See discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/265602602 Fuels and Combustion CHAPTER – 4 FUELS AND COMBUSTION 4.1 Introduction 4.2 Requirements of a Good Fuel Chapter · October 2010 CITATIONS READS 0 6,042 1 author: Syed Shabudeen P.S. Kumaraguru College of Technology 193 PUBLICATIONS 137 CITATIONS SEE PROFILE All content following this page was uploaded by Syed Shabudeen P.S. on 15 September 2014. The user has requested enhancement of the downloaded file. Fuels and Combustion 4.1 CHAPTER – 4 FUELS AND COMBUSTION 4.1 Introduction Fuel is a combustible substance, containing carbon as a main constituent, which on proper burning gives large amount of heat, which can be used economically for domestic and industrial purpose. Example : Wood, charcoal, coal, kerosene, petrol, diesel, producer gas, oil gas etc. During the process of combustion, carbon, hydrogen, etc., combine with oxygen with a liberation of heat. The combustion reaction can be explained as C + O2 2H2 + O2 CO2 + 94 kcals 2H2O + 68.5 kcals The calorific value of a fuel depends mainly on the amount of Carbon and Hydrogen. 4.2 Requirements of a Good Fuel A good fuel should have the following characteristics: o High calorific value. o Moderate ignition temperature. 4.2 Applied Chemistry o Low contents of non-combustible matters. o Low moisture content. o Free from objectionable and harmful gases like CO, SOx, H2S. o Moderate velocity of combustion. o Combustion should be controllable. o Easy to transport and readily available at low cost. 4.3 Classification of Fuels Fuels are classified into (i) Primary or Natural fuels - These are found in nature. (ii) Secondary or Artificial fuels - These are derived from primary fuels. Primary and secondary fuels may also be divided into 3 classes namely solid, liquid and gaseous fuels. Fuels Primary or Natural Fuels Solid Fuels Ex.: Wood Secondary or Artificial Fuels Liquid Fuels Ex.: Oil. Solid Fuels Ex.: Charcoal Gaseous Fuels Ex.: Natural gas Liquid Fuels Ex.: Petrol Gaseous Fuels Ex.: LPG Fuels and Combustion 4.3 Fossil fuels Fossil fuels are those, which have been derived from fossil remains of plant and animal life. They are found in the earth’s crust. All conventional fossil fuels whether solid, liquid or gaseous (coal, petroleum or Natural gas) contain basically carbon and / or hydrogen. The fuels on combustion in presence of oxygen in the air release heat energy. This heat energy can be utilized for domestic and industrial purposes. Advantages of Solid fuels 1. Handling and transportation of solid fuels are easy. 2. Solid fuels are cheap and easily available. 3. They have a moderate ignition temperature 4. This type of fuel can be stored conveniently without any risk. Disadvantage of solid fuels: 1. During burning, solid fuels produce a large amount of ash and disposal of ash is a big problem. 2. The calorific value of solid fuel is comparatively low. 3. Since a lot of air is required for complete combustion, its thermal efficiency is not so high. 4. A large space is required for storage. 5. Combustion is a slow process and it cannot be easily controlled. Advantages of Liquid fuels 1. Liquid fuels do not yield any ash after burning. 2. They require comparatively less storage space. 4.4 Applied Chemistry 3. Calorific value of liquid fuel is higher than that of solid fuels. 4. Their combustion is uniform and easily controllable. Disadvantages of liquid fuels: 1. Liquid fuels are comparatively costlier than the solid fuels. 2. They give combustion. unpleasant odour during incomplete 3. Some amount of liquid fuels will escape due to evaporation during storage. 4. Special type of burners are for effective combustion. Advantages of gaseous fuels: 1. Gaseous fuels can be easily transported pipes. through the 2. They do not produce any ash or smoke during burning. 3. They have high calorific value than the solid fuels. 4. They have high thermal efficiency. Disadvantages of gaseous fuels 1. They are highly inflammable and hence the chances for fire hazards are high. 2. Since gases occupy a large volume, they require large storage tanks. 4.3.1 Solid Fuels 1.Coal and its varieties (or) Ranking of Coal Coal is an important primary solid fuel that has been formed as a result of alteration of vegetable matter under some favourable conditions. Fuels and Combustion 4.5 The process of conversion of lignite to anthracite is called coalification (or) metamorphism of coal. Coal is classified on the basis of its rank. The rank of coal denotes its degree of maturity. Vegetable matter, under the action of pressure, heat and anaerobic conditions, gets converted into different stages of coal namely, Wood → Peat → lignite → sub-bituminous → bituminous coal coal ↓ anthracite With the progress of coal forming reaction, moisture content and oxygen content reduces and % of carbon increases. Also calorific value increases from peat to bituminous. (Table 1.1). Classification of coal a) Peat 1. Peat is the first stage in the formation of coal. 2. Its calorific value is about 4000-5400 k cal/kg. 3. It is an uneconomical fuel due to its high proportion of (80 -90%) moisture and lower calorific value. 4. It is a brown fibrous mass. b) Lignite 1. Lignite is an intermediate stage in the process of coal formation. 2. Its calorific value is about 6500-7100 k cal/kg 3. Due to the presence of high volatile content, it burns with long smoky flame. 4.6 Applied Chemistry Table 4.1 4.1 Classification of solid fuels & its calorific values Table Fuel Peat Lignite Subbituminous coal Bituminous coal Anthracite Nature Highly fibrous light brown in colour Fibrous, brown coloured coal Black coloured, homogenious smooth mass, Black, brittle, burns with yellow smoky flame Hard & most matured coal, burns without smoke Calorific value k.cals/kg 4000 5400 Compo sition % C = 57 H = 06 O = 35 Domestic fuel, power generation 6500 7100 C = 67 H = 05 O = 26 C = 77 H = 05 O = 16 Manufacture of producer gas & steam Manufacture of gaseous fuels 8000 8500 C = 83 H = 05 O = 10 8500 8700 C = 93 H = 03 O = 03 Power generation, coke making, domestic fuel Boiler heating, metallurgical furnace 7000 7500 Uses Here peat is the most immatured coal, hence it is lowest in rank where as anthracite is the most matured coal, and hence it is highest in rank c) Bituminous coal Bituminous coal is further sub-classified on the basis of its carbon content into three types as: i) Sub- bituminous coal, ii) Bituminous coal and iii) semi-bituminous coal. d) Anthracite 1. Anthracite is the superior grade of coal. 2. Its volatile, moisture and ash contents are very less. 3. Its calorific value is about 8650 k cal/kg. Fuels and Combustion 4.7 4.4 Analysis of Coal In order to asses the quality of coal, the following two types of analysis are made. I. Proximate Analysis o It means finding out weight percentage of moisture, volatile matter, fixed carbon and ash in coal o This analysis gives the approximate composition of the main constituents of coal. o It is useful in deciding its utilization for a particular industrial use. Determination of moisture content in coal About 1 gm of powdered, air dried coal sample is heated in silica crucible at 100 to 105 °C for one hour. Percentage of moisture can be calculated from the loss in weight of the coal sample as Loss in weight of coal ∴ % of moisture in coal = ×100 Weight of coal initially taken Determination of Volatile Matter (V.M.) in coal After the analysis of moisture content the crucible with residual coal sample is covered with a lid, and it is heated at 950 ± 20 °C for 7.0 minutes in a muffle furnace. Percentage of volatile matter can be calculated from the loss in weight of the coal sample as ∴ % of volatile matter in coal Loss in weight of moisture free coal = ×100 Weight of coal initially taken 4.8 Applied Chemistry Determination of ash in coal After the analysis of volatile matter the crucible with residual coal sample is heated without lid at 700 ± 50 °C for 30 minutes in a muffle furnace. Percentage of ash content can be calculated from the loss in weight of the coal sample as ∴ % of ash in coal = Weight of ash formed ×100 Weight of coal taken Determination of fixed carbon It is determined by subtracting the sum of total moisture, volatile and ash contents from 100. % of fixed carbon = 100 - % of [moisture + V.M + ash] Significance (or) Importance of Proximate Analysis Moisture High moisture content in coal is undesirable because it, i) Reduces Calorific Value of coal ii) Increases the consumption of coal for heating purpose iii) Lengthens the time of heating. Hence, lesser the moisture content, better is the quality of coal. Volatile Matter During burning of coal, certain gases like CO, CO 2, CH4, H2, N2, O2, hydrocarbons etc. that come out are called volatile matter of the coal. Fuels and Combustion 4.9 The coal with higher volatile content, o Ignites easily (i.e : it has lower ignition temperature) o Burns with long yellow smoky flame o Has lower Calorific Value o Will give more quantity of coal gas when it is heated in absence of air. Ash o Ash is the combustion product of mineral matters present in the coal. It consists mainly of SiO2, Al2O3 and Fe2O3 with varying amounts of other oxides such as Na2O, CaO, MgO etc. o Ash containing oxides of Na, Ca and Mg melt early. (Low melting ash). During coke manufacture, the low melting ash forms a fused lumpy - expanded mass which block the interspaces of the ‘grate’ and thereby obstructing the supply of air leading to irregular burning of coal and loss of fuel. o High ash content in coal is undesirable because it (a) increases transporting, handling, storage costs, (b) is harder and stronger, (c) has lower Caloific Value. Fixed Carbon It is the pure carbon present in coal. Higher the fixed carbon content of the coal, higher will be its Caorific Value. II. Ultimate Analysis o It means finding out the weight percentage of carbon, hydrogen, nitrogen, oxygen and sulphur of the pure coal free from moisture and inorganic constituents. o This analysis gives the elementary constituents of coal. o It is useful to the designer of coal burning equipments and auxiliaries. 