperatures and ozoneconcentrations therefore are expected to be negligible(Figure 32).Increased water vapour concentrations in the uppertroposphere can be expected if air traffic increases asprojected, especially if aircrafts begin to use hydrogen asfuel. At these altitudes, increased water vapour maycause cirrus clouds to form. This would increase ordecrease heat radiation, depending on the height andthickness of the cloud, and might lead to either coolingor warming of the atmosphere.It is difficult to establish reliable estimates of the potentialwater vapour release from aircrafts, and even harderto model the effects of extra water vapour on this highlysensitiveregion of the atmosphere. Emissions dependstrongly on engine design, and the effects will be verydifferent depending on the altitude, air temperature,exhaust temperature and background humidity.If hydrogen combustion engines were used widely inaircrafts, another source of concern could be emissions ofNO x . Even under present-day conditions, NO x emissionsare believed to significantly perturb the amount of ozonein the upper troposphere . These processes in theupper troposphere and lower stratosphere region are stillthe subject of much research, and more measurementsand better models are needed to assess them reliably.3. Soil uptakeThe uptake of atmospheric hydrogen by soil microorganismsor organic remnants is associated with largeuncertainties. Studies using isotopically-labelled hydrogensuggest that soil uptake provides about 75% of thetotal hydrogen sink, but there is a large margin of error.Little is known about the detailed processes by whichhydrogen is absorbed in the soil.At the moment there is no sign that the process ofhydrogen uptake in the soil is becoming saturated.Increased fossil fuel combustion has presumablyincreased atmospheric hydrogen concentrations significantlyin the last century, but there has been nodetectable increase since 1990. If hydrogen uptake in thesoil were becoming saturated, we would expect theconcentration of hydrogen in the atmosphere to haveincreased, even if hydroxyl radical concentration wereincreasing as well.Since we do not expect the amount of hydrogen releasedto change very significantly in the next few decades, wecurrently have no reason to expect serious consequencesfrom changes in the soil uptake rate. This is rather speculative,however, and further research is urgentlyrequired.
62Risø Energy Report 3Hydrogen and the environment6.14. Carbon dioxide emissionsIn a recent study, today's surface traffic fuels wereassumed to be replaced by hydrogen generated fromrenewable sources leading to a 20% CO 2 emission reduction. However, as long as hydrogen is generatedfrom fossil fuels, CO 2 emissions from reforming caneasily rival today's emissions from power plants andtraffic. From the standpoint of avoiding CO 2 emissionsin the short to medium term, centralized facilities appearpreferable, because this might allow efficient capturingand storing of the CO 2 produced. 9 In the long term, it isobvious that hydrogen generation has to be based onrenewable sources to avoid the environmentally adverseeffects of carbon dioxide.5. Air quality effectsProbably the most immediate implication of a large-scaleshift to hydrogen, especially in road transport, would bea significant drop in emissions of air pollutants (NO x ,benzene and other VOCs) and an associated decrease inground-level ozone concentrations.In most regions of the world, ozone formation is limitedby the amount of NO x in the atmosphere. However,many big cities emit such large amounts of NO x thatozone formation is limited instead by the availability ofVOCs and carbon monoxide, which are produced byplants and soil bacteria as well as vehicles and industrialprocesses.As a result, it is well known that lowering emission levelscan actually increase ozone concentrations at first; onlyif the reduction is large enough will ozone concentrationsdecrease. This effect probably lies behind observationsthat though emissions of ozone precursors havedecreased significantly in Europe over the past decade orso , summertime surface ozone concentrations haveremained stable. All this means that the reduction ofNO x and VOC emissions following the introduction ofhydrogen vehicles could initially increase ozone levels insome areas. However, the reduced NO x and VOCconcentrations will bring their own health benefits, andozone levels downwind of the city will decrease. As