Fuels and Combustion With 80% theoretical air, the combustion equation becomes CH, + 5(0.8))0; + 5(3.76)0.8)N, —> aCO + bCO, + 4H,O + 15.04N, Carbon balance : 3 =a +b Oxygen balance: 8=a+2b+4 By solving: a=2,5=1 The combustion equation can thus be written as: CyHy +40, + 13.04N, —+ 2CO + CO, + 4H,0 + 15.04N, 4.11.4 Dew Point Temperature From the combustion equation, the mole fraction of water vapour @y,0) formed can be estimated, THO "Ho 0 HO Meat Meo, + eo +H, + Aso, +N, + MH,0 xy (4.37) where 7 represents the number of moles. The partial pressure of water Vapour in the mixture of gases constituting the flue gas is given by Pio = XH,0P = %y,0 * | atm = 24,9 atm (4.38) where p is the total pressure of the exhaust gas mixture which is 1 atm in all utility boilers. The saturation temperature at the partial pressure of water vapour is called the dew point temperature (d.p.t.). The flue gases are cooled in heat exchangers like economiser and air preheater so as to minimize the exhaust losses through chimney. These gases, however, should never be cooled below the dew point temperature (Fig. 4.8), as read from the steam tables. If cooled below the d.p.t., the water vapour condenses into liquid droplets which react with SO, or SO, to form acid. This acid corrodes the metal surfaces of the ducts through which the flue gas flows. | T Fig. 4.8 Dew point temperature of the exhaust flue gases 4.11.5 Heating Value of a Fuel Heats of reaction of coal constituents are given in Table 4.3.184] Power Plant Engineering Table 4.3 Heats of reaction of coal constituents Formula Product of combustion Heat of reaction and state and state (kJ/kg mol) Carbon (coke) Cis) CO, (g) ~ 407,000 Carbon ls) CO,{g} 397,000 Carbon monoxide COlg) CO,{g) - 283,000 Hydrogen Hale) H,0() - 286,000 Sulphur Sis) SO,(g) = 291,000 For | kg of coal containing C kg carbon, the heat released by the carbon combustion (taking carbon to have heat of reaction of coke) at standard conditions is Heat released by carbon combustion ke-1 = Cke x 407,000 —S ,, Ke-mol _ 5339 kg-mol 12kg Similarly, heat released by sulphur = 221008 — go945 ii/kg The available hydrogen is that hydrogen which is available for combustion, and is the total hydrogen less than that required to combine with the oxygen in the coal, (x -$). Heat released by hydrogen combustion. = (»-3) 286000 _ 143,000 (u-2} kivkg, 8) 2 8 Therefore, the total heat released by complete combustion of 1 kg coal is ° HHV = 33,9170 + 143 (1 -3) + 9.0948 Mi/kg (4.39) The equation is very close to Dulong’s formula, as given by Eq. (4.5). 4.11.6 Control of Excess Air Proper control of the right amount of excess air maintains optimum combustion efficiency. Amounts of CO, and O, in combustion gases are indexes of excess air. The desirable CO, level depends on the fuel and the optimum excess air for the furnace (Fig. 4.9). Desirable O, values depend much less on the type of fuel (Fig. 4.10). This makes O, measurement the preferred method for combustion control, If the measured O, content is more than that desired, the air supply is to be reduced. If the O, measured is less than that desired, air supply is to be increased,Fuels and Combustion ae PE a ee , =p . Cop, ees ae ih &* Bi whi. Seo —— Excess air Fig. 4.9 CO, variation in flue gas with fuels and excess air O) in flue gas —— % by volume —— Excess air Fig. 4.10 0, variation in flue gas with excess air Boiler losses are estimated as outlined in Section 4.13 for different steam outputs. The excess air is then adjusted by controlling air supply to show the optimum value of CO, or 3. The optimum value of excess air for best combustion efficiency is then ascertained (Fig, 4.11). The excess air can also be determined using the following relation (Skrotzki and Vopat, 1960). Incomplete gombustion loss Opt. zone of excess air Exhaust loss Loss due to ‘exhaust gas Exhaust L Optimum excess air —— Excess air Fig. 4.11 Optimum excess air for maximum combustion efficiencyPower Plant Engineering 0, -05C0 0.264N, — (0, — 0.5CO) where O;, CO and N, are the volumetric percentages in the dry flue gas. An approximate formula for the excess air is CO 1) _ 9p] 22-0500 10 | oe | 10 21-0; | where (CO})y = % CO; in the stoichiometric dry products, CO,, CO, O,=% in the actual products. Instruments are used to regulate the air flow, gas flow and steam flow, It aids combustion control, % excess air = x 100 (4.40) % EXCESS ail 4.12| MASS BALANCE OF A STEAM GENERATOR Analyses of fuel, refuse from ash pit, and flue gas, and the dry bulb and wet bulb temperatures of entering air are recorded. On the basis of 1 kg coal, Fig. 4.12 gives the material balance for a boiler furnace, where W’, is the amount of air supplied. L kg coal = CHH+OFS+N+M+A Wj, =€Ox +CO + Oy + Np + S02 je Wa jer furnace §— |} ——* Wiy.q=9H+M+ 7a Refuse =A+C—Cyy Fig. 4.12 Material balance for a boiler furnace Wy+C+H+O+S+N+M+A=Wy, +9H+M+tA+C-Cy Was Wey 8 (u-3] =Cy-N-S (441) Mass of dfg produced per kg coal, Wy, = % 12(CO, + CO) _ Gal ICO, +700 +80, +7100 - CO, -CO-0,)] 3(CO, +00) Cy (4CO, + 0, +700) ss (4.42) 3(CO, + CO)Fuels and Combustion Volume of flue gases (wet) produced per kg coal a= . i ig where the pressure of gas p, is in kPa and My, is the molecular weight of dfg. The dry refuse analysis by mass gives dp + Cy = 1.00, where subscript R represents the refuse, In | kg coal, A = I’, X Ap, Where I¥g is the amount of refuse per kg coal and Ap is the mass fraction of ash in the refuse. A Ag m (4.43) W Wy, 1, +273 le fe ane Le 101325 Pe Waa Mass of unburnt carbon in refuse per kg coal = Ci’, = Cy Carbon