4.10 Applied Chemistry Determination of carbon and hydrogen in coal A known amount of coal is burnt in presence of oxygen there by converting carbon and hydrogen of coal into CO2 (C + O2 → CO2) and H2O (H2 + ½ O2 → H2O) respectively. The products of combustion (CO2 and H2O) are made to pass over weighed tubes of anhydrous CaCl2 and KOH, which absorb H2O and CO2 respectively. The increase in the weight of CaCl2 tube represents the weight of water formed while increase in the weight of KOH tube represents the weight of CO2 formed. % of carbon and hydrogen in coal can be calculated as follows. Let X - the weight of coal sample taken Y - the increase in the weight of KOH tube Z - the increase in the weight of CaCl2 tube a) Carbon C + O2 → CO2 12 32 44 44 gms of CO2 contain 12 gms of carbon. 12 1 gm of CO2 contains gms of carbon 44 12 Y gm of CO2 contains = × Y gms of carbon 44 % of C in coal = 12 Y × × 100 44 X b) Hydrogen H2 + ½ O2 2 16 → H2O 18 18 gms of water contains 2 gms of hydrogen. Fuels and Combustion 4.11 1 gm of water contains 2 / 18 gms of hydrogen. 2 × Z gms of Hydrogen. ∴ Z gms of water contains = 18 % of hydrogen in coal = 2 Z × × 100 18 X Determination of Nitrogen in coal Nitrogen estimation is done by Kjeldahl’s method. A known amount of powdered coal is heated with con. H2SO4 and K2SO4 in a long necked flask (called Kjeldahl’s flask), there by converting nitrogen of coal to ammonium sulphate. When the clear solution is obtained (i.e. the whole nitrogen is converted into ammonium sulphate), it is heated with 50% NaOH solution. (NH4)2 SO4 + 2NaOH Na2SO4 + 2NH3 The ammonia thus formed is distilled over and is absorbed in a known quantity of standard 0.1N HCl solution. The volume of unused 0.1 N HCl is then determined by titrating against standard NaOH solution. Thus, the amount of acid neutralized by liberated ammonia from coal is determined. Let, Volume of 0.1N HCl Volume of unused HCl Acid neutralised by ammonia We know that 1000 ml of 1 N HCl (A - B) ml of 0.1N HCl = A ml = B ml = (A - B ) ml = 1 mole of HCl = 1 mole of NH3 = 14 gms of N2 14 ×( A B ) × 0.1 = gms of N2 1000 ×1N 4.12 Applied Chemistry X gms of coal sample contains = 14 x ( A B) x 0.1 gms of N2 1000 x 1N % of Nitrogen 14 x Volume of Acid consumed x Normality x 100% 1000 x Weight of coal sample(X) = = 1.4 x Volume of Acid consumed x Normality % Weight of coal sample(X) Determination of Sulphur in coal A known amount of coal is burnt completely in bomb calorimeter in presence of oxygen. Ash thus obtained contains sulphur of coal as sulphate, which is extracted with dil HCl. The acid extract is then treated with BaCl2 solution to precipitate sulphate as BaSO4. The precipitate is filtered, washed, dried, and weighed, from which the sulphur in coal can be computed as follows. Let, X = weight of coal sample taken M = weight of BaSO4 precipitate formed. S + 2O2 SO4 32 BaSO4 233 233 gms of BaSO4 contains 32 gms of sulphur 1 gm of BaSO4 contains 32 / 233 gms of sulphur ∴ M gms of BaSO4 contains (32 / 233) x M gms of sulphur % of sulphur in coal = 32 M x x 100 233 X Fuels and Combustion 4.13 Significance (or) Importance of Ultimate Analysis i) Carbon and Hydrogen 1. Higher the % of carbon and hydrogen, better the quality of coal and higher is its calorific value. 2. The % of carbon is helpful in the classification of coal. 3. Higher the % of carbon in coal reduces the size of combustion chamber required. ii) Nitrogen 1. Nitrogen does not have any calorific value, and its presence in coal is undesirable. 2. Good quality coal should have very little nitrogen content. iii) Sulphur Though sulphur increases the calorific value, its presence in coal is undesirable because 1. The combustion products of sulphur, i.e, SO2 and SO3 are harmful and have corrosion effects on equipments. 2. The coal containing sulphur is not suitable for the preparation of metallurgical coke as it affects the properties of the metal. iv) Oxygen 1. Lower the % of oxygen higher is its calorific value. 2. As the oxygen content increases its moisture holding capacity increases and the calorific value of the fuel is required. 4.14 Applied Chemistry Carbonisation of coal Heating of coal in absence of air at high temperature to produce a residue coke, tar and coal gas is called as carbonisation. i. Caking of coal When coal is heated strongly, the mass becomes soft and coherent, then it is called caking of coal. ii. Coking of coal Otherwise if the mass produced is hard, porous and strong then it is called coking of coal. All the caking coals do not form strong, hard and coherent residue coke. Hence all the caking coals are not necessarily coking coal but all the coking coals have to be necessarily caking in nature. 4.5 Metallurgical Coke When bituminous coal is heated strongly in absence of air, the volatile matter escapes out and a lustrous, dense, strong, porous and coherent mass is left, which is called metallurgical coke. Properties or Characteristics of Metallurgical Coke The most important industrial use of coke is in the metallurgical industry, especially in the blast furnace. Good coke for metallurgy should possess the following requirements. i) Purity Low moisture and ash content are desirable in metallurgical coke. It must contain minimum % of P and S. Fuels and Combustion 4.15 ii) Porosity High porosity is desirable in furnace cokes to obtain high rates of combustion. iii) Strength The coke should be hard and strong to withstand pressure of ore, flux etc in the furnace. iv) Size Metallurgical coke must be uniform and medium size. v) Calorific value The Calorific Value of coke should be high. vi) Combustibility It should burn easily. vii) Reactivity It refers to its ability to react with O2, CO2, steam and air. The metallurgical coke must have low reactivity. viii) Cost It must be cheap and readily available. Why is Coke superior as a Metallurgical fuel? i) ii) iii) Coke is stronger and more porous than coal. Coke contains lesser amount of sulphur than coal. Coke does not contain much volatile matter. 4.16 Applied Chemistry 4.5.1 Manufacture of Metallurgical Coke Mainly two types of ovens are used for metallurgical coke production. They are i. Beehive Coke Oven Process. ii. Otto Hoffman’s by-product method. i) Beehive Coke Oven Process The oven is a dome shaped structure and made up of firebricks. There are two openings, one at the top and the other at the side. Coal is charged through the top circular opening whereas coke is removed through the side door after carbonization. The side door also acts as air inlet. Its typical dimensions are, height = 2 m; base dia = 3.5 m and capacity = 5 tons of coal. (Fig .4.1) First some air is supplied in to the oven to ignite the coal. The volatile matter present in coal escapes and burns inside. Therefore heat for carbonization is supplied by burning of volatile matter and partly by coal itself. Charging door Refractory lining 2m Coal 3.5m Door for air supply and coke discharging Fig Fig 4.1 4.2 Beehive coke oven Carbonization proceeds, from top to bottom. It takes about 3 to 4 days to complete. The hot coke is then removed through the side door and quenched with water. Fuels and Combustion 4.17 Demerits Since volatile matter present in coal escapes into atmosphere as waste, we cannot recover any byproduct. Large coking time and coke yield of only 60% are other demerits. ii) Otto Hoffman’s by-product Coke Oven In order to increase the thermal efficiency of the carbonization process and recover the valuable by products (like coal gas, ammonia, benzene, etc.) Otto Hoffman developed modern by-product coke oven. The oven consists of a number of silica chambers. Each chamber is about 10 - 12 m long, 3 - 4 m height and 0.4 - 0.45 m wide. Each chamber is provided with a charging hole at the top, it is also provided with a gas off take valve and iron door at each end for discharging coke. A, B, C, D - Coke Ovens 1,2,3,4 - Heat re-generators To Chimney Coal gas To Chimney Producer gas Air 4.2 Otto Hoffman’s by-product coke oven Fig 4.3 Coal is introduced in to the silica chamber and the chambers are closed. The chambers are heated upto 1200°C by burning pre heated air and the producer gas mixture in the interspaces between the chambers. 4.18 Applied Chemistry The air and gas are preheated by sending them through 2 nd and 3 hot regenerators. Hot flue gases produced during carbonization are allowed to pass through 1st and 4th regenerators are heated by hot flue gases, the 2 nd and 3rd regenerators are used for heating the incoming air and gas mixture. rd For economical heating, the direction of inlet and flue gases are changed frequently. The above system of recycling the flue gases to produce heat energy is known as the regenerative system of heat economy. When the process is complete, the coke is removed and quenched with water. Time taken for complete carbonisation is about 12 - 20 hours. The yield of coke is about 70 %. The valuable by products like coal gas, tar, ammonia, H2S and benzene, etc are removed from the flue gas. Recovery of by products i) Tar The coke oven gas is first passed through a tower in which liquor ammonia is sprayed. Tar and dust get collected in a tank below, which is heated by a steam coil to recover back the ammonia sprayed. ii) Ammonia The gas is then passed through the other tower where water is sprayed. Ammonia gets converted to NH4OH. iii) Benzene and other aromatic compounds The gas is then passed through the next tower in which creosite oil is sprayed. Benzene and other aromatic compounds are dissolved in the oil and recovered. Fuels and Combustion 4.19 iv) Hydrogen sulphide The gas then enters into a purifying chamber packed with Fe2O3, which removes any sulphur compound present in coal gas. Advantages of Otto Hoffman’s process o High thermal efficiency and carbonization time is less. o Valuable by products (like coal