Energy Sources The source of almost all the worlds energy, including coal, oil, natural gas, wood,

food, waves and wind, is the solar power in the form of radiation from the sun. At the earths surface, solar energy shows itself in a number of different ways. a) The most obvious being direct radiation- this may be utilized by man, since it can be focused whilst diffuse radiation (radiation scattered by clouds) requires a different technology for harnessing it. b) Evaporation of water by the sun and the resulting gain in potential energy is the source of power for hydroelectricity c) Solar heating of the earths surface gives rise to winds which in turn generate waves d) Associated with solar heating are also the temperature gradient and currents within oceans, which can provide yet another source of power e) Green plants use solar energy in converting CO2 and water into carbohydrates proving food for animals and also a wide range of useful materials such as wood and which may be useful as a fuel. Green plants are the original source of fossil fuels. There are also many other sources of energy which are not directly linked to the sun. These are: Nuclear energy- the most capital source of energy which is contained in uranium, and deuterium, which though exhaustible, is potentially a very large source of energy Tidal energy- which is due mainly to gravitational energy between the earth and the moon Geothermal energy- may be result of the natural nuclear decay of radioactive materials in the earths core Fossil Fuels By far the most used source of energy by industrial plants (metallurgical plants included) is the energy released from the combustion of fossil fuels. In this case chemical energy stored in the fuels is converted to heat energy which can be used directly (to heat materials)or converted to another form (mechanical energy) before finding its end use. Classification of Fossil Fuels A greater part of energy on the earth eminates from the Sun and a store of this energy has been accumulated in the form of fossil fuels particularly coal, crude petroleum and natural gas. For most industrial applications the energy requirements are being met by these fossil fuels. Fossil fuels are broadly classified into primary and secondary fuels. Primary Fuels These occur naturally and undergo no chemical processing before utilization. These are further divided into sub-divisions; solid, liquid and gaseous fuels. Examples are coal, wood and peat, crude petroleum, the products of distilling crude petroleum, and natural gas. Secondary Fuels Involve some chemical treatment before utilization in that their composition or structure is modified during a chemical processing stage. They are derived mostly from primary fuels. These are also further classified into solid, liquid and gaseous secondary fuels. Examples

are coke, coal gas, the products of cracking and reforming petroleum products and synthetic natural gas. PRIMARY FUELS: Solid Fuels, Coal Coal is a primary fuel, although physical operations (cleaning, drying, screening and washing) are involved in its production there is no change in its composition or structure before it is burned to liberate heat. Formation of Coal Coal is a stratified rock which has formed over many million years ago from the remains of decaying trees and vegetation. It is organic in composition and contains the elements carbon, hydrogen and oxygen with small amounts of nitrogen and sulphur, and only traces of inorganic material, which are not chemically combined with organic material forming most of the coal. Coal is formed from decaying vegetation and mineral matter, compressed beneath many layers of fallen trees, leaves and soils. Cellulose from fallen vegetation (which is the principal constituent) is slowly converted to CO2 and water as the tree and plants rots away leaving little trace. The products of decomposition are subjected to a high pressure (stemming not only from mass of the hundreds of metres of material above them, but also from movement of the earths crust) and heat (by molten igneous rock below the seam). Variations in the conditions of temperature and pressure to which the material was exposed led to the variations in the transformation of the decaying wood. As decomposition proceeded, hydrogen and oxygen were gradually excluded from the residual solid so that the various stages in the decomposition from cellulose to graphite show reduction in the hydrogen and oxygen content of the fuel. Table 1: Approximate compositions of various coals
Coal Cellulose (pure) wood peat lignite Semi-bituminous Bituminous coal anthracite graphite %C C 44.5 50.0 59.9 61.8 69.5 78.7 91.0 100.0 100 100 100 100 100 100 100 100 Parts of H 13.9 12.0 10.0 7.8 7.9 6.0 4.7 CV (KJ/kg) O 111 88 57 54 36 21 5.2 19 770 18 663 20 930-25590 27 200 32 100 32 560 32 910