burnout in dry gas C= C- & (4.44) Ag g| ENERGY BALANCE OF A STEAM GENERATOR The fuel supplied to a furnace when completely burned releases its heating value. This energy converts the feedwater pumped to the boiler into steam (Fig. 4.13). w Pros @ pwn 1 kg fuel = 4 C+H+O4S+N4+M+A Lol me Wagg = COs +CO + Oz + Nz | ute | Wg = 9H + M + Ay [—* Wp=A+C-C, (03+N,) x “ Feed water Steam wave Fig. 4.13 Energy balance of a steam generator Basis: 1 kg fuel 1. Usefiel energy a kJ Q= Fe [a AN =m A (4.45)Power Plant Engineering where — w, = steam generation rate, ke/s ww; = fuel burning rate, kg/s mm, = mass fraction of inlet steam bled from the h.p. turbine before reheating 2. Energy loss due to dry exhaust gas Qs = Wags Spy, (ty - ta) kg (4.46) where H4,,= mass of dfg produced per kg fuel, & = average specific heat of dfg, kJ/kg K 1, = exhaust gas temperature, °C i, = ambient temperature, °C 3. Energy loss due io unburnt carbon Q;= mass of unburnt carbon * its heating value = (C—Cy) 407000 - 33917 - Cy) kike (4.47) 12 4. Energy loss due to incomplete combustion Loss of energy per kg of C oxidized to CO (from Table 4.3) . 28.000 kJ/kg carbon = 2358.3 ki/kg carbon Loss of energy per kg fuel kg dig = 7——— * ‘ke fuel Os= 23583 carbon kg fuel 28CO kg CO, 12 kg carbon x——_ 800 __*st0 44CO, + 28CO +320, + 28N, kg dig — 28keCO = 10100 Wy, ——_28€@ 8 44CO, +28CO +320, + 28N, kg 5, Bnergy toss due to moisture in fuet (4.48) Qs = M [4.187(100 — f,) + 2256.8 + 2.09 (4, — 100)1= (4.49) where /; = temperature of fuel entering the furnace. 6. Energy loss due to hydrogen in fuel y= 9H [4.187(100 — £4) + 2256.8 + 2.09 (1, - 100) e (4.50) ‘B 7. Energy loss due to moisture coming with air supplied. Or = ¥y Wa x Ep (ty — 1), kik (4.51) where 74 = specific humidity of air, (kg moisture)/(kg dry air)Fuels and Combustion &p = specific heat of superheated water vapour 8. Energy loss due to ash and slag Os = [(C— Can) + Al ep (thy — to) Keg (4.52) where he average specific heat of ash, kI/kg K t;,= the temperature of the furnace, °C 9. Energy loss due to convection and radiation from the boiler surface. y= (he + hy) A (by ~ i) (4.53) where 4, = convective heat transfer coefficient, W/m” K h, diative heat transfer coefficient, Wim? K A= total surface area exposed to the ambient air, m 4, = temperature of the wall surface of the boiler, °C i, = ambient temperature, °C 2 Energy released by complete combustion of | kg fuel = HHV. Energy utilized in the heating of the working fluid, Q, = HHV - E energy losses = HHW ~(Q; + Qs +» + Qy) Therefore, efficiency of the steam generator, energy utilized | HHV — £ energy losses ht geo Chergy released — HHV (4.54) — Ml, - hy + (=) Uy — hy] ye kKHHV x HAV (4.55) All energy losses at a particular load can be measured, and from Eq. (4.54) the efficiency of the steam generator can be estimated. Then, with the help of Eq, (4.55), the fuel consumption rate of the boiler can be determined. 4] DRAUGHT (OR DRAFT) SYSTEM Large amounts of air are needed for combustion of the fuel. The gaseous combustion products in huge quantity have also to be removed continuously from the boiler furnace. To produce the required flow of either air or combustion gas, a pressure differential is needed. The term “draught” or “draft” is used to define the static pressure in the furnace, in the various ducts, and the stack. The function of the draught system is basically two-fold: 1. To supply to the furnace the required quantity of air for complete combustion of fuel. 2. To remove the gaseous products of combustion from the furnace and throw these through chimney or stack to the atmosphere. There are two ways of producing draught: (a) natural draught and (b) mecha- nical draught.Power Plant Engineering 4.14.1 Natural Draught The natural draught is produced by a chimney or a stack. It is caused by the density difference between the atmospheric air and the hot gas in the stack. For a chimney of height H metres (Fig. 4.14) the draught or pressure differcnce (Nim?) produced is given by p= gH (p,~ Py) (4.56) Gas to atmosphere “Exhaust flue gas Fig. 4.14 Draught produced by a chimney where p, = density of atmospheric air, kg/m’ P, = average gas density in the chimney, kgim* g = acceleration due to gravity, 9.81 m/s? Let us assume that the volume of the products of combustion is equal to the volume of air supplicd for combustion, both volumes being measured at the same temperature. Thus, the volume of | kg of flue gas at NTP 0.287 x 273 101.325 The volume of m kg of air per kg fuel at temperature 7, = 0.7733 m/kg ¥,= 0.7733 mx 2 273 2. 1_ 23, 1,293 (2) kg/m? 0.7733 oT, The mass of flue gas will be (m + 1) kg and its temperature is 7).Fuels and Combustion mt 0.7733 x mx T,/273 ~ 1205 (78) (mt) 238 (mt) i, m T, m <. Draught produced (from Eq. 4.56) Density of flue gas, 2, = Ap= 1.293273 | Lm! 1 lay i, om =3s3g{t-meht (4.57) i om i If the draught is measured in terms of water column and the value is h mm, Ap = 10° ghx 10-9 = 383 gy | L- met Zoom i jLom+i tl rom T, * h= 353 (4.58) where h is in mm and is inm For given H and T,, the natural draught depends on the average gas temperature T,. Higher is the T,, higher is the draught produced. But a high T, means a large exhaust loss through chimney resulting in a lower boiler efficiency, With an optimum T,, the amount of draught produced by density difference is thus limited. Tall and conspicuous from a distance, chimneys or stacks are used in all power plants. In early steam generators, all the needed draught used to be produced by stacks alone to overcome all the pressure losses at the required gas flow rates. In modem boilers, the fuel burning rate is high, and so the rate of air supply as well as the rate of flue gas removal is high. There are also various heat exchangers like superheaters, reheater, economizer, and air preheater on the way ta cause large pressure losses for which stacks alone are insufficient, and fans are added for producing mechanical draught. Stacks have thus two functions: 1. To assist the fans in overcoming pressure losses. 