CHAPTER FUELS “There is a sufficiency in the world for man’s needs but not for man’s greed” Fundamental Definitions ot a Glance * Chemical Fuel can be defined as any combustible substance containing carbon as the main constituent whic!. ...ing combustion gives large amount of industrially and/or domestically useful heat. Calorific value of a fuel is the total quantity of heat liberated from the combustion of a unit mass (or unit volume) of the fuel in air or oxygen. Higher or gross calorific value (HCV) is the total amount of heat liberated, when unit mass or unit volume of the fuel has been burnt completely and the products of combustion are cooled to room temperature, Lower or net calorific value (LCV) is the net heat produced, when unit mass or unit volume of the fuel is burnt completely and the combustion products are allowed to escape. Proximate analysis is so called because the data collected vary with the procedure adopted. It gives valuable information about the practical wility of coal. In other words, we can assess the quality of coal by proximate analysis, It includes the deter- ‘mination of Moisture, Volatile matter, Ash and Fixed carbon. The ultimate analysis is useful for combustion calculations, It includes the determination of ultimate constituents present in dry coal like Carbon, Hydrogen, Nitrogen, Sulphur, Ash and Oxygen. The term bio-mass is used for the dead plants and trees and the waste material of living organisms. Biomass includes wood, sewage, cattle dung, agricultural wastes or crop residue such as rice-husk. Biomass ‘or Bioconversion means the direct burning of waste paper, wood, cattle dung or any form of biomass or converting them to a fuel, The cheapest and most easily available biogas is gobar gas. The major biogas is methane. It burns with a blue flame and its average calorific "value is about 5300 kcal /m°.464 ENGINEERING CHEMISTRY mak Colling )_{ Acid | Fusewire Cotton ws + equivalent of (temperature * correction )~ (correction * correction * cornecion™ Weight of fuel SF Net calorific value (NCV) = [GCV - (0.09 x %H 587)] cal/ gm 1 INTRODUCTION In recent years man’s dependence on energy has increased tremendously m because of the increase in the standard of living and rapid technological advances. T energy comes chiefly from the fossil fuels such as petroleum, coal and natural gas. Sin Sources of energy will never last forever hence their proper utilization is the main go these days. In this chapter we will be having the basic understanding of the various fu available to the mankind. This understanding is necessary also for their proper utilization ang conservation for future use. ‘day 2 DEFINITION AND CLASSIFICATION OF "A fuet can be defined as any combustibie sistance which during combustion gives large amount of industrially and/or domestically useful heat. "Chemical Fuel; 200,821 7¢ Can be defined as any combustible substance ‘containing carbon as the main constituent which during combustion gives large | amount of industrially and/or domestically useful heat. Heat evolved by burning of fuels is used mainly for heating purposes, it can al) perform other very important functions like coal, in locomotive engines ; and petrol. in internal combustion engines, are used for doing mechanical work. Coal is also used as? reducing agent in blast furnace. Classification!?™ 2002), Fyels can be classified : (A) On the basis of their occurrence : @ Natural or primary fuels, Fuels which are found in nature as such are calle! natural fuels e.g., wood, coal, peat, petroleum and natural g, Artificial or secondary fuels. Fuels which are prepared artificially generally fea primary fuels are called artificial fuels, Examples of artificial fuels ar kerosene oil, petrol, coal gas etc. (B) On the Basis of physical state of aggregation. On this basis, there are three yp" viz. solid, liquid and gaseous.Chapter 13; FUELS 465 ‘The important examples of Naturals and ar tificlal fuel . Classifications of Chemical Fuels WYPTV, 2002) ‘se ablated below. Wood, peat, lignite, Dung, bit and anthracite coal NOUS coal Petrol, diesel and various other fractions of petroleum Coal gas, ofl gas, Bio gas, water gas etc. The primary or main sources of Fuels like coals and lay. These are also called ‘Fossil Fuels’ * Pens ceecing RACTERISTICS OF A GOOD FUEL [¥?T. 2003, 10, 11) High Calorific value. Calorific value of a fuel is “The total quantity of heat liberated, bustion of a unit mass (or volume) of the fuel in air or oxygen. A good fuel should high calorific value, since the amount of heat liberated and temperature attained depends upon this property of fuel, Moderate ignition temperature. The lowest temperature to which the fuel must be ited so that it starts burning smoothly is called ignition temperature. Low ignition fature (can cause fire hazards) during storage and transport of fuel, on the other hand, ignition temperature is safe for storage, handling, and transport but their might iculty during ignition of fuel. Hence, an ideal fuel should have moderate ignition leads to loss of money, because moisture is paid for at the same rate as the ft should have low moisture content. vy non-combustible matter content. The non-combustible matter of fuel remains in ‘ash or clinker, after combustion. It also reduces the heating value. There is ost of storage, handling and disposal of the waste involved with it. Hence, a fuel content of non-combustible matter. te rate of combustion. If the rate of combustion of fuel is low, then a part of ited may get radiated, instead of raising the temperature hence the required high emay not be attained. On the other hand, too high combustion rates of fuel are also combustion products. A fuel should not pollute the atmosphere by emitting other poisonous gases during combustion.9. Low storage cost 10. Controllable combustion so that combustion can be started or stopped when require 11. Uniform size. In case of solid fuel, the size should be uniform so that combustion regular, 12. High efficiency. A fuel should bum in air with efficiency without much smoke. Relative merits of solid, liquid and gaseous fuels are tabulated below in Table 2. Table 2 Relative Merits of Solid, Liquid and Gaseous Fuels '?