pach process, Refining of Gasoline, Knocking, (Ocrse rating, Cetane rating Now-pesieum foels Beazol power sicahol) ‘Combestion 3 Analysis of fue : gases (Ors apparatus) te FUELS hore is something incredible waiting 19 jy somewhere. tnere #5 $ known.” Preserice y 2 amount of heat that can be us) and industrial purposes, 1 combustible 10 es a larg oxygen produc cconomically for domestic ven us unlimited stores of the substances wig | can be used as fuels-v.g. wood coal, kerosene Combustion of these fuel Is is used as a source of heat and power, During combustion of these fuels, a chemical reaction involving | breskave of bonds of reactants and formation of new bonds it place which is accompanied by a large moi Nature be chare the products ta Hence these fuels are termed as chemical fuels of he: It is now well established that combustion is not neces) | to produce heat, Nuclear energy is also used as soli) | of feat. In case of nuclear fuels, energy is liberated by fissil Or fusion of nuclei, This energy is very much greater than int case of chemical fuels for Fuels in the broad sense, include the stored fuels tila) ) *Yalable in the earth’s crust i.e. fossil fuels or the fuels Will) | © detived from fossil fuels The term “fossil fuels? derived from the fossilized remains Tobe a pa pee) Uallale from these fuels ean be 1 Stored solar energy, The solar energy is by the pI plants durin following a Process of photosynthesis av Sonlight s Ciiowpig? Carbohydral PA of cas} beet : nace ae is used as food by plants S©and other constituents of Ve 40 + co, ‘The vegetable m dies, the organic energy is used 21) CLASSIF Fuels can be ct (@ On the b Primary Gi) On the b Solid Fug Liquid Fe Gaseous The classtable matter thus becomes the source of high chemical Poten , matter oxidizes to form peat and finally into coal. energy, the vee" dies, the organic Tolar | Photosynthesis Energy Vegetation Cellulose Fossilization ‘Chemical Energy [J] 2.4/ CLASSIFICATION OF FUELS Fuels can be classified on the basis of their (i) Occwance and (ii) Physical state, fi) On the basis of their occurance they are of two types Primary fuels: Fuels which occur in mature as such are called primary fuels, These can be used either without processing or after little processing which does not change the chemical composition of the fuel les: wood, peat, coal; petroleum and natural gasy Secondary fu The fuels which are derived from the oor secondary fuels. Examples: cokeychi 5 etc. (ii) On the basis of their physical state these may be classified as: Solid Fuels Liquid Fuels Gaseous Fuels . The Classification can be summarized as: Chemical Fuels Primary Fuels ict Gaseous Solid ne eg, Natural e.g. Coke, an ses epatrest88 Engineering Chemistry Calorifie Vahue ts defined as the’ total quantity of Heat liberated when a unte massiof a fuel Units of Calorific Value: Units of calorific value for solid, liquid and gaseous fuels are given below, Units of Calorific Values | System Solid/Liquid Fuels | Gaseous Fuels | cas | Caloriesgm Caloriesfcm* MKS Keabike k cal/m* | BTU BTUNb [ste ff The quantity of heat can be measured in the following. units: (i) Calorie: It is defined as the amount of heat required to raise the temperature of 1 gram of water through 1°C (from 15-16" eo | Calorie = 4.185 Joules = 4.185*10? ergs’ (ii) Kilo Calorie: This respresents the unit of heat in MKS system. It is defined as the amount of heat required to raise the temperature of one kilogram of water through 1° C (from 15°16" C) 1 k cal = 1000 cal (B. Th. U or B.T-U.) It is defined as the amount of heat required ture of | pound (Ib) of water through 1° F (from 60° F to 61°F) @B. Th u = 252 Cad = 0.252 kcal = 1,054.6 Joules = 1,054.6%107 ergs, 1.koeal = 3,968 By Th. U (iv), Centigrade heat unit (C.H.U)/it is defined as the amount of heat required to raise the temperature of 1 pound’of water through 1°-Gs (from 15° to 16°C), I)k-cal = 3,968 BTU =2.2:6.H.U. GROSS AND NET CALORIFIC VALUE Gross Calorifie Value: It is the total ‘of heat ; : i i i eben generated When! a unit quantity of fuel is us tt de os of esha ee a room Usually, all the fuels have sufficient ee ec amount of hi . ii Combustion is converted into steam, As t ae eae ee oats ue he products of combustion are cooled down to roam eee the steam bets fondensed into water and latent heat is evolved. Thus in the p ererien of gross calorific value, this latent heat also gets included in the measured heat. lerefore gross calorific value is algo called the bigher calorifie value. ’ Nes which is determined by Bomb calorimeter gives the Gross oF Higher peveRMINE |} 1, Determinat ofsolids and | Principle: transferred to ‘te principle «ie ae n ater vapour, formed due to the presence: of hydmagen in the fuel, are not condensed and escape along with hot combustion’ gases. Hence, q lesser amount than gross calorific value is available, Therefore, this is called net calorific value. It is also known lower Calorific Value, (LCV) LCV = HCV-Latent heat of water vapours formed. Since | part by weight of hydrogen gives nine parts by weight of water fe, LCV = HCV — Weight of hydrogen’ *9 latent heat of steam m = HCV — Weight of hydrogen x 9 % 587 (.. Latent heat of steam = 587 cal/g) DETERMINATION OF CALORIFIC VALUE at 1. Determination of Calorific Value of Solid\and Non votatite Liquid Fuels: The calorific value of solids and non volatile liquid fuels is determined by bomb calorimeter. Principle: A known amount of the fuel is burnt in excess of oxygen and the heat liberated is transferred to a known amount of water. The calorific value of the fuel is then determined by applying ed the principle of calorimatery ive. F) Heat gained = Heat lost Construction: A simple sketch of bomb calorimeter is shown in Fig, 2.1. It consists of the following parts: (1) Steel bomb: Steel bomb consists of cylindrical container made up of stainless steel he which is capable of withstanding pressure of atleast 50-atmospheres. The bomb is generally provided with a gas-tight screw cap or lid. The lid in turn is provided with tworholes:for i ind one oxygen intet valve. ort for slica crucible. (i) The bomb is placed in a copper calorimeter containing a known amount of water, The calorimeter is provided with an ¢lectrical stirrer and a Beckmann thermometer, ‘ | (ii) The copper calorimeter is surrounded by the air jacker and water Jacket to prevent any | loss of heat due to radiation. tiv) A ae eres which ontains the fuel. The crucible is placed inside ring attached to one of the electrodes. Working: A known amount of the given fuel (about .5 to 1g) is taken in the silica erucible *Seponed over the ring. A piece of fine magnesium wire is tightly stretched across the electrodes, pee ful sample, The lid of the bomb is tightly screwed and bomb filled with oxygen mate atmospheric pressure. The bomb is placed inside the copper calorimeter which contains ‘own amount of water. After thorough stirring, initial temperature of water is noted with | , thermometer, which can read accurately, temperature difference upto 1chemistry 400 Engineer" 4 the circuit is completed of Ere heat produced Oy buming oF vhnent by the electric stirey sito cool the water in the connerted 10 6-volt pattery a7 tition of hi pout the expe! 2d, Time taken -phe electrodes are then fe orueible burns with the evoll of 8 deere’ red through “The fuel in th fuel is transferred 10 watel ‘Maximurt jemperature shown bY thermometer js recorde! calorimeter from. maxima temperature to 700M temperature is also noted, The calorific value cof the fuel is calculated aS below Wei Calculations Let Weight of the fuel sample taken = XB Het Weight of water in the calorimel We ne ‘water equivatent of the,ealorimeter, stirrer bomb: Initial temperature of water = 4°C Co (a) mperature of wate' «of gross calorific value = C Heat gained by = p t gained by water = W * Abs neat of pecific heat of water W (yt) ¥ 1 cal Heat gained by Calorimeter Heat liberated by Heat liberated by the fuel e ined by water and water and calorimeter xc ) cal jens jet calorimeters also determined by buming a fuel of known eal rific valueand using euivalent e lorifi f raiue: ms Gey = V+ w)ty~t))Net Calorific Value Let percentage of hydrogen in the fuel =H. oH i008" (2 1gm of hydrogen produces 9 gm of H,0) Heat liberated during condensation of steam = 0.09H*587 cal ‘Net (Lower) calorific value = GCV-Latent heat of water formed = C = 0,091%587 cal/g Weight of water produced from 1 gm of the fuel = Corrections: For obtaining the accurate results the following corrections ate also incorporated: | {a) Fuse wire correction: Mena ee the heat generated. by burning of Mg wire is also includ fe value as measured abover Hence this amount of eat, has, tosbe,subtracted. from. theatpraliNelne * Orygen 6V Battery Beckmann's Electrically thermometer operated aa ster € Electrodes copper calorimeter Fuse wire Stainless steel bomb Solid fuel Fig. 2.1 Bomb calorimeter tion: During combustion, sulphur and nitrogen present in t we veeids under high pressure and temperature. aeIiberated is not obtained in fhe heat ‘us corrections must be mage subtracted. : ) 143 calories: must be sul uitaneous processes. As the temperature . mi 8 : cooling are si , io eee Coating Correction: Heating and e ror eat dors oveur due 10 radiation, and te {e)'Coelt erature, the loss room tempe fises above the 1 highest temperature recorded will be slight ‘an that obtained, if no loss of heat took P ill be slightly less than that obtain | ighest BA cnpeatixe correction (cooling correction) is therefore necessary 10 Ba Iie or 2 tion) Be i ction (ci Pl ‘i comeet rise in temperature a : ‘a linute of cooling is dt/ minute, ttenthe eerie ane f fed 10 the observed rise in temperature. Gross Calorific Value, i=l Watwlltxe t+ Cooling corection)-[Acid + fusecorrections] /Massof thefuel 2; Determination of Calorifie Value of Gaseous. and Volatile Liquid Fuels; The calotifie vals of taseous and volitie liquid fuels is determined by Boy's Gas Calorimeter Construction: A sketch of Boy's Gas Calorimeter is shown in Fig. following parts: Working: Bi initial warming Oe tune atcha kaown volun’ ot gas ata known piessine ie reas ‘le The volume of the gas is measur Known pressure is burnt at a uniform during combustis ed by a meter fitted near the inlet of the Bas. when the condit 2.2. It consists of the |) : . (®) Volume Wats es fom te op ohh <2PP* CO, Water at a een rate is flown. ? a bottom of the chi ant Si, Passes through the oute, il to the Se al mney and then moves iy T coils, moves Pwards through the in Weight | (iii) Tempers (iv) Weight | Calculation ve ah ner coils, and exit from Gi) The thermometers 1 4nd tate fitted : We eocciey ‘0 note the temperature of incoming and outgoing G¥)A comainer : 2, ss | Provided {op Sllecting water whigh : am produced ding ombud 1 The whole assembly is Nosed nan, eifreFlubber tubing Insulated container copper call, <— Gaseous oF liquid fuel Fig. 2.2 Boy's gas calorimeter Working: Burning of fuel and circ inifal warming up period. Wi n of Water are cont ued for about 15 minutes for at produced by buming of iS transferred to w in the copper coil and the steam formed inside the chimney Gufing Combustion gets condensed to water which is collected. The following readings are noted, | when the. conditions become steady Base 1) Volume of gas burnt at a given temperature and pressure in time t. Thi Sonverted into STP. BY) Weight of water passed through the coil inthe: same-time MH) Temperature of incoming and outgoing water. () Weight of water condensed during this time. leulations: Let Volume of the gas burnt at STP in a certain time t = Vin? Weight of water passed through the coil in time t = W kg ‘of water condensed during this time =m d Temperature of incoming water = qT, ; ¢ of outgoing water = T is volume is thenF chemist ea cal ise in temperature ~ 2 : i E Gross Calorfie VANE Tn ny tating water = _ carbed by the circul ve Heat absorbed combustion of fuel = Heat produced by Heat lost = Heat gai vc = W (TT) fic Value’® Gross Calor NetCalorific Value S of gas = m/V ke Weight of water condensed per m? of gas = 1 mx5! Latent heat of steam per m? of gas = ——"— k cal p Net Calorific Value = [Gross Calorific Value — 3. Theoretical Calculation of Calorific Value of a Fuel: Theoretically, the calorific value oFs fel canbe calculated if the percentages of the constituent elements are known. According Dutong, the Calorific value of a fuel is the sum of the calorific values of its constituents. The ealotifc value of C, H and § are found to be 8080, 34500 and 2240 k cal/kg respectively, D Substrate Calorific value Carbon: 8080 Hydrogen 34500 {_Silfphur 22240 HF oxygen is also: pr ye - em pan the combined form gst it combines with hydro gen to form Hj0. Thus . in is eal p20) Thus the hydrogen Fixes ie, ed hydrogen. 