gas, ammonia, benzene, etc. are recovered as by products. o Heating done externally by producer gas. 4.6 Liquid Fuels Petroleum Petroleum or crude oil is a naturally occurring brown to black coloured viscous oil formed under the crust of earth, on shore or off shore. Chemically it is a mixture of various hydrocarbons with small amounts of N, O, S compounds. The approximate composition of petroleum is C = 80 - 84% H = 10 - 14 % S = 0.1 - 0.5 % N+ O = Negligible Classification Petroleum is classified on the basis of various types of hydrocarbons. i) Paraffin based oil - Contains mainly n - alkanes (Ex : Pennsylvanian and gulf coast oil) 4.20 ii) iii) Applied Chemistry Asphalt base oil - Contains aromatic and alicyclic hydrocarbons. (Ex: Californian oil) Mixed base oil - Contains higher proportion of aromatics and naphthenes (cyclo alkanes). (Ex : Mexican oil) 4.6.1 Refining of Petroleum (or) Crude Oil Definition The process of removing impurities and separating out the oil into various fractions having different boiling points is known as refining of petroleum. Uncondensed gases Loose cap Petroleum ether Gasoline Chimney Naptha Tray Kerosene Crude oil Diesel oil Lubricating oil Heavy oil Furnace at 400° C Fractionating Column Fig Fig.4.3 4.4 Fractional distillation of crude oil Fuels and Combustion 4.21 i) Removal of Impurities The impurities present in the oil are the fine water droplets, NaCl, MgCl2, Sulphur etc. The crude oil is an extremely stable emulsion of oil and salt water. Water is separated from the oil by Cottrell’s process using ring electrodes. In this method, the crude oil is allowed to flow between two highly charged electrodes. The colloidal water droplets combine to form large drops, which are then separated from oil. Modern techniques like electrical desalting are used to remove NaCl and MgCl2 from oil. Sulphur is removed by treating the oil with copper oxide and separated by filtration. ii) Fractional Distillation The purified crude oil is heated in a furnace called oil heater where the temperature will be around 400o C. Here the oil gets vapourised. The hot vapours are then sent to the fractionating column (Fig. 1.3 ). It is a tall cylindrical tower consisting of a number of horizontal stainless steel tray at short distances. Each tray is provided with a small chimney, which is covered with a loose cap. The tower will be hot at the lower end and comparatively cooler at the upper end. When the oil vapours go up in the tower, they become cool and condense. The heavier compounds having higher boiling points get cooled first and condensed in the trays whereas the fractions having lower boiling points condense near the top of the tower. 4.22 Applied Chemistry Lower fractions are used after purification while the high boiling point fractions are subjected to cracking operation to get more useful lower fractions. The gasoline obtained by this fractional distillation is called straight-run gasoline. Various fractions obtained at different trays are given in Table 1.2. Table 4.2 Various fractions, Compositions and their uses Sl.No 1. 2. 3. 4. Name of the Boiling fraction Range oC Uncondensed Below 30 gases Petroleum ether 30-70 Gasoline or 40-120 petrol Naphtha or 120-180 solvent spirit 5. Kerosene oil 180-250 6. Diesel oil 250-320 7. Heavy oil 320-400 Range of Uses C-Atoms C1-C4 As a fuel under the name of LPG C5-C7 As a solvent C5-C9 Fuel for IC engines C9-C10 As a solvent in paints and in dry cleaning C10-C16 Fuel for stoves and jet engines C15-C18 Diesel engine fuel C17-C30 Fuel for ships and for production of gasoline by cracking. Fuels and Combustion 4.23 Heavy oils on refraction gives S.No 1. 2. 3. 4. Name of the Fraction Lubricating oil Petroleum jelly or Vaseline Grease Paraffin wax 5. Pitch at above 4000C Uses as lubricants Used in medicines and cosmetics Used as lubricant Used in candles, boot polishes etc., Used for making roads, water proof roofing etc. Some important fractions of petroleum i) Petrol (or) Gasoline (C5-C9) o It is a low boiling fraction of petroleum obtained between 40 - 120o C. o It is a mixture of hydrocarbons pentane to nonane (in terms of carbon atoms C5 - C9). o Its calorific value is about 11,250 kcals/kg. o It is used as fuel in ICE of automobiles and aero planes. o Its antiknock value can be improved by the addition of Tetra Ethyl Lead (TEL). Uses : It is used as a fuel in IC engine and also used in dry cleaning and as a solvent. ii) Naphtha (C9-C10) It is a colourless, light fraction obtained between 120 C to 1800C during fractional distillation of petroleum. It is a mixture of hydrocarbons such as nonane and decane. Uses Naphtha is also called as white spirit, which is generally used in dry cleaning and as thinner for varnish, floor and 0 4.24 Applied Chemistry furniture polishes etc. The lightest portion of the distillate is used as solvent for fats and rubbers, whereas the heaviest portion of the same is used as a fuel. iii) Kerosene( C10-C16) It is relatively a high boiling fraction obtained between 180-250oC during fractional distillation of petroleum. It is a misture of hydrocarbons such as decane to hexadecane.s approximate composition is C = 84%, H = 16%, > 0.1% S. Its calorific value is about 11,100 kcal/kg. Uses: It is mainly used as a domestic fuel in stoves and lamps. It is also used as jet engine fuel and for making oil gas. iv) Diesel (C15-C18) It is also a high boiling fraction obtained between 250320oC during fractional distillation of petroleum. It is a mixture of hydrocarbons such as C15H32 to C18H38. Its calorific value is about 11,000 kcal/kg. Uses It is used as a very good diesel engine fuel. v) Heavy oil or Residual fuel oil (C17 – C30) The left over portion of petroleum after distilling off all the lighter fractions are called Fuel Oil. The approximate composition of fuel oil is C = 86%, H = 12%, S = 1%, H2O = 0.6%; sediments = 0.4%. Its calorific value is about 9200 kcal/kg. The following fractions are obtained on further vacuum distillation of the fuel oil. i) Light fuel oil = 350 -420oC ii) Heavy neutral oil = 420-500oC Fuels and Combustion 4.25 Uses: It is used as fuel for ships and also used in metallurgical furnaces. Gasoline is also obtained from oil by cracking process. vi) Asphalt Asphalts are obtained by i) The oxidation of residual heavy oil in presence of air at higher temperature. ii) The deep vacuum distillation of residual heavy oil. Asphalts are available in the market in liquid, semi-solid and solid forms. Uses: It is used for road making and making water-proofing roofs. It is also used for the manufacture of water proofing concrete and water proofing paints. 4.7 Cracking Cracking is defined as “the decomposition of high boiling hydrocarbons of high molecular weight into smaller, low boiling hydrocarbons of low molecular weight” C10H22 C5H12 Decane n-Pentane B.Pt : 174°C + C5H10 Pentene B.Pt : 36°C The crude oil on fractional distillation yields only about 15 - 20 % gasoline. This is known as Straight Run Gasoline. The quality of straight run gasoline is not so good. It contains mainly straight chain paraffin’s, which ignite readily and more rapidly than any other hydrocarbons and hence it produces knocking (unwanted sound) in IC engines. 4.26 Applied Chemistry In order to overcome these difficulties and also to improve the quality of gasoline, high boiling fractions are cracked into more valuable low boiling fractions suitable for SI engines. The gasoline obtained by cracking is called Cracked Gasoline. During cracking o Straight chain alkanes are converted into branched chain hydrocarbons. o Saturated hydrocarbons are converted into mixture of Saturated and Unsaturated hydrocarbons. o Aliphatic alkanes are converted into cyclic alkanes. o All hydrocarbons obtained by cracking have lower boiling point than the parent hydrocarbons. Types of cracking There are two kinds of cracking 1. Thermal cracking 2. Catalytic cracking 1. Thermal Cracking When cracking is carried out a higher temperature and pressure without any catalyst, it is called Thermal cracking. There are two types of thermal cracking: i) Liquid phase Thermal cracking In this method, the heavy oil is cracked at a temperature of 475-5300C under high pressure of 100 kg/cm2 to keep the reaction product in liquid state. The cracked products are then separated into various fractions in a fractionating column. The yield of gasoline is about 50-60% and the octane number is 65-70. Fuels and Combustion 4.27 ii) Vapour phase thermal cracking In this method, the heavy oil is first vapourised and then cracked at a temperature of 600-6500C under a lower pressure of 10-20 kg/cm2. The yield of gasoline is about 70%. This process is suitable only for those oils which are readily vapourised. Catalytic Cracking When cracking is carried out at lower temperature and pressure in the presence of suitable catalyst, it is called Catalytic Cracking. The Catalyst used are aluminium silicate or alumina. There are two types of catalytic cracking. 1. Fixed bed catalytic cracking The heavy oil vapour is heated to 420-450oC in a preheated chamber. The hot vapours are then passed through a catalytic chamber, maintained at 425-450oC and 1.5 kg/cm2 pressure, where catalyst ( artificial clay mixed with zirconium oxide), are kept in fixed beds. During this passage through the catalytic chamber about 40% of the heavy oil is converted into gasoline and about 2-4% carbon is formed. The carbon gets adsorbed on the catalyst bed. The cracked vapours are then passed through the fractionating column, where heavy oil gets condensed at the bottom. The vapours of gasoline are then sent through the cooler where gasoline gets condensed along with some gases. The gasoline containing some dissolved gases is then sent to a stabilizer, where the dissolved gases are removed and pure gasoline is recovered. After 8-10 hours, the catalyst loses its activity due to the deposition of carbon. It is reactivated by burning off the deposited carbon. 