2. To help disperse the gas effluent into the atmosphere at a sutficient height ‘to cause minimum atmospheric pollution. Stacks introduce pressure losses of their own. These pressure losses are caused by wall friction and the pressure equivalent to the kinetic energy of the gases leaving the stack. Therefore, the actual draught produced is less than the theoretical value Ap given by Eq. (4.58), so thatPower Plant Engineering v fH Ap = Ap-p, | 1+2* 4.59) Pact = AP ~ Pg =( | (4.59) where = friction factor, dimensionless A= stack height, m D = stack inside diameter, m V = stack exit velocity, m/s Py = average gas density in the stack, kg/m’ Dispersion of the flue gases into the atmosphere is defined as the movement of the flue gases horizontally as well as vertically and their dilution by the atmosphere. Existing wind causes the horizontal motion of the flue gases. The vertical motion of flue gases results from the upward motion of high-velocity warm stack-exit gases to much higher elevations. The exit velocity of flue gases at stack exit results in a plume tise AH above the actual stack (Fig. 4.15). The gases bend in the direction of wind flow. The plume height AV is the height ofa virtual point source above the stack obtained by extending the lines of dispersion backward. The effective stack height /7, is, thus, given by H.=H+sH (4.60) ‘Virtual source Wind velocity Concentration profile Fig. 4.15 Dispersion of flue gases at stack exit Higher is the velocity of flue gases at stack exit, higher will be the plume rise AH and greater will be the dilution of exiting gases. There are several analytical methods of estimating AH. Most of these utilize a momentum term that accounts for the vertical momentum of the gas caused by the stack exit velocity and a buoyancy term that accounts for the difference between stack gas and atmospheric densities, pertinent to the prevailing situation of mixed convection in the stack.Fuels and Combustion Correlation of Carson and Moses FD s AH= 20 — 0,029. (4.61) where, © V, = stack gas exit velocity, m/s D= stack diameter, m = wind velocity at stack exit, m/s Q, = heat emission, J/s = me, (T, -T,) m = gas mass flow rate, kg/s cp = specific heat of gas = 1005 J/kg K for dry air at low temperature T,= gas temperature at stack exit, K. “T, = air temperature at stack exit, K Correiation of Briggs _ hacr'? #, w AH (4.62) where C= dimensionless temperature gradient parameter A@ = 158-414 —— ‘AZ z A@ — = air temperature gradient, K/m which is zero for neutral atmospheric stability conditions gh DT, -T,) 4T, , g = acceleration due to gravity = 9.81 m/s* F= buoyancy flux = m*/s? 4.14.2 Condition for Maximum Discharge through the Chimney Mass of hot gases flowing through the chimney mz = p, AV, Since the density of hot gases is inversely proportional to its temperature, P, = C/T,, where C, is constant and the velocity of gases , = C./284, , we tt, = x4xc pet, where H, = hot gas column in m. have a mm, = AC, [2gHPower Plant Enginecring For a given height of the chimney, H, we can write 1/2 : mol mn, —c,| Mt * ier hf, | Thus the maximum discharge is a function of T,, dri, a, r, T,= 27, and <2 = (4.63) m+ a. Tom Now, Ap = p, gH, = 353 gH me We 353 m+ . Since p, = —- ———. on substitution " 8 q, Ho=H| 4-1 s m+1T, m osm+l ~a( 2 -t)-n m+l m Thus the height of the hot gas column is equal to the chimney height for maximum discharge, The draught in mm of water column m 7 “oil met he mm 2(m+1) (4.64) 4.14.3 Mechanical Draught Mechanical draught is produce: by fans. There are two types of fans in use today: forced draught (FD) and induced draught (ID) fans. When either one is used alone, it should overcome the total air and gas pressure losses within the steam generator, Forced draught fans are installed at inlet to the air preheater. They handle cold air, So they have less maintenance problems, consume less power (since cold air has low specific volume, and work input per unit mass flow rate is given by Jvdp) and therefore, their capital and operating costs are lower. If @, is the fuel burning rate, vis the specific volume of inlet air and Apep is the pressure head developed by the fan to overcome all the pressure losses, then the power required to drive the FD fan is given byFuels and Combustion Ww, x Ax vx ap Power input = ——&—_— (4.63) ep where 4/F is the air—fuel ratio and 7Ppp is the efficiency of the foreed draught fan. For good reliability two forced draught fans operating in parallel are normally used, each capable of undertaking at least 60% of full load air flow when the other is out of service The forced draught fan if used alone, as in many large steam generators and almost all marine applications, maintains the entire system up to the stack entrance under positive gauge pressure. The furnace is then said to be pressurized. Utmost care is taken so that noxious gases do not leak out to the atmosphere. It thus needs a gas-tight furnace construction and properly designed ignition openings and inspection doors. The stack in such a situation is shorter and meant only for disposal of flue gases. Induced