™, 200%) | ; 3. Risk offre Least Greater Very high | hard (Gecause these fuels ae | highly ilammable) | 4 (@ Combustion | Slow process Quick Very rapid and rite efiien (©) Combustion | Not easy Can be controlled or | Possible by controling contr stopped when needed | aie suppl 5. Handling cost | High Low (Because labour is (Gecause Liquid and gaseous fuels can required in their storage, | be easly transported through pipes) transport etc) 6 Ash ‘Ash is always produced | No ash problem ‘No ash problem Possible‘Thermal Unit’ (B.Th.UL) is defined as the quantity of heat required to increase ‘of one pound of water through one degree Fahrenheit. This is the English 1.B.Th.U.=252 cal=0.252 kcal ‘Lkeal =3.968B.ThU. ‘heat unit’ (CHLU,)is the quantity of heat required to raise the temperature water through one degree centigrade. Tkeal=3.968B.ThU.-22CHU. en is found to be present in almost all fuels and when the calorific value of fuel is determined experimentally, the hydrogen is converted into ‘of combustion are condensed to the room temperature, the latent heat of Jt Caloric Value (ucv) F770, 0710.1, 12) ‘any fuel, the water vapour and moisture, etc. escape as such alongwith hotee ee Oe Tee LCV=HCV — Latent heat of water vapour formed Since 1 part by mass of hydrogen produces 9 parts by mass of water. Hence LCV HCV ~ mass of hydrogen x 9x Latent heat of steam, ‘The latent heat of steam is 587 kcal (kg. = ‘Steam t ‘Veporization les Ae as Ge rte ec entetaen | ddwtied x oso cn ‘steam. water. | Be Hydrogen Combat Water vapours or steam — | (Ceti, Water (1) + Latent heat of steam Heat liberated as result of condensation of steam into water is known as Latent heat o& ‘condensation of steam. 3._| CCV =Hesttberated from (combustion of fuel plus condensation of steam) Figure 7 Bomb Calorimeter,Steel electrodes and an oxygen inlet valve. To one ofthe electrodes, a small ring is or stainless steal crucible can be supported. The bomb is placed ng 2 known weight of water. The copper calorimeter is surrounded jacket and water-jacket to prevent loss of heat due to radiation. The calorimeter is ‘with an electrical stirer (for stirring water) and Beckmann’s thermometer (which can read ‘temperature difference upto 1 /100th of a degree). rking, A weighed amount (about 0.5 to 1.0 gm) of the given fuel is taken in clean crucible is then supported over the ring. A fine Mg wire, touching the fuel sample, is d across the electrodes. The bomb ld is tightly screwed and bomb filled with oxygen to ospheric pressures. The bomb is then lowered into copper calorimeter, containing a ater. The initial temperature of the water is noted after thorough stirring. The e then connected to 6 volt battery and circuit is then completed. The ignition is g a large voltage across a bare fuse wire which has been suitably fixed into . This fixing is normally performed by tying one end of a known mass and ton thread around the fuse and the other end around the sample. The voltage fuse which triggers the combustion reaction. The sample burns and heat is is transferred to water. Uniform stirring of water is continued and the attained is recorded. The calorific value of the fuel can now be ss of fuel sample taken in crucible (in gms) ; ‘of water in the calorimeter (in gms) er equivalent of calorimeter, stirrer, thermometer, bomb, etc. in gms heat ed by burning of fuel=(xL) cal ped by water. © = WxSx(T, -T)Ncal d by apparatus = (W'xSx(T; -T,) =w(T, -T,)} cal 21 21, and 1 cal= 4.186] or 42] gmc470 ENGINEERING CHEMISTRY Hence, total heat absorbed by water, apparatus etc. =[Wx1x(T, -T,)+wx1x(, -T,)]=[(W +)x1(, -T,)J cal According to principle of calorimetry : Heat liberated by the fuel = Heat absorbed by water, apparatus etc. d xL=(W+w)(, -T,) or Bev of et = —T cat/gm Note The water equivalent of the calorimeter (w )is determined by burning a fuel of known calorific value and using the above equation. The fuels used for this purpose are benzoic acid (HCV= 6,325 kcal /kg) and naphthalene. (HCV = 9,688 kcal /kg). Let H=% of hydrogen in fuel. Then gms of hydrogen present in 1 gm fuel =1 «EE gm. As all fuels contain some hydrogert and when the calorific value of hydrogen con taining fuel is determined experimentally, hydrogen is converted into steam according t Hyd Ope 18,0 2gm 18gm Igm 9gm : ie, weight of water produced from 1 gmH, =9gm weight of water produced from mem, (or 1 gm fuel) =9x aaem= 0.09 gm Moreover, Latent heat of steam = 587 cal / gm ~ Heat taken by water in forming steam (or Latent heat of water vapour formed) = 0.09 x 587 cal LCV =HCYV - Latent heat of water vapour formed oe To get more accurate results, the calorific value of a fuel : the following corrections must be considered wire correction. The heat liberated, as measur: of the fuse wire used. it must be subtracted from the total value, ed above, includes the heat give"Chopter 13 : FUELS 471 (ii) Acid correction. Fuels containin i pressui per ieet 8 S and N are oxidized, under hi; temperature of ignition, to H,SO, and HNO, respectively. ene ce S+H, +20, —> H,S0, +Heat 