Fuels and Combustion Fuels are substance primarily composed of hydrocarbons which upon combustion release heat energy. Combustion is the rapid chemical union with oxygen of an element whose exothermic heat of reaction is sufficiently great and whose rate of reaction is fast enough that useful quantities of heat are liberated at elevated temperature. Classification of fuels: According to nature of source: 1. Natural or Naturally occurring fuels. 2. Synthetic or manufactured and industrial by products. According to Physical Structured: 1. Solids fuels Coal, coke, peat, briquettes, wood, charcoal, bagasse, and a variety of waste products including coconut shells and rice husks. 2. Liquids Fuels Petroleum and its derivatives, synthetic liquid fuels manufactured from natural gas and coal, shale oil, coal-by- products and alcohol. 3.) Gaseous Fuels Natural gas or methane, liquefied petroleum gas (LPG) primarily composed of butane and propane which are stored and delivered as liquids under pressure but are consumed in the gaseous state. Fuel and Lubricant Properties: Specific Gravity SG A dimensionless parameter, it is the ratio of the mass of a unit volume of fuel to the mass of the same volume of a standard substance at a specified temperature. In Mathematical expression, SG = density of liquid fuel density of water or SG = density of gaseous fuel density of air Specific gravity of a fuel normally measured at 15.60C affects the spray penetration as the fuel is injected into the cylinders aside from being a measure of fuel heat content. Correction factor as applied to specific gravity at a certain temperature expressed in degrees Celsius: SGt = SG15.60C - 0.0007(t - 15.6), SI / metric SGt= SG9600F - 0.0004(t - 60), English American Petroleum Institute Gravity Unit, 0API The accepted standard by the petroleum and oil industry, it was drawn up to correct the values measured by incorrectly calibrated hydrometers. 1 In mathematical expression: 141.5 API = SG 0 – 131.5 15.6 C o Baume Gravity Unit, 0Baume Another standard commonly associated with brine, expressed mathematically as: 140 o Baume = SG 0 - 130 15.6 C Viscosity Property of a fluid by virtue of which it offers resistance to shear and angular deformation Considerably varies temperature, i.e. as temperature increase, viscosity for liquids decrease and for gases increase. Viscosity indicates how readily the oil atomize and it will affect the injection pump, it affects the fuel spray governing the atomization and penetrating qualities of the spray. Viscosimetry Laboratory instruments used to measure viscosity are of the efflux type which consists of a tank fitted with a small orifice; most common instrument used is the Saybolt viscosimeter, consisting of a temperature bath surrounding a standard oil tube: The time in seconds for 60 cc of oil at 37.80C to flow through the tube is know as the Universal Viscosity (abbreviated SUV) of the fluid, or seconds Saybolt Universal (Abbreviated SSU). Generally, there are two types of Saybolt viscosimeters: Saybolt Universal Viscosimeter Used for light lubricating oils having an efflux time greater than 32 seconds, V centistokes = 0.308 (SSU – 26) Viscosity for most diesel fuels varies from 30 to 45 SSU at 37.80C. Furol Viscosimeter Used for very viscous fluids, as heavy oils above 250 SSU; similar to the Saybolt Universal, except that it has a larger diameter tube resulting in an efflux time approximately one- tenth that of the Saybolt Universal Viscosimeter. Viscosity index is in terms of Saybolt Furol Viscosity (Abbreviated SFV), or seconds Saybolt Furol ( Abbreviated SSF ). 