aresult, the damaging effects of ozone on crops andnatural ecosystems will be reduced.Simulations also show the positive trend for the airquality that drastic cuts in NO x emissions are especiallyeffective in reducing peak ozone concentrations and thenumber of days on which air quality standards areexceeded .Thus there is little reason to doubt that the widespreaduse of hydrogen should bring significant improvementsof air quality. This would only be untrue if coal-firedpower stations with little emission control were used toproduce the hydrogen (in particular in developing countries,e.g. China). In this case NO x emissions might actuallyincrease compared to today, with a further rise intropospheric ozone concentrations.ConclusionsWhile there are still large uncertainties about the currentbudget of atmospheric hydrogen and the consequencesof a large-scale shift towards a hydrogen economy,present knowledge indicates that there are no majorenvironmental risks associated with this energy carrier,and that it bears great potential for reducing air pollutionworld wide, provided that the following rules arefollowed:• Hydrogen should not be produced using electricitygenerated by burning fossil fuels. Instead, natural gasor coal reformers should be used at first, and replacedby renewable energy sources as soon as possible. CO 2capture from reformers should be seriously considered.• Hydrogen should be used predominantly on theground rather than in aircrafts, and to achieve fullbenefits, fuel cells would be preferable against internalcombustion engines.• Leakage in the hydrogen energy chain should belimited to 1% wherever feasible, and global averageleakage should not exceed 3%.Atmospheric hydrogen concentrations should be carefullymonitored. Enough research should be carried outto obtain a better understanding of hydrogen sourcesand sinks, and to provide an early warning system in casewe have overlooked something.9. Using electricity from coal fired power plants, for example, could increase CO 2 emissions by a factor of 2-4. But, as long as efficient technology isemployed we would not expect significant change in CO 2 emissions in the coming decades.
Risø Energy Report 3Hydrogen safety 636.2Hydrogen safetyNIJS JAN DUIJM, RISØ NATIONAL LABORATORY; LIONEL PERETTE, INERISSafety issues of hydrogen as an energycarrierHydrogen's extreme flammability implies safetyconcerns with its introduction as an energy carrier, especiallyin mobile applications such as cars. Many peoplerelate the hazards of hydrogen to the Hindenburg accident,but a more realistic scenario would be the accidentthat happened in Stockholm in 1983 (see box). Wouldthe intensive use of hydrogen by consumers result inmore, and more serious, accidents than the one in Stockholm?On Thursday 3 March 1983 a truck was delivering various industrialgases to sites in the Stockholm area. As a rack of argon gas cylinderswas being unloaded, hydrogen escaped from a rack of 18interconnected cylinders; each had a volume of 50 l and a workingpressure of 200 bar. Recent analysis estimates that the resultingexplosion involved about 4.5 kg of hydrogen. It injured 16 people,heavily damaged the facade of the nearest building, damaged tenvehicles and broke windows within a radius of 90 m .Hydrogen has some properties that make it moredangerous than conventional fuels such as gasoline, LPG(liquefied petroleum gas) and natural gas. Hydrogen'slower flammability limit in air is higher than that of LPGor gasoline, but its flammable range is very large (4-75%hydrogen in air). In the concentration range of 15-45%,the ignition energy of hydrogen is one-tenth than that ofgasoline. The “quenching gap” the smallest holethrough which a flame can propagate – is considerablysmaller for hydrogen than for the other fuels, whichmeans that the requirements for flame arrestors andsimilar equipment must be higher.Hydrogen has a number of other properties that mightcause hazardous situations if not properly accounted for,such as:• hydrogen is a strong reducing agent, and in contactwith metal oxides (rust) the resulting reaction canproduce heat;• hydrogen damages or is otherwise unsuitable for usewith many materials conventionally used for vessels,pipelines and fittings;• in contrast to other compressed gases, lowering thepressure of hydrogen increases its temperature (in engineeringterms, hydrogen has a negative Joule-Thomsoncoefficient at ambient temperature). When hydrogen