Coals are ranked according to their carbon content. Rank of a coal is a measure of the change it has undergone in the transition from wood to graphite. A low rank indicates a small change (e.g. peat) whilst a high rank indicates a large change e.g. in anthracite. Under the action of heat and pressure, some chemical action took place to expel water and oxides of carbon from the coal. Volatile matter content therefore varies with rank. The lower the rank, the higher will be the volatile matter content of the coal. The calorific value (CV) of coal increases with rank. The coking power of coal rises to maximum and then decreases as the rank increases. Analysis of Coal

It can analyzed in two ways depending on the data required; ultimate and proximate analysis. Ultimate Analysis It gives a more detailed and useful analysis of coal. It involves the determination of the more important chemical elements in coal, C, H, N, O, S and occasionally P and Cl. The results of an ultimate analysis are important for several reasons: a) Concentration of C, H and O are particularly relevant for classification of coal and combustion calculations. b) Amount of S and P have a significant bearing on the metallurgy of iron and steel. c) Concentration of As is important to know if the fuel is going to be used in food and brewing processes d) Cl and V vital in considering corrosion and problem of boiler deposits. To evaluate the amount of C and H present, coal is completely combusted in oxygen and the concentration calculated from the amounts of CO2 and H2O formed. Proximate Analysis It involves the determination of the moisture, ash, volatile matter, coke and fixed carbon, all as percent of the original weight of the coal sample. The term proximate is used as the analysis varies with the procedure adopted. Results vary particularly with the temperature of heating in determining the volatile matter content, duration of heating, type of crucible used and the atmosphere under which the drying takes place. The term fixed carbon is hypothetical and does not imply existence of uncombined carbon nor does it bear any resemblance to the total carbon as determined in the ultimate analysis. The fixed carbon content is not determined experimentally, but calculated as; 100- (% moisture + %volatile matter + %ash) Results of both the proximate and ultimate analysis may be expressed as either as sampled (coal as received) or on a dry, ash free basis

Table 2: Example of analysis of some coal

Basis Carbon Hydrogen Oxygen Nitrogen Sulphur Moisture Ash Volatile matter Fixed carbon As sampled 80.35 5.00 4.31 1.48 0.86 2.20 5.80 65.1 100% proximate Dry, ash free 87.34 5.44 4.69 1.61 0.92 0 0 29.4 70.6 100% proximate

100% ultimate

100%

ultimate

Significance of Analysis Data Ultimate Analysis a. Carbon

The amount of carbon depends on type of coal and increases with rank in passing from lignites to anthracite. It provides an important basis for classification. Knowledge of carbon content is vital in combustion calculations, especially in evaluating the air requirements and actual air used. b. Oxygen It is also important in classification of coals, as the amount is high in lignites and low in anthracites. The presence of oxygen in coal reduces the available hydrogen. The greater the percent of oxygen in a coal, the lower will be the tendency to form high grade coke. c. Nitrogen The nitrogen varies from 1-2.25%, and is the chief source of ammonia compounds, cyanides, which are important by-products in gas manufacture by carbonization process. d. Sulphur The sulphur content in most coals varies between 0.5-2.5%. It occurs essentially in three forms: pyrites (FeS2), organic compounds in which the S is combined with carbon in the coal substance and gypsum, CaSO4. The presence of pyrite in coal can have disastrous effects in combustion process, as the resultant clinker, fuses at relatively low temperature with firebars (resulting in severe corrosion). When coal is carbonized, 6570% of the sulphur remains in the coke. Coke thus contaminated with S cannot be used for metallurgical processes (<0.6%S necessary). In combustion processes, sulphur forms its dioxide and some trioxide which may produce a film of corrosive H2SO4 acid. e. Phosphorus The amount of phosphorus in coal is relatively low (about 0.1%) and yet this can have an important bearing on metallurgical processing. Blast furnace cokes should not exceed 0.01% phosphorus wherever possible. Proximate Analysis a) Moisture It is present in coal in three forms. Surface Moisture: -acquired during washing and spraying of coal during storage and cleaning. Inherent Moisture: - absorbed and adsorbed in capillaries in the coal substance Combined Moisture: - held in loose combination, as hydrates (CaSO4.2H2O) On exposure to the atmosphere, surface moisture and some inherent moisture evaporate until residual moisture is in equilibrium with the surroundings coal is said to be air dry. The concentration of moisture depends on the relative humidity of air and coal maturity. The lower the rank of a coal, the higher will be the percent moisture retained. Moisture diminishes the gross CV of a fuel. b) Ash It is defined as the incombustible material which remains when coal is burned. Ash may be defined either as inherent or accidental depending on source from which it is derived. Inherent Ash:

present in the original vegetable material from which the coal was formed and is inseperable from the coal substance consist of oxides of K, Na, Mg, Ca and silicon etc. makes up 0.7-1.2% of the coal.

Accidental/Extrinsic Ash - dirt and material picked up from adjacent earthy or stony bands in the coal seam - consists of various materials such as shales, clay, pyrites and ankerites - some but not all of the extrinsic ash can be removed during washing, most through flotation processes. Ash is detrimental in combustion processes for the following reasons: o it lowers the CV of the coal o must be removed and disposed off after combustion o firebars tend to be covered in ash, thus increasing resistance to the flow of air o forms a clinker which fuses with fire-bars (resulting in severe corrosion) c) Volatile Matter It is defined as % loss in weight when finely powdered coal is heated in its own atmosphere at 1200K for 2400s. In its determination, it is important to prevent oxidation of the sample during both heating and cooling. Volatile matter contains essentially three components: i. ii. iii. Gases These are all combustible and include H2, CO, CH4, ethane and H2S Tar This is a complex mixture of hydrocarbons and other organics e.g. benzene, toluene, phenols, cresols, naphthalene and free carbon. Ammonia Liquor It contains N and S compounds with cyanides in aqueous condensate, formed not from tree or inherent moisture but by decomposition of hydrates. In combustion processes volatile matter is the main cause of smoke. Storage of Coal The prime hazard concerned with storage of coal is that of spontaneous combustion of the coal, and it is worth noting that oxidation at the surface of coal takes place at all temperatures, is exothermic and promoted by the rise in temperature. Spontaneous combustion is more likely to occur where there is a high percentage of combined moisture and a large amount of fine coal present. It is therefore advantageous to store screened coal. The mechanism of spontaneous combustion is that to be associated with the formation of very unstable products known as peroxides. The normal reaction for the oxidation of ethane may be written: C2H6 + 7/2O2 2CO2 + 3H2O However it is possible, to form peroxide materials in the following chain of events: C2H6 + O2 CH3O.OCH3 ethane peroxide