62 SSF = 600 SSU Units of Measurement Absolute Viscosity, Expressed as the ratio of shear intensity to velocity gradient, in metric system, 1 gram mass 1 poise = 1 cm x 1 sec 2 Numerically equal to 1dyne x 1 sec , or 0.1 Pa-sec 1cm2 in English system, 1 reyn = 1lb force x 1sec 1 in2 the poise being a large unit for ordinary use, centipoises (0.01 poise) is generally used; centipose is almost equal to the viscosity of water at 200C which is 1.005 centipoises. Kinematic Viscosity, v Expressed as the ratio of absolute Viscosity to the fluid density as measured indirectly by the viscosimeter; In mathematical expression: v= absolute Viscosity μ fluid density ρ In metric system, 1 stoke = 1 cm2 / sec measurement is limited to a Newtonian fluid, a fluid in which the velocity gradient is directly proportional to the shear stress: the stroke is also a large unit for ordinary use, centistokes (0.01 stoke) is generally preferred. Volatility It is the ability of a liquid fuel to change into vapor which is manifested in the temperature range at which various portions of the fuel are vaporized. High- speed engines require larger fractions of low boiling point compounds as compared to low – speed engines since the latter needs more time for combustion. American Society for Testing and Materials (ASTM) Distillation Test: A measured sample of oil is slowly heated; as the various boiling points of its compounds are reached, they then distilled, allowed to condense and measured. After complete distillation, data obtained are used to construct a distillation curve should be smooth for good balance of compounds. Average range between initial boiling point and endpoint is 1630C to 37100C. Carbon Residue Also referred to as conradson carbon, it is the carbonaceous residue which remains after destructive distillation, expressed in percentage by weight of the original sample. Flash and Fire Point Flash point is the temperature at which a substance will give off vapor that will burn momentarily. Fire point is the temperature which the vapor will continue to burn after being ignited. Flash and fire points- serve as safely precaution for handling and storing fuels, the lower the flash point, the greater the hazard. 3 measuring instrument used are the Cleveland open tester (open – type) and the pensky- martens closed tester ( closed type) Cloud and Pour Point Cloud point- is the temperature at which the hydrocarbon components if a liquid fuel become insoluble; this means that the paraffin wax and other solid substance in the lubricating oil begin to crystallize and separate from the lubricating oil. Pour point – is the minimum temperature at which a certain amount will become insoluble to prevent the flow under specified conditions. Dropping Point It is the temperature at which grease will pass from a semi- solid to a fluid state; ASTM method D- 566 is the procedure used in determining dropping point. Grease, semi- fluid oil, primarily consists of soap materials and mineral oil with an alkali; common types of soap used are sodium, lime, mixed base (soda lime) lithium, lead, aluminum, barium or strontium. Aniline Point This is an indication of the paraffinity of a compression – ignition engine fuel; technically, it is the temperature at which equal volumes of the fuel and Aniline are just miscible. Composition of Fuels: Liquid and gaseous fuels are usually mixtures of hydrocarbons which may be classified as follows: Paraffins, CnH2n+2 Saturated hydrocarbons, very stable in character Olefins, CnH2n unsaturated hydrocarbons, characterized by the presence of a double bond between carbon atoms. Diolefins, CnH2n-2 less unsaturated than olefins, characterized by the presence of two double bonds. Analysis of Fuel Composition Ultimate Analysis The straightforward chemical analysis of the material in terms of the component elements; common elements specified are carbon, hydrogen, oxygen, nitrogen, and sulfur. Proximate Analysis The determination of the moisture, ash, volatile matter (CO, H2, CH4, C2H6 and H2S), coke and fixed carbon. Volumetric Analysis For gaseous mixture of fuel 4 Heating Value of fuels, HV or calorific value, it is the amount of heat evolved when a unit amount of the fuel is burned completely and the combustion products cooled to a base or reference temperature. Classifications 1. Higher Heating Value (ASME), HHV or gross calorific Value (ASTM), it is the amount of heat evolved during a fuel’s complete combustion where the water leaves in the liquid state. 2. Lower Heating Value (ASME), LHV or Net Calorific Value (ASTM) it is the amount of heat evolved during a fuel’s complete combustion where the water leaves in the gaseous or vapor state. LHV = HHV - 9H2(2442) where: 9H2 = lb. of water formed per lb. or cu. ft. of fuel burned 2442 = latent heat of vaporization of 1kg.water also, h2 =26 -15 (SG), percent by weight Methods of determining heating value: A fuel’s content can either be determined experimentally or calculated based on its composition. 