Hydrogen as Future Energy Source

M. Klell
HycentA Research GmbH, Inffeldgasse 15, A-8010 Graz, Austria E-mail: klell@hycenta.at

Abstract
After an overview of the physical and chemical characteristics of hydrogen, methods of production of hydrogen are discussed. Hydrogen can be produced from a number of sources, advantageously using renewable energy. Efficient storage with high energy density plays a key role for its application. Storage methods as compressed gas, cryogenic liquid, and in compounds are analyzed. Hydrogen is used in a wide variety of applications e. g. in chemical industry or in metallurgy. As carbon free fuel, hydrogen can be burnt with low or no emissions in turbines, internal combustion engines, or fuel cells. The usage of hydrogen as energy carrier is discussed for stationary, mobile, and automotive applications.

Introduction
In view of the limited availability of fossil fuels and the growing environmental impact of pollutant emission, research activities for using hydrogen as future source of energy are gathering momentum. A number of technical challenges regarding production, distribution, and storage still have to be solved before the common use of hydrogen, though [1].

forms chemical compounds with nearly all other elements, so called hydrides. Due to their ability to form long chains and complex molecules, combinations with carbon hydrocarbons play a key role for organic life. Hydrogen is of crucial importance as energy carrier in the metabolism of plants, animals, and humans. It is found in sugar, fat, proteins, alcohols and oils. Thermodynamic data of hydrogen are available in tables and graphs. At ambient condition, temperature T, pressure p and Volume V of the gas fulfill well the ideal gas equation (1) with R as gas constant: p V = m R T. (1) For thermodynamic analysis the Ts diagram with lines of constant pressure, density, and enthalpy is helpful. Changes of states can clearly be described in the Ts diagram with the reversible heat corresponding to the area below the curve of process course. Given an isochoric or isobaric process, the reversible heat corresponds to the work or change of enthalpy correspondingly. The Ts diagram for hydrogen at low temperatures is shown in Figure 1 [2], an overview of properties of hydrogen is given in Table 1 [3].

Properties
Hydrogen is the most abundant element in the universe, more than 90 % of all atoms are hydrogen. Hydrogen is the main component and main energy source of stars. Hydrogen is the simplest atom, consisting of one proton and one electron only. Due to its one valence electron, hydrogen is very reactive and combines to the molecule H2 at ambient conditions. At normal temperature and pressure, hydrogen is a colourless, odourless gas with no toxic effects. It is the lowest density element and therefore requires a large storage volume, whilst also having a high diffusion coefficient. After Helium, element No. 1 has the lowest melting and boiling points. On earth hydrogen is rarely found in pure form, but usually in a wide variety of inorganic and organic chemical compounds, the most common being H2O water. Hydrogen

Figure 1: Ts diagram of hydrogen. Hydrogen is highly inflammable (EU rating F+ and R12) with broadly spaced ignition limits in air (lower explosion limit 4% by volume, upper explosion limit 75.6% by volume) and low ignition energy (0.017 mJ for a stoichiometric mixture with air). As with all fuels, the use of hydrogen requires compliance with safety regulations, with EU safety sheets specifying: S9: keep containers in a well-aired location

S16: keep away from ignition sources do not smoke (explosion areas) S33: take precautions against electrostatic charge. TABLE 1: PROPERTIES OF HYDROGEN Value & Unit 2,016 kg/kmol 120 MJ/kg -259,35 C (13,8 K) 0,07 bar 0,125 kg/m 77 kg/m 58,5 kJ/kg -252,85 C (20,3 K) 445,4 kJ/kg 70,8 kg/m 8,5 MJ/dm 9,8 kJ/kgK 5,8 kJ/kgK 0,099 W/mK 11,9 x 10-6 Ns/m 1089 m/s 1,34 kg/m 0,16 MJ/dm 12,2 kJ/kgK 6,6 kJ/kgK 0,017 W/mK 1,11 x 10-6 Ns/m 355 m/s -239,95 C (33,2 K) 13,1 bar 31,4 kg/m 0,09 kg/m3 0,01 MJ/dm 14,32 kJ/kgK 10,17 kJ/kgK 0,184 W/mK 0,61 cm/s 8,91 x 10-6 Ns/m 1246 m/s 4 Vol% H2 ( = 10,1) 29,6 Vol% H2 ( = 1) 75,6 Vol% H2 ( = 0,1) 585 C (858 K) 0,017 mJ