H2O + CH3CHO

acetaldehyde

(+3/2O2) CO2 + H2O + HCHO (+O2) H2O + CO2 formaldehyde

PRIMARY FUELS (LIQUID AND GASEOUS) The main naturally fuel occurring naturally as a liquid is crude petroleum and is usually associated with natural gas. Crude petroleum is used directly as a fuel, but is separated into its various components or fractions by physical processes (distillation). Since no chemical processing is involved in this operation, it is convenient to classify distillation products as primary fuels. Origin Petroleum was formed from animal, vegetable or mineral origins by anaerobic decay of marine plant and animal life. In very calm, shallow sea, dead plants and animals fell to the bottom to be covered by a layer of silt. Under such conditions, the dead organic matter which was settling continuously decayed under an-aerobic conditions. The steady accumulation of mud above the organic matter led to an increase in temperature and rise in pressure. Composition of Petroleum Crude petroleum is usually liquid at room temperature and on combustion leaves very much less ash than coal. It is completely soluble in organic solvents e.g. benzene. Its composition and appearance vary widely depending on the source. Many crudes are dark in colour and contain solid wax. The major components in crude petroleum may be grouped under four headings: a. Hydorcarbons They form the greater part of most crudes and are present in a wide range of molecular weights, varying from dissolved gasses to solid waxes. The main group of hydrocarbons is the paraffins and compounds in the series above C16H34 are present as solids (straight chain structure). Also contained within this group are cyclic compounds such as naphthalene and pyridine, olefins, aromatics (i.e. containing a benzene ring) b. Oxygen Compounds Organic compounds containing oxygen are also present in small amounts e.g. naphthenic acids (carboxylic acids containing a naphthene ring). Such acids present problems in the processing and handling of the crude because of corrosion problem and formation of an emulsion of water in the oil. c. Sulphide Compounds

The amount of sulphur in crude oil varies from a trace to several percent depending on source. Among sulphur compounds in oil are mercaptans or thiols (e.g. CH3CH2SH), which have a strong unpleasant odor, thio-ethers and ring compounds such as thiophene. d. Inorganic Compounds They usually exist in very small amounts. Usually in the oil as either suspended particles of mineral matter or dissolved organo-metallic salts. Small amounts of water, often containing inorganic salts, may be present in the crude, frequently as suspension or an emulsion if natural emulsifiers are present. Physical Processing of Crude Petroleum After dirt and water have been removed from crude petroleum and the bulk of the associated natural gas separated, the next stage of processing is physical separation. The primary separation process which is used in almost every stage of petroleum processing is fractional distillation. This involves the separation of a mixture of liquids into its components or fractions, each with limited range of molecular mass, by virtue of their different boiling points. In primary distillation of crude petroleum the aim is to divide the feed into say 8-10 fractions, each with a limited range of boiling points. These fractions are then separated into their various components by subsequent distillation operations. The main unit in which distillation is carried out is the fractionating column. Feed at about 330oC enters the column which usually contains a large number of trays each fitted with bubble caps. The temperature on each tray decreases up the column and hence the liquid on each tray, which is boiling over a fixed temperature range, has a different composition. As the hot vapour pass up the column, the heavier components with higher boiling points condense out and return as liquid to a lower tray. The latent heat released vaporizes lighter components which rise as vapour up the column. Each tray therefore serves to continuously condense and partially re-evaporate the liquid. At steady state, each tray contains liquid within a limited range of temperature, hence composition, which may be drawn off as a side stream. The result of distillation is a wide range of compounds which can be used as a stand fuel. However the market demand of these fuels may require further processing by chemical treatment methods. Natural Gas It is a mixture of light weight alkanes which is usually found in association with crude petroleum. Table 3: Typical composition of natural gas
Methane Ethane Propane Butane Hydrogen Carbon dioxide Oxygen Nitrogen Hydrogen sulphide Rare gases CH4 C2H6 C3H8 C4H10 H2 CO2 O2 N2 H2S Ar, He, Ne, Xe 70-90 <7% 0-20% <4% Nil 0-8% 0-0.2% 0-5% 0-5% trace

Composition varies depending on the source. Natural gas can be used directly as a fuel in both domestic and industrial applications. It is however very dangerous because of its high flammability if it leaks without being dictated. It can also be blended with coal gas or reformed to produce coal gas. In some cases, natural gas can be reformed to produce synthesis gas which is vital for the petro-chemical industry, e.g. from the synthesis gas ammonia can be produced to make fertilizers. Fluidised Bed Combustion It utilizes a bed of inert material such as sand or ash, in which passage of the combustion air is such that the solid-air mixture behaves as a fluid. The advantages of such a system are: High degree of mixing High rates of heat transfer The system can also cope with low grade coals (i.e. coals with high ash and sulphur concentrations, because of the low bed temperature of 1075-1225K compared with the grate)