Hydrogen Energy

Hydrogen Energy
Physical Properties of Hydrogen
Colorless Highly flammable Light in weight Pure hydrogen is a gas under normal conditions Melting point : - 259.2 C Boiling point :- 252.8 C Autoignition temperature : 520 C Heat of combustion (lower heating value) : 120 MJ/kg Lower flammable limit (in air) : 4% by volume Upper flammable limit (in air) : 75% by volume Stoichiometric mixture (in air) : 29.5% by volume Density (20C, 100kPa) : 0.61 cm2/s Viscosity (20C, 100kPa) : 8.814 Pa-s Flame temperature (in air) : 2045 C Minimum ignition energy (in air) : 0.017 mJ

Hydrogen Production Hydrogen from fossil fuels

Hydrogen can be produced from most fossil fuels. Since carbon dioxide is produced as a by-product, the CO2 should be captured to ensure a sustainable (zeroemission) process. The feasibility of the processes will vary with respect to a centralised or distributed production plant.

Production from natural gas

Hydrogen can currently be produced from natural gas by means of three different chemical processes: Steam reforming (steam methane reforming SMR). Partial oxidation (POX). Autothermal reforming (ATR).

Although several new production concepts have been developed, none of them is close to commercialisation.

Steam Methane Reforming

Steam reforming involves the endothermic conversion of methane and water vapour into hydrogen and carbon monoxide. The heat is often supplied from the combustion of some of the methane feed-gas. The process typically occurs at
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temperatures of 700 to 850 C and pressures of 3 to 25 bar. The product gas contains approximately 12 % CO, which can be further converted to CO2 and H2 through the water-gas shift reaction. CH4 + H2O + heat CO + 3H2 CO + H2O CO2 + H2 + heat

Partial Oxidation
Partial oxidation of natural gas is the process whereby hydrogen is produced through the partial combustion of methane with oxygen gas to yield carbon monoxide and hydrogen. In this process, heat is produced in an exothermic reaction, and hence a more compact design is possible as there is no need for any external heating of the reactor. The CO produced is further converted to H2 as described in equation. CH4 + 1/2O2 CO + 2H2 + heat

Autothermal reforming
Autothermal reforming is a combination of both steam reforming and partial oxidation. The total reaction is exothermic, and so it releases heat. The outlet temperature from the reactor is in the range of 950 to 1100 C, and the gas pressure can be as high as 100 bar. Again, the CO produced is converted to H2 through the water-gas shift reaction. The need to purify the output gases adds significantly to plant costs and reduces the total efficiency.

Comparison of technologies for H2 production from natural gas

Production from coal

Hydrogen can be produced from coal through a variety of gasification processes (e.g. fixed bed, fluidised bed or entrained flow). In practice, high-temperature entrained flow processes are favoured to maximise carbon conversion to gas, thus avoiding the formation of significant amounts of char, tars and phenols. The reaction takes place in which carbon is converted to carbon monoxide and hydrogen.
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C(s) + H2O + heat CO + H2 Since this reaction is endothermic, additional heat is required, as with methane reforming. The CO is further converted to CO2 and H2 through the water-gas shift reaction. Hydrogen production from coal is commercially mature, but it is more complex than the production of hydrogen from natural gas. The cost of the resulting hydrogen is also higher. But since coal is plentiful in many parts of the world and will probably be used as an energy source regardless, it is worthwhile to explore the development of clean technologies for its use.

Electrolysis
The process of splitting water into hydrogen and oxygen by means of a direct electric current is known as electrolysis : this is the simplest method of hydrogen production. In principle, an electrolysis cell consists of two electrodes, commonly flat metal or carbon plates, immersed in an aqueous conducting solution called the electrolyte. A source of direct current voltage is connected to the electrodes so that an electric current flows through the electrolyte from the positive electrode (or anode) to the negative electrode (or cathode). As a result, the water in the electrolyte solution is decomposed into hydrogen gas (H2) which is released at the cathode, and oxygen gas (O2); released at the anode. Although only the water is split, an electrolyte (e.g. KOH solution) is required because water itself is a very poor conductor of electricity.