max. laminar flame speed adiabatic combustion temperature

ca. 3 m/s ca. 2100 C

Property molar mass (gravimetric) calorific value Hu at triple point: temperature pressure density gaseous density liquid heat of fusion at boiling point at 1,01325 bar: boiling temperature Ts heat of vaporization liquid phase: density (volumetric) calorific value specific heat capacity cp specific heat capacity cv thermal conductivity dynamic viscosity speed of sound gaseous phase: density (volumetric) calorific value specific heat capacity cp specific heat capacity cv thermal conductivity dynamic viscosity speed of sound at critical point: temperature pressure density at standard conditions 0 C und 1,01325 bar: density (volumetric) calorific value specific heat capacity cp specific heat capacity cv thermal conductivity coefficient of difusion dynamic viscosity speed of sound mixtures with air: lower explosion limit stoichiometric mixture upper explosion limit ignition temperature minimal ignition energy

Because hydrogen is a very light and diffusive gas, increasing concentrations can normally be prevented easily through adequate ventilation. In the case of compressed gas CGH2 storage, compliance with pressure vessel regulations is required. Direct contact with cryogenic liquids and gases can cause serious frostbite or freeze-burns. Furthermore, exposure to cryogenic hydrogen can cause embrittlement of a variety of materials including most plastics and mild steel, which can in turn lead to fracture and leakage.

History
Hydrogen was first discovered by Henry Cavendish in 1766 from the reaction of zinc with sulfuric acid. Zn + H2SO4 ZnSO4 + H2 (2) Cavendish called the gas inflammable air. A few years later Antoine Lavoisier repeated the experiments and suggested the name hydrogne. Its first application was in a balloon, 1783 Jaques Charles took off in a balloon in Paris a few weeks after the brothers Montgolfier who had used hot air. In 1807 Francois de Rivaz invented the first internal combustion engine with hydrogen and a vehicle driven by this engine, see Figure 2.

Figure 2: Vehicle with hydrogen engine. In 1839 William Grove presented his gas battery, the fuel cell, burning hydrogen and oxygen to produce water and energy. Due to the invention of the more powerful dynamometer, the fuel cell was not used as an energy converter until its application in the space program and recent utilization as a clean power converter. Since Fritz Haber and Carl Bosch developed their method to produce ammonia from hydrogen and nitrogen around 1910,

hydrogen has been a widely used gas in chemical industry. Demand for hydrogen increased sharply with the use as propellant for space rockets since the 1960s.

Production
Like electricity, hydrogen is an energy carrier that has to be produced, as hydrogen is not found in pure form. Hydrogen can be produced by a number of methods from many different sources. The amount of hydrogen globally produced equals 600 billions Nm per year corresponding to about 1,5 % of global energy consumption. More than 40 % of the produced hydrogen comes from industrial processes where hydrogen is a by-product, like the reforming of gasoline or the production of ethen, methanol, or chlorine. For the large-scale-production of the remaining 60 % the reformation of fossil hydrocarbons is widely used. The most cost-effective process is the steam-reforming of short chained hydrocarbons such as methane. The industrial production takes place in huge reactors at temperatures around 500 C. First a so called synthetic gas of carbon monoxide and hydrogen is formed: CH4 + H2O CO + 3 H2 RH = 206 kJ/mol (3)

between 350 bar and 750 bar is widely used. For mobile applications storage in compounds such as methane is a further possibility. For compressed hydrogen storage the gas is normally compressed to pressures between 200 bar and 350 bar, though more recently storage pressures of 700 bar and even higher have been under trial. Gaseous hydrogen storage takes place in a closed system, with the result that gaseous hydrogen can be stored without losses for extended periods. At 700 bar, the density of 40 kg/m is somewhat 500 times higher than at ambient pressure, whilst the energy required for compression is around 15 % of the fuel energy content. Such enormous pressures require consideration of questions regarding material choice, component dimensioning and safety, with such tank systems ending up quite heavy; storage weight is around 20 to 30 kg per kg stored H2. For the tank systems compliance with pressure vessel regulations is required. An example of a tank in automotive application with compressed hydrogen at 300 bar is shown in Figure 3.