2N+H, +30, —> 2HNO, +Heat Formation of these acids are exothermic reactions. So, the measured heat also includes the heat given out during the acid formation. The amount of these acids is analysed from washing of bomb by titration ; while H,SO, alone is determined by precipitation as BaSO,. The correction for 1 mg of Sis 2.25 cal ; while for1 mL of 0.1N HNO, formed is 1.43 cal. (iii) Cooling correction. Time taken to cool the water in calorimeter from maximum temperature to room temperature is noted. From the rate of cooling (d T°/minute) and the actual time taken for cooling (t minutes), the cooling correction of dT x tis added to the rise in temperature. (fe) Cotton thread correction. As cotton thread is used for igniting the fuel, so its burning also generates heat. A 0.80 g sample of solid fuel was completely combusted in the excess of oxygen using omb calorimeter. The rise in temperature of water in calorimeter was 25°C. Calculate the High calorific value of the fuel, if water taken in calorimeter is 2000 g and water equivalent of calorimeter is 2200 g. Also calculate Low Calorific Value. [UPTU, Ist Sem., 2008-09] The high calorific value of the fuel = HCV ie ae ea HCV = (2000+ 7) 25) = 13125 cal/gm.472 ENGINEERING CHEMISTRY Let, a The low calorific value of the fuel = LCV As | LeV=HCV 009 #1587) LCV = 13125 - 0.09 x 2.2x 587 = 13008.0 cal/g. Example 2 0.72 gm of a fuel containing 80% carbon, when burnt in a bomb calorimeter increser the temperature of water from 27.3 °C to 29.1 °C. Ifthe calorimeter contains 250 grams ey and if its water equivalent is 150 grams, calculate the HCV of, E (UPTU, Ist Sem., 2009-10 ; 2nd Sem, 2005.11) Solution. Given, re Weight of water taken in calorimeter = W = 250 g, Water equivalent of calorimeter == 150 g “Rise in temperature =T, -T, =29.1-273=18°C, Weight of soli fuel combusted inthe excess of oxygen using bomb ealorimeter=x =072g Let, The high calorific value of the fuel = HCV - Ngeiom Hcy = 2502150) 08) . 1000 cal/gm. Example 3 Write the relationship between high and low calorific values. IFHCV of a coal sampleis ~ 7500 cal/g and 96H = 5. Calculate its LCV. Given ; latent heat of condensation of steam =580 2. - ; TUPTU, 2nd Sem, 200810) Solution. The relationship between high calorific value (HCV) and low calorific valve (LCV) is given below : Given HCV = 7500 cal/g 2 he %H=5 LCV =7500 ~ 0.09(5) x 580 = 7239 cal/g Example 4 The following data is obtained in a bomb calorimeter experiment: Weight of crucible = 3, 649 gms, Weight of (crucible + fuel) = 4.678 gms, Water equivalent of calorimeter = 570 gms, ‘ Water taken in the calorimeter = 2200 gms,Chopter 13; Fuets 473 Observed rise in the temperature = 2,3 °C ‘ Cooling correction = 0.047 °C Acid correction = 62,6 °C Fuse wire correction = 3,8 £C Cotton thread correction Calculate the gross calorific value of = 16 calories, the fuel sample, If the fuel contain 6.5% H, determine the {UPTU, 2003, 2011) net calorific value, = 2770 x 2,347 - 68 1.029 649319 _ 6251.88 cal / gm = [6251.88 ~ 0,09 x 6.5 x 587)] cal /gm = [6251.88 ~ 343.395] cal /gm = 5908.48 cal/gm. ©5 A sample of coal containing 89% C:8%H ; 3% ash. When this coal was tested in the tory for its calorific value in the bomb calorimeter, the following data were obtained : Weight of coal Burnt =0.85gm ; Weight of water taken = 650 gm ; Water equivalent of bomb and calorimeter = 2500 gm ; Rise in temperature =2.5°C; Cooling correction = 0.03 °C ; Fuse wire correction =10 cal Acid correction = 50Cal ; that the latent heat of condensation of steam as 580 cal / gm, calculate the (i) gross and ‘values of the coal in cal / gm.ee eo se ESOS SSD (OS BCD 5 9 cal pm 0.85 (NEV (orev) = HCV - 0.091% 580 = 9205.2 -0.09x 8x 580 = 8787.6 cal/ gm Example 6 A sample of coal contains C=93% H=6% and ash =1% The following data were ‘obtained when the above coal toas tested in bomb calorimeter : (@) Weight of coal burnt = 0.92 ¢ © Weight of water taken = 2200 ¢ (©) Water equivalent of bomb calorimeter = 550 ¢ (@) Rise in temperature = 242°C © Fuse wire correction = 10.0 cal (f) Acid correction = 50.0 cal Caleulate gross and net calorific values of the coal, assuming the latent heat of condensation of ‘steam as 580 cal/g. TUPTU, 2003-04) Weight of coal but =x =0.92gm; Weight of water taken = W =2200gm Water equivalent of bomab calorimeter = w= 550gm; Rise in temperature =T, -T, =2.42°C ” Fuse wire correction = 10.0 cal; and Acid correction = 50.0 cal. Ecy = {(2200+ 550) (2.42))- (50.0 + 10.0) 0.92 =7168.478 cal / gm a = 7,168.5 cal / gm Now, net calorific value Se NCV =71685 - 0.09 x 6 x 580 : = 6,855.3 cal / gm.Chapter 13: PUAS 475 Coal ke poe from fhe fossilised remains of animals and Plants, hence it is known as fossil fuel. other fossil fuels are used up much more rapidly than it is replenished by mature. Thus it might ultimately result in a fuel shortage, But it has been estimated that in India good quality coal reserves may last for few decades only. pia ade: eee usage of coals in huge tonnage quantities are : low cost, least In fact, the action of decay, pressure and heat convert vegetable and woody remains, deposited many years ago, into coal. The time required for coalification is of the order of 107 10° years. Coalification is known to take and anthracite) have high % of carbon content and are thus classed 2» high rarik, ‘The progressive transformation of wood to anthracite can be written as : Wood -> Peat - Lignite > Bituminou. -> Anthracite t results in increase in carbon content, hardness and calorific value and decrease in er, moisture and H, O, N and $ contents. ‘carbon contents, calorific values and main applications of