isreleased from a high-pressure vessel, the resultingincrease in temperature can contribute to ignition;• hydrogen forms explosive mixtures with many othergases, including chlorine and other halogens;• hydrogen diffuses easily through many conventionalmaterials used for pipelines and vessels, and throughgaps that are small enough to seal other gases safely;and• the safety literature suggests that releases of hydrogenare more likely to cause explosions than releases ofmethane [2,3].In contrast to LPG and gasoline vapour, hydrogen isextremely light and rises rapidly in air. In the open thisis generally an advantage, but it can be dangerous inbuildings that are not designed for hydrogen. Manycountries' building codes, for instance, require garages tohave ventilation openings near the ground to removegasoline vapour, but there is often no high-level ventilation.Hydrogen released in such a building collects atroof level, and the resulting explosion can be extremelydestructive.Hydrogen has been used widely and on a large scale formore than a hundred years in a variety of industrialapplications. Of course there have been incidents withhydrogen, as there have been with other hazardousmaterials including gasoline, LPG and natural gas. Ingeneral, though, experience shows that hydrogen can behandled safely in industrial applications as long as usersstick to the appropriate standards, regulations and bestpractices.But this experience does not cover the use of hydrogen atextremely high pressures (over 350 bar), as a cryogenicliquid and as hydrides – all technologies that are likely tobe required in a hydrogen economy. Most importantly,there is no precedent for the safe handling of hydrogenby people who have not received specific training to aprofessional standard. At present, hydrogen is handledin industries where operators receive training andinstructions concerning safety, and hydrogen installationsare subject to professional safety management andinspection by safety authorities. It will be a challenge todevelop technologies and systems that can be used bygeneral consumers, where similar dedication to safety ishard to enforce.Regulations and standardsRegulations and standards help to ensure sound andconsistent approaches to safety. They are thereforeimportant in promoting the safe use of hydrogen on awider scale.Regulations and standards have different purposes. Regulationsreflect legal constraints translated into safetyobjectives. They are set by governments, usually based
64Risø Energy Report 3Hydrogen safety6.2InternationalISOIECISO and IEC standardsEuropeFranceU.K.GermanyU.S.A.CanadaCENAFNOBSIDINANSISCCCENELECUTEBECVDEANSISCCNational contributionsEuropean standards (EN)National standardsstandards NF - BS - DIN,...standards NF-EN, BS-EN, DIN-EN,...standards NF-ISO, BS-ISO, DIN-ISO,...standards DIN/DKE-ICE, BS-ICE,...SupersedeVoluntary enforcementNF: Normes Françaises BS: British Standards DIN: Deutsches Institut für NormungFigure 33: Standards bodies at international, European and national levels.on European directives, to ensure the protection of citizens'health and fair trade. Regulations are mandatory.Standards set out the technical means by which safetyobjectives can be reached. They are built on consensusbetween companies in the industries concerned, andthey are voluntary. Standards reassure stakeholders andend-users that safety matters have been considered. Theyprovide a framework in which companies can carry outtechnical development, and companies can gain acommercial advantage by promoting the adoption oftheir own safety solutions as standards. Standardisationusually takes place at international or, for Europeancompanies, at European level.In emerging technologies, standards always precederegulations. Creating new regulations takes time andrequires considerable experience of the technology orproduct concerned. Poorly-drafted regulations can seriouslyhinder companies, but lack of regulations canequally be a problem for industry. Regulations help tomake the business environment more predictable;without regulations there is always a risk that subsequentlaws will force companies to abandon technologies orproducts in which they have already invested money. Forthis reason, companies and industry bodies actively pushgovernments to design new regulations.Hydrogen regulations and standards: who isdoing what?StandardsStandardisation work in hydrogen technologies is takingplace mainly at international