4 MM 15 NOt available for. com - bustion a Amount Of hydrogen available for com! i = Total Now. # pans by we Mass of hydro, S weight of ox i 8en-hydrogen combi get for every & pants of aad Combines with 4 en combined with oxy PAN Of hyctowen Part OY Weight of Bets fixe hydrogen to form walt Gro whe SOLVE FUELS Examp! Fin calorific SolutioFuels 105 Dulone’s formula for calculating the calorific value i ei ven as: Gross calorific Value (HCV) = cal/kg. where | P respectively, Net Calorific Value (Ley) = [pov —S, ms] k callkg 100 = [HCV-.09H x 587] & calke, aa NUMERICALS BASED on DETERMINATION OF CALORIFIC VALUE OF Example 2.1: The following data were obtained in a bomb calorimeter experiment Weight of Coal but = 6.994 » Weight of water in calorimeter = 2592 g Weight of bomb, calorimeter etc = 3940 2 Rise in temperature of water = 2.732°C Mean specific heat of the apparalus = 0,098 Find the gross calorific value of the fuel. If the fuel contains 8% hydrogen, calculate its lower valorific value. (Latent heat of condensation of steam = 587 cal/g). Solution: Weight of the fuel, x = 0.994 g Weight of water, W = 2592 g Weight of apparatus = 3940 g Mean specific heat of apparatus = 0.098 + Water equivalent of apparatus, w = 3940x0.098 = 386.12 Rise in temperature of eater = 2.732°C .. Gross calorific value ~ (Wer allte=t) = 8185.3-0,09*8*587 cal/gm = §185.3-422.64 cal/gm = 7762.6, cal/gm tains 92% C, 5% H, and 32% ash. When this coal was on -, the following results were obiinetr 406. Engineering chemist equivalent of bomb Water cad calorimete eee < es ieee in temper 60.0 Cal and ‘Acid Correction = 6 a i ion = 01 ing Correction a es 10.0 Cal. i tion = Fuse wire Correc - i t of condensation of steam « gross calorific value of coal Given latent heal ‘late the net an Cale _ (W+w(h-T + Cooling Correction) - (Acid + Fuse corrections) Soltuion: GCV = ect (2000+ 700)(2.48 +0.02) (60+ 10) i 0.95 = 1031.6 cally Net Calorifit Value = GCV-0.09H%587 cal/g 703 1.6-0,09%5*587 - x 6767.45 cal/g N Example 2.3: During the determination of calorific v: the following results were recorded, alue of a gaseous fuel by Boy's calorimeter, ke Volume of gaseous fuel bumtat NTP. = 0.098 m? =e Weight of the water used for Sooling the combustion products. = 50 kg Weight of steam condensed = 0.051 ky ‘Temperature of inlet water = 26,19 ¢ Temperature of outlet water = 46.50 ¢ Determine the gross and net calorific values. Solutic * Gross calorific value Gey = W(t2—n) Vv = 50%(46.5~26.1) Saree = 104082 ik catim Net ealoritic vate = Gtoss calorific ValueEsomple 2.4: Calculate the gross and net calorific value of « coal sample having the following. composition, C: 82 per cent, H3: 8 per cent, Oz: 5 per cent, S: 2.5 per cent, Ny: 1.4 per cent gad ash 2.1 per cent i al) 9 solution: Gcv = ig 8044-2) ssaoe rs] zag] 880% 82+ 4500/85), 2040.2, 100! 2 + ry +2240x 2.5 a eno Fp [962560 + 254437.6 + 5600] 9225.9 k calrkg Net Calorifie Value = GCV-0.0911«587 9225.9-0.09%8%587 8803.26 k calkg Example 2-5: A coal has the following composition by weight: C = 92%, = 2.0%, § = 0.5%: N= 0.5% and ash = 1.5%, Net Calorific value of the coal was found to be 9,430 K tallkg. Calculate the percentage of hydrogen and higher calorific value of coal. 100 = [7433.60+345 H-86.25+11.2] kcal/kg = [7358,55+345 H] kcal/kg, Also HCY = (Net Calorifie Value + 0.091587) k cal/kg = 9430 + 0.09 Hx587 = 9430+52.83 H Solution: HEV = ato 92434500 (u = 2) $2,240 sean From (i) and (ii) (7358,554345 H] = (9430+52.83 H] 292,17, H = 2071.45 2071.4 ie + Percentage of H = a577 = 7.09 HOV. = (7358,55+345 H) k cal/kesing Cneris a sive because calorific value orifice va calorie Mau per unit mass or volume, Id possess mount of Heat he fuel show ie ris the eyavency ofthe fuel HB {a igh atric valve: determines the ofc + temperature to which the fuel est temperat ature: Ignition temperature i oe ould hve moder 5 that it starts burning smoothly. * FR fuel have low ignition tempera aoee it can cause fire hazards. 1f, on the ae transportation and storage becom better the fel (ii) Ignition temper oe ‘her hand the ignition asier but it causes nce it become dangerou temperature is too high, the difficulty in kindling, Moisture content: The Jowers the effective cal atter content: The ce of non combustible matte P esence of high moistur moisture content should be low because presence of igh mosis es of the fuel oi forms clinkers after non combustible matter reduces the heating value and also Non combustible combustion. The pr involves the cost of dis (i) Velocity of combustion: Velocity of combustion should be moderate Too high velocities e not required, whereas too low yelocities cause loss of heat due to Be. r the combustion: of combustion radiation, (vil) Nature of the products: The products formed should not be harmful. The gaseous combustion should be such that they do not cause unpleasant odours and other harmful effect products evolved durin, (vii) Cost of fuel: The fuel should hae a low cost and should be a at-a cheap rate. {ix) Smoke: Formation of smoke should be as low’ as possible, jlable in large amount Control of the process: The fuel should be such that controlled i. it can be easily started or stopped. its combustion can easily be A comparison between the solid, liquid and Sharacteristics is given in a tabulated form below: eous fuels for the above mentioned Tabi = 2.1; Relative Merits of the Three Physical Forms of Fuel Seid fuels a, the storage and transportation Liguid fuels Gaseous fuels Relatively cheap and casi Sei ly | More'eostly than solid fuels but Except heap in countries of origin eee ee ere ous fuels are derived from solid : find liguid fuel tenant CC be tanspoted ea iquid fuels and hence costly, ling ar quite Witt forage ae ely rom Laie ke ‘eu onal fgueties Borage tanks through system to be stored in leak proof and puified products we ies. Greater core must be ‘containers and! need considerable ‘he 10 stoRe them in e sorage spi very ear 4p a them in closed Space; can be distriyuted mites Songs tiay | MCHA Pn Doe cn ‘thecoat ste fa s9lK and gaseous ss canbe ranged etherthroue Solid fue (seconda coal con derived Woe deforest: low cos Whe dried co 10 the « having 1 and non content |Fuels 109 | Liquid: tuets Fz Gaseous fuels solid faels | femtmsonisin poses | Conus usps eine sared mst BE quickly. The proces of Move realy miseibie wih ait wines byt, Thecontl | combustion canbe central Sep at tel opring of combustion cx stopp when neta bustion takes place rapidly and ee oles more efficiently, Airrequted ie fils Newalondiang ore: sing atnesphees an be ai tamed by convling a suPPy ands grea exit te ode jnvariably some ash is: The burning is clean and n Ns i ‘ produced and thei dis- | shisprotces babs ee | | rats prob high bah an aroma with produced ¢| Labour is required for The labour demand is fess e lat et eaecel rie ainirauad Ta Not used in internal | Used in interna combustion Used jn internal combustion tombussion engine erigines (petrol engine (CNG) i Have low thermal Their thermal efficiency ‘Their thermal efficiency is cfisiency | isthigher than that of sob fuels highest. i| i 24 SOLID FUELS Sid fuels that occur naturally (primary fuels) as well as those, that are processed and prepared nd industrial purposes, Wood, and different types of (econdary) are widely used in domestic Galette the important primary solid fuels. Charcoal, coke ele are the secondary solid isla | derived from the natural varietic: ‘Wood: Wood has been used as 4 fuel ‘eforestation, wood is no longer used except in OW cos. When freshly cut, wood contains sroent moisture, Normally it is Reverting with 10 0 15 percent moisture content Its heating value is directly proportional Woe water content. The combustible part of wood is mostly made up of cellulose and lignin Wiving races of mineral ash. Resins and waxes are also presen? dried wood is about 3,500 10 4,500 i eallkg. Jt bums with a Tong et unt of ash. Aunoueh ash conte 1S LOH Ss ‘isvery high. This makes, even dry wood a fuel of low calorific value: Still, its tow ignition aad ‘non-smoky flame and absence of ash disposal problems are the points of advantage: 14's Iargely used as a domestic fuel. : : Wood charcoal is obtained by destructive distillation of wood. ‘The major use si vost ee is “iieducing anveted carbon which finds extensive apprieation fr decolourizatio industry. from ancient times. However, due to large scale forest areas where wood is available at a very 25 to 50 pe js used in an ait fossil fuel produced from the vegetable debris under conditions of highsmicallYs 5s Chetogen and SUPT ether W' ‘oal tal the vegeraple debris 1° c is stags ‘piochemical or pes . id prod ero organisms: The en ‘various. mic = 2(Co Hin In ism? js stages metamorphism: 19 this, © f igee raotstre and volatlle SOF temperature and pressure: ThE Pet gets entiche Aram ases, The spongy peat transforms in hard ort forthe formation of young brown coals of the order ature coals is 310" years. (ii) Chemical stage © sedimentary deposits 2.4b Classification of Coal Coats are mainly classified on the basis of their rank, wh from the parent material, wood. When wood is conver the concentration of carbon and decrease in the per coal is highly comple: the peat deposit b nents under the effect 4 in carbon whereas its oxygen d brittle coal gradually. The time r ‘kes place in two stages: ue jing thi e, the plant_materials were He OE juct of this stage 1S peat ich is defined as the degree of c0a ted into coal, there is gradual in ceniage of oxygen and nitrogen. re given 2 ranking depending upon the carbon content of the coal from wood to ‘The ranking can be represented as in table 2.2. Table: 2.2: Classification of coal according to rank Percentage (dry, mineral Type of 6 i ype of coil fatter free basis) % P € H a = ; 0 N VM ___|_moisture : 5 5-6 | 20-40 | 0.0.5 = 70-90 Peat 45-60 | 35-65 5 5 | 2045 | 0,75-3 5 5-3 | 45.75 | 70.90 Brown coal 5 ? 