Ideally, a voltage of 1.23 volts should be sufficient for the electrolysis of water at normal temperature and pressure. For various reasons, especially the slowness of the electrode processes that lead to the liberation of hydrogen and oxygen gases, higher voltages are required to decompose water. The decomposition voltage increases with the current density (i.e. the current per unit area of electrode). Since the rate of hydrogen production is proportional to the current strength, a high operating current density is

Hydrogen Energy

necessary for economic reasons. Hence, in practices the decomposition voltage (per cell) is usually around 2 volts. Theoretically, 2.8 kW-hr of electrical energy should produce one cu.m. of hydrogen gas. Because of the higher than ideal decomposition voltage, however the actual electrical energy requirement is generally from 3.9 to 4.6 kw-hr per cu.m.). This means that the efficiency of electrolysis (i.e. the proportion of the energy supplied that is used in electrolysis) is roughly 60 to 70%. The electrolysis efficiency can be increased by decreasing the decomposition voltage for a given current density. To achieve this, the electrode surface must be able to catalyze (i.e. expedite) the electrode processes. One of the best catalyst is platinum in a finely divided form deposited on a metal base. However, because of the high cost of platinum, other electrode surface materials are used commercially. For practical water electrolysis, the electrodes are generally of nickel-plated steel. The effective electrode surface area (and hence the rate of the electrode process) is increased by depositing porous nickel on a wire gauge, or a highly corrugated steel base. Research is being directed at the development of improved electrodes that will give better electrolysis efficiency at a reasonable cost. Diaphragms prevent electronic contact between adjacent electrodes and passage of dissolved gas or gas bubbles from one electrode compartment to another (leading to a decrease in current efficiency and possibly to explosions), without themselves offering an appreciable resistance to the passage of current within the electrolyte. Dissolved-gas crossover is serious only in pressure operations; to prevent the passage of gas bubbles, the diaphragm must consist of small pores whose capillary pressure is greater than the maximum differential pressure applied across the cell. Asbestos is the most common material for cell diaphragms. At atmospheric pressure, woven asbestos cloth is used, sometimes with fine nickel wire to support the structure. Pressure electrolyzers usually have a mat made of woven or felted asbestos fibres that produces a fine pore structure, giving a higher resistance to the generation of gases. This mat is sometimes supported by the electrodes. Three major factors determine the usefulness of an electro-chemical cell for hydrogen production. One is the energy efficiency, related to the cell's operating voltage: another is the capital cost of the plant, related to the rate of hydrogen production from a cell of a given size. These two factors are closely interrelated. The third factor is the life time of the cell and its maintenance requirements, which involve the materials used in its construction and the operating conditions selected.

Hydrogen Energy

A number of advantages can be gained from operating an electrolyzer at higher pressures, including (a) reduction in specific power consumption, (b) delivery of gas at pressure, thus reducing or eliminating the cost of gas compressors; and (c) reduction in the size of electrolysis cells. It can be shown theoretically that the reversible cell voltage increases with pressure. However, as decreased gas volume and higher operating pressures result in a reduced over potentially there is usually a small overall reduction in the cell voltage. This real gain in efficiency is offset by increase in the cost of pressure vessels or stronger components. Operating voltages as stated above can be lowered for a given current by using electrodes that carry precious-metal catalysts or incorporate sophisticated metallurgical structures, both of which are expensive but increase efficiency. Several large electrolytic hydrogen plants, consuming over 100 MW, have been operated successfully, while thousands of smaller units are in use for special applications. General Electric company of Lynn, Massachusetts (U.S.A.), has been developing a water-electrolysis system based on solid polymer electrolyte (SPE) fuel-cell technology. SPE fuel cells were first used in space exploration during the Gemini program, where they provided primary on board power for seven of the space craft flights. The SPE is a thin, solid, plastic sheet of perfluorinated sulfonic acid polymer having many of the physical characteristics of Teflon. Unlike Teflon, however, when a thin sheet of this material is saturated with water, it is an excellent ionic conductor, providing low electrical resistance. Used in an electrolysis cell, it is the only electrolyte required; there are no liquid acids or alkaline in the system. Hydrated Hydrogen ions (H +. x H2O) move through the sheet of the electrolyte. A cell consists of a thin sheet of SPE with a finely divided precious metal (e.g. platinum) coated on each side to catalyze the electrode processes. Metal plates pressed against the surfaces of the SPE provide electrical contact with the coatings and serves as electrodes for connection with the voltage source.