This gas exits the reformer at temperatures around 850 C. After cooling, CO is oxidated in the shift reaction at around 400 C: CO + H2O CO2 + H2 RH = -41 kJ/mol (4)

Efficiency of up to 80 % can be achieved. Natural gas, water, and energy are used, the energy coming from the natural gas. Other industrial production processes include the gasification of coal or of other fossil or biological hydrocarbons. All production methods based on hydrocarbons are producing CO2 though. The production of hydrogen from water via electrolysis is free of emissions if the needed electricity is produced from renewable energy sources such as wind, water or solar energy. In electrolysis efficiencies of up to 75 % can be achieved [4]. As hydrogen can be stored better than electric energy, the vision is to produce electricity from renewable sources, use a given surplus of electricity to produce hydrogen which can be stored and used as fuel in stationary and automotive applications.

Figure 3: Hydrogen storage at 300 bar (Source Dynetek). Relatively high storage densities can be achieved with liquid hydrogen (50 70 kg/m). However its very low boiling point at -253 C means that the generation of liquid hydrogen is complex and requires 20 % to 30 % of its energy content. The storage of liquid hydrogen is technically challenging. Containers with high levels of insulation are used, consisting of an inner tank and an outer container with an insulating vacuum between them, an automotive example is shown in Figure 4. The austenitic stainless steel most commonly used for such tanks retains its excellent plasticity even at very low temperature and does not embrittle. The evacuated space between the nested containers is filled with multi layer insulation (MLI) having several layers of aluminium foil alternating with glass fibre matting. Nevertheless, heat transfer cannot be prohibited completely. As a result of inevitable inward heat leakage, hydrogen evaporates in the container leading to increases in pressure and temperature. Liquid hydrogen containers must therefore always be equipped with a suitable pressure relief system and safety

Storage
Hydrogen is stored as compressed gas, as liquid at very low temperatures or in physical or chemical compounds. For storage and distribution of large quantities the liquid form is favored because of the higher energy density. For automotive applications also storage as compressed gas with pressures

valve. Liquid storage therefore takes place in an open system in which released hydrogen has to be dealt with by means of catalytic combustion, dilution or alternative consumption. Evaporation losses on todays tank installations are somewhere between 0.3% and 3% per day, though larger tank installations have the advantage as a result of their lower surface area to volume ratio. With todays liquid hydrogen storage systems, the storage weight is around 20 kg per kg stored H2.
inner container super-insulation level sensor filling pipe gas outlet liquid outlet filling port outer container inner container support liquid hydrogen (-253C) safety valve gaseous hydrogen (+20C to +60C to engine); main shut-off valve electrical heating selector valve for gas / liquid hydrogen heater Source: Linde gas

Figure 5: Energy density and work for CGH and LH. Hydrogen combines with a variety of materials in solid, liquid, or gaseous form in physical or chemical binding. The important evaluation criteria for bound hydrogen storage are temperature, pressure and duration for charging and discharging the system as well as the potential number of charging cycles. Despite theoretically high storage densities, most forms of bound storage are still at the trial stage, with commercially available storage materials offering a storage weight of around 30-50 kg perkg stored H2, this means 3-5 mass%. Chemical compounds of hydrogen are known as hydrides, the most common being water, alcohol and carbon-based (e.g. petrol, diesel) hydrides. Metal hydrides, for example with light metals, are used as storage materials for hydrogen, see left side of Figure 6. In the case of physical adsorption, hydrogen is bound to the surface of a material, an example being deposition on carbon in the form of nanotubes, see right side of Figure 6.

Figure 4: Tank system for cryogenic liquid hydrogen. The intended consumption of hydrogen in the engine requires additional arrangements like cryo-pumps, deliberate energy injection for vaporization or the raising of tank pressure. Apart from the tank itself, the filling support infrastructure is also technically demanding, with transfer pipes, filling connectors etc. also requiring vacuum insulation and chilling to -253 C prior to liquid filling. Figure 5 shows the dependency of density and energy density on the pressure for liquid and gaseous compressed hydrogen. It is clear that gaseous hydrogen only reaches the densities of liquid hydrogen at pressures of more than 1000 bar. The graph also shows the ideal minimum work required for the liquefaction and compression of hydrogen in percentages of its calorific value Hu. Isothermal compression work assumes an ideal cooling process. The liquefaction and compression work represented here does not take into account the cycle efficiencies that lie at about 30 % to 50 % with liquefaction and compressors.