4.28 Applied Chemistry Fig 4.4 Fixed bed catalytic cracking 2. Moving bed or Fluid bed catalytic cracking In this process, the solid catalyst is finely powdered, so that it behaves as a fluid, which can be circulated in oil vapour (Fig 1.5) . The heavy oil vapour is heated to 420-450oC in a preheater and it is mixed with the catalyst powder. Then this mixture is forced into the reactor, which is maintained at a temperature of 500oC and a pressure of 5 kg/cm2, where cracking takes place. Near the top of the reactor, there is a centrifugal separator ( called cyclone), which allows only the cracked oil vapours to pass on to the fractionating column leaving behind the catalyst powder in the reactor itself. The catalyst powder gradually becomes heavier, due to coating of carbon and it settles down at the bottom of the reactor. Then it is forced into the regenerator maintained at 600 oC, where carbon is burnt and the regenerated catalyst is again recirculated along the heavy oil vapour. Fuels and Combustion 4.29 Fig 4.5 Moving bed catalytic cracking From the reactor, the cracked oil vapours are passed into the fractionating column, where heavy oil settles down and the vapours are then passed through the cooler where gasoline condenses along with some gases. The dissolved gases are separated from gasoline by passing it through a stabilizer. 4.8 Manufacture of Synthetic Petrol Petrol can be synthesized by any one of the following methods. I. Polymerization a. Thermal Polymerization b. Catalytic Polymerization II. Hydrogenation of Coal a. Bergius Process (or) Direct Process. b. Fisher Tropsch Process (or) Indirect Process. III. Alkylation 4.30 Applied Chemistry I. Polymerisation The gases produced in cracking contain C3 and C4 olefins (iso propylene, iso butylene etc) and alkanes (methane, ethane, propane, butane). These gases undergo polymerisation in presence of catalyst, (H3 PO4) at suitable temperature and pressure to give gasoline (Polymer petrol), rich in branched chain hydrocarbons. Hence, polymerisation is mainly for the production of superior gasoline and is complementary to catalytic cracking. Polymerisation is of two types i) Thermal Polymerisation Polymerisation of cracked gases is carried out at 500 600 C and 70 - 350 kg/cm2 pressure. The product is the gasoline and gas oil mixture, from which gasoline is separated by fractionation. o ii) Catalytic Polymerisation This process is carried out in presence of catalyst like H3PO4 . By this method isobutylene can be polymerised to give higher olefin’s which is hydrogenated to gasoline hydrocarbons. II. Hydrogenation of Coal Coal contains 4.5 % of Hydrogen, where as petrolium contains 18 % of hydrogen. So coal is a hydrogen deficient compound, if coal is heated with hydrogen at high temperature and high pressure, it is converted in to gasoline. The preparation of liquid fuels from solid coal is called Hydrogenation of coal. Petrol can be synthesised by destructive hydrogenation of coal (Bergius process) and liquification of coal (Fischer Tropsch process). Fuels and Combustion 4.31 i) Bergius Process (or) Direct Process The raw materials used in this process are coal dust, heavy oil and nickel oleate or tin oleate. A coal paste is prepared by mixing coal dust with heavy oil and catalyst. It is then pumped into the converter where the paste is heated to 450 - 500o C under 200 - 250 atm in presence of hydrogen. (Fig. 4.6) Cooler Powdered coal Catalyst Gases Gasoline Paste Middle oil Heavy oil H2 Heavy oil Converter Fractionating Column Fig Fig.4.6 1.5 Bergius Process The reaction products mainly contain mixture of hydrocarbons. Coal dust suspended in heavy oil + H2 450 °C Mixture of hydrocarbons 200-250 atm Condensation Crude oil 4.32 Applied Chemistry Since the reaction is exothermic the vapours leaving the converter are condensed in the condenser to give synthetic petroleum or crude oil. The oil is then fractionally distilled to give (i) Petrol (ii) Middle oil (iii) Heavy oil. Middle oil is again hydrogenated in presence of solid catalysts to produce more amount of gasoline. Heavy oil is used for making paste with fresh coal dust. Yield is about 60 %. II Fischer - Tropsch Process The raw materials used in this process are hard coke, steam to produce water gas i.e., water gas is obtained, by passing steam over red hot coke. H2 Water gas Cooler Gases Fe2O3 Gasoline Middle oil Heavy oil Fe2O3+ Na2CO3 Compressor Converter Cracking Fractionating Column Fig. 4.7 Fisher Tropsch Process Fuels and Combustion 4.33 C + H2O 1200oC CO + H2 Water gas The first step in this process is purification of gas. To remove H2S, the gas is passed through Fe2O3 and to remove organic sulphur compounds, the gas is again passed through a mixture of Fe2O3 and Na2CO3.( Fig. 4.7 ) The purified gas is compressed to 5 - 25 atm. and passed over a catalyst bed containing oxides of Th, Co and Mg at 200 300o C. While passing the purified gas through this catalyst bed, it is converted to straight chain paraffin and olefins. n CO + (2n + 1) H2 n CO + 2n H2 CnH2n+2 + n H2O n – paraffins CnH2n + n H2O olefins Since the reactions are exothermic, the vapours leaving the vessel are condensed in the condenser to give petroleum. It is fractionally distilled to yield petrol and heavy oil. III. Alkylation Replacement of hydrogen atom from a hydrocarbon by an alkyl group is known as Alkylation. Example: Anhydrous H3 C CH CH 3 + H2C C CH3 CH3 CH 3 Iso butane Iso butene HF H3C H3 C CH CH2 H 3C C CH3 Iso octane CH 3 4.34 Applied Chemistry The reaction of isobutane and isobutene in the presence of anhydrous HF at room temperature gives isooctane. This process is highly useful for the production of high quality petrol. Table 4.3 Comparison of straight run, cracked and polymer gasoline Straight run petrol 1. Obtained from straight distillation of crude oil. 2.Contains only n-alkanes. Cracked petrol Polymer petrol Obtained heavy oil. from Obtained from low molecular weight gaseous fraction. Contains Contains more of isoparaffins and branched chain hydroaromatics. carbons Narrow range Very narrow range. 3.Composition range C5 – C9 4. Low octane Higher number number octane Higher octane number Purification of Petrol (or) Gasoline Gasoline or petrol obtained either from crude oil or synthetic process may contain some undesirable impurities. They are mainly unsaturated olefins, colouring matters, sulphur compounds etc. The unsaturated olefins get oxidised and polymerised there by causing gum and sludge formation on storing On the other hand, sulphur compounds lead to corrosion of ICE and also affect tetra ethyl lead (TEL) which is added to gasoline to obtain good petrol. So these undesirable contents must be removed from gasoline. Unsaturated olefins and colouring matter are removed by using adsorbent like Kieselguhr, fuller’s earth. Fuels and Combustion 4.35 Sulphur containing petrol is known as sour spirit. The process of desulphurisation of petrol is called sweetening of petrol. Desulphurisation It can be done by Doctor’s treatment. i.e.; petrol is treated with an alkaline solution of sodium plumbite (Doctor’s solution) and little of sulphur. 2RHS + Na2PbO2 Sodium Plumbite (R-S-S-R) Pb + 2NaOH Lead mercaptide The resulting disulphide ( lead mercaptide) in gasoline are extracted by using suitable solvent. After refining of gasoline, some inhibitors or antioxidants are added in order to retard the oxidation of olefins (olefin peroxide) which cause the formation of gum on storage. 4.9 Knocking Fractions like petrol and diesel oil are used as engine fuels. Piston engines can be divided into spark ignition (SI) and compression ignition (CI) engines. The former consumes petrol and the latter operates on diesel oil. SI Engines In a four stroke SI engine, petrol vapour is mixed with air in the carburetor. It is sucked into the cylinder during the suction stroke. The mixture is compressed by the piston in the compression part of the cycle. Then the compressed mixture is ignited by an electric spark. The product of combustion increases pressure and pushes the piston out, providing an output of power. 4.36 Applied Chemistry In the last part of the cycle, the piston ascends and expels the exhaust gases from the cylinder. Knocking in SI Engines (Petrol Engines) Normally the fuel - air mixture should burn smoothly and rapidly by sparking. In some cases, as a result of compression, the fuel-air mixture may get heated to a temperature greater than its ignition temperature and spontaneous combustion occurs even before sparking. This is called pre-ignition. Further, the spark also is emitted which makes the combustion of the rest of the mixture faster and explosive. So, we have a sudden, badly controlled burning and explosion results a characteristic metallic or rattling sound from the engine. This is called knocking or detonation or pinking. Knocking lowers the efficiency of engine which results in loss of energy. Chemical Structure and Knocking The knocking tendency decreases as follows : n-alkanes isoparaffins olefins naphthenes aromatics n-alkanes have lowest antiknock value. So the presence of maximum quantity of aromatics and minimum quantity of n-alkanes is desirable in petrol. Octane number (Measurement of knocking in SI engines) Octane number expresses the knocking characteristics of petrol. n - heptane (a constituent of petrol) knocks very badly, so its anti-knock value has been given zero. On the other hand, isooctane (also a constituent of petrol) gives very little knocking, so its anti-knock value has been given 100. Fuels and Combustion 4.37 Percentage of iso-octane present in iso octane & n-heptane mixture, which matches the same knocking characteristics of gasoline mixture test sample. If a petrol sample behaves like a mixture of 60% iso-octane and 40% n-heptane, its octane number is taken as 60. Leaded Petrol (or) Improvement of Anti-knock Value Adding some additives in it increases octane number of petrol. In motor fuel about 1.0 to 1.5 ml tetra ethyl lead (TEL) is added per litre of petrol. Petrol to