draught fans are normally located at the foot of the stack. They handle hot combustion gases. Their power requirements are, therefore, greater than forced draught fans. In addition, they must cope with corrosive combustion products and fly ash. Induced draught fans are seldom used alone. They discharge essentially at atmospheric pressure and place the system upstream under negative gauge pressure. If v, is the specific volume of flue gases handled by the ID fan and A pp is the pressure head developed, then the power needed to drive the ID fan is given by Power input = —-——+— (4.66) Mo. When both forced and induced draught fans are used in a steam generator, the FD fans push atmospheric air through the air preheater, dampers, various air ducts, and burners into the furnace, and the ID fan sucks out the flue gases through the heat transfer surfaces in the superheaters, reheaters, economiser, gas-side air preheater and dust collectors and discharge into the stack (Fig. 4.16). The stack because of its height, adds a natural driving pressure of its own, In such a case the furnace is said to operate with balanced draught, meaning that the p ire in it pproximately atmospheric. Actually, it is maintained at a slightly negative gauge pressure to ensure that any leakage would be inward. Modern boilers are mostly designed with balanced draught firing. A typical large power plant (600 MWe) may require two 1320 kW forced draught fans and two 3000 kW induced draught fans. 4.14.3 Pressure and Flow Measurement The total pressure at a point in the system is the sum of static and dynamic pressures: Pu Pst Pa (4.67)Power Plant Engineering Atmospheric pressure T T ' I ECO Dust collectors ' i ' 1 | APH | 1 i ' ! 1 t A?ip ——| Fig. 4.16 Balanced draught system in a modern boiler where P, = total pressure, N/m? p,= static pressure, N/M? Pp a= dynamic pressure = 0 —- »Nim? P= gas density, kg/m? V = velocity of gas, m/s Although the SI units of pressure are pascals (N/in’), it is still customary to state the static and dynamic pressures in mm of water since measurements are commonly made using a simple, standard U-tube with water as the manometer fluid. One metre head of water produces a pressure of p= pel = 1000 xs «9.81 ™ x 1m=9810 Nim? m $ In terms of mm of water, the dynamic pressure head, p;, which would be measured by a pitot tube connected to a water filled manometer, becomes. 2 2 pV _ Pal Pam Spiga % 19> Tagg > mm HO where g, is in kg/m’ and V’is in m/s. Then the volume flow rate of gas in a duct is given by 2 R= [sot mis : where 4 is the duct cross-sectional area in m?.Fuels and Combustion F, = 4.434 Jp, m/s (4.68) where p, is in mm of water and p, is in kg/m’, The flue gas density depends on the moisture content and temperature. For 5% moisture and at 560 K, flue gas density is approximately 0.649 kg/m’. Combustion air density at $60 K, is 0.636 kg/m’, 4.15] FANS FD and ID fans operate continuously for long periods, up to I or 14 years. So, these must be well designed, ruggedly constructed, well balanced, and highly efficient over a wide range of outputs, Typical fans have capacities of 700 m?/s of volume flow producing 152 mm water static pressures (about 0.15 bar). There are two types of fans, viz., centrifugal and axial. In the centrifugal fan, the gases are accelerated radially through curved or flat impeller blades from rotor to a spiral or volute casing. In the axial fan, gases are accelerated parallel to the rotor axis. This is similar to a table fan, but here the fan is housed in a casing to develop static pressure. Axial fans have higher capital costs. Centrifugal fans can have forward-curved, flat or backward curved impeller blades (Fig. 4.17). The velocity triangles at exit from the tip of the blades are shown, where the absolute velocity of gas / is the same in all the three cases. It is seen that for the same V the blade tip velocity /, is the highest for the backward-curved blades (c) and the lowest for the forward-curved blades (a). Since V, = (@D.N/60, for the same tip diameter D, the rpm Nis the highest for the backward-curved and the lowest for the forward-curved blades. The FD fans should have high /, so as to rotate at high speeds and handle large volume flow of air. Therefore, centrifugal fans with backward-curved blading are normally used for FD fans. The [D fans handle dust-laden flue gases and so the blades are subject to erosion by the fly ash. The erosion rate of blades is lower if the blade tip speed M, is less and the fan rotates at lower speeds. Therefore, centrifugal fans having forward-curved or flat blading are used for ID fans. Low-speed fans. with flat blades are used for particularly dirty or corrosive gases. There are two common methods of controlling the output of fans: damper control and variable-speed control. In damper control, a damper (butterfly valve) is used to control the flow of gas by regulating the flow area according to the load. It has the advantage of low capital cost since it needs a simple constant-speed induction ac motor. It, however, offers additional flow resistance which is overcome by increasing the power input. Dampers are usually put on the outlet side of the fan, although dampers at inlet to the fan are sometimes used. Inlet dampers consume less power than outlet dampers but are only effective for moderate load changes near full load. When used with FD fans, they are normally used in combination with outlet dampers. The use of a two-speed ac drive motor in conjuction with damper control can also reduce power consumption, since