Figure 6: Metal hydride and carbon storage. To give an overview, the achievable volumetric and gravimetric hydrogen densities of different hydrogen storage modes have been summarised in Figure 7. It is obvious that, with regard to volumetric storage density, bound storage has the greater theoretical potential. A greater amount of hydrogen per unit volume can be stored in compounds than in pure form. Due to the fact that this often requires very low or very high temperatures and high pressures as well as long charging times, gaseous and liquid storage tends to prevail at the moment.
160 density 5 g/cm 2 g/cm
Cnano H0.95

1 g/cm
Al(BH4)3 dec.373K m.p. 208K

0.7 g/cm

Volumetric H2 density [kg H2/m]

140

BaReH9 <373 K, 2 bar LaNi5H6 300 K, 2 bar FeTiH1.7 300 K, 1.5 bar

Mg2FeH6 620 K, 1 bar

120

MgH2 620 K, 5 bar NaAlH4 dec. > 520K KBH4 dec. 580K

NaBH4 dec. 680K

C8H18

liq.

LiBlH4 dec. 553K

H2 chemisorbed on carbon CH4liq. b.p. 112K

100

Mg2NiH4 550 K, 4 bar

80
H2liq. 20.3K

LiAlH4 dec. 400K

LiH dec. 650K

C4H10 b.p. 272K H2 physisorbed on carbon

liq.

60
1000 800 500 1000 800 Pressurized H2Gas (composite material) p[bar] 500

40

reversible Hydride irreversible Hydride Kohlenwasserstoffe

200 130

20

200 130

Pressurized H2 (steel) p[bar]

Gas

0 0 5 10 15

20

25

Gravimetric H2 density [mass%]

Figure 7: Volumetric vs. gravimetric density for different

methods of hydrogen storage [5]. By means of relatively simple thermodynamic simulations, satisfactory results for the analysis of hydrogen storage systems can be achieved [6]. This holds true for gaseous high pressure vessels with respect to energy needed for the compressor, for liquid hydrogen in respect to energy needed for liquefaction and also for the simulation of filling processes, pressure build-up, and boil-off. From the results and comparisons with measurements it can be concluded that compression of gaseous hydrogen to high pressures needs up to 15 % of the calorific energy content. Compressed hydrogen can be stored in closed tank systems at volumetric densities of around 20 50 kg/m and gravimetric densities of around 5 10 %. By observing the necessary safety measures and correct material choice, CGH can be stored safely. From the point of view of storage gravimetric density, the liquid storage of hydrogen currently offers the best results with up to 70 kg/m and gravimetric densities of around 5 10 %. The extremely low storage temperature, however, places high demands on the materials used and on the insulating capacities of storage systems. The liquefaction consumes up to 30 % of the calorific energy content. Sophisticated processing systems are necessary in order to avoid losses caused by diffusion, evaporation and impurity. Storage systems in bound form with a high potential both in regard to volumetric and gravimetric densities are still at the trial stage.

CO2 formed, from hydrogen comes water H2O. Depending on the C:H ratio, considerable amounts of CO2 can be formed. The combustion of 1 kg of gasoline or diesel yields an amount of 3,2 kg CO2 at an energy output of about 43 MJ (11,9 kWh). The combustion of natural gas (methane CH4) is cleaner, there are 2,8 kg CO2 produced per kg of methane at an energy output of 50 MJ (13,9 kWh). Hydrogen is the only available carbon free fuel and thus can be burnt without the emission of carbon dioxide CO2 or other products of the non-ideal combustion like carbon monoxide CO, particles C, and hydrocarbons HC. Combustion of hydrogen H2 with oxygen O2 yields only water H2O. If burnt in a fuel cell in a so called cold combustion, it produces electric energy free of emissions. If burnt in a hot combustion in a turbine or an internal combustion engine, hydrogen has the highest gravimetric calorific value of all fuels (Hu = 120 kJ/kg = 33,3 kWh/kg). Due to the high temperatures in internal combustion engines the combustion with air emits nitron oxides NOx, which can be reduced by applying high air excess ratios. Application in fuel cells and internal combustion engines is discussed in more detail.