which TEL is added is called leaded petrol. Mechanism of knocking Knocking follows free radical mechanism, leading to a chain growth. If the chains are terminated before their growth, knocking will cease. TEL decomposes thermally to form ethyl free radicals, which combines with the free radicals of knocking process and thus the chain growth is stopped. Disadvantage of using TEL TEL forms lead oxide, which deposits on spark plug and creates problems. So, to remove it, ethylene dibromide is added. During burning lead bromide is formed which evaporates away in the heat engines and goes out together with exhaust gases. This creates atmospheric pollution for human beings. Hence, at present aromatic phosphates are used instead of TEL. CH2 - Br PbBr2 + CH2 = CH2 Pb + CH2 - Br 4.38 Applied Chemistry 4.10 Diesel o It is relatively a high boiling point fraction of petroleum obtained between 250 - 320o C. o It is a mixture of hydrocarbons in terms of carbon atoms C15 - C18 o Its calorific value is about 11,000 kcals/kg. It is used as fuel for compression ignition engine. o Its antiknock value can be improved by doping with isoamyl nitrate. CI Engines In a CI engine, air is alone compressed. This raises the cylinder temperature as high as 300o C. Then the oil is injected or sprayed, which must ignite spontaneously. Now combustion products expand and power stroke begins. Knocking in CI Engines Some times, even after the compression stroke is over and even after the diesel oil is sprayed, burning may not start. So, more and more fuel is injected automatically and sudden ignition may occur and burn the whole of the oil. This delayed ignition results an uncontrolled, excessive combustion produces ‘diesel knock’. So in SI - engine, knocking is due to premature or too early ignition in CI - engines, knocking is due to delayed ignition or ignition lag. Cetane number (or) Cetane Rating Cetane number expresses the knocking characteristics of diesel. Cetane (C16 H 34) has a very short ignition delay and hence its cetane number is taken as 100. On the other hand, - methyl Fuels and Combustion 4.39 napthalene has very large ignition delay and hence its cetane number is taken as zero. Cetane number is defined as “the percentage of cetane present in a mixture of α –methyl naphthalene and cetane”. CH3 CH3 - (CH2)14 - CH3 n-cetane (cetane number = 100) n-Hexadecane Chemical Structure and Knocking The knocking tendency in CI - engines increases as follows, n-alkane iso paraffins Olefins naphthenes aromatics Octane numbers decreases in this order. Therefore an oil of high octane number has a low cetane number and vice-versa. Consequently, petroleum crude gives petrol of high octane number and diesel of low cetane number. Diesel Index The quality of a diesel oil is indicated by diesel index number using the following formula Diesel index number Specific gravity (API) x Aniline point in o F 100 Aniline point and specific gravity is noted from API (American Petroleum Institute) Scale. = 4.40 Applied Chemistry Table 4.4 : Comparison between Petrol and Diesel in Internal Combustion Engines (ICE) S.No PETROL DIESEL 1. Low boiling petroleum (C5 – C10) Fuel for SI engine Knocks due to premature ignition Knocking tendency measured in octane rating Anti-knocking is improved through addition of TEL Lower thermal Efficiency More consumption High boiling fraction of petroleum containsC15– C18 hydrocarbons Fuel for CI engine Knocks due to ignition delay 2. 3. 4. 5. 6. 7. Knocking tendency measured in cetane rating. Anti-knocking is improved by doping with isoamyl nitrate Higher thermal efficiency Less consumption Improvement of cetane number Centane number can be increased by adding additives called dopes. E.g.: ethyl nitrate, isoamyl nitrate 4.11 Aviation gasoline Low molecular weight petroleum fraction, which is used as a fuel in aeroplanes is known as Aviation Gasoline. It condenses at 30o -120o C during fractional distillation of crude oil. Its octane number is 100 or even more. Aviation gasoline may also be produced by the polymerisation , alkylation, isomerisation and reforming process. Fuels and Combustion 4.41 Generally aviation gasoline is made up of higher perecntage of isoparaffins and smaller percentage of naphthalenes an aromatics. Aviation gasoline possesses very good stability, higher volatility and antiknock value than ordinary gasoline. And also in some cases TEL is mixed with avaiation gasoline. 4.12 Natural Gas Natural gas is always found above the oil in the oil wells. It is also called Marsh gas. It conssists of methane and other saturated hydrocarbons. The average composition of natural gas is as follows : Its calorific value varies from 12,000 to 14,000 kcal/m3. Constituents Methane Ethane Propane Butane Pentane Percentage(%) 88.5 5.5 4 1.5 0.5 If natural gas contains lower hydrocarbons like methane and ethane it is called lean or dry gas. In the natural gas contains higher hydrocarbons like propane, butane along with methane it is called rich or wet gas. Uses 1. It is used as a domestic and industrial fuel. 2. It is used as a raw material for the manufacture of carbon black and hydrogen. 3. It is also used for the generation of electricity by using it in fuel cells. 4.42 Applied Chemistry 4.13 WATER GAS (or) BLUE GAS. Water gas essentially a mixture of combustible gases like CO, H2 with a little non combustible gases like CO 2 and N2 Calorific Value Its Calorific Value is 2800 kcals/m3. Composition The average composition is H2 = 48 % CO = 44 % CO2, N2 and CH4 = rest Manufacture A Water gas generator is a steel cylindrical vessel. At the top, it is provided with a hopper for adding coke. Water gas outlet is provided near the top. At the bottom, it is provided with an arrangement of taking out ash formed (Fig. 1.8 ). It is obtained by the action of steam on a bed of coke heated to 1000o C. C + H2O + 28 k.cal CO + H2 Since the above reaction is endothermic, the coal cools down after a few minutes and the reaction proceeds in a different way to form CO2 and H2 instead of water gas (CO + H2). C+ 2 H2O CO2 + 2H2 - 19 kcals Fuels and Combustion Cup and cone feeder 4.43 Coke Water gas outlet Red hot coke at 900-1000oC Grate Air supply Steam supply Refractory brick lining Ash outlet Ash Fig Fig4.8 : 7 Water gas production In order to avoid the above undesirable reaction, the blow of air replaces the blow of steam. The following reaction now occurs. C + O2 CO2 + 97 kcals 2C + O2 2CO + 59 kcals Due to exothermic reactions, the temperature of the bed rises and when the temperature increases to 1000° C, air entry is stopped and steam is again passed. Thus steam and air are blown alternatively. Therefore, the manufacture of water gas is intermittent. Properties It has high Calorific Value & burns with non- luminous flame. Its flame is short but very hot. Uses i) It is used for the manufacture of ammonia by Haber’s process. ii) Carbureted water gas (water gas + oil gas) is used for lighting 4.44 Applied Chemistry and heating purposes. iii) Water gas is also used for welding purposes. iv) Used for the manufacture of methyl alcohol. v) Used for the manufacture of synthetic petrol. 4.14 Producer Gas It is prepared by passing air mixed with a little steam over a red hot coal (or) a coke bed maintained at above 1100 ° C in a special reactor called ‘‘ Gas Producer’’. Composition It is a mixture of CO and N2 . Its average composition is N2 = 50 % CO = 30 % H2 = 10 % CO2 and CH4 = rest. Calorific Value Its Calorific Value is 1800 kcals/m3 . Manufacture The furnace used for the manufacture of producer gas is known as producer. It consists of large airtight mild steel cylindrical tower, lined inside with refractory bricks. At the bottom, it is provided with pipe for blowing air and an arrangement for removing ash. Coal is added through a hopper at the top and producer gas comes out from an exit near the top. a. Combustion zone Fuels and Combustion 4.45 When a mixture of air and little steam is passed through a bed of red hot coal, carbon (of the coal) combines with oxygen (of the air) in the lower part of the furnace to form CO2 C + O2 Distillation zone Reduction zone Combustion zone Air mixed with a little steam CO2 + 97 kcals Coke Cup and cone feeder Producer gas outlet Refractory brick lining CoalO 1000C Exit for ash Fig 4.8 4.9 Gas Producer Fig b. Reduction zone CO2 so formed rises up through the red-hot coal and gets reduce to CO during its passage CO2 + C 2CO - 39 kcals N2 of air remain unaffected throughout the process. Thus a mixture of CO and N2 with traces of CO2 and hydrocarbons comes out through the exit at the upper end of the producer. Properties i) It is a poisonous gas. ii) Insoluble in water. iii) Heavier than air. 4.46 Applied Chemistry Uses i. It is used as fuel for heating open - hearth furnaces (used in steel and glass manufacture), muffle furnaces (used in coal gas and coke manufacture). ii. It provides reducing atmosphere in certain metallurgical operations. 4.15 Liquified Petroleum Gas (LPG) It is a mixture of propane and butane. It is obtained as one of the top fractions in the fractional distillation of petroleum. It is easily liquified and so can be economically stored and transported in cylinders. Composition Its approximate composition is n-Butane = 70 % Isobutane = 17 % n-Propane = 11 % Butylene and Ethane = rest. Calorific Value Its Calorific Value is 27,000 kcals/m3. Uses i. It is used as a fuel for domestic cooking. ii. Used for heating industrial furnaces. iii. Used as an alternate for Gasoline in automobiles. Fuels and Combustion 4.47 4.16 Biogas These gases generally produced by the fermentation of bio wastes, sewage wastes etc., by anaerobic bacteria. For example, natural gas is a Biogas, which results after a long periodic decay of animal and vegetable matters burried inside the earth. The cheapest and easily obtainable biogas is Gobar gas, which is produced by anaerobic fermentation of cattle dung. The biogas is burnt to raise steam, which can drive turbines to produce electricity. Steel gas holder Inlet tank Ground level Dung + water slurry Gas outlet to kitchen Outlet tank for manure 10 cm pipe 10 cm pipe Digestion well Masonry work Fig.4.10 4.9 Gobar gas plant Fig 1.16.1 Gobar Gas i) It is essentially methane. 