level. The InternationalOrganization for Standardization (ISO) and the InternationalElectrotechnical Commission (IEC) are involved.International standards can eventually be converted intoEuropean standards, with or without modifications,which then supersede any national standards in Europe.At a European level, CENELEC (the European Committeefor Electrotechnical Standardization) deals with the samerange of subjects as the IEC, and CEN (the EuropeanCommittee for Standardization) covers a similar area tothat of ISO. National standardisation committees exist inIEC and ISO member countries. Figure 33 shows the relationshipsbetween ISO, IEC, CEN, CENELEC and variousnational organisations in Europe and north America.IEC concerns itself with standards related to electric andelectronic appliances. It therefore has a legitimate role instandards for fuel cells, including safety standards. IECTechnical Committee (TC) 105 is in charge of this work.More hydrogen-related subjects, including safety inhydrogen storage and distribution, are handled by ISOworking groups. ISO TC 197 has been at work in this areasince 1990. To avoid overlaps, information is exchangedbetween IEC and ISO, and TC 197 also has links to TC 22(road vehicles), TC 58 (gas cylinders) and other ISO TechnicalCommittees.Most of the work of ISO TC 197 is dedicated to mobileapplications. Canada, USA, and Germany are the mostactive countries in these working groups. IEC TC 105 hasalso been very active, even though it was established aslate as in 1998. So far, ISO standards have been publishedon product specifications for hydrogen as a fuel (ISO14687) and vehicle fuelling interfaces for liquidhydrogen (ISO 13984). Documents close to beingpublished by both IEC and ISO cover basic safety considerationsfor hydrogen systems, fuel cells and airportfuelling applications. Work in progress covers vehiclestorage for gaseous, liquid and hydride-absorbedhydrogen, fuelling systems and service stations,hydrogen generators and fuel cells. Safety is specificallyaddressed, for example in separate sections in the IECdocuments.At European level, CEN/CENELEC has created a technicalcommittee known as Fuel Cell Gas Appliances to
Risø Energy Report 3Hydrogen safety 656.2deal with domestic fuel cells with capacities of up to 70kW. This initiative follows demonstration projectsinvolving small fuel cell systems, where neither appropriateregulations nor standards exist.RegulationsEuropean directives (the Machinery Directive, ElectromagneticCompatibility Directive, Gas Appliance Directiveand others) apply to hydrogen systems whose manufacturersseek CE labelling. All these directives basicallycome down to risk assessment and safety features, andthey apply to all self-contained products and systems,including portable and stationary fuel cells andhydrogen generators. CE labelling is compulsory for anyproduct that is intended to be sold, rented or lent on theEuropean market.Large hydrogen plants such as steam methane reformersrely on the Major Hazards Directives and related nationalregulations.Other European directives apply to cars. Existing directivesdo not cover neither gaseous nor cryogenic storageof hydrogen in cars. As with compressed natural gas(CNG) and LPG vehicles in the past, discussions are nowtaking place in Geneva under control of the dedicatedworking group UNECE WP29 (United Nations EconomicCommission for Europe, Working Party 29). Currentwork is based on two draft documents for on-boardhydrogen storage (gaseous and liquid), submitted by theEuropean-funded European Integrated Hydrogen Project.(EIHP)Prospects for the safe use of hydrogen as anenergy carrierRecent and future work on regulations and standardsfocuses on the safe use of hydrogen by untrained people.These regulations and standards are based on:• experience learned from past incidents and accidents;• a scientific approach; and• public expectations.So far, experience with new hydrogen technologies isscarce and is usually subject to commercial secrecy. Standardsthat are drawn up too early might miss crucialsafety points. A substantial input from scientificresearchers is therefore required. This scientific processshould focus on:• the long-term effect of hydrogen on materials used forpiping, vessels and fittings under extreme conditionsof pressure or temperature;• requirements for equipment in potentially explosivehydrogen atmospheres;• requirements for ventilation in car parks, garages,tunnels and