two-speed motors are less expensive than variable-speed ac drives.Power Plant Engineering Fig. 4.17 Centrifugal blading: (a) forward-curved, (b) flat, and (c) backward-curved. Vector diagrams show blade tip velocity V,,, gas velocity relative to blade V,, and absolute velocity of gas leaving blade V. In all cases, V is the same Variable-speed control has the advantage of less power consumption and is the most efficient method for fan control. The effect of speed on fan performance is Volume flow e N Pressure head N? Power input c N* where NV is the rpm of the fan. Thus, reducing speed, say by 70%, reduces the capacity to 70%, the pressure to about 50%, and the power input to about 35%. The types of drives are _ variable-speed steam turbine . hydraulic coupling . Variable-speed de motor multiple speed ac motor electronically adjustable motor drive The major disadvantage of variable speed control is the higher capital casts than damper control. pwFuels and Combustion Two other types of fans are used in power plants: primary air fans and gas recirculation fans. Primary air fans supply air to dry and transport pulverized coal to the furnace. Gas recirculation fans are used to recireulate gas from a point between the economizer and air preheater back to the bottom of the furnace as part of a steam temperature control system. Fans are a major source of noise in power plants. To reduce this noise, they are often housed in thick masonry acoustical enclosures or equipped with silencers, or both. 16] HEAT OF COMBUSTION ‘The first law of thermodynamics was treated so far ignoring such energy terms as chemical, electrical, and magnetic, in the energy balance for a system. When dealing with combustion systems, however, the chemical energy term cannot be ignored. 4.16.1 Open System For a chemically reactive system (Fig, 4.18), the steady state steady flow energy equation can be written as cy Fig. 4.18 A steady-state steady flow chemically reactive system Ay t Qoy = Hp + Wey (4.69) ignoring the changes in kinetic and potential energies. Here, Hy and H, are the enthalpies of the reactants and products, respectively, evaluated for their constituents at their respective pressures and temperatures; Ocy is the net heat added to the system from the surroundings (which is usually negative, since in combustion heat is usually rejected to the surroundings); and W_y is the net work done by the system. Both the reactants and products are usually composed of several constituents. Therefore, Eq. (4.69) is written in the form Eqmh) + Oy = E(onh) + Woy (4.70) where m is the mass and A is the specific enthalpy of each constituent. Let us consider the combustion of ethane. C,H, + 3.50, + (3.5) (3.76) N) —> 2CO, + 3H,0 + (3.5) (3.76) Ny (4.71)Power Piant Engineering The enthalpies of the various reactants and products are those that start at the same datum of composition, temperature and pressure, which are arbitrarily chosen as the elemental substances at 25°C and | atm, respectively. For example, C,H, is formed from elemental carbon C and hydragen H, (Fig. 4.19). When the reactants carbon and hydrogen enter the reactor at 25°C, | atm and the product CH, is cooled back to 25 °C, | atm, 2817.3 kJ/kg C,H, of heat is rejected. The reaction may be written as 2C + 3Hy—> CH, + 2817.3 ki/kg C,H Similarly, for CO;, C+ 0, — CO, + 8946.8 kikg CO, wane LN 125°C tau pa Ocy = 2817.3 kiékg CoHe = (ip oatig Fig. 4.19 Formation of ethane Table 4.4 Enthalpy of formation hi, at 25 °C, 1 atm Substarice Formula Molecular weight — State. hy (ed kg) Carbon 12.011 Oxygen 32.000 gas Hydrogen 2.016. gas Nitrogen 28.016 gas Sulphur 32.060 solid Carbon monoxide 28.011 gas Carbon dioxide 44.011 gas Water 18.016 liquid vapour Methane 16.043 gas Ethane 30.070 gas Propane 44.097 gas Butane 58.124 gas Octane 114.230 liquid vapour Nitric oxide 30.008 gas Nitrogen dioxide 46.008 gas Sulphur dioxide 64.060 gasFuels and Combustion The quantities 2817.3 and 8946.8 leave the system and hence are negative. They are called enthalpies of formation (h°;). Table 4.4 gives values of h°; for various substances at 25°C, 1 atm. The enthalpy of all elements at the standard reference state (25 °C, | atm) is assigned the value of zero. It may be noted that if the combustion equation involves a liquid, such as octane or water, there will be two enthalpies of formation, depending upon whether they start or end in a liquid or vapour state, Because chemical reactions, such as Eq. (4.70) are balanced in terms of moles and not masses, and because m = nj, where n = number of moles and = molecular weight, Eq. (4.70) may be written as Enh, + Oey = Engh, + Wey (4.72) where fi is in kJ/kg mol, Table 4.5 gives the values of the enthalpy of formation op of a number of substances in kJ/kg mol at 25 °C, 1 atm. In most cases, however, the reactants and products are not at 25°C, | atm. Therefore, the change of enthalpy (in a constant pressure of SSSF process) between 25 °C, | atm and the given state must be known. Thus the enthalpy at any temperature and pressure, hy, , is Fey, 5 = (hf )asax, 1 um CAR) 98, 1m —s Tp For convenience, the subscripts are usually dropped, and hyp hot Ah (4.73) Table 4.5 Enthalpy of formation, Gibbs function of formation, and absolute entropy of various substances at 25 °C, 1 atm pressure Substance Molecular he ze 5, ; 5, Weight, M kJ/kg mol avg mol kul/kg mol K COlg) 28.001 - 119529 - 137150 197,653 cO.