4.48 Applied Chemistry ii) iii) Its Calorific Value is 5400 kcals/m3. Its average composition is CH4 CO2 H2 = 60 % = 30 % = 10 % It is obtained by fermentation of Gobar (dung) in absence of air. In a typical Gobar gas plant, the dung in the form of slurry is introduced into a brick - lined well called fermentation well. An inverted drum is placed air tightly on the well. It acts as gasholder and it can be moved up and down with the help of pulleys (Fig. 1.10). Formation of gas starts in a week. The optimum temperature for this fermentation is 34 - 48o C. As the gas starts collecting in the drum, the drum begins to rise and float. The gas is taken out from the exit provided at the top of the drum. It is used as a domestic fuel in villages. It is used for domestic heating and small pump running. 4.17 Combustion Combustion is an exothermic chemical reaction, which is accompanied by development of heat and light at a rapid rate, temperature rises considerably. For example, combustion of carbon in oxygen: C(s) +O2(s) CO2 (g) + 97 kcal For proper combustion, the substance must be brought to its kindling (or) ignition temperature, which may be defined as Fuels and Combustion 4.49 the minimum temperature at which the substance ignites and burns without further addition of heat from outside. Factors affecting the rate of combustion The rate of combustion depends on the following factors: 1. The concentration of the fuel and air. 2. The nature of the combustable substance 3. The temperature 4. With increase in pressure or surface area of the fuel the rate of combustion can be increased. 5. It increases with in increase in pressure of air. 6. It Increases with preheating of fuel and air. 4.18 Calorific Value It is the most important characteristic property of any fuel. Calorific value may be defined as “the amount of heat liberated by the complete combustion of a unit mass of a fuel”. The quantity of heat can be measured by the following units. i. Calorie ii. Kilocalorie iii. British thermal units iv. Centigrade heat units Calorie The amount of the heat required to raise the temperature of 1gm of water through 1OC (15 to 16 OC) HIGHER AND LOWER CALORIFIC VALUE i) Gross (or) High Calorific Value (GCV or HCV) 4.50 Applied Chemistry The total heat generated when a unit quantity of fuel is completely burnt and the products of combustion are cooled to room temperature. For example, when a fuel containing hydrogen is burnt, it under goes combustion and will be converted to steam. If the combustion product is cooled to room temperature, the steam gets condensed into water and the latent heat is evolved. Therefore the latent heat of combustion of condensation of ‘steam’ so liberated is included in gross calorific value. Dulong’s formula (Theoretical calculation) Dulong’s formula for the theoretical calculation of calorific value is 1 O GCV (or) HCV = (8080 C + 34500 [ H ] + 2240 S ) kcal/kg 100 8 where, C, H, O & S represent the % of the corresponding elements in the fuel. It is based on the assumption that the calorific values of C, H & S are found to be 8080, 34500 and 2240 kcal, when 1 kg of the fuel is burnt completely. However, all the oxygen in the fuel is assumed to be present in combination with hydrogen in the ratio H : O as 1 : 8 by weight. So the surplus hydrogen available O for combustion is H . 8 ii) Net (or) Lower Calorific Value (NCV or LCV) The net heat produced when a unit quantity of fuel is completely burnt and the products of combustion are allowed to escape. NCV = GCV – Latent heat of condensation of steam produced 1 part by weight of H2 produces 9 parts by weight of H2O as follows. The latent heat of steam is 587 cal/gm. Fuels and Combustion H2 + 2gms 1 4.51 ½ O2 16gms 8 H2O 18gms 9 Thus, 9 H ×587 kcal/kg 100 NCV = GCV – 0.09 H ×587 kcal/kg NCV = GCV – where , H = % of H2 in the fuel. 4.19 Determination of Calorific value using Bomb Calorimeter The calorific value of a solid or liquid fuel can be determined by using bomb calorimeter ( Fig 4.11 ). 4.52 Applied Chemistry Fig 4.11 Bomb Calorimeter Fuels and Combustion 4.53 4.54 Applied Chemistry Fuels and Combustion ii) Acid correction 4.55 4.56 Applied Chemistry Problems based on Calorific Value 1. Calculate the Gross and Net calorific values of a coal having the following compositions, C = 80 %, H2 =08 %, O2 = 08 %, S = 2 % and ash=2. Latent heat of steam is = 587 cal/gm. Solution (i)Gross Calorific Value (GCV) 1 O (8080 C + 34500 [ H ] + 2240 S ) 100 8 1 8 (8080 × 80 + 34500 [8 – ] + 2240 × 2 ) kcal/kg = 100 8 1 (646400 + 241500 + 4480 ) kcal/kg = 100 GCV = Fuels and Combustion = 4.57 1 (892380 ) kcal/kg 100 = 8923.8 kcal / kg. (ii) Net Calorific Value (NCV) 9 H ×587 kcal/kg 100 9 = 8923.8 – ×8×587 kcal/kg 100 = 8923.8 – 422.64 kcal/kg = 8501.16 kcal / kg = GCV – 2. Calculate the Gross and Net calorific values of a coal having the following compositions, C = 63 %, H2 = 19 %, O2 = 03 %, S = 13 % and ash=2. Latent heat of steam is = 587 cal/gm. Solution (i) Gross Calorific Value (GCV) 1 O (8080 C + 34500 [ H ] + 2240 S ) kcal/kg 100 8 1 3 (8080 × 63 + 34500 [19 ] + 2240 ×13 ) kcal/kg = 100 8 1 (509040 + 64562 + 29120 ) kcal/kg = 100 1 (1180722 ) kcal/kg = 100 GCV = = 11807.22 kcal / kg. (ii) Net Calorific Value (NCV) 4.58 Applied Chemistry 9 H ×587 kcal/kg 100 9 = 11807.22 – × 19 ×587 kcal/kg 100 = 11807.22 – 1003.77 kcal/kg = 10803.45 kcal / kg = GCV – 3. Calculate the Gross and Net calorific values of a solid fuel having 80% of carbon & 20% of hydrogen. Latent heat of steam is = 587 cal/gm. Solution (i) Gross Calorific Value (GCV) 1 O GCV = (8080 C + 34500 [ H ] + 2240 S ) kcal/kg 100 8 Here, the % of H2 and S are Zero. 1 0 = (8080 × 80 + 34500 [20 ] + 2240 ×0 ) kcal/kg 100 8 1 [646400 + 690000 ] kcal/kg = 100 1 [1336400 ] kcal/kg = 100 = 13364 kcal / kg. (ii) Net Calorific Value (NCV) 9 H ×587 kcal/kg = GCV – 100 9 = 13364 – × 20 ×587 kcal/kg 100 = 13364 – 1056.6 kcal/kg = 12307.4 kcal / kg Fuels and Combustion 4.59 4. A coal sample on analysis gives C = 75%,H2= 6 %,O2 = 3.5 % S = 03 % and the rest ash. Calculate the Gross and Net calorific values of the fuel. Latent heat of steam is = 587 cal/gm Solution (i) Gross Calorific Value (GCV) GCV = 1 O (8080 C + 34500 [ H ] + 2240 S ) kcal/kg 100 8 1 3.5 (8080 × 75 + 34500 [6 ] + 2240 ×3 ) kcal/kg 100 8 1 = [606000 + 191906 + 6720 ] kcal/kg 100 1 = [804626 ] kcal/kg 100 = = 80462.6 kcal / kg. (ii) Net Calorific Value (NCV) 9 H ×587 kcal/kg = GCV – 100 9 = 80462.6 – × 6 ×587 kcal/kg 100 = 80462.6 – 316.98 kcal/kg = 80145.62 kcal / kg 5. On analysis, a coal sample has the following composition by weight; C = 75 %, O2 = 04 %, S = 05 %, and ash = 3%. Net calorific value of the fuel is 9797.71kcal / kg. Calculate the percentage of hydrogen and gross calorific value of coal. Solution 4.60 Applied Chemistry (i) Gross Calorific Value (GCV) We know that, GCV = [NCV + 0.09H x 587 ] kcal / kg = [ 9797.71 + 0.09H + 587 ] kcal / kg = [ 9797.71 + 52.8 H ] kcal / kg ………….(1) 1 O GCV = (8080 C + 34500 [ H ] + 2240 S ) kcal/kg 100 8 1 4 (8080 × 75 + 34500 [H ] + 2240 ×5 ) kcal/kg 100 8 1 = [606000 + 34500 H 17250 + 11200 ] kcal/kg 100 = [6060 + 345H – 172.5 + 112] kcal / kg = = 5999.5 + 345 H kcal / kg …………..(2) Equation (2) is substituted in equation (1) 9797.71 + 52.8 H = 5999.5 + 345 H 9797.71 - 5999.5 = 345 H - 52.8 H 3798.21 = 292.2 H H= 3798 .21 292 .2 % of H2 = 12.99 (i.e 13 % ) Substituting the value of H2 in the GCV equation 1 4 (8080 × 75 + 34500 [13 ] + 2240 ×5 ) kcal/kg GCV = 100 8 Fuels and Combustion 4.61 1 [606000 + 431250 + 11200 ] kcal/kg 100 1 = [1048450 ] kcal/kg 100 GCV = = 10484.5 kcal / kg. 4.20 Theoretical Calculation of Minimum Air required for Combustion In order of achieve efficient combustion of fuel, it is essential that the fuel is brought into intimate contact with sufficient quantity of air to burn all the combustible matter under appropriate conditions. The correct conditions are i). Intimate mixing of air with combustible matter and ii). Sufficient time to allow the combustion process to be completed. If these factors are inappropriate, inefficient combustion occurs. The elements usually present in common fuels which enter into the process of combustion are mainly C, H, S and O. Nitrogen, ash and CO2 (if any) present in the fuel are incombustible matters and hence they do not take any oxygen during combustion. Air contains 21% oxygen by volume and 23% of oxygen by weight. 4.62 Applied Chemistry Hence from the amount of oxygen required by the fuel, the amount of air can be calculated. From the combustion reaction equations, we can calculate the quantity of oxygen by weight or volume and from this, the weight or volume of air required can be calculated. For example, i) Combustion of Carbon C + O2 12 32 CO2 44 (by weight) 12 parts by weight of carbon require 32 parts by weight of oxygen for complete combustion. (or) 1 part by volume of carbon requires 1 part by volume of oxygen for complete combustion. C parts by weight of carbon require = 32C parts by weight of O2 12 ii) Combustion of Hydrogen Oxygen when present in the fuel is always in combination with hydrogen. So, the quantity of hydrogen in combination with oxygen, which is present in the fuel, will not take part in the combustion reaction. Therefore, the quantity of hydrogen in combination with oxygen is deduced from the total hydrogen in the fuel. Now, the quantity of hydrogen available for combustion O reaction will be, H where H is the total quantity of hydrogen 8 and O is the total quantity of oxygen in the fuel. (In water the quantity of hydrogen in combination with oxygen is one-eighth of the weight of oxygen). Fuels and Combustion 4.63 2H2 + O2 2 x 2 32 2H2O 36 (by weight) 4 parts by weight of hydrogen require 32 parts by weight of oxygen for complete combustion. (or) 2 parts by volume of hydrogen require 1 part by volume of oxygen for complete combustion. ∴ H parts by weight of hydrogen requires 32H = parts by weight of O2 4 But, some of the hydrogen is present in the combined form with oxygen (i.e, as H2O). This combined hydrogen does not take part in the combustion reaction. Therefore, the quantity of combined hydrogen must be deduced from the total hydrogen in the fuel. O part by weight of hydrogen requires ∴ H 8 O [ H ] ×32 O 8 = 8[ H ] parts by weight of O2 4 8 iii) Combustion of Sulphur S + O2 32 32 SO2 64 (by weight) 32 parts by weight of sulphur requires 32 parts by weight of oxygen for complete combustion. (or) 1 part by volume of sulphur requires 1 part by volume of oxygen for complete combustion. 