these solid fuels are | below in Table 3. Galorific values and main applications of solid fuels. $125 to 5900 | Used when there is dediciency of thigh rarik coals, 6500 10 7100 | Used for steam generation in thermal power plants and for the prodiuction of producer a 8000 $0 #500 | Used for steam generation in thermal gilants and ‘ior ic heating, It is aio wed for making cou yas $650 0 8700 | Used in metallurgical purpowes where mo smoke and | igh local heat is desined. Di ano ane in honaweheid es and shea cayGenerally coal is not analysed by measuring well-defined physico-chemical propertss since its Composition varies according to the source and age. Mostly consumer-oriented empirical tests are performed for the sack of comparison and for getting some meanings) insights. In order to ascertain the quality of coal, it is subjected to two types of analysis, nz Proximate and ultimate analysis. Proximate analysis 'T. 211] is s0 called because the data collected vary with te Procedure adopted. It gives valuable information about the practical utility of coal In other Words, we can assess the quality of coal by proximate analysis. It includes the determination of Moisture, Volatile matter, Ash and Fixed carbon. The ultimate analysis is useful for combustion calculations. It includes the determination of ultimate constituents present in dry coal like Carbon, Hydrogen, Nitrogen, Sulphur, Ash and Oxygen. 7.1 Proximate Analysis "7: 20%. 2009) Proximate Analysis involves in the following determinations : (0 Moisture Content High percentage of moisture is undesirable because : 1, It increases the cost of coal as well as its transportation charges. Hence, lesser the moisture content, better the quality of coal as a fuel. 2. It quenches the fire in the furnace, However, presence of moisture upto 10% Produces a more uniform fuel-bed and less of “fly-ash”. 3. Moisture in coal evaporates during the burning of coal and it takes some of the liberated heat in the form of latent heat of evaporation. Therefore, moisture lowers the effective calorific value of coal, __ Determination of moisture: Itis the loss of weight of coal when heated at about 105°Cin# § known amount (A gm) of the finely powdered coal sample, taken in a silica crucble. is heated in an electric hot air oven. Heating is done at a temperature of 105° 110°C for about _one hour. After which crucible is taken out with the help of tongs, cooled in a desiccator and The process of heating, cooling and weighing is repeated till the weight of the containing anhydrous coal becomes constant. The dry coal residue weighed B §™ in weight is reported as (on percentage basis),Bases (like CO, and N,), a Eprees of non-combustible Bases is always undesirable, since they do not add to the heat value. Moreover the volume of the furnace tequired is also large. a, When @ coal has high volatile matter content then a large proportion of fuel Over as gas or vapour, a large Proportion of which escapes unburnt. So, higher volatile content in coal is undesirable, a 3. A high volatile matter containing coal burns with (i) a long flame, (ii) high i = and (iti) low calorific value. Hence, lesser the volatile matter, better the rank ee of the coal. 4. The volatile matter affects the furnace volume and arrangement of heating space. A furnace with small combustion volume is not suitable for burning high Volatile coals at high rates of combustion. This is because a large proportion of Volatile matter will escape unburnt in such circumstances. 5. In coal gas manufacture and in carbonization plants, volatile matter content is of Special significance particularly when by-product recovery is the main object. High-volatile matter containing coals does not cake well ; where as medium- volatile matter content coals (containing 26-30 % volatile matter) give hard and strong coke on carbonization. © Low volatile matter containing coals does not cake at all and thus unsuitable for coke making. Determination of Percentage of volatile matter content. B gms of moisture free coal is taken crucible and covered with a lid. It is then placed in an muffle furnace, maintained at for 7 minutes. The crucible is then taken out and cooled first in air, then inside a and weighed again. The residue weighed C gm. Loss in weight is reported as tter on percentage basis. volatile matter is the loss in weight of moisture-free coal when heated in a e in an muffle furnace at about 950°C for seven minutes. useless matter which is left behind when all the combustible been burnt off from coal. It is undesirable due to the following reasons : duces the calorific value of coal. chil to the flow of air and heat, thereby decreases the efficiency.478 ENGINEERING CHEMISTRY 3. It also increases transporting, handling and storage costs. There is also additionai cost involved in ash disposal. 