{g) 44.001 — 393522 — 394374 213.795 H,O{g) 18.015 = 241827 = 228583 188.883 H,0(1) 18.015 ~ 285838 - 237178 70.049 CH,(e) 16.043, — 74873 - 50751 186.256, CHa) 26.038 + 226731 + 209234 200.958 C)H,le) 28.054 + 52283 + 68207 219.548 CaHele) 30.070 — 84667 -3277T 220,602 CaHgle) 44.097 - 103847 -23316 270.019 CyHy oleh 58.124 — 126148 + 16914 310.227 CeHysla) 114.23 ~ 208447 +16859 466.835 gH, ,(1) 114.23 —249952 + 6940 360.896 where Af represents the difference in enthalpy between any given state and the enthalpy at 298 K, I atm.Power Plant Engineering Table A.4 in the appendix gives the values of Ah = h°— hr 99, in kJ/kg mol for various substances at different temperatures. 4.16.2 Closed System Combustion equations for fuels burning in a closed system, such as a cylinder or bomb, may be obtained by writing the energy balance for the closed system. Thus, Ugt =U, +6 (4.74) where His the non-flow work. For gases, H= U+p¥=U+aRT where R is the universal gas constant. #17} HEATING VALUES: ENTHALPY OF COMBUSTION The enthalpy of combustion is defined as the difference between the enthalpy of products and the enthalpy of the reactants when complete combustion occurs at a given temperature and pressure. Therefore, Age = Hp ~ Hy or Ryp= Engh? + Ah), — En(h? + Ah), (4.75) where f gp is the enthalpy of combustion of the fuel. The values of the enthalpy of combustion of different hydrocarbon fuels at 25°C, 1 atm are given in Table 4.6, The internal energy of combustion, i gp is defined in a similar way. Typ = Up-Up = En, (i + Ah - Pv), ~En, (i + ah - pv), (4.76) If all the gaseous constituents are considered ideal gases and the volume of liquid and solid considered is assumed to be negligible compared to gaseous volume, if gp = Mpp RT (n, (4.77) In the case of'a constant pressure or steady flow process, the negative of the enthalpy of combustion is frequently called the heating value at constant pressure, which represents the heat wansferred from the chamber during combustion at constant pressure. The internal energy of combustion, i pp is defined in a similar way. gascous products ~ gascous reactants) Typ = Uy Up = En(iy' + Ah — pit), —En (he +h — pv) (4.76)Fuels and Combustio: Table 4.6 Enthalpy of combustion of some hydrocarbons at 25°C | Liquid H,0 in Vapour HO'in | Products Products [Negative of (Negative of Higher Heating Lower Heating | Value) Value} i | Liquid Gaseous Liquid Gaseous Hydrocarbon Hydrocarbon Hydrocarbon Hydrocarbon kel kg kifkg kJ/kg ka keg Hydrocarbon Formula fuel fuel fuel fuel Paraffin family Methane CH, - 55496 - 50010 Ethane CH 51875 - 47484 Propane C3Hg - 49975 - 50345 - 45983 - 46353 Butane CH, 49130 -49500 -45344 ~~ 45714 Pentane CsHijy ~ 48643 -49011 - 44983 -45351 Hexane CoH}, = 48308 = 48676 = 44033 =45101 Heptane CyHig -48071 - 48436 - 44587 = 44922 ‘Octane CsHyy = - 47893 ~ 48256 - 44425 - 44788 Decane CyoHog = - 47641 - 48000 - 44239 - 44598 Dodecane CHa = - 47470 - 47828 - 44110 - 44467 Olefin family Ethene CoH, — 50296 47158 Propene CyHy -48917 - 45780 Butene C.Hy ~ 48453 — 45316 Pentene CsHin - 48134 - 44996 Hexene CHa - 47937 - 44800 Heptene CoH ~ 47800 — 44662 ‘Octene CoHig ~ 47693 -44556 Nonene CoHig —47612 44475 Decene Ciao 47847 44410 Alkylbenzene family Benzene Cp, = 41831 42266 —40141 —40876 Methylbenzene CH, -42473 ~ 42847 ~ 40527 - 40937 Ethylbenzene C,H, -42997 43395 - 40924 - 41322 Propylbenzene CgH\, - 43416 - 43800 -41219 - 41603 Butylbenzene CigH,, -43748 - 44123 = 41453 - 41828 If all the gaseous constituents are considered ideal gases and the volume of liquid and solid considered is assumed to be negligible compared ta gaseous volume, (4.77) In the case of a constant pressure or steady flow process, the negative of the enthalpy of combustion is frequently called the heating value at constant Hf pp = htpp — RT Utgaseous products ~ "gaseous reactants)Power Piant Engineering pressure, which represents the heat transferred from the chamber during combustion at constant pressure. Similarly, the negative of the intemal energy of combustion is sometimes designated as the heating value at constant volume in the case of combustion because it represents the amount of heat transfer in the constant volume process. The higher heating value (HHV) or higher calorific value (HCV) is the heat transferred when H,O in the products is in the liquid state (see Section 4.2.3). The lower heating value (LHV) or lower calorific value (LCV) is the heat transferred in the reaction when H,O in the products is in the vapour state. 18] THEORETICAL FLAME TEMPERATURE If a combustion process occurs adiabatically in the absence of work transfer or changes in KE and PE, then the steady flow energy equation becomes: Ha= Hp or Enh = Enh, mp rl ee (Rear or En, (ie +a) = En, hi +a). (4.78) For such a process, the temperature of the products is called the adiabatic or theoretical flame temperature, which is the maximum temperature achieved for the given reactants. The maximum theoretical flame temperature of a fuel corresponds to complete combustion with just the theoretically required quantity of pure oxygen. Similarly, the maximum flame temperature using air corresponds to complete combustion with the stoichiometric quantity of air. This temperature is lower than the maximum flame temperature in pure oxygen because of the dilution effect of nitrogen. In actual combustion chambers, flame temperature is further reduced due to incomplete combustion, excess air requirements, heat losses to the surrounding walls, and by heat loss to ash particles suspended in the combustion products. The adiabatic flame temperature can be controlled by the amount of excess air supplied. The maximum permissible temperature in a gas turbine is fixed from metallurgical considerations (i.