Fuel Cells
Fuel cells as energy converters offer a number of advantages. Due to the direct conversion of the chemical energy of the fuel into electricity it offers a high efficiency and is not limited by the Carnot efficiency for converting heat into work. Also the fuel cell reaches its highest efficiency at low temperatures and low load. A comparison of the efficiency of the Carnot cycle and a fuel cell is shown in Figure 8.

Application
Nearly half of the hydrogen produced globally is used to produce ammonia via the Haber-Bosch-process. Another quarter of the hydrogen is used in refineries to process oil, as in hydrofining and hydrocracking. Further applications include chemical industry, food industry, water treatment, and metallurgy. In this presentation, utilization of hydrogen as energy carrier for combustion will be addressed more detailed.

100

80

Wirkungsgrad in %

60

40

c (Tu = 323.15 K)

20

th der Brennstoffzelle

Combustion
As an energy carrier and with respect to fossil fuels, hydrogen has advantages with regard to environmental impact and availability. Since the discovery of fire, mankind has used fossil fuels as source of energy. Fossil fuels are limited though and produce CO2. The produced amount can be calculated from the equation of ideal combustion of hydrocarbons CxHy equation (5):

0 273 523 773 1023 1273 1523 1773 2023

Temperatur To in Kelvin

Figure 8: efficiency of Carnot cycle and fuel cell. With hydrogen fuel cells produce electric power without emission of pollutants or noise. The energy output of a single cell is small, though, fuel cells are expansive and their durability has yet to be proven in everyday use. The principle of a fuel cell is explained using a fuel cell with hydrogen as fuel and oxygen in an alkaline electrolyte, see Figure 9. Technically, a fuel cell functions as the reversion of an electrolyser. Hydrogen as fuel is reacting at the anode with

y y C x H y + x + O 2 x CO 2 + H 2 O 4 2

(5)

The amount of carbon in the fuel determines the amount of

hydroxid ions to form water and release two electrons. The oxidation reaction at the anode is: H2 (g) + 2 OH (aq)

example of a submarine with fuel cells as alternative propulsion system is given in Figure 10.

2 H2O (l) + 2 e (6)

The electrons are conducted through an external electric circuit to the cathode, thus yielding electric energy. At the cathode the reduction of oxygen takes place, water is reacting with oxygen and two electrons to form hydroxid ions: H2O (l) + O2 (g) + 2 e 2 OH (aq) The complete reaction thus is: H2 (g) + O2 (g) H2O (l) RH = -285 kJ/mol (8) Figure 10: Submarine U212 with fuel cells (Source HDW).
Anode 2e 2e Kathode+

(7)

Internal Combustion Engines

Already as early as in the 1930s internal combustion engines were operated with hydrogen successfully. As compared to fuel cells, internal combustion engines offer a high power density at moderate costs, the technology is well established and reliable as well as approved in mass production. For many years hydrogen powered engines have been operated at the Institute for Internal Combustion Engines and Thermodynamics of Graz University of Technology, see Figure 11 [9].

2OH H2

O2

H2O

H2 + 2 OH 2 H2O + 2 e

H2O + O2 + 2 e 2 OH

Figure 9: Principle of a fuel cell. A variety of types of fuel cells are in use, being classified by their electrolytic material and their fuel, details see [7]. An overview of the application and range of power of common fuel call types is given in Table 2. TABLE 2: FUEL CELLS Fuel Cell AFC PEMFC DMFC PAFC MCFC SOFC Power [kW] 10 - 100 0,5 - 500 0,01 -1 - 10.000 - 100.000 - 100.000 application aeronautics, vehicles aeronautics, vehicles electric devices power stations power stations power stations

Figure 11: Research engine with hydrogen. The combustion of hydrogen can be achieved in conventional spark ignition combustion engines, given that all materials and components are compatible for the use of hydrogen as fuel. Adaptations in fuel mixture formation and engine control are necessary though due to the properties of hydrogen. As hydrogen has very wide ignition limits, a low ignition energy, and high flame speed, backfiring can occur in an internal combustion engine with external mixture formation. Therefore the engine has to be operated with excess air in a lean combustion mode. This improves the