4.64 Applied Chemistry ∴ S parts by weight of sulphur requires 32 × S = = S parts by weight of O2 32 Consequently, theoretical amount of oxygen required for the complete combustion of 1kg of solid or liquid fuel. Theoretical minimum O2 = [ 32 O ×C + 8(H ) + S ] kg 12 8 Since mass % of O2 in air is 23, the amount of air required theoretically for combustion of 1 kg of the × fuel is, Air (theoretical) = 100 32 O [ ) + S ] kg ×C + 8(H 23 12 8 Volume of Air Required for Complete Combustion of Gaseous Combustible Matters i). H2(g) + 1/2O2 H2O 1 vol. 0.5vol. 1 volume of H2 (g) requires 0.5 vol. of oxygen ii). CH4 + 2 O2 CO2 + 2 H2O 1 vol 2 vol 1 volume of CH4 requires 2.0 volume of oxygen iii). CO(g) + ½ O2 CO2 1 vol 0.5 vol 1 volume of CO requires 0.5volume of oxygen Fuels and Combustion 4.65 iv). C2H4(g) + 3O2 2CO2 + 2H2O 1 vol 3 vol 1 volume of C2H4 (g) requires 3.0 vol. of oxygen Amount of O2 required by the fuel will be given by subtracting the amount of O2 already present in the fuel from the total or theoretical amount of O2 required by the fuel. ∴ Net amount of O2 required = Total amount of O2 required – O2 already present in the fuel. Air contains 21 % of O2 by volume and 23 % of O2 by weight. Hence from the amount of O2 required by the fuel, the amount of air required can be calculated. 100 x minimum O2 23 o Minimum weight of air required = o Minimum volume of air required = o Molecular mass of air is taken as 28.94 g/mol o Density of air at NTP = 1.29 kg/cm2 o 22.4 litres (or 22,400 ml) of any gas at NTP (i.e 0°C and 760 mm of Hg) has a mass equal to its 1 mol (gram molecular weight) o Thus 22.4 litres of CO2 at NTP will have a mass of 44 g (44 is the molecular weight of CO2 ) 100 x minimum O2 21 4.66 Applied Chemistry Excess air for combustion It is necessary to supply excess air for complete combustion of the fuel. It is found out from the theoretical amount of air as follows. The amount of air required if excess air is supplied. Theoretical amount of air x [ 100 + % of excess air ] 100 4.21 Flue Gas Analysis [ Orsat’s Method ] The mixture of gases (like CO2, O2, CO, etc.,) coming out from the combustion chamber is called flue gases. The analysis of a flue gas would give an idea about the complete or incomplete combustion process. The analysis of flue gases is carried out using orsat’s apparatus. Description of orsat’s apparatus It consists of a horizontal tube. At one end of this tube, an U-tube containing fused CaCl2 is connected through a 3-way stop cock. The other end of the tube is connected with a graduated burette. The burette is surrounded by a water jacket to keep the temperature of gas as a constant. The lower end of the burette is connected to a water reservoir by means of a rubber tube. The level of water in the burette can be raised or lowered by raising or lowering the reservoir. The horizontal tube is also connected with three different absorption bulbs I, II and III for absorbing CO2, O2 and CO. Fuels and Combustion 4.67 I - bulb : It consists of ‘potassium hydroxide’ solution and it absorbs only CO2. II - bulb : It consists of ‘alkaline pyrogallol’ solution and it absorbs only CO2 and O2. III - bulb : It consists of ‘ammoniacal cuprous chloride’ solution and it absorbs CO2, O2 and CO. Seperating funnel Gas burette Flue gas I III II I CaCl2 for drying Absorption bulb for CO2 Absorption Absorption bulb for O2 bulb for CO Water Jacket Fig 4.12 Working The 3-way stop cock is opened to the atmosphere and the reservoir is raised, till the burette is completely filled with water and air is excluded from the burette. The 3-way stop cock is now connected to the flue gas supply and the flue gas is sucked into the burette and the volume of flue gas is adjusted to 100 cc by 4.68 Applied Chemistry raising and lowering the reservoir. Then the 3-way stop cock is closed. a) Absorption of CO2 The stopper of the absorption bulb-I, containing KOH solution, is opened and all the gases is passed into the bulb-I by raising the level of water in the burette. The gas enters into the bulb-I, where CO2 present in the flue gas is absorbed by KOH. The gas is again sent to the burette. This process is repeated several times to ensure complete absorption of CO 2. The decrease in volume of the flue gas in the burette indicates the volume of CO2 in 100 cc of the flue gas. b) Absorption of O2 Stop cock of bulb-I is closed and stop cock of bulb-II is opened. The gas is again sent into the absorption bulb-II, where O2 present in the flue gas is absorbed by alkaline pyrogallol. The decrease in volume of the flue gas in the burette indicates the volume of O2. c) Absorption of CO Now the stop cock of bulb-II is closed and stop cock of bulb-III is opened. The remaining gas is sent into the absorption bulb-III, where CO present in the flue gas is absorbed by ammoniacal cuprous chloride. The decrease in volume of the flue gas in the burette indicates the volume of CO. The remaining gas in the burette after the absorption of CO2, O2 & CO is taken as nitrogen. Fuels and Combustion 4.69 Significance (or) uses of flue gas analysis 1. Flue gas analysis gives an idea about the complete or incomplete combustion process. 2. If the flue gases contain considerable amount of CO, it indicates that incomplete combustion is occurring and it also indicates that the short supply of O2. 3. If the flue gases contain considerable amount of O 2, it indicates that complete combustion is occurring and also it indicates that the excess of O2 is supplied. Ignition Temperature It is defined as “the lowest temperature to which the fuel must be heated, so that it starts burning smoothly”. The ignition temperature of coal is about 300°C. In the case of liquid fuels, the ignition temperature is called the flash point, which ranges from 200 – 400°C. For gaseous fuels, the ignition temperature is in the order of 800°C. Spontaneous Ignition Temperature (SIT) It is defined as the minimum temperature at which the fuel catches fire (ignites) spontaneously without external heating. If the ignition temperature of a fuel is low it can catch fire very quickly. On the other hand if the ignition temperature is high it is difficult to ignite the fuel. If the heat evolved in a system is unable to escape, temperature of the system goes on increasing and when SIT is reached, the system burns on its own. 4.70 Applied Chemistry Explosive Range (or) Limits of Inflammability Most of the gaseous fuels have two percentage limits called upper limit and lower limit. Those limits represent percentage by volume of fuel present in fuel-air mixture. The range covered by these limits is termed as explosive range of the fuel. For continuous burning the amount of fuel present in the fuel-air mixture should not go below the lower limit or above the upper limit. For example, the explosive range of petrol is 2 – 4.5. This means that when the concentration of petrol vapour in petrol-air mixture is between 2 and 4.5 by volume, the mixture will burn on ignition. When the concentration of petrol vapour in petrol-air mixture is below 2% (lower limit) or above 4.5% (upper limit) by volume, the mixture will not burn on ignition. Calorific Intensity (or) Flame Temperature It is the minimum temperature reached when the fuel is completely burnt in the theoretical amount of air. Problems Based on Combustion 1. Calculate the volume of air (Volume % of O2 in air = 21) required for complete combustion of 1 litre of CO Solution The combustion equation of CO is written as follows CO + ½ O2 CO2 1 vol 0.5 vol One volume ( litre) of CO requires 0.5 volume (litre) of O2 for complete combustion. We know that, Fuels and Combustion 4.71 21 litres of O2 is supplied by 100 litres of air. 100 × 0.5 lit of air ∴ 0.5 litres of O2 is supplied by 21 = 2.38 litres of air Result The volume of air required for the complete combustion of 1 lit of CO = 2.38 litres 2.What is the volume of air required for the complete combustion of 1m3 of mixture containing 75 % of CH4 and 25 % of C2H6 ? Solution i) 1m3 of the mixture contains 75 100 = 0.75 m3 of CH4 25 = 0.25 m3 of C2H6 100 ii) The combustion equations of CH4 and C2H6 are written as follows CH4 + 2 O2 1 vol 2 vol CO2 + 2 H2O i.e., 1 volume ( or m3 ) of CH4 requires 2 volume ( or m3 ) of O2 for complete combustion. 2 × 0.75 ∴ 0.75 m3 of CH4 requires = = 1.5 m3 of O2 1 C2H6 + 1 vol 7 /2 O2 3.5 vol 2CO2 + 3H2O i.e., 1 volume ( or m3 ) of C2H6 requires 3.5 volume ( or m3 ) of O2 for complete combustion. 4.72 3.5 × 0.25 1 iii) Total volume of O2 required ∴ 0.25 m3 of C2H6 requires = Applied Chemistry = 0.875 m3 of O2 = 1.5 + 0.875 m3 = 2.375 m3 We know that, 21 m3 of O2 is supplied by 100 m3 of air 2.735 ×100 = 11.31 m3 of air. ∴ 2.735 m3 of O2 is supplied by 21 Result The volume of air required for the complete combustion of 1m3 of mixture = 11.31 m3 3.Calculate the minimum volume of air required for the complete combustion of 1m 3 of a gaseous fuel containing the following composition by volume. CO = 25 %, H2 = 10 %, CH4 =08 %, CO2 = 5 %, N2 = 50 % and O2 = 2 %. Solution 1. 