Fossil Fuel Methods

Mostly a gaseous mixture of carbon monoxide and hydrogen is formed in the first stage, in the production of hydrogen by using a fossil fuel (i.e. natural gas, petroleum product, or coal). Such a mixture can be made by any method used for an intermediate heat value fuel gas, synthesis gas or water gas. The procedures in common use are steam reforming of methane or other hydrocarbon gas or light liquid hydrocarbon and partial

Hydrogen Energy

oxidation of a heavier hydrocarbon in the presence of steam at a high temperature. In all these cases part of the hydrogen produced originates in the hydrocarbon. To remove the carbon monoxide, the mixture is submitted to the water gas shift reaction with steam. The carbon monoxide is thereby converted into carbon dioxide with the formation of additional hydrogen. CO + H2O = CO2 + H2 + 1440 kJ/kg. The carbon dioxide is an acid gas that can be absorbed in an alkaline medium. If the small amounts of carbon-monoxide and dioxide remaining are undesirable; they can be converted into methane which can be separated as a liquid by cooling to a moderately low temperature. Several processes proposed for converting coal into gaseous and liquid hydrocarbon fuels require a hydrogen-rich gas. The hydrogen would then be made by reacting coal or Char obtained in the early stages of coal treatment, with steam and a limited amount of oxygen. The heat generated when the carbon in the coal (or char) reacts with oxygen produces the high temperature required for the carbon-steam reaction. The product is a mixture of hydrogen and carbon monoxide. The carbon monoxide may be removed in the manner described above. Air can be used instead of oxygen to supply the heat for the carbon steam reaction, but about half (by volume) of the product gas is inert nitrogen from the air. Although this procedure is more economical, the high proportion of nitrogen which cannot be removed easily, is often a drawback. However, the iron-steam process, described below is designed to use air, steam, and coal char to make hydrogen essentially free from nitrogen and also from carbon monoxide without the need for water gas shifts. This method, which depends on the reaction of steam with iron at a temperature of about 815oC at a pressure of 70 atm (7 MPa). The products are fairly pure hydrogen gas and a solid iron oxide; thus Fe + H2O FEO + H2 Iron + steam Iron oxide + Hydrogen The iron is recovered from the oxide in a separate vessel and returned for further reaction with steam. The conversion (reduction) of iron oxide to iron is achieved by means of a reducing-gas mixture of carbon monoxide, hydrogen, and nitrogen at a temperature of 1095oC made by the air-steam char process (refer Fig.). Carbon monoxide and nitrogen are absent from the product, as the iron-steam reaction occurs in separate vessel.

Solar Energy Methods

(i) The following two approaches are under consideration i.e. Bio photolysis, and
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(ii)

Photo electrolysis

Bio photolysis. This method utilizes living systems (or material derived from
such systems) to split water into its constituents hydrogen and oxygen. In normal photosynthesis in green plants the green pigment chlorophyll takes up energy from sunlight and in a complex series of reactions breaks up water molecules into oxygen gas, hydrogen ions (i.e. hydrogen with a positive electric charge), and electrons (i.e. particles with a negative charge). The oxygen is evolved from the green plant, but the hydrogen ions and electrons are removed by interaction with carbon dioxide (from the air) to produce simple sugars. Certain single-called green algae are able to make the enzyme (i.e. biological catalyst) hydrogenase. In these algae, the second stage of photosynthesis can be circumvented by eliminating carbon dioxide. The hydrogen ions and electrons then combine in the presence of hydrogenase to form hydrogen gas. Thus exposure of these algae to sunlight and water (plus essential mineral salts) yields a mixture of oxygen and hydrogen gases that can be separated in various ways. The formation and activity of hydrogenase are inhibited by accumulated oxygen gas; consequently, the gases produced are removed by a flow of nitrogen. Blue-green algae differ from green algae in several respects. In particular, in addition to normal photosynthesis cells in which reaction with carbon dioxide occurs, they contain some larger cells (heterocysts) where hydrogen can be formed. In the presence of nitrogen (e.g., from the atmosphere), however, the nitrogen combines with the hydrogen ions and electrons to produce ammonia. By preventing access of nitrogen (e.g. in an inert argon atmosphere), blue-green algae decompose water in sunlight to yield hydrogen and oxygen. Instead of using living algae to obtain hydrogen from water, a more convenient approach is to utilize biological materials obtained from plants or bacteria. One advantage is the ability to vary the conditions to optimize hydrogen production. Chloroplasts, the small bodies containing the chlorophyll in green plants, retain their photosynthetic activity when extracted from the plant. Hydrogen and oxygen can then be obtained from water by exposing chloroplasts to sunlight together with the enzyme hydrogenase and ferredoxin an electron carrier, also of biological origin. It is possible, although less efficient to replace the ferredoxin by a synthetic electron carrier and the hydrogenase by an inorganic (platinum) catalyst. An ultimate objective of research on the decomposition of water by sunlight is the efficient simulation of biological processes without using biological materials.