4 Clinkers (ie, fused ash lumps) block the interspaces of the grate, on which coa! is being burnt. This in turn causes obstruction to air supply. Thereby ie buming of coal becomes irregular. Hence, lower the ash content, better tne quality of coal. Determination of Ash. It is the weight of residue obtained after burning 2 weighed amount of dry coal in an open crucible (i.e, in presence of oxygen or air) at 700 ~750°C for half an hour in a muffle furnace. Heating cooling and weighing is repeated till a constant weight is obtained. The last residue was found to weigh D gm. (WW) Fixed Carbon After the determination of moisture, volatile matter and ash contents, the remaining material is known as fixed carbon. It also represents the quantity of carbon (in coal) that can be burnt by a primary current of air drawn through the hot bed of a fuel. The % of fixed carbon helps in designing the furnace and the shape of the fire-box, because it is the fixed carbon that burns in the solid state. Higher the % of fixed C, greater is the calorific value, smaller is % of volatile matter and better the quality of coal. Hence, high % of fixed C is desirable. Determination of fixed C. It is determiried indirectly by deducting the sum total of moisture, ash and volatile matter from 100, __ Importance, The amount of C, the major combustible constituent of coal depends on the ‘coal and its % increases with rank from lignites to anthracites, Thus, % of C forms the er, His mostly associated with the volatile matter and hence, it affects the use ' is put. rmination, A known quantity of coal (About 1-2 gm) is burt in a current of 6° when C and H present in coal are oxidized to CO, and H.,0 respectively.Chapter 13 : FUELS 479 The ‘gaseous products of combustion are - Passed through CaCl, tube and potash bulbs. CaCl, tbe contains weighed : amount of anhydrous CaCl, and it absorbs water, CaCl +7 H,O—+CaCl,.7H,0 ie Potash bulb contains weighed amount of KOH and it absorbs carbon dioxide ( 2KOH +CO, —+K,CO, +H,0 _ The increase in weights of CaCl, and KOH in the bulbs are then determined. The in the weight of CaCl, bulb represents the weight of water formed, while the increase the weight of KOH bulb represents the weight of CO, formed. ‘Combustion tube ratus for Carbon and Hydrogen Determination. 6.0)-—9C0,,;,H, + 50, —> H,0 12 “4 2: 18 weight of Carbon (C) __Atm. weight of C (12) (CO, [=Increase in weight of KOH tube] _ Mol. weight of CO, (=44) __ Mol. weight of hydrogen (H, =2) Mol. weight of H;0(=18)480 ENGINEERING CHEMISTRY (i) Determination of Nitrogen Importance. Since nitrogen is an inert and incombustible gas, hence its presence i, undesirable. Thus a good quality coal should have very little nitrogen content. Determination. Nitrogen estimation is carried out by Kjeldahal’s method (a) About 1 gm of accurately weighed powdered coal is heated with conc. H.S0, along with K,SO, and CuSO, in a long-necked flask (called Kjeldaht’s flask) [Fig. 3(a)] Splash Head (Kjeldahl Tap) NH; Stream Liquid — Water in ‘Conical flask Known volume of standard H,SO, acid Figure 3 Estimation of Nitrogen by Kjeldahi’s method. (®) When clear solution is obtained (ie, when whole nitrogen is converted into ammonium sulphate) it is treated with excess of NaOH to liberate ammonia. {¢) The ammonia thus produced is distilled over and absorbed in a known volume (V;) of 0.1 NH,SO, solution [Fig. 3()]. : N, +H,50,—>> (NH,)7S0, eae PNa,SO, + 2NH, +2H,0 2NH, +H,SO, —@ > WNH,)250, @ The volume of unused H,SO, is then determined by titrating against 0.1 N NaOH solution. Let V, ml. of 0.1N NaOH was required to neutralize excess acid. Thus, the amount of acid neutralized by liberated ammonia (from coal) is determined. Amount of H,SO, used to neutralize the ammonia evolved =0.NxV, -0.1NxV, =01(V, -V;) milli eq. GA AV eee, qi equivalentsChopter 13 FURS 481 Wag cfv = SV) 1g YeofN=—__weightofN ‘weight of coal sampletaken (-Igm) «10° = 21%; = ¥2)/1000 T *14x100=01(V, -V,)x14 \ value, on oxidation it produces al and corrosion causing SO,, and SO, gases. Oxides of sulphur (formed as combustion Pollute the atmosphere. Sulphur is, usually present to the extent of 0.5 to 3% and is rived from ores (like iron pyrites, gypsum, etc.) mines along-with the coal mines. "Presence of sulphur is highly undesirable in coal to be used for making coke for iron Since it is transferred to the iron metal and badly affects the quality and properties af mination. A known amount of coal is burnt completely in bomb calorimeter in a oxygen, by which sulphur present in coal is oxidized to sulphates. |Ash from the bomb calorimeter is extracted with dilute hydrochloric acid. The acid then treated with barium chloride solution to precipitate sulphate as BaSO,. The p is filtered, washed, dried and heated to constant weight. s—%, 502-22, paso, 2 23 weight ofS __atomic weight of S(= 32) weight of BaSO, mol. weight of BaSO, (= 233) ght of BaSO, precipitate is W, gm weight of $= x W, gm of coal taken =W, gm weight of sulphur eee pacar of coal carn kent Bom Galocineieh 1482 ENGINEERING CHEMISTRY (v) Determination of Oxygen Importance, Oxygen |s present in combined form with hydrogen in coal and thus, hydrogen available for combustion is lesser than the actual one. High oxygen content coals have high inherent moisture and low calorific value, An increase in 1% oxygen content decreases the calorific value by about 1.7 % Thus a good quality coal should have low % of oxygen. Determination. It is determined indirectly by deducting the combined % of (C,H,N,S and ash) from 100, % of Oxygen = 100 ~ % of (C+H +N +S +ASH). Solved Numerical Examples based on Proximate and Ultimate Analysis Example 7 A sample of coal was analysed as follows : Exactly 1.5 gm of coal was weighed into a silica crucible. After heating for one hour at 100°C, the residue weighed 1.415 gm. The crucible was then covered with a vented lid and strongly heated for exactly seven minutes at 950+ 20°C. The residue weighed 0.528 gm. The crucible was then heated without the cover, until a constant weight was obtained. The last residue was found to weight 0.254 gm. Calculate (The percentage results of the above analysis, (ii) To which type of analysis does the above description below ? Why is the analysis so-named ? [UPTU, 2nd Sem., 2010-11] Solution. (i) (a) % of moi _ Loss in weight due to removal of moisture oS ‘weight of coal sample taken _ 15-1415 15 x100=|4=8) 100 Al «100 = 5.67% () % of volatile