¢., the material used for gas turbine blades), So, close control of the temperature of the products is achieved by controlling the excess air. For a given reaction, the adiabatic flame temperature can be theoretically computed by trial and error. The energy of the reactants Hp being, known, a suitable temperature is chosen for the products so that the energy of the products. Hp at that temperature becomes equal to the energy of the reactants Aig. This helps in the selection of material for the combustor. Figure 4.20 shows the variation of adiabatic flame temperature with excess air, Combustion temperatures so calculated are higher than actual because dissociation of some of the products takes place at high temperatures. For example, some CO, may dissociate to form CO and 40,, which is an endothermic reaction that lowers the temperature. Chemical equilibrium occurs ata certain temperature when the reaction rate is the same in both directions, i.e., whenFuels and Combustion Maximum theoretical ” flame temperature Adiabatic Name —> temperature ——~ Excess air Fig. 4.20 Variation of adiabatic flame temperature with excess air co+ 50: — co, and, + 402 — HO The higher is the temperature, more is the dissociation. However, the effect of dissociation is lower for lean mixtures because the excess oxygen tends to drive the reactions toward completion, and for higher furnace pressure. Thus, the effect of dissociation is not significant in steam generator furnace combustion, which occurs with excess air at about 1500 °C. It may be noted that all combustion calculations can be done if there is heat transfer to or from the environment, work done by or on the system, or even changes in kinetic or potential energy between products and reactants by including the appropriate terms in the steady state steady flow energy equation. is} FREE ENERGY OF FORMATION The thermodynamic potential which controls equilibrium in a system depends on the particular constraints imposed on the system. If the constraints are constant temperature and pressure, for any process dGyp<0 (4.79) where G is the Gibbs function defined as G = H — TS, which is also called the free energy. For a process at constant T and P, G always decreases and becomes a minimum at the state of equilibrium. It is the free energy, G, which determines whether a chemical reaction will occur spontaneously, The driving force in a chemical reaction is the difference in free energy between the initial and final states, AG, where at constant temperature AG= AH — TAS (4.80) The free energy of the chemical elements at I atm. 25°C is arbitrarily assumed to be zero. The standard free energy of formation ofa compound, gh, is the free energy change when one mole of the compound is formed directly from its constituent elements, both the reactants and the products being at 298 K and partial pressures of | atm. If the reaction takes place at some higher temperature, the free energy of formation g?will have a different value. In actualPower Plant Engineering situations, the partial pressures of the reactants and products will not be | atm. The effect of such pressure changes on the free energy of a substance can be evaluated from the relation at constant temperature dg = odp where v is the molal specific volume. For an ideal gas in an isothermal process from the standard pressure py to the operating pressure p,, = j ‘odp = RTIn Ft (4.81) x Po where R is the universal gas constant. The free energy change f+ Rrin (4.82) 0 If p is expressed in atmospheres and py = | atm AG= Bf +Ag AG= gf + RTInp, (4.83) If the substance is not an ideal gas, we define a quantity f called the fugacity such that tim = 1 (4.84) poop and AG= B+ Bind. (4.85) 0 4.20) EQUILIBRIUM CONSTANT Ky, Let us consider a reaction C,H¢(g) + 3.5 O,(2) —> 2COx{g) + 3H,0(g) taking place at temperature 7. The initial state is defined by a partial pressure of ethane, Pog and the partial pressure of oxygen, po,. In the final state, CO, and H,O have partial pressures of peg, and pyo. Using the free energies of formation, the free energy change for the system Ag can be expressed as AG = 2(Agdeo, + 3(Agpy,0~ MAgpc2ns + 3.5 (Agpor] (4.86) where from Eq. (4.83) 2Agaco, = 2(Fdco, + R Tin p’co, 3 (Agdy.o= 3(2"dnot R Tin p'y,0 (Agden, = (Fens + R Tin pon, 3.5 (Ago, = 3.5 (Bo, +R Tinp'*y, Substituting in Eq, (4.86), the free energy change becomesFuels and Combustion AG= UF deo, +3 (Fano = UF Dewy, +35 (Fo) +R Tn poo, +N P'y,0~ In Pes, !9 Po) (4.87) The first four terms of the above equation represent AG®, the change in the free energy for the reaction when the products and the reactants all have partial pressures of | atm, while the remaining terms represent the effect of partial pressures on the free energy change. Making the standard free energy change Agtas AG? = nygs + nga ~ M18) — Br where v's are the stoichiometric coefficients and g's are the free energy of formation, Eq. (4.87) can be written as 2 os Peo, Pi AG= AG? + RT in <2 (4.88) Pon, Po, In generalized notations, AG= AG +R T in BP (4.89) Yi ‘i where p; and p, are the partial pressures of the products, and p, and p, are those of the reactants for the reaction nyAy + mA; —4 myAy + ng Ag For exothermic readings, AG” is negative and for endothermic reactions it is positive. In Eq. (4.89), AG" is normally much higher than the second term representing the effect of partial pressures. In a chemical reaction, as the reactants are consumed and the products are formed, the partial pressures of the reactants decrease and those