Hydrogen Energy

Photo-electrolysis. In ordinary electrolysis, water is decomposed into hydrogen

and oxygen by passing an electric current, from an outside source, between two electrodes in an electrolyte solution. In photoelectrolysis, a current is generated by exposing on or both electrodes to sunlight. Hydrogen and oxygen gases are liberated at the respective electrodes by the decomposition of water, just as an ordinary electrolysis. Atleast one of the electrodes in photoelectrolysis is usually a semiconductor; a catalyst may be included to facilitate the electrode process. In the cells studied so far, the efficiency for the conversion of solar energy into hydrogen-oxygen energy has been very low. Research is being directed at increasing this efficiency by selection of electrode materials, electrolyte solutions, and electrode catalysts.

Hydrogen-Storage
One of the advantages often claimed for a hydrogen energy systems is that hydrogen is storable. However, it must be realized that storage of hydrogen is not an easy problem compared with storage of liquid fuels such as gasoline or oil. It is only when it is compared with electricity that storage of energy as hydrogen seems relatively easy. It is when hydrogen is considered as a replacement fuel in applications currently met by natural gas and oil, that bulk energy storage becomes very important. There are five principle methods that have been considered for hydrogen storage these are: (1) Compressed gas storage, (2) Liquid storage (cryogenic storage in vacuum insulated or super insulated storage tank). (3) Line pack system (allowing the pressure in the tran smission of distribution system to vary). (4) Underground storage (in depleted oil and gas fields or in aquifer systems0. (5) Storage as metal hydrides. 1. Compressed Gas storage. Hydrogen is conveniently stored for many applications in high pressure cylinders. This method of storage is rather expensive and very bulky because very large quantities of steel are needed to contain quite small amounts of hydrogen. In the conventional industrial hydrogen system, compressed gas is used to supply relatively small amounts of hydrogen, but when hydrogen is considered as a fuel, it is soon realized that tank storage of hydrogen is not really a practical proposition. 2. Liquid Storage.. A more practical approach is to store the hydrogen as liquid at a low temperature, (i.e. cryogenic storage). For example, the liquid hydrogen fuel used as rocket propellant in the space program is stored in large tanks. Very large facilities for
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hydrogen liquifaction have been designed and built, and large storage tanks have also been constructed one major difference exists between handling liquid natural gas and liquid hydrogen the storage temperature. Liquid hydrogen boils at 253 oC and therefore must be maintained at or below this temperature in storage unless pressure build up can be tolerated. It is commonly regarded as necessary to use vacuum insulated storage vessels, where liquid natural gas can be maintained in the liquid state at a considerable higher temperature by using super insulation, but without the need for vacuum jackets. The principal need for vacuum-jacketed containers is that the liquid hydrogen is below the temperature at which air condenses on the surface, and thus any air in the contact with the cold walls of the hydrogen container. There is also a flammability danger from the fact that liquefied atmospheric gases (rich in oxygen) would concentrate in the vicinity of the hydrogen tank. Another problem concerning storage of liquid hydrogen is the considerable amount of energy required to convert hydrogen gas into the liquid phase. Not only must the latent heat of the phase change be removed from the system, but some additional precooling is required to bring the gaseous hydrogen down below the JouleThompson temperature above which liquid hydrogen heats up on expansion. Thus, a liquid hydrogen plant normally requires some kind of primary refrigeration, such as a liquid nitrogen plant, to precool hydrogen. The net result is that about 25 30% of the heating value of hydrogen is required to liquefy hydrogen. (3) Line Packing. The use of line pack storage in the natural gas industry provides a relatively small-capacity storage system, but one with a very fast response time that can take care of minute by minute or hour by hour variations in demand. A hydrogen transmission and distribution system running on hydrogen would have a similar capability although the capacity would be reduced by a factor of about 3 because of the reduced heating value of hydrogen, compared with natural gas. (4) Underground Storage. The cheapest way to store large amounts of hydrogen for subsequent distribution would probably be in underground facilities similar to those used for natural gas; these facilities would include depleted oil and gas reservoirs and aquifers. More expensive alternatives would be caverns produced by conventional mining or by dissolving out salt with water. Since hydrogen gas tends to escape readily through a porous material, some geologic formations that may be suitable for storing natural gas may not be suitable for hydrogen. (5) Metal Hydrides. Considerable interest has been shown recently in the possibility of storage of hydrogen in the form of a metal hydride. A number of metals and alloys form solid compounds, called metal hydrides, by direct reaction with hydrogen gas. When the hydride is heated, the hydrogen is released and the original metal (or alloy)
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is recovered for further use. Thus, metal hydrides provide a possible means for hydrogen storage. An important property of metal hydrides is that the pressure of the gas released by heating a particular hydride depends mainly on the temperature and not the composition. At a fixed temperature, the gas pressure remains essentially constant until the hydrogen content is almost exhausted. Several studies are being made to find a metal hydride that would satisfy the requirements for hydrogen storage. These requirements include the following: (i) the metal (or alloy) should be fairly inexpensive, (ii) the hydride should contain a large amount of hydrogen per unit volume and per unit mass, (iii) the hydride should be formed without difficulty by reaction of the metal with hydrogen gas, and it should be stable at room temperatures, and (iv) the gas should be released at a significant pressure from the hydride at a moderately high temperature (preferably below 100oC). Three of the more promising hydrides are those of lanthanum-nickel (La Ni 5) iron titanium (Fe Ti), and magnesium-nickel (Mg 2 Ni) alloys. The maximum hydrogen contents are represented approximately by the formulae (La Ni5) H6, (Fe Ti) H2 and (Mg2 Ni) H4 respectively.