1.) Laboratory experimentation a.) bomb calorimeter for solid and liquids fuels b.) gas calorimeter for gaseous fuels 2.) Calculation using empirical or derived formulas note: units expressed in kJ/ kg A Dulong’s formula for solid fuels of known ultimate analysis HHV = 33,820C + 144,212 (H – 0/8) + 9304S A ASME formula for petroleum Products HHV = 41,130 + 139.6 (0API) A Bureau of Standard formula HHV= 51,716 - 8,793.8(SG)2 Fuel Foundation Processes: 1. fractional Distillation the primary method of crude oil refining 2. thermal cracking changing heavy oil into gasoline by means of high pressure, high temperature and longer exposure time 3. Catalytic Cracking Subjects oil to high pressure and high temperature in the presence of a catalyst; permits an accurate control of the compounds formed and produces a gasoline of higher octane number that he one produced in thermal cracking 4. Hydrogenation Process of catalytic cracking in a hydrogen atmosphere; obtained are more saturated products than those from cracking process alone 5. Isomerization Process by which the atoms of carbon and hydrogen in normal hydrocarbons are re- arranged to produce a more complex structure of higher antiknock value 6. Polymerization Makes use of high pressure,high temperature and a catalyst to combine light and volatile gases into gasoline 7. alkylation process of combining an isoparaffin usually iso- butane, with an olefin usually butane or propane, to form a larger isoparaffin molecule, usually iso- octane or iso- heptane, having a very high octane number 5 8. reforming used to obtain fuels with substantially higher than 100 octane number currently used to process about forty percent of motor gasoline 9. Hydrodesulfurization Process of adding hydrogen to unsaturated hydrocarbons and reducing the sulfur content of the resulting fuel oil Stoichiometry and Energetic of combustion The following may be use in analyzing combustion processes: 1. Composition by weight 76.8 percent nitrogen, 23.2 percent oxygen thus, for 100 lb of air 76.8/ 23.2= 3.3 lb of nitrogen / lb of oxygen 2. Composition by volume 79.0 percent nitrogen, 21.0 percent oxygen thus, for 100 moles of air 79.0 /21.0 = 3.76 moles of nitrogen/ mole of oxygen 3. Molecular weight, MW note: Units expressed in kg/kmol air = 28.97 H2 = 2 O2 = 32 N2 = 28 C = 12 S =32 Typical combustion Reaction Fuel + air → products of combustion or flue gases 1.) Theoretical air – fuel ratio, (A/F)t exact amount of air needed to furnish oxygen for complete theoretical combustion (stoichiometric condition) Combustion of solid fuel with known ultimate analysis, kg air / kg fuel (A/F)t = 11.5C + 34.5 (H - 0/8) + 4.3S 2.) Actual air – fuel ratio (A/F)a determined by the presence of excess air which is defined as the amount of air supplied over and above the theoretical air in mathematical expression Percent excess air = (AF/)a – (AF)t (AF)t Classification of combustion 1. combustion reaction with chemically correct or stoichiometric condition generally chemical formula of the fuel is CnHm CnHm+ (n+0.25m)O2 + 3.76(n + 0.25m)N2 → nCO2 + 0.5mH2O + 3.76(n+0.25m)N2 2. combustion reaction with greater, amount of theoretical air, having fuel – lean mixture 3. combustion reaction with lesser amount of theoretical air, or having a fuel – rich mixture 6 Equivalence ratio for a given mass of air actual mass of fuel in combustion (A/F)t Φ = stoichiometric mass of fuel used = (A/F) a Note: Φ = 1, for stoichiometric mixture Φ < 1, for fuel lean, mixture; Φ > 1, for fuel – rich mixture Sample Problems 1. A cylindrical oil tank 2.4m diameter x 6m long is filled to the neck with fuel oil which is checked at 21° Bé at 31 °C. Estimate the kJ heating value stored in this tank. SOLUTION: 2.4 m 6 m Baume = 140 − 130 SG15.6° ; 21 = 140 − 130 SG15.6° SG15.6°C = 0.927 SGt= SG15.6°C – 0.0007 ( t – 15.6°C ) @t = 31°C SG31° = 0.927 – 0.0007 (31-15.6) SG31°C = 0.916 HHV = 51716 – 8793.8(SG)2 HHV = 51716– 8793.8(0.916)2 HHV = 44333.96 kJ/kg Mass of oil mf = vf