matter Loss in weight due to removal of volatile matter ‘weight of coal sample taken ee OED top 50% 15 weight of ash formed D 0.254 % of ash = SBN Of 20h formed, 190 =| 2 |..100 = 9:24 « 100 = 16.93% © weight of dry coal taken [7-100 Moun 10°" (4) Fixed Carbon (%) = 100 - % of (moisture + volatile matter + ash) =100 ~ (5.67 +59 +16.93) = 18.4% (ii) This type of analysis is known as proximate analysis because the data collected vary _ with the procedures adopted.Chapter 13: FUELS 483 Ne 325 gm of the coal was Kjeldahlized and NH, gas thus evolved was absorbed in 45 ml. of 01 NH,5S0,, After absorption, the excess (residual) acid required 11.5 mL of 0.1 N NaOH {for exact neutralization, Determine the percentage of nitrogen in the sample of coal. {UPTU, 2009] Solution. Amount of sulphuric acid used to neutralize the ammonia evolved = (0.1 x 45 ~ 0.1 x 11.5) milli equivalents = 0-1 (45 - 11.5) 1000 0.1 (45-115) 1000 equivalents Weight of Nitrogen = x14 = 0.0469 _ Weight ofnitrogen RINSE’ ” Waightof cbal eampletaken "°° va = ee 100 = 1.44% Example 9 0.1 gm of @ sample of coal was used in a bomb calorimeter for the determination of "calorific value. The ash formed in the bomb calorimeter was extracted with acid and the acid extract was heated with barium chloride solution and a precipitate of barium sulphate was obtained. The precipitate was filtered, dried and weighed. The weight of precipitate was found to be 0.01 gm. Calculate the percentage of sulphur in the coal sample. a ~ Weight of BaSO, obtained x 32 x 100 Solution. Percenta; f sulphur = —————___+$—_______—_—_ Be of Sulphur = Weight of coal sample taken in bomb x 233 _0.01 x 32x 100 pevetise 259 = 1.3734% [UPTU, 2003, 2007] bio-mass is used for the dead plants and trees and the waste material of living, iomass includes wood, sewage, cattle dung, agricultural wastes or crop residue energy or Bioconversion means the direct burning of waste paper, wood, any form of biomass or converting them to a fuel. in micro organisms produce either alcohol or methane gas by digesting biomass in - of air. The alcohol or methane gas themselves give energy on combustion. can be considered to be another form of indirect use of solar energy as tined through the process of photosynthesi ‘times, when forests were in plenty relative to population, Firewood was tinable energy resource and many peoples dependent on it for cooking food and4B ENGINEERING CHEMISTRY 4 By producing gobar gas, we in fact are optimally utilizing waste '& It can provide the flame temperature of 540°C, with proper burners. Limitation : Gobar gas should be used within 10 metres of the gobar gas plant. Applications : 1, Gobar gas is used as domestic fuel in many villages ; 2. Gobar gas is also used for lighting and power purposes ; 3. Gobar gas also gives simultaneously excellent yield of good manure which has ‘2% nitrogen content as against 0.75% in farm yard manure 10 consustion fens ‘Combustion is an exothermic chemical reaction. It is accompanied by development of ‘neat and light ata rapid rate, and thus the temperature rises considerably. During the process of combustion of a fuel (like coal, the atoms of carbon hydrogen, ‘etc, combine with oxygen with the simultaneous liberation of heat at arapid rate, This energy {s liberated due to the formation of new compounds having less energy (or heat content) in then and therefore, the energy (or heat) released during the combustion process is the difference in the energy of the reactants and that of the proctuct formed. For example, combustion of carbon in oxygen ; liberates 97 kcal of heat ie, €@)+0, (@ —>+ CO, (Q) +97 keal Ignition temperature is the minimum temperature at which the substance ignites and ‘bums without further addition of heat from outside. The fuel must be preheated to ignition ___Tofind the amount of oxygen and hence, the amount of air required forthe combustion es ‘of a fuel, i is necessary to apply the following chemical principles: nS always combine in definite proportions. These proportions are determines their molecular masses” For example fr the combustion of carbon, the combustion suse C#0;@ —4€0, 0 ae 2 “ of carbon, oxygen and carbon dioxide are (12:32:44). +32 gm of oxygen and 44 gm of CO, is formed alterChopler 13: ARs 487 F< BARA Lob any gas st 0°C and 760 mm presoue (cat STP) has a mass qual tots} mol. [| Sect e malar mae of, is 32g thus, 241 ofO, at STP wil have a mane of 2—m, | __SAlrcontains 21% of oxygen by volume; and 29% of oxy 3 oxygen by mass. Hence from the || amount of oxygen required by the fuel the amount of air can be calculene For instance, Teg oxygen is supplied by I 45g of ai Um’ of aggen supped by 22. 76m? ota = Theoretical oxygen required ~O, present in the fuel & Minimum O, required should be calculated on the basis of complete combustion. If Products contain COand O,, then excess O, is found by subtracting the required to bum CO to CO, ‘mass of any gas can be converted to its volume at certain temperature and ‘by assuming that the gas behaves ideally and using the gas equation : al amount of hydrogen is ether present in the combined form (ie, asH,O) or Inydrogen is a non-combustible substance. Hence it does not take part in of hydrogen called available hydrogen only take part in combustion 2H, +O, —+ 2H,0+Heat pera ‘hydrogen combines chemically with 8 parts by mass of oxygen so the (i) $+0, —4s0,488 ENGINEERING CHEMISTRY (ii) CO+10, —+00, (@) CH, +20, —+OO, +2H,0 () C,H, +30, —+200,+3H,O = (®)_ C,H, +30, —+200, +245 (vil) C,H, + $0, —+ 200, +H,O Nitrogen, ash and CO, present in the Fuel or air are incombustible matters and hens they do not take any oxygen during combustion. The total amount of oxygen consumed by the fuel will thus be given by the sum of te amounts of oxygen required by the individual combustible constituent present in the fue) Table 4 Procedure of Combustion Calculations \6 +0, —+c0, » x xgm orm? i H, +050, —+ HO yf ; - yx05 ygm or m’ €0+050, —+ 16 ease ato > 2x05 xgceca! | $+0; —+S0, ene | P gmorm?