other enclosed areas;• the consequences of the diffusion of stored hydrogen,and ways to mitigate this;• the consequences of accidental releases from storageand distribution systems, and ways to mitigate these;• safety aspects of the behaviour of untrained consumersand their interaction with hydrogen technology, suchas refuelling and vehicle maintenance.The EIHP working group on safety concludes that overallhydrogen is no more hazardous, than conventional fuels. However, says this group, the many ways in whichhydrogen differs from conventional fuels make it necessaryto perform detailed risk assessments for every stagein the hydrogen supply chain. A general requirementwill be that hydrogen-based applications are always saferthan the corresponding applications using conventionalenergy carriers.Standards are based on consensus among companieswho may be more interested in the technological andeconomic aspects than the science of safety. There musttherefore be a dialog between standardisation workinggroups and safety experts, so that any doubts by thelatter can be expressed and dealt with.Safety was an integral activity of the EIHP , and thiswork will continue in a newly-created network of excellenceentitled HYSAFE (Safe Use of Hydrogen as anEnergy Carrier). HYSAFE brings together hydrogen safetyexperts from companies and research institutes acrossEurope, creating a meeting point for experts, standardsworking groups and national authorities. To promote itsscientific and risk-based approach, HYSAFE plans tocreate a wide range of experimental and numerical toolswhich it can then use to investigate the safety ofproposed standards.The European Hydrogen and Fuel Cell platform and itsdedicated working group on regulations and standardskeeps an overview of the development of standards andidentifies the need for new initiatives in this area.Conclusions and recommendationsThe international discussions now taking place will helpto ensure adequate safety in the new hydrogen technologies.Early attention to safety issues, yet with carenot to rush into premature technological pronouncements,and striving for international consensus all reinforcethe idea that safety should be an integral part ofhydrogen technology, and will help rather than hinderthe growth of the hydrogen economy.If these recommendations are followed there is no reasonto believe that hydrogen will be riskier than conventionalfuels. Accidents will happen, but careful planningwill provide an acceptable level of safety and ensure thataccidents such as the one in Stockholm remain rare.
Risø Energy Report 3Index 677IndexARGEMUC H2, 12ATR, 26BCC solid solution alloys, 35Carbon nanotubes, 33CEN, 64CENELEC, 64CEP, 11chemisorption, 33CHP plants, 40Clean Energy Partnership, 11CPO, 25, 26CUTE, 12, 54direct methanol fuel cells, 38, 47DMFCs, 38, 47, 48, 49, 50, 51DOE, 12, 13ICEs, 42IEA, 3, 13, 14IEC, 47, 64intermetallics, 34, 35internal combustion engines, 12, 40, 42, 47, 59, 62International Partnership for Hydrogen Energy Economy, 13IPHE, 3, 6, 13, 14Japan Hydrogen and Fuel Cell Demonstration Project, 12LHV, 9MCFC, 18, 37MCFCs, 12, 13, 47metal hydrides, 5, 10, 21, 33, 35, 36, 44, 49, 51nanoporous materials, 10New Hydrogen Project, 12EFP, 17EIHP, 65energy vectors, 24EU High Level Group for Hydrogen and Fuel Cells, 14European Hydrogen Energy Thematic Network, 14FreedomCAR partnership, 13Fuel cells, 13, 14, 15, 17, 18, 19, 20, 21, 25, 26, 29, 37, 38, 40, 41,42, 47gas turbines, 13, 40, 41, 42GTs, 40HCCI, 40High Level Group on Hydrogen and Fuel Cells, 6, 54HLG, 13, 14, 54Homogeneous charge compression ignition, 40hydrogen infrastructure, 3, 5, 6, 7, 9, 10, 11, 12, 13, 14, 15, 45, 52,53, 54Hydrogen infrastructure, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 45, 52, 53,54, 55hydrogen-rich fuels, 5, 37HyNet, 3, 13, 14, 15, 54HYSAFE, 18, 21, 65organometallic compounds, 10PAFC, 37, 38PAFCs, 12, 37, 38PEMFC, 18, 37, 38, 39, 40, 41, 46, 49, 50, 51PEMFCs, 10, 12, 13, 17, 21, 30, 37, 38, 42, 43, 44, 47, 48, 49, 50, 53,54, 57, 58, 59photobiological processes, 26photofermentation, 27physisorption, 33portable electronic, 5, 47POX, 25PSO, 17SECA, 12, 13SOECs, 30SOFC, 18, 19, 37, 38, 39, 40, 41, 51SOFCs, 10, 12, 13, 17, 18, 21, 37, 38, 40, 41Solid State Energy Conversion Alliance, 12thermochemical cycles, 24thermochemical processes, 28uninterruptible power supplies, 38, 47, 49, 52UPSs, 38, 47, 49, 52WE-NET, 12
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