6075 | asss | inas | ors2 | 4s: , $-2 60 | 30. _ Bituminous Coal 75-90 i t 40-55 | 2030 | 0 73-2 | 1150 | 10-20 05-2 carbon cont ®Xygen, nitrogen, lent and calorifi ze Volatile matter, ~ —1. Proximate Analysis 2 Ultimate Analysi The results of analysis are generally reported in the following way @ As received basis * Air dried basis Moisture free basis (oven dried) ® Moisture and ash ree basis Parra ANALYSIS / Proximate analysis is an empirical but important analysis, The data varied with the procedure adopted and hence it is called proximate analysis. It gives information about the practical utility. of coal. Proximate analysis of coal dete: ‘mines the moisture, ash, volatile matter and fixed carbon of coal 1 Moisture Content: Owing to its nature d origin coal is always associated With moisture When a wet coal is exposed to atmosphere, the external moisture evaporates but the apparently ary coal still contains some moisture, This moisture is referred to air dried: moisture, Air dried moisture is determined by heating ¢ known amount of coal (air dried) to 105-110°C inan electric hot air oven for about one hour. After one hour, it is taken out from the oven aad cooled in a dessicator and weighed. Loss in weight of coal is reported as moisture content 01 percentage basis. Lossin weight Percentage of moisture = ae — * 100 Percentage of molsiwe 7 7 aeahaci aia Significance * Excess of moisture is undesirable in coal, * Moisture lowers the heating value of coal and takes away appreciable amount of the liberated heat in the form of latent heat of vapourisation, For every percent of moisture present 1% ‘of heat is lost. Moisture also increases the transport costs, * Excessive surface moisture may cause difficulty in handling the coal, * Moreover presence of excessive moisture quenches fire in the furnace. Hence lesser the moisture content, better is the quality of coal as a fuel. Hower Volatite Matter: The yolatile matter in coal consists of a complex mixture of liquid product: aesulting from the thermal decomposition of the coal. Vi re of coal, It consists mainly of ¢ ctg chemisttv 412. Engineerins al of volatile matter 00 ple taken | Loss of weight due to remev i ir al samy i Percentage of Volatile matter Weightof 0 4 Sigaifieance a lange proportion of fuel is burnt as a gay + A high perce ‘or vapour of may €scap* The high volatile matter cont of volatile matter indicates that e unburnt it gives long flames, high smoke and relatively low heating ent giv i eh ter) have to be bur | For efficient use of fuel, the outgoing combustible gases (V olatile a nora tobe bur * hy supplying secondary air. This requires a larger combustion space ‘combustion volume or of short flame is not suitable for burning high volatile coals, since | « large proportion of volatile matter will escape unburnt. : ' « Tae high volatile coals do not cake well (described later) whereas medium-volatile coals; containing 20-30% of volatile matter are capable of forming hard and strong coke on carbonization. in # Coals containing less than 14% of volatile matter do not cake at all and are thus not suitable for manufacturning coke. However, high volatile matter content is desirable in coal gas manufacture because volatile matter in @ coal denotes the proportion of the coal which will be converted into gas and tar products by heat Small quantities of lime, magnesia etc: Ash content is determined by heating the residue left after t the removal of volatile matter at an hour without covering. Th 1e i ‘of the residue, the Percentage of ash is Oe ie a be Weight of the residue teft Weightof the coat _* !0° | 5 3. Ash: Coal contains inorganic mineral substances which are converted into ash by chemical Teactions during the combustion of coal. Ash usually consists of silica, alumina, iron oxide and > Percentage of ash The minerals responsib le for th i intris tein Foray MN a *irinsie ash content is relatively higher. Significance * The higl Hage of ash is und } high percent 3 cr the contrary it reduces me The ash does not co . of coal, fl value ance content is lent See betemoved by any mechanical | ut 2 10.3. percent) whereas the i)Fuels 113. nace grate, the ash may re oe. ee es ae sl . Festrict the passage of air and lower the rate of combustion. + High? ae losses and cause problems of clink } Higgs been estimated that one percent rise in coal ash ie ee | decrease in boiler efficiency, al ash is equivalent to 0.3 to 4 percent {the composition of ash and fusion range The ton is of considerable fusion range also iniences the eee) of coal. Its and metal composition portance in metallurgical operations as it affects the slag {when coal is used in boiler, the fusion te fasion temperature lies eee fusion SesTpEratuts ote ea significant. Generally 200° C is called finible frand ch OO a C. Ash having fusion temperature below i je ash and above 1430°C is pact ae es a xing temperature it leads to clinker formation called refractory ash, Wash fuses at « Apart from loss of efficiency of coal, clinker formation alsp leads te toss ef fuel Besails game coal particles also 2 embedded in the clinkers. wm direct contact with the jowever, some ash is desirable since s Ke ome ash i able since it protects the grate f oxidation of the grate bars. incandescent coal, which might ca nn low ranking coals such as lignite to high xed carbon greater is its calorific tity of carbon that can be burnt ases fr | Fed Carbon: Fixed carbon content anthracite. Higher the percentage of ranking coals such as salve and better is the g primary current of 2 ality of coal. This represents the qui + = 100-[% of Moisture+Volatite matter tash] that, what is left after the amount of moistuse volatile matter and fixed carbon. However, the term fixed carbon s0 along with carbon. from the above it 4 formed is subtracted, ¢ iE misnomer because it contains other » orresponds to the n volatile elements al Significance: @ Higher the percentage of f xed carbon help 'd carbon that is the calorific value. eva designing the furnace and shape of the fire:Pex ‘burns in the solid siate: xed ¢ # The percentage of fi because it is the fixe ULTIMATE ANALYSIS the composition of coal. For the utilization ave the percentages of Various components the coal to different uses depending ation of carbon, hydrogen, sulphar, Gime analysis of coal is carried out t0 ascert sary to deter coal for industrial purpose. it is neces f ito classify the coal, to fix its price, along with patting bet its composition. Ultimate analysis includes the stim and oxygen. in a combustion tube and is burnt of coal is taken ‘The carbon and hydrogen present | Carbo n'and hydrogen: A known amour: * TE a ure and CO) excess, from moi of pure oxygen (Fee FO, Tc snecively IMthe fuel are converted to CO, an’ C+ 0,9 C2414 Engneering icant a. >. Nite 4 through two bulbs, one containing we} a oducts of combustion are PASS. other containing Weighed amount gf ‘The gaseous pr hich absorbs water, an\ d hydrogen are calculated from, hydrous CaCl, wht of carbon and hydrogs amount of anhyarns on dioxide. The percentage KOH which absorbs carber etive absorption tubes the increase in weight of the resp Sample in | patinum container Soa . Combustion tube | t od Excess 0, | Fumace i. ae | Pure dry oo Anhydrous CaCl, KOH Solution Fig. 23 Estimation of carbon and hydrogen 2KOH ECO; 4 K;CO,+H,0° CaCl, +730 + CaCl,7H;0 Let, weight of coal sample taken = x ¢ Increase in weight of CaCl, tube = z g Increase in weight of KOH tube = y g 44 g of CO, contain = 12 g of carbon yg of CO; contain = ax y @ of carbon a | Percentage of carbon = 12, __y*100_ 44° weight of coal taken 18 g of water contain = 2 g of hydrogen Z g of wate i coe & of water contain jg" 28 of hydrogen Percentage of hydrogen = 2 ,___2x 100 i ees 18 weight of coal taken An Yalue of a fuel is direct it ly related to its cay on ¢ lent M Brats is the calorific value of the hgh net Hence reste the ge of carbon also reduc of -2, Nitrogen: d of mn quantitatively. «The contents are then transferred to a round H. «The NH gas thus liberated is absorbed in a (NH,),$0, NH, +H,S0, > Let the weight of coal taken = Volume of the Normality of the acid = ¥, mL of N; acid V5 mb of IN NH, = cid used up = But 1000 mL. of 1 normal ammonia solution V5 mb of 1 normal ammonia solution Percentage of nitrogen = ) flask Te Organ ia yore 7 so, Kjeldahi's Nitrogen present in the coal sample can be es ‘= A known weight of the given coal sample along with ig heated with conc. H,SO,. Nitrogen present in coal gets converte Saw # The unused acid is then determined by titrating with N by NH; liberated, the percentage of nitrogen can be calculated, »Na,S0, +2NH;+2H,0 Fuels 115 ated by which acts as a catalyst 1d to (NH,), SO, boitmed flask and the solution is heated with known voll OH. From the volume of acid used (NH,),SO. We v, ml Mh V, mL. of Ny NH, V.xN, mL of acid 17 g of NH, = 14 g of Nitrogen x Nj) x Vig of Nitrogen (--V; =Nj Vim) 1000 4 “14 Nix Wx 100 1000 LaxNyx¥ Kjeldahl trap Contents of the Kjeldaht's flask after digestion + NaOH416 Engineering Chemisty \ en 1 and’ percent. It has no calorific sol Significance: a sples However, it is useful in carbonization Industries and hence ence is ii ae Fee able by products like NH, (NH), S04 and pyridine bases, which recover @ part 5 iH is 45, Suiphiur: Sulphur present in the coal is oxidize acid into sulphuric acid. The a ated as BaSO, 8 ditio , quantitatively. Alternatively, the sulphur can also be determined by the washings obtained from the Known mass of coal | tied ina bomb calorimeter for the determination of its calorific value. The washings contain sulphur in the form of sulphate from which it is precipitated as BaSO, by the addition of BaCl,. ‘he precipitate of BaSO, s0 obiained from either of the above method is filtered and heated to a vonstant weight. Ftom the weight of BaSO, obtained, the sulphur present in the coal ts aloulated. Let the weight of coal sample = W g the mass of the precipitate be = W, g 233 g of Bas of sulphur | Exa’ W, g of BaSO, = We ote aaa! bom Pareontese of sulphur = 2 “x10 solu . ; 233 W weig Although sulphur contribute to the calorific yalue of coal, it is aK | in ti t. It emits corrosive $03, SO during combustion a a e : 2 combustion and highly objectionable H. carbonization of coal. These gases also cause atmospheric nS oe oe sole BTU Gs tus revaston of meulirical cole os 4 asvencly ctheee eee of metal. For example, the presence of sulphur in s te on ed he ee cee wrant he coke used in iron industry affects the 4, Ash: It is di i - , ¢ The oxygen is usually determined by . ait y the method of difference. The = and sulphur are expressed in percent basis and their sum ty erate ero | _Peenage of oxygen = 10-06 of eaton + hydrogen sum is subtracted from 100. Exar Significance: Less is the oxygen content, be gen + Nitrogen + Sulphur + ash) | in 5 y rll ed. with m ‘ Nao sed later), Moreove a Pe oes oo ino for } mbustion is lesser than the total hy coal and thus Solu ‘The calorific value decreases’ by’ about 1.7% fo nidrogen present, 7% for ‘ : oxygen, IATE ANALYSIS SOLVED Nut MERICALS BASED ON PROXIMATE AND ULTIML _ Example 2.6: A samy covered with venteSolution: Mass of moisture in coal sample = 2.000-1.975 = 0.025 g Mass of volatile matter = 1.975-1.328 = 0.647 & Mass of ash = 0.205 g 0,025 x 100 Percent of moisture = 5 = 1.25% 32.35% Percent of volatile matter = Percent of ash = Percent of fixed carbon Example 2.7: 1.0 g of a sample of coal was used in a bomb calorimeter for the determination sf calorific value. Calorific value of coal was found to be 8,800 cal/g. The ash formed in the bomb calorimeter was extracted with acid and the acid extract was heated with barium mitrais e was obtained. The precipitate was filtered, dried and solution and a precipitate of barium sulpha Weighed. The weight of precipitate was found to be 0.08 g, Calculate the percentage of sulphur in the coal sample. Solution: Percentage of sulphur in the coal s 100 coalsampletakenin bomb _ Wtof BaSO, ppt.obiained 3 233 Wiof 0.088% 32 x100 233 1g = 1.098% Example 2.8: 1.56 g of a sample of coal was kjeldahlized and NH gs thus evolved was absorbed in 30 mal of 0-1 N H,S0,, After absorption, the excess (residual) acid required 6.25 ml of 0.1N NaOH for exact neutralization. 