Hydrogen Transportation
Pipe lines. At present, the long distant pipelining of hydrogen is an operation that is carried out by only a few specialized companies in different parts of the world. It is of interest to compare the design requirements of a pipeline for hydrogen with those of a pipeline for natural gas. Heating value of hydrogen is only 12.1 MJ/cu m, as compared to about 38.3 MJ/cu m for natural gas. This implies that to deliver the same quantity of energy, three times the volumes of hydrogen must be transmitted. On closer inspection, however, one finds that the capacity of a pipeline depends upon the square root of the density of the gas, and because the density of hydrogen is about one ninth (1/9) that of natural gas, there is a compensating facvtor of the one third that results in the given pipe having essentially the same energy carrying caqpacity for natural gas as for hydrogen. This is true at atmospheric pressure. As the pressure increases to typical pipeline operating pressures of 50 kg/cm2 (5 MPa) or so, the compressibility factor for hydrogen is somewhat different that for natural gas, and this results in a slightly unfavourable carrying capacity for hydrogen. At 50 kg/cm 2 (5 MPa), the ratio of heating values for a given compressed volume of hydrogen and natural gas has changed from 3 : 1 to 3.83 : 1. Long distances gas transmission lines of lengths greater than about 90 km must be supplied with pipeline compressors at fairly regular intervals. Hydrogen compressors
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must handle a considerably greater volume of the gas -somewhere between three to four times the number of cu m for the same energy capacity. Secondly, the horse power required to drive a hydrogen compressor is considerably greater than that needed to drive a natural gas compressor for the same gas energy throughout. Thirdly, the design of rotory compressors commonly used for natural gas lines appears to be inadequate for hydrogen operation. It is possible to estimate the cost of transmitting hydrogen by pipeline from a knowledge of the required pipeline diameter, compressor capacity and horse power, and energy throughout required. In the case of design of a pipeline of hydrogen transmission the cost of fuels used to drive the engines for compressors is also a highly deciding factor, because the compression energy is so much higher than that of natural gas. One of the principal concerns about hydrogen transmission is the fear of hydrogen embrittlement of the pipeline materials. A number of metals lose their mechanical strength on exposure to hydrogen; the phenomenon called hydrogen embrittlement, is sepcially significant for steel in hydrogen under pressure. Operating experience with common pipeline steels at pressures upto about 35 kg/cm 2 (3.5 MPa). However the behaviour at higher pressure is uncertain, and more experimental work needs to be carried out to get some definite data. Liquid Hydrogen Transportation. Hydrogen in bulk can be transported and distributed as the liquid. Double-walled, insulated tanks of liquid hydrogen with capacities of 7000 gal (26.5 cu m) or more are carried by road vehicles and upto 34,000 gal (129 cu m) by rail road cars. Distribution of liquid hydrogen by pipelines, jacketed with liquid nitrogen, has been proposed. The costs would be substantially greater than for gas pipelines, but it might be justifiable for certain fuel applications where the liquid is required. Metal Hydride Transportation. Hydrogen can also be transported as a solid metal hydride. The main drawback, as stated earlier, is the weight of the hydride relative to its hydrogen content. Application of Hydrogen Gas Hydrogen gas can be utilised for: (i) Residential uses (ii) Industrial uses (iii) Road vehicles (iv) Aircraft (v) Electric power generation (Utilities)