Fuel Cells are used in a wide variety of applications. In small portable applications for electric devices like laptops or as local energy generator, often with direct methanol fuel cells, in vehicles of all kinds on grounds, air, or water [8]. An

thermodynamic efficiency, but engine power decreases with the lower calorific value of the mixture. Supercharging of the engine partly allows for a compensation of this effect. Recent research is focussed on direct injection of hydrogen into the cylinder, thus avoiding the danger of backfiring and allowing for a high power output. Recently also mixtures of hydrogen and natural gas are investigated as fuel, combining the advantages of a given infrastructure and higher volumetric calorific value of natural gas with the fast and clean combustion of hydrogen. The combination allows for very lean engine operation, thus avoiding the formation of nitrogen oxides and increasing engine efficiency. A natural gas powered vehicle was converted to hydrogen operation with an option to use all possible mixtures of hydrogen and natural gas at the Institute for Internal Combustion Engines and Thermodynamics in cooperation with the HyCentA, see Figure 12. The car is equipped with 350 bar pressure tanks for compressed hydrogen, natural gas or mixtures thereof.

station density is currently being established all over the world and in Europe is supported by a variety of EU-projects. Also in energy engineering hydrogen applications can only be found in niches at the moment. To guarantee future supply of energy it is necessary to promote alternative energy sources worldwide. In this context hydrogen can be used as energy storage for excess energy produced by renewable energy sources during peak periods. The stored hydrogen can be converted back into electricity or combusted in internal combustion engines, turbines, and fuel cells.

Acknowledgement
For the support in the preparation of this contribution I thank the staff of Hydrogen Center Austria, the first research and filling facility for hydrogen in Austria at the premises of Graz University of Technology, see Figure 13.

Figure 12: Gas vehicle and engine on test bed. Hydrogen rich gases like waste gas from biological processes are used in big stationary engines [10]. In commercial vehicles as well as in passenger cars internal combustion engines have been built as demonstrators or small series. Internal combustion engines by MAN power a number of public busses operated in Europe. Recently combustion engines with hydrogen were introduced by Toyota in the RX8 H with a rotary engine and in the BMW Hydrogen 7. The BMW was produced in a small series of hundred cars delivered to test drivers all over the world. The car has a cryogenic tank with liquid hydrogen. All cars are bifuels that can be switched to gasoline operation. Figure 13: HyCentA, Hydrogen Center Austria in Graz.

References
[1] H. Eichlseder, M. Klell, Wasserstoff in der Fahrzeugtechnik. Erzeugung, Speicherung, Anwendung, Vieweg+Teubner, 2008. [2] G. Gstrein, M. Klell, Stoffwerte von Wasserstoff, Institute for Internal Combustion Engines and Thermodynamics, Graz University of Technology, Graz 2004. [3] National Institute of Standards and Technology, NIST. [4] C. H. Hamann, W. Vielstich, Elektrochemie, Verlag Wiley-VCH, Weinheim 2005. [5] L. Schlapbach, A. Zttel, Hydrogen storage-materials for mobile applications, Nature, vol. 414, 2001, pp. 23-31. [6] M. Klell, M. Zuschrott, H. Kindermann, M. Rebernik, Thermodynamics of Hydrogen Storage, 1st International Symposium on Hydrogen Internal Combustion Engines, Institute for Internal Combustion Engines and Thermodynamics, Graz University of Technology, Graz 2006. [7] P. Kurzweil, Brennstoffzellentechnik, Vieweg, Wiesbaden 2003. [8] A. Lon (Edt.), Hydrogen technology, Springer 2008. [9] H. Eichlseder, T. Wallner, R. Freymann, J. Ringler, The Potential of Hydrogen Internal Combustion Engines in a Future Mobility Scenario. SAE Paper 2003-01-2267, 2003. [10] G. Herdin, F. Gruber, J. Klausner, R. Robitschko, Use of hydrogen and hydrogen mixtures in gas engines, 1st International Symposium on Hydrogen Internal Combustion Engines, Institute for Internal Combustion Engines and Thermodynamics, Graz University of

Conclusion
Due to ecological reasons and to reasons of security of energy supply, mid-term to long-term hydrogen has a high market potential in the fields of energy and traffic engineering. Due to commercial reasons a high market penetration cannot be expected in the near future though. Because of the local absence of emission, e. g. public transport companies shall be a target for the introduction of hydrogen technologies. Vehicle infrastructure and filling

Technology, Graz 2006.