2.60 g of the coal sample in a quantitative analysis gave 0.1755 @ of BaSO,. Calculate the percentage of N and $ in the coal sample. Solution: 625 ml of 0.1 N NaOH = 6.25 ml of 0.1 N H,SQ, . Volume of H,SO, used to neutralize NH, evolyed = 50 ml of .) N ~ 6.25 ml of N H,SQ, 43.15 ml of .1 N H,SO, Vol. of H3SQ, used x Norm: Weight of coal sampletaken Percentage of Nitrogen = 56 Ss _ wt.of BaSO, ppt. obtained x 32 x 100 sulphur = ¥1-0f BaSO, ppt. obtained x32 5100 Desountage: of svnhur 233 x wt. of coal sample taken 0.1755 x92 100 ‘ SE KS = 0.927% 233 x 2.60ufacture of Coke) sence of air, toa sufficiently jue which is ric! 2.44 Carbonization of Coal (Mani ay ; Carbonization of cost is the process of heallNf the coal temperature, so that the coal undergoes decomposition ‘carbon content than the original fuel. This residue is mass and is known as coke. In other words the proces in abs it and yields a resid 's of converting coal into coke is a carbonization. Caking and coking of coals: converted into coke. Some coals ha form a solid coherent mass with por 5 “dis called coke. If the coke i ig formed, it is called cokiig coal This pri thenee only bituminous coal can be coked. Anthracite, sub-bituminous, li + It must be emphasized here that all types of coal cannot be have a tendency to soften and swell at higher temperatures, to ous structure. Such coals are called caking coals. The residue hard, porous and strong, than the coal [, from which it operty is found only in bituminous type of coal and ignite coals are non-coking coals, but only some of the caking coals fall under the category: coals, All coking coals are caking ‘of coking coals. In general, coals with a high percentage of volatile matter are not fit for ‘coking’ and are used for gas making. The coals having 20-30% volatile matter are good coking coals. Coals Caking Coals Non Caking Coals Coking Non Coking Coals Coals First moisture and occluded gases are driven off. ) Process of Carbonization: At about 260° - 270° carbon, water and Hy S, some low molecular alkenes and alkaniFusis. 119 _, wemperature carconization, ips emperaare carbonization. Jy temperature Carbonization: When the femperature carbonization is practised for the producti auch a Le cake or cher. production of semi coke which is also a ter re bOHN SH uns7S SON he coke thus produced contains 51015% volatile reaner and is not sufficiently strong to be used as metallurgical fuel he various products of low temperature carbonization ate semicoke, low temperature far, crude low temperature spirit and gas. The quality and yield of these products depend jpon the process and the coal used. Low temperature carbonization (LTC) plants normally ise low rank coals. These low rank coals produce excessive smoke on burning, but the coke obtained from them is a clean fuel ‘Semicoke from LTC is hii nly reactive and can be easily ignited into a smokeless flam: Thisis an ideal domestic f gas which is obtained as a byproduct has higher calori value of about 6.500-9,500 k cal/m*., The yield of the gas is about 130-150 m?/tonne of the coal carbonized and constitutes a v aluable fuel. The tar which is also obtained as the ty product contains more of paraffinic hydrocartons and a small amount of aromatic fydrocarbons, along with higher phenols and various substituted nitrogeneous compounds. ‘There are two main commercial LTC plants in India, One is in Tamil Nadu (Neyveli) and ) other is in Andhra Pradesh (i) High-Temperature Carbonization: High temperature carbonization is carried Out at 900- 1200°C: High temperature carbonization (HTC) is used for the production of pure, hard, prong and porous metallurgical coke, containing dusoiazeivolatile matter. The yield ot the coke is 65 to 75% Hibs byproducts~gas and tar have greater amounts of aromatic Hydresttens. Ti Mich 1g obtained has lower calorific value of about 5000 to: 6000 cal/m? than that Sisticed in LTC; but the yield of the gas is higher (370-480 m= tonne) TR formation of lower amount of paraffins and formation of higher amount of gas, indicates that Sacking of paraffinic compounds present in coal takes place at high temperature, resulting ih the formation of gases and greater aromatization. “The coke obtained is very much harder than the coke obtained from LTC process and Tees sc cciicd tard coke- This is used, a5 an industrial as well as domesie Hela gable 2.3: Low and High Temperature Carbonizations High Temperature mperature Lor ere Carbonization CarbonizationUsed for metallurgi= purposes: Used for domestic tae ield of the gas Higher (About 309. I °/ tonne) Lower (About 130-150m"7 io a Lower (5,400-6000 k: Higher (6500-9, 500 k cal/m’). ; § Calorifie value of “a the 23s 9, Percentage of straight ddrocarbons in the by-products (ar and gas) 10, Percentage of aromatics in the by- products 11. Smoke produced on burning Higher ‘Smokeless 2.4e Metallurgical Coke uae inal The properties of coke depend on porosity, reactivity and the amount of volatile matter retained ty coke during carbonization. Coke is mainly used as a heat source and reducing agent metallurgy: A good coke used in metallurgical process should possess the following requisites. () Purity: The metallurgical coke should contain lowest percentages of moisture, adh) sulphur and phosphorus. Moisture reduces the calorific value whereas ash hinders the heating and also restricts the passage of air and lowers the rate of combustion, High percentage of ash also aids in slag formation. { Sulphur and phosphorus if present adverse! (ii) Porosity: The coke should be porous so as y affect the quality of the metal being produced. to i (©) Combustibiticy: atte of the= tivity: Reactivit coke i: “wil a ad Bt oke is generally considered as its ability 10 react with CO» steam, : ctivity should not be too high. However the coke used for water manufacture must be reactive to represel a steam. vit n t reduction of CO, according to the equation, estes ra aa F 603 @ @ HA 2CO 4, and is significant in producer gas manufacture vill) ‘Cost: Coke should be cheap and easily available near the site of the metallurgical plant. Manufacture of Metallurgical Coke Coke required for metallurgic purposes can be prepared by two methods which are as follows: (i) Beehive oven j) Otto Hoffmann oven i (i) Beehive Oven: Upto the end of 19th century, the entire requirement of the metallurgical coke of the world was fulfilled by the coke manufactured in ‘beehive ovens’. A beeiive oven is a fire-brick chamber having ped structure. It is called beehive oven because it resembles in shape to that of a e The dimensions of a typical oven are 4m wide and 2.5in high, The roof is provided with for charging the coal from the top. Another hole, the discharging hole is provided in the circumference of the lower part of the wall. A number of vers are built in a row with common walls between neighbouring evens. Coal charging door Refractory lining Heat radiated trom the roof to the coal bed Zone of combustion Door for air supply or coke 05m discharging —— 4m Fig. 2.5 Beehive Coke Oven ‘The coal is introduced through the top hole in the dome-and is spread evenly on the floor ® Produce a layer of about 60 to 90 cm deep. ‘Some air is supplied initially to ignite the coal. : te matter burns inside the partially closed side door. The ion proceeds from the top to bottom of the charge and is completed in 80 10 1 ‘is supplied by the burning ‘of the volatile matter and hence no by-products are are allowed to escape to the atmosphere. At the end of carb d ed manually through the slide door, qd) ‘is discharge i ee an ie ery eat to initiate the carbonization of the ition starts and yolatil422 Engineering Chemistry at by operating a series of ovens in such @ way gy nical by opera y ye evonom e the charge i al are utilized to ignite the charge in the adjacen, cess can b The proves 6 ping to the atmosphere the hot oven gases esCal oven. Demerits of Beehive Ovens: The demerits are products, whieh are use b fal chemicals and are allowed to escape + No recovery of by » Lower coke yield due to partial combustion, « Lack of flexibility of operation. inspite of he above demerits, the beehive ovens are still in use because of their low capita inspite of the above demerits, the bee : and running costs The bi ‘ovens have been mostly zenerative principle of heat economy 's. Moreover (i) Otto Hoffmann’s Oven or By-product Ove replaced by the chamber oven: ie. utilization of the waste fuel rn all the valuable: products are recovered from the outgoing flue gases. Construction: The Otto Hoffmann chambers made up of silica bricks. Th number of narrow rectangulat 4m length, 4 t0 5 m height oven consist dimensions and 5 m width. The chambers are tightly closed so that no a enter. At the top of each chamber there are three holes for charging the coal. Each chamber is further provided with a 6 take off and refractory-lined cast iron door at each end for discharging the coke. These carbonization chambers are erected side by side with vertical flues or inte for combustion in Between them, The ovens (chambers) form a sort of battery of 10 to. 100 ovens. One single able of holding 16 to 24 ton es of coal Coal bunkers \~ Coal charging cars Rotractoy 99 lined iron oor ay Gas take off Coke Ram (Coke chamber usher) Regenera Fig. 2.6 Schematic repre Working: the ends. ‘The lon of wai Coal ix charged into the chamb Goke ovens are heated 10, 1399% ingle chamber of Oto Mattia er and the by burn 3s Oven ‘chambers ate closed ti z tightly at both INE RASEOUE fuels (usually coke OVERJ is converted into c ‘asthe co@ coke, there is decrease j ee ease i isi fie mae: inte frm of rand a shou ese in Volume, This i because ofthe removed ai the plastic mass solide tate he oot further higher temperate (around sO jeydrogenation companied by aren eer as called coke. The barnes erative principle is employed to achiey Mite « produced during combustion (flue eases) a as cea i as economical heating as possible. The waste Be mospere rove he cine ses) ate passed through the regenerators and then let i generators are built undemeath the ovens. The flue t pass their sensible heat to the check Boe Tie Tow ot heat ne er brick work of regenerators until the temperature flue gases is then reversed and the inlet gases (fuel gas jo ai) used for combustion are passed through the heated checker brie Bie, aes are preheated before entering ite the wees ee Gait ee a fine, te flow of gases is again reversed so that the waste combustion gases again heat the checker pack work, Thus regenerator work on the principle of alternate heating and ‘cooling eyslas. This se achieved by periodically changing the direction of fl BIDEN ion of flow of ga al © Sominutes OF 50. of gases through the vertical flues every Carbonization of a ch: iscomplete, red hot coke is cake falls into a quenchi of coal takes about between 11 to 18 hours. After the process shed outside by means of a ram which is electrically driven. The The yield of the coke is about 75% of coal (Chambers loaded with coal => Coal gas space between chambers for flow of but gases | Gas burns here. regenerators Outgoing waste {gases heal regenerators belore escaping tO chimney Wise gases Ar Producor Was set : ir Producer ‘ochimney oes to chimney Fig. 2:7 Otto Hoffmann Byproduet coke overing Chemistry 424 Enginee! water (wet quenching) oF by passing rageous over wet quenching wet quenching the sensible .s after quenching the coke neat the boiler-feed water is achieved by spraying of red hot coke is achieve ying, “boilers (dry quenching). Dey si ver se. duced is more strong, and 097 ernnsted whereas in dry quenchiNE the in ae m ‘become heated up and are then circulated to boilers ‘where they P' aid then recirculated for cooling fresh charge of coke. s evolved on carbi very of by-products: The gases and vapouls ev n on In coke Oe ie temix with the combustion and are collected separately. The & by | First the gas whi ‘oven gas is treated separately for the recovery of the valuable by Pree aa a aie | at high temperature is allowed to bubble through water in the hydraulle Mi Te water seal preventing the passage of the gases back into the retort whel pened. (Fig. 2.8) (G) Recovery of Tar: The gas from the coke ovens 1s passed through a tower in which liquor oi ammonia is sprayed. Tar and dust get collected ina tank, The tank is provided with heating coils to recover back the ammonia. The ammonia Is used again. Tht oal tar’ is a valuable source of chemicals. The tar obtained is ¢ istilled to give a number of products like crude benzole, phenolic compounds, pyridine bases, heavy naphtha, anthracene oil ete. ‘The quenehit jnert gases from | pecause the coke nization in coke ovens are {i Recovery of Ammonia: Next, the gases are then passed through a tower where water is sprayed to recover ammonia, The ammonia can also be removed by dissolving it in H,SO, te form (NH), SO, which is then used as a fertilizer, The removal of ammonia from: of the gas pipes in the form of (NH,)3 the gas is necessary otherwise it may cause blocka co; ii) Recovery of Naphthalene: The gases are passed through a cooling tower, where water al 4 low temperature is sprayed. The gas is scrubbed with water until its temperature reduces ‘The naphthalene gets condensed here which is collected along with water and recovered. (iv) Recovery of Benzol: The gases are then introduced into a lig) 5 j benzene along with its homologue is removed and calcd a ee te esis vit the benzene homologues is known as the light oil. (Light see a Sealers ts ate light oil. It is a mixture of low boiling Cpe Ee euorrees en the solvent used for washing The solvent is a mixture of ethyl mie Beene, viswethyl benzene et.) Separation of different componets of the a distillation. The solvent is returned to the scrubber, ‘? (y) Recovery of HS: 1,8 9 4S and other sulph Br declines toon sate a er present in coal gas must be ut corrosion. Moreover aie Grea sulphur along iphur and H,$ gas, the gas i ffensive odour, Bas is passed’ EA wn a prepese pokes > 32 2FeS:+40; 4 2FeO+350, T 4FeO +0, + 2Fe,0, $0, obtained can be used for the m ‘ e Bs NH, Reaithecod ee anufacturing, sulphuric acid, which can be used Te purified coke OVEN 22 is finally stored ov oy on 2 jer water i i doves lin counties where coals hep The man coupons otek a Gat ven gas are CH, and H, along with small percentage of CO,, CO, Np and oxygen. LIQUOR ase AMMONIA wares RAT f Ha LOWTEM WASH OIL 1 coh awae = ANS] [fee Teun aN. T tn NH.OH NAPHTHALENE Fig. 2.8 Schematic Diagram of Coke-Oven Gas Treatment Plant 25 QUID FUELS industrial and domestic fields, Their importance ‘mbustion engines run on them, The use 's also expanding at an increasing rate. Jorific value of petroleum is about the other sources also Lud fuels are used extensively these days Bhs understood by the fact that almost all intemal com Siigid fuels in heat generation in ovens and furnaces & Guat! larzest source of Ii M0 idike! Though petroleum accounts ent the requirement of liquid fuels s m coal etc. : ’ “The term petroleum means ‘rock oil! (in Latin, petra means 06k and olen called mineral oil. Petroleum is @ complex mixture of paraffinic, Clefinke sn with small quantities of organic ‘compounds containing oxygen, nitrogenthough, the chief application of commerci e ig atso used for the production of olefins ie ee of viscosity of straight rtin residues. Cracking can be carried out by two methods wo methods: Cracking: When c: ermal Cracking: When rskng kes lise aa called therhal cra elace simply by the application of heat and press ceure, when the bigger Kee oils are subjected to co ea ps cic The thermal sally among the Canoe fear fortis ae Paraffins < naphthenes (alieyclics) < aromatics sum fractions increases as - tions. T' i ae ions. Thermal cracking may be carried out either in liquid phase or vapour (a) eee oe _By this method, any type of oil (residues, heavy oil) ea Beis tbo wea? pt in the liquid form by applying high pressures of the range i g/cm” at a suitable temperature of 476-530° C. The cracked products we separated in a frectionating column. The important fractions are: Cracked gasoline (30- 35%); Cracking gases (10-45%); Cracked fuel oil (50-55%). The cracked gasoline has an octane number of about 70, The cracking gases constitute raw materials for petrochemicals. The cracking residue is used as a fuel (b) Vapour phase thermal cracking: By this ‘method, only those oils which can vaporize at low temperatures can be cracked. The petroleum fractions of low boiling range like Kerosene il, are heated at a temperature of 670-720 C under low pressure of 10-20 ke/em?. ‘The time required for cracking in this process is much less as compared to liquid phase thermal tacking. Petrol obtained from vapour phase cracking has better aniknock properties bat poorer stability In general, thermal cracking produces petrols which are less stable than straight run petrols due to the presence of highly reective unsaturated hydrocarbons in them: ‘Table 2.6: Comparison of liquid and vapour phase thermal cracking Characteristic ] Liquid Phase-Thermal ‘Vapour Phase-Thermal | Cracking Cracking Cracking. temperature 475 ~ 30°C 610 — 720°C Pressure 100 kglem?™ 10-20 kg/om* 65-10 70 Octane rating of Petrol ay hewvy ol’ can be cracked (Oi aN Be 30H SEIS Mechi ing is believed to follow free radical 7 eracking: Thermal cracking is fetes, Cue Knee illustrated by taking the example of n-nonane: ‘Type of oil+192, Enginenting oro : are zs CH; -CH2 -CH + CH=CH, 4 ep seis dical is formed. his B ible radic till a thermally more stal iss inves, ‘ jssion continu a cm CHy- Ch) — C2 CH; + CH = CHa A CH=CH, -~CH ‘ cry(CH) cH +OHs > CHa CHa), CH” a> CRs Hay | 27 ition give rise to hyd ‘ne no c-c bond in the B position B The radicals having radicals. . : CH,CH, > CH) =CH2 +H Termination CHy+CH) 3 CHj-CH3 2CH,—CH, + CH,- CH ~ CH; -CH, CH;-CH, +H — CH;~CH; ‘Catalytic Cracking: In this method the ctacking is brought about in the presence ofa © at much lower temperatures and pressures, The catalyst used is usually a mixture of sili} alumina (hydrated aluminium silicate). The most recent catalyst used is zeolite. The qui Yield of gasoline produced by catalytic cracking is greatly improved The catalstic eracking has following advantages over the thermal cracking : (i) High temperatures and pressures are not : Tequired in presence of a catalyst and is saving in the production costs,Fusis 133 jx) Compared with the thermal process, 7 is) are iieile produces, Process, the catalytic cracking yields less coke, less gas and (x) The evolution of by-product of desired petrol 84S can be further min ized, thereby increasing the yield (x) Catalysts are selective in action and hence cracking of only high boiling fractions takes place. ig (ai) Coke forming materials are absorbed by the catalysts as soon as they are formed. Depending upon how the catalyst is used, the ‘atalyst cracking is of two types: ig: In this type of Se pellets or granules are u i d catalyti acki @ ee Slee een cracking the catalyst is in the form of used in the form of fixed beds in catalyst towers. Catalyst Cooler Stabler -—* Gases Cracked ‘ lE< Gasoline Heavy oll charge j—tHeavyatl Froctonatng saline some dissolved gas Fig. 2.14 Fixed-bed type catalytic cracking The heavy oil charge is passed through a heater and heated to a cracking temperature (420- 450°C). The charge is then passed through a catalyst chamber. The catalyst used is either silica-alumina gel (SiO,. Al,O;) or bauxite, mixed with clay and zirconium oxide. The eatalyst tower is also maintained at 420°-450° C and at a pressure of 1 to 5 kg/om?. Cracking of the heavy oil vapours takes place in the catalytic chamber and about 30-40% Of the charge is converted into low molecular weight hydrocarbons. The carbon formed {about 4%) during the cracking process gets adsorbed on the catalyst thereby deactivating it. The cracked vapours are passed through the fractionating column, where the gasoline Yapours are recovered from the top and the heavy oil gets condensed at the bottom, The Bioline vapours are subjected to a cooler where gasoline along with some other gaseous Products gets condensed. Thereafter the gasoline is sent to a stabilizer, where the dissolved S883 are removed from the top and pure gasoline is obtained, having the desired boiling fange (Fig. 2,14). Dar oe oo the catalyst stops working after about 10-11 hours, due to. the ‘Gposition of carbon particles formed during the cracking process. This is reactivated by ing off the carbon in a stream of hot air. During the reactivation of the catalyst, the ; of heavy oil are diverted through another stand by catalytic chamber So that the On procee jinuously, Bere aanaibiianit, the temperature in the catalytic chamber salt (mine of sodium nitrate and sodium nitrite) in pipes ates434 Engineering Cremis"Y vi hi wi d catalytic crackin is is also known a5 fluid be yt tin is king: tic Cracl a h flows dows in the form of fine pe der which flows the catalyst is ixed with the heavy oil sha hopper. The catalyst ee oe a ams. The plan aaa the cacking chamber Scan Tate and behave mucl generator placed sigg tor and a regenera a ed catalyst cracking cons! a reacl ed of moving by side (Fig, 2.15 } ing bed Catal i) Mowing of cracking. oe be circu! sts of coe . tal Ly a (E> oases seen eae S Feary ot SF oS Se_ceeue Fracionating luna Air Fig. 215 Moving-bed type catalytic cracking The heavy oil is heated in heater and the vapours are allowed to mix with the hot eal in the form of fine powder, which is introduced from the regenerator. The mixture is forced inl a lange feactor maintained at S00? C. Due to the high temperature of the catalyst (600° C), the Cracking of the heavy oil starts even before its entry into the reactor. This facilitates the crackiNe of the high boiling fractions also. After cracking of the heavy oil in the reactor, the cracked vapouis Selene Mead aac, te fsetionating column, through the intemal cyclone. ‘The HHEt Centered i the tp of the reactor which allows only the cracked off vapours to pass 4 fractionating column, retaining the catalyst Powder in the reactor itself through the centri action. The catalyst powder gradually beco, . i rs Wy mes heavier due to the deposition of carbon and forced by an air blast to the re ‘intail : y generator maintained at 600° tn a ne nf at fatalystis reactivated. The reactivated ete then flows ¢oW dowry pla ase wt 2 hcg. el re a a Mi » Fetaining the catalyst parti i fegeneration process 'S used to preheat the Catalyst. oe te withing is believed to involve i ermediates,. carbonium-ion ates, Th example of S-Noniane, First, due to hemlet ee ; ced is thus protonated. by the catalyst. Beem oy 5 Bs=CH)- CH= cH Gi, WoHg — (CH) 3 — fe ~ (CHg)3 —CHg oe ‘2 CH, ~ CHa -CH— CH, — CH — (CH), CH — (CH), — CHa + CHa - CHy~ CHy — CHa ‘The nonyl carbonium ion then | undergoes B cleavage to yield an alkene and 2 smaller carbonium ion. Ane Pea awe GG (lor) ® Cis OHe CHa" CH" CH-CHiy-CH,-CH,-CH, —> CHs-CHy-CH;+CHg-(CHy)s- CH=CH: The primary carbonium jon rearrange to the more stable secondary carbonium ion by 1,2 jydride shift. 