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Advantages claimed for hydrogen-fuel engines are: (i) They can higher efficiencies i.e. utilize a higher proportion of the energy in the fuel than gasoline engine. (ii) The amount carbon monoxide and hydrocarbons in the exhaust would be very small since they would originate only from the cylinder lubricating oil. It can be stored in gaseous form (convenient for large scale storage), in liquid form (convenient for air and space transportation) or in the form of metal hydrides (convenient for surface vehicles and other relatively small scale storage requirements). It can be transported over large distances through pipelines or via tankers (in most of the cases more efficiently and economically than electricity). It can be converted into other forms of energy in more ways and more efficiently than any other fuel, e.g., through catalytic combustion, electrochemical conversion and hydriding, as well as through flame combustion. Hydrogen as an energy currency is environmentally compatible, since its production from electricity (or directly from solar energy), its storage and transportation, and its end use do not produce any pollutants (except some NO X if hydrogen is burned with air) or any other harmful effects on the environment. It also does not produce any greenhouse gases, particularly CO2. Hydrogen Technology Development in India The Department of Non-conventional Energy Sources (DNES), ministry of energy. India has so far supported 22 Research and development projects of repute and universities on various aspects of Hydrogen technology namely; (i) Production of hydrogen by photoelectrolysis of water using solar energy. (ii) Production of hydrogen by blue green algae and by certain bacterial species. (iii) Storage of hydrogen through metal hydrides/non-metal hydrides (rice husk and misch-metal). (iv) Problems relating to utilization of hydrogen as a fuel, that is, development of suitable engines and burners etc. (v) Liquid hydrogen production, storage and utilisation etc Research in the development of phosphoric acid fuel cell (PAFC) systems and polymer electrolyte membrane fuel cell (PEMFC) systems. PAFC power packs of up to 50-kW capacity have been developed and tested in the country.

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Bharat Heavy Electricals Ltd (BHEL) is working on the development of a 5-kW PAFC power pack with improved control and instrumentation system. An improved 3-kW capacity PEMFC power pack, which can also work as an uninterrupted power supply (UPS) system, is under trials at the SPIC Foundation, Tuticorin. Science

A fuel cellbattery hybrid van has been developed in India. The van is powered by

a10-kW-capacity fuel cell along with a leadacid battery bank. The range of the vehicle is about 70 km per charge. This van has logged more than 2500km. Satisfactory progress has been reported on the various funded projects advancing the state of art one step further.

Conclusion With hydrogen, we can realize the vision of a safe, clean, abundant, and affordable energy future.

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