of the products increase, which make AG less negative and thus, decrease the net driving force for the reaction. In the reverse reaction, A, may react with A, to form A, and 45. The free energy change for this reverse reaction nyAy + Mydy—> mA, + Ay AG= (AG Yescnet RT In (4.90) Py As the forward reaction proceeds the driving force for the reverse reaction increases. Because of the competing reactions, the reactive system tends to teach an equilibrium condition in which the two driving forces are equal. When this occurs, we have NB) +12 By= MyBs + My hy so that AG = 0 at equilibrium and from Eq. (4.87), > Hr pts AG =—-R Tin BP (4.91) i ie PU PrPower Plant Engineering In an isothermal process, AG° and Tare constant, and so the logarithm of the quotient on the rh.s. of Eq. (4.91) is constant for equilibrium at a given temperature. This constant is called the equilibrium constant K, expressed in terms of partial pressures. Therefore, Eq. (4.91) can be expressed as AG@=-RT nk, (4.92) 4 yt where Ky~ ae (4.93) Pr Py When any of the reactants is not an ideal gas, the appropriate partial pressure must be replaced by a fugacity ratio. If 4, is not an ideal gas, then Ya K,= oa (4.94) PY Al fn? If one of the compounds is a solid, the fugacity ratio for that compound is unity. If 4, is a solid, pe pls K,= S4 (4.95) Pi From Eq. (4.90), the equilibrium constant at a given temperature Tis given by Ky= Ae 4.96) ep XP | (4.96) With data of AG* as a function of T being available, the values of log K, for typical reactions relevant to combustion are computed and plotted in Fig. far. In the combustion of coal, there are several competing reactions which determine the degree of carbon combustion: ‘C(S) + On(g) —— CO,(g) (4.97a) cis) + ; O,(g) == CO(g) (4.97b) C(S) + CO,(g) == 2CO(g) (4.97¢) cow) +5 O,(g) == CO,(g) (4.97d) The hydrogen and sulphur present are burned to H,O and SO,. The equilibrium constant for the reaction (4.97a) is given by kK, Peo, (4.98) Po, and for the reaction (4.97c), it is 2 K,= Weol_ (499) Poo,Fuels and Combustion Log Kp ‘Temperature (K) Fig. 4.21 Equilibrium constants for selected chemical reactions In modern coal burning plants, the gases leaving the flame are above 450 °C and the equilibrium constant K, is very large for reactions (4.97a), (4.97(b) and (4.97d). It is, therefore, normally assumed that these reactions are completed. Reaction (4.95c) is a slower reaction with the relative amounts of CO, and CO given by Eq. (4.98). The temperature dependent value of the equilibrium constant is obtained from Fig. 4.21. #21] EFFECT OF DISSOCIATION It was mentioned in Section 4.16 that the effect of dissociation is to reduce the flame or products temperature since heat is absorbed (endothermic process) in the dissociation. At high temperatures of combustion, dissociation of the products becomes significant. For example, in the combustion of carbon monoxide: co+ 50, == co, The reaction proceeds in both directions, and a fraction, a, of CO, produced is dissociated into CO and O,: #00,—+a(co++o, } In the equilibrium condition, the products consist of (=a) CO, +aCO# $40,230) Power Plant Engineering The degree of dissociation, a, can be determined from the total pressure of the products mixture, p, and the equilibrium constant &, (which is a function of temperature). For the above reaction, Po, Poo (Po, ad Under appropriate conditions carbon can reduce water vapour to produce CO and Hs, which is an important reaction for coal gasification. However, in the presence of oxygen, CO and H, produced will again get oxidized, and the reduction of steam need not be considered in normal combustion calculations. In case of incomplete combustion, the amount of heat released depends upon the relative amounts of CO, and CO formed, which in turn depend on the chemical equilibrium achieved as given by K (4.100) PEO Peo, Let us consider the combustion process as given by the overall equation, Ky= IC+1H+ 6S + (S+b+a) (O, + 3.76N,) —— (l-x-p)C +yC0, +160 + £ 1,0+580;+(d+ 444) G.76.N;) (4.101) By oxygen balance, eptdqyt re ssn 4 24 x tind ” 2 or, x=2(d-y) The partial pressure of CO is then given by box x _x 60 oo xryeSebs(ae2eo)ars @ 2 4 2(d—y) a Poo> a where p, represents the partial pressure of a component x. Hence: l-a@ oe 1? (4.102) l-a@tat=a l+re 2 z lap a Peo= A and Po,= 2 T l+-@ l+ca@ 2 2Fuels and Combustion 213) v2 l-a@|a@+2 Kye a [3 ? | (4.103) Eas In an oil fired boiler the fuel had an analysis by mass: catbon 84%, drogen 10% sulphur 3.2%, oxygen 1.6%, remainder incombustible. The analysis of dry flue gas by volume gave: combined CO, + SQ, 15.72%, O, 1%, there being no CO or SO,. Calculate per kg of fuel (a) mass of air supplied, (b) percentage excess air supplied, (c) mass of dry fue gas formed, and (c) mass of water vapour formed. Solution Let us consider 100 kg of fuel oil. Let x moles of oxygen are supplied for combustion, The combustion equation can be written as—~--—-—~ 84 1, 32 16 hoy Oy, 43254180, +20, 43.7628 120 Fg Met gg 8+ gp Oz 7202 3-76 2N2 — > bCO, + dSO, + eO; + fN, + gH;0 Equating coefficients: Carbs bi b b=7 ‘arbon a” a b= 10 Hydrogen 74 o ges 1.6 g Oxygen aeeptdte+® ve 32 2 Sulphur 32. « d=01 32 Nitrogen 36x =f Volumetric analysis: b+d € ——————_ = 0.1572, Fada, 70.01 b+dte+f b+dtet+f ‘On dividing, bed = 15.72 e or e=7.1/15.72 = 0.452 Substituting in O, — balance, 0.05+x=7+0.1+0452+25 or x= 10.002 Mass of oxygen supplied = 10.002 x 32 = 320.1 kg 320.1 -. Mass of air supplied for 100 kg fuel = ——— = 1380 ky pp! zB 0.232 8 ©. Mass of air supplied per kg fuel, W’, = 13.80 kg Ans.(a)