® = a | CH, +20, —+0, +210 282 oe os trae qx2 CH, +30, —+ 20, +2H,0 gm orm? GH, +250, —+ 200, +H,0 /|.bgm orm? —CiHyy +650, —+ 40, +51, 0 im? ie Cig +60, —+ 400, +4H,0 orm?ies weight of 0, required for combustion of 12 gm of carbon = 32 gm WSei of, required for combustion of 1 gm of carbon = 2 gm wight of cxypen required by 3 kg of cazbon = 2x3=8hg ‘of air (containing 23% O,) required = Dxa-st7eig 32 gm (1 mole) of oxygen occupies 22 4 litres at NTP 8x 1000 gm 0, wil occupy = 24 «8x 1000= 56001 — To x 5c00 = 2666667 Litres = 26.67 m*. the minimum weight of air required for complete combustion of 1 I of fue? =90% H=35% O=30% $=05% H,O=1% N =05% and ash = rest. Ae CUPTU, 2005, 2010} of fuel contains : H= 35 gm S=5 gm O=30 gm N=5 gm H,0~ 10 gmand ash= rest.ee ~[ Besos Hbass+3 5] ~30 = 2655 gm. +. Minimum Quantity of air required = 2655 3 = 1154348 gm = 115k. Example 12 Calculate the volume of air required for complete combustion of 1 m? of gaseous ful having the composition : 00 =46% CH, =10% H, =4% C,H, =2% Nz =1%and remaining being CO,. {UPTU, July, 2002] c0+ 40, +c0, CH, + 20, + C0, + 24,0 #, +40, +40 0.04 x2 = 0.02 2 1x33 - 00 m? GH, + 30,3 2C0, +2H,0 | 002x3= 0.06 Now, total volume of oxygen needed for the combustion of 1 m° of gaseous fuel = (0.23 + 0.20 + 0.02 + 0.06) m? =051m> ee ‘Volume of air required for complete combustion of 1 m> of gaseous fuel 100 =0.51 x — (m’) HO [azaare Now, total volume of oxygen needed for the combustion of 1 m® of gaseous fuel oo = (0.28 + 0.16) m? =0.44 m? 0, in fuel = 0.14 m3 Net volume of oxygen needed for the combustion of 1m? of gaseous fuel : = 0.44 -0.14 =03m* =300L of air required for 1m? of gas using 25 % excess air = 300x100, 125 _ 79577 21 100 ‘weight of air actually supplied per m? of the gas 1mol ), (2897 gm =17857Lx{ =o = 23095 785, ux( at) } gm. Solved Questions which on heating in the absence of air becomes soft, plastic and fuse together to form known as caking cocis. ‘which on heating give porous, hard and strong residues (ic, coke) are known as492 ENGINEERING CHEMISTRY 5. Give the condition when GCV = NCV. Ans. If the fuel (¢.g., pure carbon, sulphur, etc.) does not contain hydrogen, then GCV = NCV. 6 What are fossil fuels and how are they formed ? Ans. Coal, petroleum and natural gas are examples of the fossil fuels. They are formed from dead animals and plants, whose remains are subjected to heat and high pressures. ———$— 7. What energy conversion takes place when a fuel is burnt ? ‘Ans, When a fuel is burnt, chemical energy is converted into heat and light. Exercises 1. What is meant by the calorific value of a fuel ? How does Gross Calorific value differ from Net calorific value ? Which of the two for a solid fuel is higher ? 2. Why and how corrections are made in determination of calorific value by Bomb’s Calorimeter ? . Distinguish between proximate and ultimate analysis of coal. | (@) Explain the proximate analysis of coal and its significance. (0) Explain briefly the ultimate analysis of coal and its significance. 5. Name the parameters to be determined under the proximate and ultimate analysis of coal. Why are the above two analysis required ? Out of many coal samples, which coal sample can be considered the best and why ? ae Objective Questions O_O jective Questions A. Multiple Choice Questions “ 1. An example of primary fuel is : (q) Lignite (8)Coke (© Coal gas (@) charcoal. 2. A fuel having high ignition temperature is : (@) Petrol (b) Wood (©) Kerosene (@) LPG 3. The calorific value of a fuel is expressed in : (2) kcal cm (6) kcal Jem? (©) kcal / m3 (@)Cal/m? 4. A good fuel should have : TUPTU 2nd Sem,, 2010-11] (@ high moisture content () low calorific value (© high ash content (d) moderate ignition temperature. 5. Bomb calorimeter is based upon the principle : (@) Action and reaction are equal and opposite. (b) Mass can be neither created nor destroyed. (© Hat lost by complete combustion of fuel is equal to heat gained by water and calorimeter. 6. The quality of the coal is assessed by (@) Proximate and ultimate analysis (©) Gravimetric analysis (0) Volumetric analysis (4) Complexometric analysis,Chopter 13: FUELS 493 Domestic cooking gas is | (@) Micture of propane and butane (©) Mixture of methane and ethane ‘& Name of domestic gaseous fuel used is (© Mixture of different hydrocarbons @ Mixture of methane and benzene. @) Oil gas ® Coal gas (©) Liquid petroleum gas (4) Producer gas Biogas is produced by ___ @) Degradation of biological matter by anaerobic bacterial action - @) Cracking of kerosene (©) Destructive distillation of coal ‘(@) The action of steam on coke at high temperature. ‘The correct relation between GCV and NCV is @GCV=NcCV (@ GCV =NCV + 0.09 H «587 (ON @s (@ Boys calorimeter TUPTU, 2011] Answers 2 3. ©) 4 @ 5. (c) 6. (a) & 9. (a) 10. (d) IL (b) 12. (a) ‘empirical but important analysis which records moisture, volatile matter, ash and as percentages of the original weight of the coal sample. together with ___(a)_____ and __ (b) ____, furnishes most of the to assess the usefulness of a given sample of coal and to grade coals of the494 ENGINEERING CHEMISTRY Puels that burn with « fame have a lower ‘The onlovific value of coke is gonorally than coal from whieh It la obtained. ‘The 81 unit fot expressing the calorific value of a wolld fel I us ‘The procens of reparation of various fractions of petroleum ik KNOWN AF ou emcee Ih the Only primary liquid fuel in nature, ae Calonific Value includes latent Neat of steam, Percentage of fixed carbon oan be determined by 14, The minimum temperature at which an oil gives off sufficient vapours to form a combustible mixture with air is known as . 