2 @ CH;-CH,-CH, —> CH,-CH-CH, In aromatic hydrocarbons, the ri s remain intact and only the side chains ate lost. CH,CH.CH,CH, H CHACHCH.CHs 4 @ 2 He + CH:CHACH.CHs ZA =H CH.CH:CH=CH, 25e Synthetic Petrol plished by obtaining petrol from cracking and by petroleum ‘ever increasing demand of petroleum has necessitated to ‘The chief methods to synthesize petrol are discussed below: 1, Polymerization: Polymerization aims at the production of Superior gasoline and is complementary 0 catalytic: cracking process. During cracking large quantities of olefins or unsaturated Hi ceaecns oe obraiond es by-product, such es etiene, pispene ta tlistes (yates {Goer are subjected to high pressure and high temperature inthe presente of aissaes of catalyst, they undergo polymerization to form higher hydrocarbons, resembling. gasoline. Chi, cll = CH, +CH)— CHa -CH = CH, > CH; = CH~CH, ~ CH(CH3), sce $-Methythexene * i trtned io cated polymer esline Cs got hgh ostne mbes (8 oe ei -20° C, two, pies cracked gases are Fated unaffected hs jgobutylene | catalyst at 160" | A great demand of petrol is accom distillation process, However. the Synesize petrol from other sources. 1-Butene‘ll 436 Engineering Chemistry { Beet e (isooctone) Polymerization can be carried out by two methods: ut by subjecting the cracked gases 10a 0 kee’. The products formed are | distillation, out in presence of a catalyst is ¢ phosphoric acid, sulphuric acid tion is increased in presence of a catalyst and the process 00°C), Some molecular combinations which are ytic polymerization. (i) Thermal polymerization: This is carried o\ temperature of 500-600° C and a pressure of 70-39 gasoline and gas oil which are separated by frac The polymerization carried ion, The catalyst used 2 (ii) Catalytic polymerization: known as catalytic polymeriz: étc, The rate of polymerization reac is cartied out at lower temperature (1 not possible by thermal polymerisation are possible by drogenation. of coal was 2 Bergius Process: The production of gasoline by destructive hy developed in Germany by Bergius. The process involves the conversion of low grade coals, gaseous fuel by hydrogenating them in the such as bituminous or brown coals into liquid and presence of catalyst Powered See cues eee Na a I . Fig. 2.16 ergius process of hy wdrogenation of coal to gasoline 490°C at a pressure of 200 atm, for about 2 hours. The hydrogen eombin r oe a field Low boiling. ti ons | a. Gostine ‘The vapours ees COR oe i fa Fesembling crude oit is, pee cma le oil, (ii) 1 su eo prquality Hp is the nds upon ste Which AP BY the le (cobalt = radicals ght chain retal from n of metal- duced. unsaturated ormation of agines, THE able odours wal of these med as Sout uum plumbite Fuels 139 ‘The process of converting sulphur 10 disulphides is k are mown formed is removed by filteration. The disulphides i oH phides in gasotine ar ‘sweetening”. The PbS (s) e extracted with a suitable (oy Removal of olefins: The unsaturated hydrocarbons or olefins ean be removed by treating gpsoline with cold 80% 1,80,. This does not react with paraffins, naphthenes and jsomatics, but reacts with unsaturated compounds forming alcohols and esters and polymerizes these to tar-like substances which are removed by filteration Gasoline can also be purified by passing through Fuller's earth which preferentially adsorbs the colours and olefins. ‘The refined gasoline, on storage may still undergo slow oxidation causing gum formation. snis can be suppressed by the use of inhibitors which suppress the oxidation processes €& sonatie amines and amino phenols Table 2.6: Comparisor of straight run, cracked and polyme ~ Straight-run gasoline Cracked gasoline Polymer gasoline | itis obtained from 1s obtained from itis obined rom tow | molecular sfraight distillation heavy oi. of erude petroleum components 2 Ic ig physically separated High molecular weigkt Low molecular weight ‘il components are br components ate poly into ow molecula merized to. give high sight components. So tmolcoular weight ‘components. So, it is is a chemical process. 1 chemical process. 10 ig having the high= ivis having higher octane fest octane number Ii contains more of ft contains more of tics, daphthenes and branched chain hydro- fhnin hydrocarbons, arbors Composition range is 4. Ir contains only fiomal alkanes aroma Composition range & 4 Composition range | ae (eC). ee very narrow (Cy-Cp) 259 Knocking vol engine. i strokes in Pe . ‘process comprises caf four stro! “aeawn into the cylinder during the induetionao Engineering Cremer 4 constituting the compression’ stroke ‘ hot gases produced dite to ajown, This is known as the ‘Power gt o, the piston ascends and expels the mixture i compresse if (iy) The fuel ait Be he pressure and push the pistor Gu) In the last stroke, termed a ‘exhaust’ strok teases from the cylinder {burn smoothly and rapidly ig Le. a tthe next eyele starts again. The fuel air mixture Bt the reaction is initiated by a spark, a flame should spread rapidly and uniformly through thi 1S mixture so that the expanding gas drives the piston down the cylinder smoothly. 18 represents the schematic diagram of a four stroke, spark-ignition engin Ie. Figure 2 Gasoline-ar inte a ji Nie pe cyuNoeR 4 PISTON z practical fae) Gag etal al autombiles ands dened ureand. . pontaneous. 60h lence. This expigg Peet it may also nbu ls of the evlinder ac produces i co sontaneots ele '¢ piston, ing way ; producing achat en‘Stion haus, after S gas Fuels 141 i id knocking: e cl emical structure an 8: The chemical struct F Leg Hatching ‘charsctesistice Structure of the fuel used has a close relation # The knotking tendency decreases with increase bonds and eyelic structures, Thus, lef antiknock properties than the in the compactness of the molecules, double ns Of the same earbon-chain length possess better corresponding paraffins * With normal paraffins, the knocking incresses w chain. Thus the tendency to knock in sty ‘th increase in the length of the hydrocarbon ight chain paraffins follow the order: n-heptane>n- hexane * Branched chain paraffins have bet >n-pentane>n-butane Her antiknock properties than straight chain paraffins. The h the number of branches and their position. Thus the different isomers of heptane follow the order achepi 2 dimethyl pentane. resistance 10 knock increases. wit knocking tendency of tane=2—methy! hexan benzene and toluene have very hig nock properties, Constituent of & fuel to knock is in the following order: Branched chain paraffins > olefins>Cyeloparaffins (Naphthenes)> Aromatics. Octane Rating: The antiknocking characteristic of gasoline (resistance to knocking) cannot Sevefined in absolute ters. In order to classify the fuels according to their knocking Property, arbitrary scale has been established by E iger in 1926, known as Octane rating or Octane umber. It was observed that n-heptane knocks very badly and hence it was assigned an antiknack Nat of Zero. On the other hand, iso octane (2, 2, 4 wimethyl pentane) has a high resistance toknocking and hence was arbitrarily assigned a value of 100 cHty I —cH—cH, HyC-CH,-CH,-CHy-CHy-CHy n-heptane Antilock value= 0 u ditions. Thus a gasoline with an octane number of 80, hy tt Sime knocking as a mixture of iso octane and n-heptane containing 80% of iso octane : Greater the ‘octane number, greater is the antiknock property. of the ;142. Engineering cherist"Y ydrocarbons some common H ‘otane Numbers of SOME Com Table 2.8: : - yroinn__ —=— N-pentane 106 Benzene oo Nehewane Tsopentane - ‘Alcohol Cyelohexne ' pentane ee operation of a gasoline engine, iy equired for knock-f ee ing octane number 94 and premium A certain minimum anti-knock 4 in two grades, regular hav USA, the motor gasoline is marketed a ee having octane number 100. In India the motor gasoline have specified oc sasolines is not entirely due to the i + ‘The octane rating of commercial gas0 lines isn i Ae ae Cenain eidives we ‘asoline to improve its. antiknock hydrocarbons only. Certain additives are added to the ; i characteristies. These additives are known as antiknock agents: ‘Benzo! and aleohols can be used as antiknock agents as these have high antiknock Tetraetiy! lead Pb (C) Hi)y is added to gasoline to increase its octane nuinber. TEL isa colourless liquid and is highly poisonous. About 0.5 ml of TEL per litre is added for motor ols and about Im! of TEL per litre is penerally added for aviation petrol. To indicate that petrol is leaded a 2% red dye is also added. ___ Knocking is believed to be a free radical mechanism leading to a chain reaction which results in an explosion pave combustion Pb (C)H,), forms Pb and PbO. These act as free radical iors and hence the propagation of the chain reaction leading to knocking do not take alues. But lead and lead oxide vapours so formed mi i s 50 fo wy contaminate the atmosphere as eis oe Eoabarien an the lead oxide is rapidly reduced to metallic lead Wen see on the spark plug points, the cylinder walls and the piston he: : ven inde w piston head. In order to prever ylene dibromide (CH,Br,) is also added, so that lead formed is converted ae ; Pb+CrH.Bh > PbBr + CH, =CH. ‘ g 2 ai bromide so formed is volatile and escape alone wi '% With other exhaust gases, aded i i ed petrol is being minimized now a days good antiknock in very low concentrations, agent. ButIn ium the jock: ised. isa oils ol is sults sical take mas sited lems, mide Fuels 143 In a diesel engine, the fuel is gnited by the ap drawn ation of heat and pressure and not by @ jr2Wn into the cylinder (suction stroke) and compressed 10 Sm" (compression stroke). Towards the end of the compression in the form of fine sorb heat from the spark. In diesel engi {pressure of about, 30 to. SO smoke, the diesel oil is injecte: droplets into the very hot compressed air. fhe fine particles of fuel a gases evolved during the j compressed air and ignite. The pressure of the Enition/combustion pushes the piston downwards (power stroke). The ele is completed at the exhaust stroke whereby the expulsion of hot gases from the eylinder ake place. Knocking in diesel engine: The main characteristic of diesel fuel is that it should easily below compression emperature. The interval between the start of fuel injection and iis ignition is termed as ignition induction lag, Itis obvious that for efficient functioning afthe diesel engine, this induction lag should be as brief a8 possible When a fuel has long induction lag, a large portion of the injected fuel gets accumulated in the cylinder even before ignition and when ignition takes place, the accumulated fuel burn violently with a sudden increase in ure and pressure n-uniform burning of the is the diesel knock aight chain hydrocarbons with minimum amount f branched chain and aromatic hydrocarbons, Thus, in contrast to gasoline, the diesel engine fuels shout s to minimize the induction lag. / Cetane Rating: F a sep fuel is known as diese The greater is the induction Chemically, diesel engine fuels con: st ve low spontaneous ignition temperatu sel engine are in contrast to petrol engine fuels, hence oils as they cannot be graded on octane number scale. seale is used Sete nina fuel will ignite under The hyérocarbon cetane (ti a Tay as compared to any diesel fiel and is assigned an arbitrary value of 100. Whereas o-methyinaphthatene has a longer ignition delay as compared to any other diesel fuel and hence is assigned a value of 0. pression, el fuel will be assigned a cetane number “Sift has the same ignition characteristics as that of a mixture of 45% eetane and 55% o-methyl = 00 ‘o-Meihylnaphthalene (Cetane No. -0)444. Engineoring Chemistry alkanes > naphthenes > alkenes > bra From the above it for knocking in petro} engines. This In petrol engines pre-ignition by temperatures. axe required. On the oth knocking and the fuels with low ignition temperat fuel is a bad fuel for diesel enginie and vice versa yy compression Ie ures The cetane number of ¢ diesel oil can be incr is clear that the conditions for diese because the cause of i : sads to knocking and hence fuels with higher ignition er