1m3 of fuel contains 25 a) = 0.25 m3 of CO 100 10 b) = 0.10 m3 of H2 100 8 c) = 0.08 m3 of CH4 100 5 d) = 0.05 m3 of CO2 100 50 e) = 0.50 m3 of N2 100 2 f) = 0.02 m3 of O2 100 N2 and CO2 are non combustible constituents. They do not burn and not require any oxygen. The combustion equations of the remaining constituents are written as follows. Fuels and Combustion 4.73 CO + 1/2 O2 1 vol 0.5 vol CO2 i.e., 1 volume (or m3 ) of CO requires 0.5 volume (or m3 ) of O2 for complete combustion. 0.5 x0.25 3 m of O2 ∴ 0.25 m3 of CO requires = 1 = 0.125 m3 of O2 H2 + 1/2 O2 1 vol 0.5 vol H2 O i.e., 1 volume (or m3 ) of H2 requires 0.5 volume (or m3 ) of O2 for complete combustion. 0.5 x0.1 3 m of O2 1 = 0.05 m3 of O2 ∴ 0.10 m3 of H2 requires = CH4 + 2 O2 1 vol 2 vol CO2 + 2 H2O i.e., 1 volume (or m3 ) of CH4 requires 2 volume (or m3 ) of O2 for complete combustion. 0.08 x 2 3 ∴ 0.08 m3 of CH4 requires = m of O2 1 = 0.16 m3 of O2 Total volume of O2 required = 0.125 + 0.05 + 0.16 m3 = 0.335 m3 of O2 ∴ Net volume of O2 required = Total volume of O2 required O2 already present in the fuel. = 0.335 – 0.02 m3 of O2 = 0.315 m3 of O2 We know that 4.74 Applied Chemistry 21 m3 of O2 is supplied by 100 m3 of air ∴ 0.315 m3 of O2 is supplied by 0.315 × 100 21 = 1.5 m3 of air. = Result The volume of air required for the complete combustion of 1m3 of the = 1.5 m3 gaseous fuel 4. A fuel contains C = 60 %, H2 = 09 %, O2 = 08 %, S = 13 %, remaining ash. Calculate the minimum quantity of air required for the complete combustion of 1kg of a fuel. Solution 1. 1 kg of fuel contains 60 a) = 0.60 kg of Carbon 100 10 = 0.09 kg of Hydrogen 100 08 c) = 0.08 kg of Oxygen 100 13 d) = 0.13 kg of Sulphur 100 The combustion equations of the various elements present in the fuel are as follows. b) C + O2 12 kg 32 kg CO2 i.e., 12 kg of carbon requires 32 kg of oxygen for complete combustion. 32x0.6 ∴ 0.60 kg of carbon requires kg of O2 = 1.6 kg of O2 12 Fuels and Combustion H2 + 1 2 kg 16 kg /2 O2 4.75 H2 O i.e., 2 kg of hydrogen requires 16 kg of oxygen for complete combustion. 16 × 0.09 ∴ 0.09 kg of H2 requires kg of O2 = 0.72 kg of O2 2 S 32 kg + O2 SO2 32 kg i.e., 32 kg of sulphur requires 32 kg of oxygen for complete combustion. 32 × 0.13 kg of O2 = 0.13 kg of O2 ∴ 0.13 kg of S requires 32 Total amount of O2 required = 1.60 + 0.72 + 0.13 kgs = 2.45 kg of O2 But the amount of O2 already present in the fuel = 0.08 kg. ∴ Net amount O2 required = Total amount of O2 required O2 already present in the fuel. = 2.45 – 0.08 kg of O2 = 2.37 kg of O2 We know that 23 kg of O2 is supplied by 100 kg of air 2.37 × 100 ∴ 2.37 kg of O2 is supplied by = 10.30 kg of air. 23 Result The minimum amount of air required for the complete combustion of 1kg of the fuel = 10.30 kg. 4.76 Applied Chemistry 5. Calculate the minimum amount of air required for the complete combustion of 50 kgs of coal containing C = 75 %, H2 = 10 %, O2 = 02 %, S = 05 %, and the rest nitrogen by weight. Solution 1. 1 kg of fuel contains 75 a) = 0.75 kg of Carbon 100 10 b) = 0.10 kg of Hydrogen 100 2 c) = 0.02 kg of Oxygen 100 5 d) = 0.05 kg of Sulphur 100 N2 is a non combustible constituent. They do not burn and do not require any oxygen. The combustion equations of the various elements present in the coal are as follows. C + O2 12 kg 32 kg CO2 i.e., 12 kg of carbon requires 32 kg of oxygen for complete combustion. 32 × 0.75 ∴ 0.75 kg of carbon requires kg of O2 = 2.0 kg of O2 12 H2 + 1 2 kg 16 kg /2 O2 H2 O i.e., 2 kg of hydrogen requires 16 kg of oxygen for complete combustion. 16 × 0.10 ∴ 0.10 kg of H2 requires kg of O2 = 0.80 kg of O2 2 Fuels and Combustion S 32 kg + O2 4.77 SO2 32 kg i.e., 32 kg of sulphur requires 32 kg of oxygen for complete combustion. 32 × 0.05 ∴ 0.05 kg of S requires kg of O2 = 0.05 kg of O2 32 Total amount of O2 required = 2.00 + 0.80 + 0.05 kgs = 2.85 kg But the amount of O2 already present in the fuel = 0.02 kg. = Total amount of O2 required ∴ Net amount O2 required O2 already present in the fuel. = 2.85 – 0.02 kg = 2.83 kg We know that 23 kg of O2 is supplied by 100 kg of air 2.83 × 100 ∴ 2.83 kg of O2 is supplied by = 12.30 kg of air. 23 The amount of air required for 1 kg of coal = 12.30 kg ∴ The amount of air required for 50 kg of coal = 12.30 × 50 kg = 615 kg Result The amount of air required for the complete combustion of 50 kgs of the coal = 615 kg. 6. Calculate the minimum amount of air required for the complete combustion of 150 kgs of fuel containing 70 % Carbon, 15 % hydrogen, 5 % sulphur and the rest nitrogen by weight. Solution 1. 1 kg of fuel contains 70 a) = 0.70 kg of Carbon 100 4.78 Applied Chemistry 15 = 0.15 kg of Hydrogen 100 05 c) = 0.05 kg of Sulphur 100 N2 is a non combustible constituent. They do not burn and do not require any oxygen. The combustion equations of the various elements present in the coal are as follows. b) C + O2 12 kg 32 kg CO2 i.e., 12 kg of carbon requires 32 kg of oxygen for complete combustion. 0.7 × 32 0.70 kg of carbon requires kg of O2 = 1.87 kg of O2 12 H2 + 1 2 kg 16 kg /2 O2 H2O i.e., 2 kg of hydrogen requires 16 kg of oxygen for complete combustion. 0.15 x16 ∴ 0.15 kg of H2 requires kg of O2 = 1.20 kg of O2 2 S + O2 32 kg SO2 32 kg i.e., 32 kg of sulphur requires 32 kg of oxygen for complete combustion. 0.05 × 32 ∴ 0.05 kg of S requires kg of O2 = 0.05 kg of O2 32 Total amount of O2 required = 1.87 + 1.20 + 0.05 kgs = 3.12 kg. We know that Fuels and Combustion 4.79 23 kg of O2 is supplied by 100 kg of air 3.12 × 100 ∴ 3.12 kg of O2 is supplied by 23 = 13.57 kg of air. The minimum amount of air required for the complete combustion of 1 kg of fuel = 13.57 kg ∴ The minimum amount of air required for the complete combustion of 50 kg of fuel = 13.57 × 150 kg = 2035.5 kg Result The minimum amount of air required for the complete combustion of = 2035.5 kg 150 kg of the fuel 7. Calculate the weight and volume of air required for the complete combustion of 1 kg of coke (or) carbon. Solution The combustion equation of the carbon is as follows. C + O2 12 kg 32 kg CO2 12 kg of carbon requires 32 kg of O2 for complete combustion. 32 × 1 ∴ 1 kg of coke requires = 2.67 kg of O2 12 We know that, 23 kg of O2 is supplied by 100 kg of air. 2.67 × 100 ∴ 2.67 kg of O2 is supplied by = 11.61 kg of air. 23 We know that, 1 gm mole of any substance occupies 22.4 litres (or) 32 kg of O2 occupies 22.4 m3 at NTP [1 m3 = 1000 litres ] 4.80 Applied Chemistry 11.61 kg of O2 occupies 22.4 x 11.61 32 = 8.127 m3 We know that, 21 m3 of O2 is supplied by 100 m3 of air 8.127 x 100 = 38.70 m3 of air. 21 ∴ 8.127 m3 of O2 is supplied by Result 1. The amount of air required for complete combustion of 1 kg of coke = 11.61 kg 2. The volume of air required for complete combustion of 1 kg of coke = 38.70 m3. 8. Calculate the minimum theoretical quantity of air needed for the combustion of 10 kg of coal which is 95 % pure Solution The combustion equation of carbon is as follows. C + O2 12 kg 32 kg CO2 i.e., 12 kg of carbon requires 32 kg of oxygen for complete combustion. 32 x 10 ∴ 10 kg of carbon requires kg of O2 12 = 26.67 kg of O2 We know that 23 kg of O2 is supplied by 100 kg of air ∴ 26.67 kg of O2 is supplied by 26.67 x 100 kg of air 23 = 115.96 kg of air. Fuels and Combustion 4.81 The amount of air required for the combustion of 10 kg of coal which is 100 % pure = 115.96 kg The amount of air required for the combustion of 10 kg of coal which is 95 % pure = 115 .96 × 95 100 = 110.16 kg Result The amount of air required for the combustion of 10 kg of coal which is 95 % pure = 110.16 kg 9. A sample of coal was found to have the following percentage composition C = 75 %, H2 = 5.2 %, O2 = 12.8 %, N2 = 1.2 % and the rest ash. Calculate the amount of air needed for the complete combustion if 1 kg of the coal is burnt with 30 % excess air. Solution 1. 1 kg of coal contains 75 a) = 0.75 kg of Carbon 100 5 .2 b) = 0.052 kg of Hydrogen 100 12 .8 c) = 0.128 kg of Sulphur 100 12 .8 d) = 0.128 kg of Oxygen 100 1 .2 e) = 0.012 kg of Nitrogen 100 N2 and ash are non combustible constituents. They do not burn and do not require any oxygen. 4.82 Applied Chemistry The combustion equations of the remaining constituents present in the fuel are as follows. C + O2 12 kg 32 kg CO2 i.e., 12 kg of carbon requires 32 kg of oxygen for complete combustion. 32 × 0.75 ∴ 0.75 kg of carbon requires kg of O2 = 2.0 kg of O2 12 H2 + 1 2 kg 16 kg /2 O2 H2O i.e., 2 kg of hydrogen requires 16 kg of oxygen for complete combustion. 16 × 0.052 ∴ 0.052 kg of H2 requires kg of O2 = 0.416 kg of O2 2 S + O2 32 kg SO2 32 kg i.e., 32 kg of sulphur requires 32 kg of oxygen for complete combustion. 32 × 0.128 ∴ 0.128 kg of S requires kg of O2 = 0.128 kg of O2 32 Total amount of O2 required = 2.00 + 0.416 + 0.128 kgs = 2.544 kg of O2 But the amount of O2 already present in the fuel = 0.128 kg. ∴ Net amount O2 required = Total amount of O2 required O2 already present in the fuel. = 2.544 – 0.128 kg of O2 = 2.416 kg of O2 We know that Fuels and Combustion 4.83 23 kg of O2 is supplied by 100 kg of air 100 × 2.416 = 10.50 kg of air. ∴ 2.416 kg of O2 is supplied by 23 If 30 % excess air is used = 10.5 x [100 + 30] 100 = 13.65 kg of air. Result The volume of air required for the complete combustion of 1kg of the fuel if 30 % excess air is used. = 13.65 kg. Review Questions: 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. What is coal ? how is it formed ? what are its types ? Describe proximate analysis.Bring out its importance What is metallurgical coke ? Describe Otto Hoffmann by product coke oven method Discuss Bergius process, What is knocking ? Explain How will you improve octane number of a fuel What is water gas ? How is it manufactured ? Write the uses of water gas. How is producer gas manufactured ? What are the uses of producer gas ? Write a brief note on CNG What is calorific value ? mention it’s units Describe Orsat’s apparatus How is flue gas analysed using Orsat’s apparatus Discuss the calculation of minimum air requirement for the complete combustion. 16. What is flue gas ?. Discuss Dulong’s formula 17. Define i) Gross calorific value ii) Net calorific value 18. 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