1S, Combustion of fuel involves chemical reaction between (uel and 16, Th combustion of fuels reaction occurs, VF, The unit of calorific value of wolid fuel is 48, Nitrogen in a fuel can be determined by 19, The GCV and NCV of volid fuel can be determined by using . calorimeter 20, The main component of bio ga ty TUPTU Int Sem, 2009-10} Answers AL Puels 2 Chemical fuels 3. Possil fuel 4. Proximate analysis 3. Ultimate analysis 6 (@) Calorific value, (>) Sulphur content % Calorifie intensity 8 Higher % kg 10, fractional distillation A, Petroleum V._ Gross or Higher 1% proximate analysis 14, ignition temperature: 1S. oxygen 16, exothermic A Callg or Vg, 18 ultimate analysix 19, bomb’s 20, Methane C, State True and False A. Ignition temperature of solid fuel is high, 2, Combustion is a chemical reaction of fuel with oxygen resulting in the production of heat, light ant i —& Synthetic and secondary fuels are one and the same thing, 4, Moisture, volatile matter, ash and fixed carbon prevent in coal ean be determined by proximate analyshs BA good fuel has high calorific value, and low moisture content, 6 A-good fuel must be most suitable for a given application, —-% GCV is always higher than or equal to NCV. f 8 Ifa fuel does not have hydrogen ax one of its constituents, then GCV = NCV, 9 Ultimate analysis can be done to find the %S in given fuel, SF Answers Tre 3 True 4 True & True & True % True: Chopter 19: FUELS 495 si ES __ Examination Questions Based on Fuels and thelr Classifications 4, Define a chemical Fuel, [U.P.Tech, 2000-01) / 2, Why are gaseous fuels more advantageous than solid fuels ? {U.P.Tech, 2000-01} 3, What are chemical fuels ? How are they classified ? 4, Waite short notes on : (/) Characteristics of a good fuel. [UPTU, 2003, 2011, 2010) (i) Relative merits of solid, liquid and gaseous fuels, (ii) Non-conventional energy sources. (U.P, Tech., 2003-04) Based on Analysis of Coal [UPTU, Ist Sem., 2011-12) d on Determination of Calorific Values anes meent by calorific value of a fuel ? [U.P.Tech, ; B.Tech. ; 1st sem., 2000-01, 2011-12 ; 2nd Sem,, 2010-11] | What is the difference between gross calorific value and net calorific value? {U.P-Tech, 2000-01] ow is the calorific value of a solid fuel determined using bomb calorimeter experiment ? {UPTU, 2001, 02, 03, 11) [UPTU, 2nd Sem., 2006-07, 2010-11, 2011-12 ; 1st sem. 2010-11) {UPTU, 2002, 20071 IUPTU, 2008, 2011) raw materials which can be utilized for bio gas manufacture. How is bio gas obtained from cattle dung ? [U.P-Tech., B.Tech., 2nd Sem., 2000-01] [U.P. Tech., 2006-071 on Calorific Values 0.83 gm of a solid fuel in a bomb calorimeter, the temperature of 3500 gm of water d from 25.5° C to 29.2° C. Water equivalent of calorimeter and latent heat of steam are 385 g, ‘cal/g respectively. If the fuel contains 0.7% hydrogen, calculate its gross and net calorific [U.P.Tech,, B.Tech, 1st/2nd Sem., 2001-02} data is obtained in a Bomb Calorimeter experiment :496 ENGINEERING CHEMISTRY Cooling correction = 0,0047°C Acid correction = 62.6°C Fuse wire correction # 3,8°C Cotton thread correction = 1.6 calories Calculate the gross calorific value of the fuel sample, If the fuel contains 6.5% H, determine the neq calorific value, [UPTU, 2002-03 ; 2nd Sem,, 2011.13) 15, A sample of coal containing 89% C ; 8% H ; 3% ash, when tested in the laboratory for its calorif value in the bomb calorimeter, the following data were obtained : Wt. of coal burnt = 085gm We. of water taken Water equivalent of bomb calorimeter Rise in temperature Cooling correction Fuse wire correction Acid correction = 50 cal Assuming that the latent heat of condensation of steam as 580 cal / gm, Calculate (i) the gross and (i) the net calorific values of the coal in cal/gm. [U.P. Tech., 2002-03) 16. Calculate LCV of a fuel which has 8.9% hydrogen and its HCV is 6500 cal/gm. (given latent heat of steam = 580 cal/gm). 1U.P. Tech., 2006-071 17, The following data were obtained in bomb calorimeter experiment : : Weight of coal = 0.85 gm, weight of water taken = 750 gm. Water equivalent of calorimeter = 200 gm. Rise in temperature = 0,30°C Acid corrections = 0.03°C If the sample contains 10% H, calculate net and gross calorific value. 18. A 0.80 g sample of solid fuel was completely combusted in the excess of ‘oxygen using bomb calorimeter. The rise in temperature of water in calorimeter was 25°C. Calculate the High calorific value of the fuel, if water taken in calorimeter is 2000 g and water equivalent of calorimeter is 2200 g. Also calculate Low Calorific Value. (Given : % Hydrogen in fuel = 2.2) [UPTU, Sem,, Ist, 2008-09] 19. 0.72 gm of a fuel containing 80% carbon, when burnt in a bomb calorimeter, increased the temperature of water from 27.5 °C to 29.1 °C. Ifthe calorimeter contains 250 grams of water and if its water equivalent is 150 grams, calculate the HCV of fuel. [UPTU, Sem,, Ist, 2009-101 Based on Numericals on Combustion Calculations 20. Calculate the weight and volume of air required for the combustion of 3 kg of carbon. [U.P. Tech,, 2002-031 21. A gas has the following composition by volume : H, = 32% CH, = 14% Ny = 40% 0, = 14% If 25% excess air is used, find the weight of air actually needed for combustion of this gas. [UPTU, Sem,, IInd, 2007-081