hand in diesel ed by addin shed alkanes > aromatics. knock are just the opposite as requingy f knocking is different in the two ne 1 engines ignition delay is the cause op are required. Thus, @ good petrol enging g certain additives. The commonly used additives are ethyl nitrate, isoamyl nitrate, acetone etc. Table 2.9: Comparative-account of Diesel O11 250-320" C and isa HyCyy Hoy bydro ture of Cy, bons It's cheaper, 3. Fuel consumption per unit of Power produced is tes. 4, Suited for compression engines petrol and diesel oil Petrol (Gasoline) ned between, of C Iisa fraction ob 40-126° C H, and is a mixt Coty, hydrocarbons. produced is more. : Be eoacs an uited for spark ignition, engines, ipitin, Knocking is caused by pre ignition, 6 Knocking characteristics are exptessed in cetane rating Knocking characteristics are expressed in octane rating. Exhaust gases contain amounts of pol Exhaust gas. Amounts. of 8 contain higher § Combustion ‘Combustion requires 3 more Pollutants expensive fuel injection device Combustion fequires s simple 9 Alby Ate ions abetone etc are used Sister as additives to reduce knock TEL, Di ss se knocking EL, Dicthy! telluride: ides are used to rece no 25 Reforming edlice knockin; In onder to iy inerease th "ype of treat ¥ Anticknock properties of the ina OWN a8 reforming Retores eo easing, i . his forming bri i ' ming brings about the ee ubjected to a special+148 Engineering Chemisty the aloo! recess . In this proce: i subjected 10 distillation. The benzene Areotropic distillation: : swith reesene of carbontetrachioride 2 wipontetrachioride as the case may De: distill sien, leaving behind absolute alcohol: The absolute alcohol « days and then subjecting it to distillatios fraction is the absolute alco! Advantages of Alcohol blended Gasolin wi) ng the rectified spirit with lime fgp 9 fractions are rejected. The middle fn. The first and 12 blending with g oline, it increases alcohol is quite high (90). Hence 0 + antiknock properties trol has b fuel consumption on blending 1. The octane number the octane number f gasoline, The al 2. There is no decrease in power output or in alcohol with gasoline. when it is used The sarting difficulties in blended form with gasoline uuse of high boiling point of aleohol is overeom 4. Alcohol-petrol blend has a tendency to absorb Disadvantages of Alcohol blended Gasoline: 1. The calorific 2. Alcoh Sin 50 the air ent ue of petrol the air required for for petrol, The ratio of flow the Size of © petrol by altering 2.6 COMBUSTION Combustion is 2 . chemical p f heat and light, It is necessarily To ensur Fe , y calculated amount of air. An excess 6, Compustion seldom takes place efficiently with theoretical of air is always used in the furnace Actual % Excess Air = — it used - Theoretical air required 100 Theoretical air 00. Oxygen present in the fuel is present in combination with hydcogen, Thus this amount of =e me is in combination with oxygen present in the fuel, does not take part in ustion, The rest of hydrogen is called availabi z ces part i eave yydrogen is called available hydrogen, only takes part in combustion 7 02 > H,O+Heat Since 1 part of hy nese yydrogen combines with 8 i Farts of oxygen present, one part Of hyd Parts of oxygen or in other words for every § therefore available hydroven vogen gels fixed and is not available for combusti0™ Mass of hydrogen —Mass of oxygen n a8 ‘Hetce theoretical amount o SEEN Fequired for complete combus ion 6} ete comb f Lkg of fuel TableFuels 161 1s Write the balanced chemical equations & | Sep 2+ Calculate the weight or volume of CayBEN eats Components. present. sep 3: Find the total oxygen required by addin Tequired by each one of them. components and subrectine the aces ae oxygen required by: individ [ : oF nt of oxygen already present. Z step 4: Convert the volume/weight of Oxygen into air a Weight of air required = Total 0, x 100 .., Volume of air required = Total 0, x 100 .,3 23 Siep 5: Find out the air actually supplied by taking into consideration excess alr. = z Siep 6 : To convert volume into weight use Avogadro’s law. Let y litre be the amount of air A required. m* 1000 L 2.4L = 1 mole = 28.948 of air 28.94 yl “x yg 22.4 Table 2.10 may be helpful for combustion calculations f Table 2.10 : n Combustion Equation ‘Volume of oxygen Weight of ones needed (m*) needed (ni) tat inet ot pice | te ee rr constituent =x") constituent =x} cFo,— co, rel xx 3212 s ea Ee eeu De Hy+50) —> 1,0 z 4162 to+10, — co, 2 . a * 3232452. Engineering Chemist IN comBusTION CALS BASED 0! quired for the combustion of 1 kgf and volume of air re SOLVED NUMERI( 2,9; Calculate the weight Example carbon. | Solution: Combustion reaction, +0, —> CO ay 38 Weight of oxygen required to burn 12 ke oF C = 32 kg Weight of oxygen required to burn I kg of C = 7p 2.67 kg, Weight of air required = 2 61x = [1.60 kg = 11600 g Volume of air required for combustion of 1 kg of C 1600 11600 == —~ * 24s x22 Molar mass of air 23.94 Al , ~ 39786 L = 8.97 mw? sees Example 2.10: Calculate the minimum amount o fe ae u of air required for the co Sc i kg of the fuel containing C = 80%, H, = 6%; 0, = 5%; S = 2% alee eat a — i 3 2 = 5%; s; and rest N, by weight. Solution: Soluti Constituent - Amant | Combustion Reaction Weight of 0, Required c G00 80 C +0; C0, Ass 32/12 » 80 = 2133 H 162 * 6 = 48 3232 x 2=2 " = 213344849 Fequited-O; present in ai 4842 = 263.3 kg oak 72633 ~5 = 2583 ig of “Amount Volume of ©, Required O.48%.5 = 24 mi Sh" 22, > CO, +217,0 0.082 = 16 m? F405 0; 1,0 0.4055 = 20m? 5 1G,!2+5,.2,, 9200, «1,0 0.025572 = 05 m3 = es + Total volume of oxygen required = 244+,16+.99+05 Volume of air required = 0.65 x m = 3.095 m’ Baaple 22: A yas tas the following composition by volume: H = 22¥6, CH, BY EO; 6% 0, = 3% and N, = 45%. If 25% excess at is used, find the’ welght oF aif ‘nuilly supplied per m? of this w Miition: Volume of gases in Imi are: H, = .22m°s CH, = .04m*; CO=20m?; CO; = 0.06m?, O=03m', N, Amount Combustion Reaction Volume of O, Required H,+40,+4,0 2240.5 = 41 m? Chl, +20; > C0, +2110 042 = 08 m 20 0, + CO, 20%.5 = 10 m 06, 03 As Volume of O, required = ere m = 1.238 m? Volume of air required = 0.26 a1547.5... molar mass of 21° iy supplied = “92.4 1ATS 98,948 22.4 i ume of @ smpasition by volume of 8 €27 t= 119%: Cally = 4.5963 Cale = et ined at 25° C and 750 mim pressure For © sample 2.13: The co! CH, = 30%: C3 amount of air would be requires ‘of the fuel. Solution: Sean | Amounr | Combustion : fy ris 40, 940 | co 0s conto, 000, | C0; 08 | cH, 0 Eroaocene | Me u Gigs 350,4260,+314,0 | a 4s Calls ws Cylly + 60, + 4CO, + 41,0 oy a ae Ny 2 certain fuel sample 259%; 0 = 2% = 1999.3 g ~ 1.999 ke 5 H = 24%; CO = 6%; CO, N= 12%. What theoretical plete combustion of Im? 24,05 = 012 06%.05 = 003 Toial volume of oxygen required for combustion = 012+.003+.6+385+.1354.15-.02 = 1.40 m? at NTP Po = 760 mm P, = 750 mm Vj= 14m vy, Volume of o: ‘ mygen required at the given temperature and pressure— qi)- CO, etical ‘ 5 exkslte the minimum sit required for compete combustion of 1 kg of coal. ue of coal sample. (Gress QP ocaleulate the higher calorific value and lower calor ary. in keallkg: C= 8,080; H = 34,500: § = 9.49 ution: of coal contains pik ; O = 121 g: N = 32g; ash = 45 tired for complete combustion of 1 ke of coal = Wt. of [C * (32/12) + H x (1672) — 0] = (100/23) = (750g = G2" 'g * (16/2) — 121 g} « (100/23) {2,000g + 416g — 121g] = (100723) or 9.978 kg Afniowm weight of air requ i) HCV = —_|8.080 2% N= 10%, the teimaining: ings = 8106 11= 40.0228 N= 1096 Ah a as ound cana Ny colt cabanlon tHE aN te the quant mi, IF amne excess at I IPE ey ve eas BY HE 0 by CO, = 1.0684 N= TAGS SY470 Engineering Chemistry i volume: Hy = 40% CH, = 4% Cy ie sae =e required for the conta In ore Feed iad ot be fomposition by volume of the dry’ prog’ ied. Find out the ae be CO, 8.73%, Ny = 87.45%, 0, rc + required for the complete combustion of | kg of weight: C = 99%, H= 3.5%, S = 0.5% N= 054 osition by weight of the dry products of combustion thas the following 54 A gateous fuel CO = 6% and Np 20% excess air is supplit combustion $5. Calculate the minimum weight and volume of ait faving the following percentage composition by ash = 2.3% Also calculate the pereentage comp’ 25% excess air is supplied. ’ = 0.07%, Ny = 73.67% = (1.84 bg, 893 m', CO, = 2.86% SO, = 0.07%, Ny = 73.67% and Oy hat | $6, 100 kg of a liguid hydrocarbon fuel containing 89.4% carbon by weight is burnt with (1) theoreti) amount of air (ii) 20% excess of the theoretically required amount of air. Calculate the volumetie composition of the products in each case (1036.82 kg, 1243.5 kg, CO, = 57. 1000 m? of a producer gas having the volumetric composition CO = 22%, CO, = 4%, = 14%, N, = 56%, 0, = 2% has to be burnt for heating a furnace. (i) C: 7.27 %y Ny = 79.28% 0; = 348%) | CH, = % Hy jculate the minimum quant of air required for the complete combustion (ii) if 40% excess air is used, what is the volumetie composition of dry fue gas? (052.38 m}, CO, = 14.19%, N, = 81.76%, 0, = 405%) 38. A gaseous fuel has the following composition; H, = 50% CH, = 30%, C,H, CO = 8%, N, = 6%. Caleulae the volume of air equired per cubic meter ofthe gas. Also find out the peicentage composition by Welt af the dey products of combusiton, if 20% excess air is supplied ree é (5.24 m’, CO, = 8.7%, Ny = 87.47%, 0; = 343%) 59. The percentage composition of @ sample of anth a found by ie le of anthracite eoal was found by weight 10 be C = 90, H= 33 os Srp orig ad Ssh 20. Calculate the minimum weight of air cequired for the eotipel f ary flue gases by weit 2% eX of tir is supplied, find the percentage composition Gill Y s by weight = 181%) Ny ~ 74.12%, O, = 7.47%, SO, = 01%) | S ; (10.78 kg, co, i. Analysis of coal used in a boi ed in a boiler is: © = 82%: 44 = 420 \ used ina boiler, the analysis of flue c aie q 8 OF flue gas was CO, = 19%, A) the amount of excess air ner ke of coal buts; eee 2 (iii) percentage of ‘EXCESS gir supy ee ir supplied for cui iene () 5.970 ii) i EXAMINATION QUESTIONS "aaa 8 Whit ste fuel? How are they classifea? ) Describe the methods employed for the vtimate ‘analysis of eos) iS of co)Fuels 171 %, (i) Meigher Calorfic value and the lower Calorie Valve f the coal sample of the coal sample ie cn 7 i Wat carbonization? Explain with a neat diagram, the Oto anufacture of metallurgical coke Hoffinan by-product oven method for the (G.G.S1LP.U, 11 Term, Dee-2000) nd 45 (@) Enumerate the characteristics of wood fuel if (b) Pilferentiate between gross calorific value and net atorhc waive ; 0 ees be the following composition by Weight C= 90%, O = 3.0%, $ =0.5%, N= 0.59% | ) and ash = 2.5% Net calorific value of the coal found to be 8,490 kcal/kg. Calculate the percentage al of hydrogen and gross calorific value of hyd: ‘ogen. (G.G.S.L.P.U, End Term, B. Tech, Mar, 2000) ic #6 (a) What is meant by knocking? How js it related to chemical constitution? Describe the function of TEL. Explain octane number and cetane number ) WO) * soe sample was found to contain: C = 66.2%, H= 42%, O = 6.196 N= 14% 6 <2 SEHOENE ts = 9.7% and ash = 9.5% by wei He the quantity of dry products of combustion, if | kg of iy eal is burnt with 25% excess ai (GGS.LP.U, End Term, B. Tech, Mar, 2000) : (8) Describe the manufacture of gasoline by Fisher-Tropsch| method _ (b) Differntiate between cal fuel and nuclear fuel. its applications (GGS.P.U, End Term, B. Tech, Mar, 2000) (t) Describe with the help ofa neat diagram, how the calorific value ofa fuel is determined hy the "Romb- calorimeter Ehin why the good fuel for pet ine i a tad fuel for diesel engine _ Term, B. Tech, Oct 2000) | ) 6) Expain with a neat diagram “moving bed catalytic cr j . (©) Write short notes on:- 4 (9) Octane Numb .) (i), Cetane Number 7 WM) Antiknocking agents é eee ia 9) Describe with the help of a neat diagram the preprtion of coal pas. cae oe : -vactly 2.500 gm was weighed into a silica crucible, After 0 1 Kempt of coal was analysed eels Bm. the crucible was next covered with ‘lit and strongly heated for cx mints PM pig ik i aa = es : be briefly ultimate analysis of cal Pe es mt ercentage composition: Q PA ane cot was oun ohare he lowing een cf aloe values GH) Main e ” F i and i i 5% Calculate () the Bro as iin be er ene oeas ‘of | kg of coat. (G.G.S.LP.U, I te '2000) = how petrol is synthesized by" Bergius Process why? higher calorific value and why’ coal gas or producer gas has ne retiove. compounds from oil & 1 = ee (G.G.S.LP.U, HE teFe, B. Tech, Oct, 2000) yeasly 2.500gm, was weighed in silica as analysed as follows aon 2.415 em. The crucribe next was covers y, fe of coal w# es yo ¢ ighed | © cs anes ee par 110 mrminutes at 950° + 20°C. THE residue Weighed sistant weight was obtained, svented lid and stronely heatee at the cover, until a constan 3 jpn The crucible was then ee ‘Caleulate the percentage results of the above analysis residue was found to weight (G.GS.LP.U, End term, B. Tech, Dee, 4 wih he tp ora not diagram explain how the eatoric wale of & fuel can be determined by static * pom calorimeter. What are the fuels use and. vy? 7. Distinguish between (a) Producer and water gas. (b) Octane and cetane amber {© Nuclear fission and nuclear tusion (® Bituminous coal and anthracite 0) Gross and Net calorific value (©) High and tow temperature cabanization (@) Proximate and ultimate analysis, (G.GSLP.U, End term, (11 Bateh), Mar 20) 76a), Describe the maving bed catalytic cracking method to obtain petro! from crude oil (b) A producer gas has the following composition by volume: CO = 30% 20 and Nj=S2% What will be the composition of dry fh i sition of dry flue ga used for buming 100m? ofthe gas? Gost . Hy = 12%, CO = 4%, CH= if 50% excess air was -S.LP.U, End term, (11 Batch), Mar. 200!) 77 (a), Detine ross calorific value & net calorific value? {b) Describe with the hel Syste Pf net diagram, how is the ealriic value of fuel determined by @ Banh ae following composition by mass: He cmp combaion fait td 3h 45% caste as minimum an eg HehtSl and the lowest calorific value of fuel at 6 “#2. The latent heat of condensation (©.6.8.1.P.U, 11 Term NOW! ior the determination of water equivalent of bomb calorie | ©) 82. Di 83. (a) 84. Wri (@) (b) 85. (a) (b) (©) 86, (a) | (b) 3weight of bomb, calorimeter etc. = 3000 ise in temperature of water = 2.593 ean specific heat of apparatus ~ 9.099 sft fuel contains 6% hydrogen, calculate its owe foam catorife wate acs SL ae Le i {g Name the enaljsis of coal in which mois significance of each component wie dotiennial le (GGL TE tenia Now, 201) Pitireniste between chemical fuel and nuctear fc m4 A psscous fue! has the foll (EGSLNU HE feat News 200) WA esses fue! has the following compass be and N, = 6.0% calculate the volume o A. aN, = he CO for combustion. Also find cof ae FEN excuse all Ue Magli sic i be 8 mixture of 80.0% N. . ny pats enhatih (ASME (G.GSLPU, md Tern Teoh Bee HH) H Write ston notes on {a) Corbonisation o Fb) Nuriear reactors (GIGS nt Tee, BWW, Dee a 16 ji) Explain knockin (hy What are adva f king 0 inal crock 6) Expiain cetane No. and N (EGS Tea Now 200 Be lg) Describe Otto-Hottim: ing Metallurgical coh (hy 202 sample of coal 4 for nitr invation by kjeldalsinetton, The evolve Nt Woes colleen $0.21 (N/10) H;S0,.T cess avid, 2S ti of0, 1 N Naot was onghient Dei he seeee ‘ffi in the given sample (GIGS LDU. Nes MRD Fi) Hov calorific value can be determined by Romb’s calrieneter? Explain with the hel ft HiMEN It) Differentiate between Net and Gross eaoritie value (GESUPU A Toe, NOH ANNE) I ACeaitasfotiowing composition by weight. C=80% 0, $% S=2.5% N= 1AM goh= 3.1 NARS lic ofthe coal was found to be 9430 K cal/ke, calculate te perceinage of Ayia ani Macher as ies (GIGS HINU A Reet Noy BND) sian the criteria foe seloeting a goa et #'S) Give the complete classification of chemical fuels and ment eterna and report the method of ts SLAP.) Bt Te hee BON) ) Explain proximate analysis of cos! 19 Disinguish beeen gross and net calorific value of el © Wha is metal 2 ettoad for its annfactiii lngical coke? Give a metho x eta P) Aca consnining 62.4% C Sc aeet Laverna; 151% moe 44 Mh bah By acy Zach gan connsincd 12.996 C0;5 02% COs 616 OLR SATII 1) The weight of air theoretically required per i # The weight of dry flue gas obxained per ki of fuel alee sat The weight of air actually used. (GING, BNE NOH snof coal (GUN KH TAH es BY174 Engineering Chemistry ‘92. Differentiate the following: calorific value. 4) Gross calorific valve end Net enor aac! ii) Low tempeianure Carbonizarion and High te Gi), Octane Number and Cetane Number gett ens {i) Liquid Phase Thermal Cracking and Vapout oe oa v the neat and labeled diagram for the refining of Petro. once (GGSLP.U,I-Term, B.Tech, ct 205) percentage composition. 5%, Ash = 4.5% im, Dra 93, Give the average composition of Petrol Name as) four separated components and give their use. 94. (a) A sample oF coal gas was found to have the following C= 71% H = 7.4%. O = 11.2%, N (@ Calculate the Higher calorific value and Lower calorific value of the coal sample, (id) Calculate the minimum air required for complete combustion of | Kg of coal. (®) A gaseous fuel has following composition by volume: X, = 4%, ‘of'eseess of air is used, find the weight of air actually supplied per m? of the gas (G.G.S.LP.U, Il-Term, B.Tech. Nov, 9S. (a) Match the following: . a (© Pateocheriats @ C-c, Gi) Naphtha (i) Presence of oxygen Gil) Carbonisiion (ii) Non-volaiteiquias (0) Bomb Calorimeter (i) GC, (6) Gastine (9) Actobic method of decomposition (Wi) Boy's Calorimeter (“}) Burning wastes in large furnaces (vii). Detived from, srude oil and natural gas (il) absence of oxygen ®) Volaiteiguids ©) Moisture content” (il) Proximate Analysis (i) Compositing (ix), Incineration 69) Combustion {b) Bret comment on the filwing () What is tieant by eatorine (ii) Why ‘should an ideal fuel a (2) Why a good fuel must ha to (¥) Why ste ne sromaticcoma st coment? SOmPoUNES are fan und in pases € OF aso 97 (003) 003) 005) Fuels 175 iter quien oF bom a4 calorimeter = 2909 lee in temperature = 2.42°C Fuse wire correction = 10.0 cal Acid eorrection = 50.0 cal Be crecne tie ah Rt ti= Sc ace pe ee coal Intent het of condensation of steam is SB0catig Cane Ce ig (G.GS..P.U, I-Term, B.Tech, Nov. 2005) i) Using suitable Nur explain the Oto-Honann’s bystodul oer metallurgical coke thod for the manufacture of (fy) Agaseovs fel undergoes combustion usin 20% excess ar, Compostion atthe stllovs,CH,=5%, I, =20%, CO =25%, CO, gna joes th ne fel oy vos) est in N;, Calculate volume of air suipplisd perm? of fuel and composition of dry flue gases (G.GSihu, ice BN] a) Match the following mi ibetrachernicals (i) Tetra ethyl lead io Aattemeite (ii) Presence ofoxygen {ii Carbonisation (ii) Non Volatile iquids {i¥)_Boinb Calorimeter (iv) Aerobie method of decomposition (9) Anti knocking agen (8) Highest eabritie value (\i)_ Boy's Calorime (vi) Burning wastes in lange Furnaces (vi) Proximate Analysis (vi) Derived trom crude oi and natural gas {viil) Compositing (iil) Absence ofaxygen (6) Incineration iy) Volatile guids 1) Combustion (x) Moistute content {t) Briefly comment on the followin () What iy meant by sweetening of petrol? (i) What is meant by wet gas? jon ratio of an LC. engine? (i) What is meant by compress {1-Term, B-Teeh, Nov. 2008) wv are they formed? (G. % a) Differentiate bermeen the two {i) Octane number and Cetane number (i) Thermal Cracking and Catalyticeracking sJrific value of eos 16 saving the following compositions, 1H) Calculate the grass and net S © 85% Ha 8% S Assim latent heat of seam IY Describe ine symbesis of petrol by Bete Po 1) 4g of carbon undergoes combustion: Calculate (0) weight of oxygen Ci) volume of oxygen i) Height of ie asin! ) volume of air 95, N= 2%, ash 87 cable PU, Term, B-Teeh. Nov. 2008) (Ge ne requirement ofthe lowing | Teri, BeTeeh, Noy, 2008) il476 Engineering Chemisry f 101. Waite short notes on the fllowine= (0) Prosimate analysis and ultinate analysis (i Octanerating andcetane rating (G.GSIP.UM-Term, B.Tech, Noy.2ong 102, (a) Match ihe folowing: (Ethanol blended Gasoline i iat (ii) Presence of oxygen a (iii) Non volatile liquids a (iv) Aerobie method of decomposition ices (V) Renovaofoefinsend “S"eonat (vi) Burning wastes in large furnaces (vil) Structural modification of gasoline (vii) Absence of oxygen () Volatile tiquids (8) Petrol from non Petroleum source (vi) Boy's Calorimeter (vil) Power alcohol (if) Compositing (6X) Incineration 6) Bomb Catorimeter (8) Briefly comment onthe following: (0. What the importance ofthe determination of fixed carbon in coal? Gi) What is wet gas? AG) ‘Why isi nesesaty to remove ‘S” compounds trom olland natural gas? OS) Whyis coke prefered tocol in metallurgical processes? 103. (a) Differentime ‘Detween the two ma ws: Exactly 2.500; heated for thr at 11 sree '8 Was Weighed into a +t having Bema men ete ema ge bl ‘until a constant ‘Weight was obtained, Th ciated wiogt, The cncible was then heated ith coves 1c astresidue weighed 0.245, ce ME results, 1g. Caley the percentage of the above 104. (a) With the hep oa sina (6.G.S..PUL TL mgeendatsy bined ace ien acon Marines os B.Tech. Nov. 2005) nal distil eben e e Calealteth quantity of dy products ot "M6 petroleum ting point, composition 10 108 109 Ho. In.pr 12.6% Nasa% g=13%6aind ash = rest falculate the minimum weight ofa im ret RECESSN) for comple combistionotl Kp ofa tapos ofthe dry products of combustion by weight Ee Way ind how corestions ae made in determination of exloritc vat ind the percentage, PAU II-Tetm, B.Tech, Nov. 2006) » bombs calorimeter? aw iy Te following data were obtained in a bom clorineter experimen ‘Weight of coal burnt ~0,996 Weight of water in calorimeter = 2490p Weight of bomb calorimeter eve. = 39008 Rise in temp of water = 2.592% Mean specific heat of apparatys = 0.099 Hide fel contain 6% hydrogen, calculate its lower calorific value assing 587.0 alg as tment eae seam (G.GS.L.P.U.L-Term, B.Tech. Nov. 2006) 106 6) Describe the terms: carbonization and eracking (t Hydroearboas that are poor gasoline fuels are quite good diese els Explain the team, (G.GSAPU.1-Term, B.Tech. Nov. 2007) 1H) Beseribe the method of ac {.coal 10 yield coke (6) S:ofasample ofeoal when dried at 110°C 10 coustant weight lef a moisture fre residue oF 4 80g On further hating out of contact with about 900°C. in a crucible with a vented lid to derive ofF all the volatile Halter, eresidue of 338g of btained. On heating the rucible with id open til all the earbon wis midised, a residue of 0.075 bined. What is the prowimate analysis of the coal (G.G.SALPU. LTerm, B.Tech, Nov. 2007) I Whatdo you understand by destructive distillation of eoul? Comment onthe statement, “the pradueis obtained skepend upon the temperature of carbonizs on”. Give data to support your answer. (G.GSAP.U, End-Term, B-Teeh, Dee, 2007) woven with examples MY ft) What is 0 fuel? How are fuels classified? Support your {6) Give an account of proximate analysis of solid fuels. What is the significance of proximate analysis? sat’s apparatus, Volume of the gaseous mixture feft after Be heweot ay gies wos salad i ni Fee a eee ee sie rll woe COC), Nel ee Wie 487 A Fees oot a ze peceoags of eh cps nthe aa 4 (G.G.S.LP.U, End-Term, B.Tech, Dee, 2007) * originally present inthe sample ‘f el coal is bumt differs from the ash og eerste (G.GSA.P.N,End-Term, B.Tech, Dee. 2007) goa