ρf 0.916 = ρf / 1000 ρf = 916 kg/m3 vf = volume of fuel = d2h = (2.4)2(6) = 27.14 m3 So, mf = (27.14)(916) = 24, 860.24 kg Finally, Qh=mfHHV = (24, 860.24)(44333.96) Qh = 1.102 x 109 kJ 7 2. A diesel engine consumes 1 bbl of industrial fuel of 25 °API of 80.6 °F in a single-day operation. Determine the amount of heat liberated by the fuel as a result of combustion. SOLUTION: Bbl =159 liter = 0.159 m3 t = 80.6 °F = 27 °C 141.5 141.5 °API = − 131.5 ; 25 = − 131.5 SG15.6° SG15.6° SG15.6°C= 0.904 @t = 27°C SG27°C = SG15.6 - (0.0007)(T-15.6) SG27°C =0.904 - (0.0007)(27-15.6) SG27°C = 0.89602 HHV = 41130 + 139.6 °API = 44620 kJ/kg ρf = (1kg/li) (0.89602) = 0.89602 kg/li mf = Vf ρf mf = (159 liter) (0.89602 kg/li) mf =142.47 kg Qh= mf x HHV Qh=(142.47 kg/24 hr) x (44620 kJ/kg) Qh=264,875.475 kJ/hr 3. A horizontal cylindrical fuel oil storage tank 2.4 m dia. x 5 m long is gauged at 825.5 mm oil depth. A delivery of oil is made which raises the level to 2165 mm, measured after the temperature of the contents had attained ground temperature, i.e., 7.2oC. This oil is purchased for $ 3.31 per bbl at 15.6oC/15.6oC. The delivery is billed at $ 380.50. Is this correct to the nearest dollar? SOLUTION: Before 2400mm 825.5mm 5000mm cos θ 0.3745 = 2 1.2 θ = 143 .63 o A sec tor = 1 2 θ 2r 1 π A sec tor = (1.2) 2 (143.630 )( ) 2 1800 A sec tor = 1.805 m2 8 1 1 θ θ bh = (r sin )(2)(r cos ) 2 2 2 2 1 2 = r sin θ 2 1 = (1.2) 2 (sin 143.630 ) 2 A t = 0.427m2 At = A =A 1 sector - At = 1.805 - 0.427 A 1 = 1.378 m2 After: oil raise to 2165mm, 2165 mm A w 2400mm = A sec tor - A t θ 0.965 = 2 1.2 θ = 72.94 0 1 1 Aw = 2 r 2 θ - 2 r 2 sin θ 1 π = (1.2) 2 [ (72.94 0 x ) - sin 72.940 ] 2 1800 sin ce : cos A w A 2 = 0.2283 m2 = Acircle - Aw = π(1.2) 2 - 0.2283 m2 = 4.3 m2 V= volume of oil deliver = (A2-A1) L = (4.3-1.378) (6) = 17.532 m3= 17,532 Li = 110.26 bbL $380.50 110.26 bbl Pr ice = $3.45 bbl No, because it exceed $3.31 per barrel Pr ice = 9 4. A coal sample has an ultimate analysis 0f 80.0% C, 4.0% O2, 4.5 % H2, 1.7 % N , 1.5 % S, and 8.3% ash. Determine the heating value and mass air/fuel ratio for complete combustion with 100% theoretical air. SOLUTION: HHV = 33820C + 144212( 9304(0.015) HHV = 32964.04 kJ/kg ) + 9304S = 33820(0.80) + 144212( ) + Theoretical Air/Fuel ratio A O 0.04 = 11.5C + 34.5( H − ) + 4.3S = 11.5(0.80) + 34.5(0.045 − ) + 4.3(0.015) F 8 8 A kg − air = 10.64 F kg − fuel 5. A fuel with a mass analysis of 83% C, 12% H2 , and 5% O2 is burned with 100% theoretical air. Determine: The complete combustion equation. The molal analysis of the products with and without water vapour considered. SOLUTION: Xi 0.83 0.12 0.05 C H2 O2 Yi = Mi 12 2 32 Xi/Mi 0.0691 0.06 0.00156 0.13066 Yi 0.53 0.46 0.01 Xi Mi Xi Mi 0.53C + 0.46H2 + 0.01O2 + aO2 + 3.76aN2 = bCO2 + cH2O + 3.76aN2 Carbon balance 0.53 = b Hydrogen Balance 0.46 = c Oxygen balance 0.01(2) + 2a = 2b + c 0.01(2) + 2a = 2(0.53) + 0.46 a = 0.75 Complete combustion equation 0.53C + 0.46H2 +0.001O2 + 0.75O2 + 3.76(0.75)N2 = 0.53CO2 + 0.46H2O + 0.75(3.76)N2 b.) Molal analysis with vapor np = 0.53 + 0.46 + 0.75(3.76) = 3.81 yCO2 = 0.53 / 3.81 = 0.14 yH2O = 0.46 /3.81 = 0.12 yN2 = (0.75)(3.76) / 3.81 = 0.74 10 Without vapour np = 0.53 + (0.75)(3.76) = 3.35 yCO2 = 0.53 / 3.35 = 0.16 yN2 = (0.75)(3.76)/3.35 = 0.84 6. A fuel oil is burned with 50% excess air, and the combustion characteristics of the fuel oil are similar to C12 H26. Determine the complete combustion equation, volumetric analysis of the products of combustion, and determine the dew point for the products if the pressure is 101 kPa. SOLUTION: CnHm + (1+e)(n + 0.25m)O2 + (1 + e)(n + 0.25m)(3.76)N2 = nCO2 + 0.5mH2O + (1 + e)(3.76)(n + 0.25m)N2 + e (n + 0.25m)O2 Complete combustion equation C12H26 + (1.5)(12 + 6.5)O2 + (1.5)(12 + 6.5)(3.76)N2 = 12CO2 +13H2O + 1.5(3.76)(12 + 6.5)N2 + 0.5(12 + 6.5)O2 C12H26 + 27.75O2 + 104.34N2 = 12CO2 + 13H2O + 104.34N2 + 9.25O2 The total mole of the product np = 12 + 13 + 104.34 + 9.25 = 138.59 mole YCO2 = 12/138.59 = 0.087 YH2O = 13/138.59 = 0.094 YN2 = 104.34/138.59 = 0.753 YO2 = 9.25 / 138.59 = 0.067 Partial water vapor pressure PH2O/P = YH2O ; PH2O/101 = 0.094 PH2O = 9.49 kPa Tdp = dew point = tsat @ 9.49kPa = 45°C 11