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FUELS FOR I.C. ENGINES
Conventional
andNon-conventional
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Types of Fuels
Fuels for engines are typically
1. Gaseous
2. Liquid3. Originally solid also but now very rarely
used.
May be
1. Naturally available or
2. Artificially derived
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Gaseous Fuels
Main fuels for engines are
1. Natural gas from nature2. Liquefied Petroleum Gas - from refineries
3. Producer gas - from coal or biomass
4. Biogas - from biomass
5. Hydrogen from many sources
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Natural Gas
Found compressed in porous rock and shale
formations sealed in rock strata underground.
Frequently exists near or above oil deposits.
Is a mixture of hydrocarbons and nonhydrocarbons
in gaseous phase or in solution with crude oil.
Raw gas contains mainly methane plus lesser
amounts of ethane, propane, butane andpentane, negligible sulfur and organic nitrogen.
Some carbon dioxide and nitrogen are present.
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Natural Gas
The only gas occurring in nature.
Origin is believed to be organic (Majority view)
Due to methanation of carbon dioxide with
hydrogen, both mineral in origin (more recenttheory)
May be found with (associated) or without(unassociated) crude oil.
Contains 60 to 90% methane, rest are propane,butane, heavier and more complexhydrocarbons, carbon dioxide and nitrogen plussome helium.
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Natural Gas (Continued)
Certain processes have to be carried out.
1. Separation of liquid and gas. Liquid may be ahydrocarbon present in the gas well along with
the gas.2. Dehydration. Water is corrosive and hydrates
may form which will plug the flow. Water willalso reduce the calorific value of the gas.
3. Desulfurization. Presence of hydrogen sulfideis undesirable. The gas is called sour. Whenthe sulfur is removed the gas is sweetened.
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Natural Gas (Continued)
Natural gas may be used as
1. Liquefied Natural Gas (LNG).
2. Compressed Natural Gas (CNG).
Natural gas when made artificially it is
called substitute, or synthetic or supple-mental natural gas (SNG).
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Natural Gas (Continued)
Natural gas has 90-95% methane plus 0-
4% nitrogen, 4% ethane and 1-2%
propane. Methane is a greenhouse gas
with a global warming potential
approximately 4 times that of carbon
dioxide. Its C/H ratio is lower than that
of gasoline so its CO2 emissions are 22-25% lower (54.9 compared to 71.9 g
CO2/MJ fuel).
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Natural Gas in Engines
When an engine was switched over to CNG from
gasoline, the non-methane organic gases like
CO and NOx, all reduced by 30-60%. Toxic
emissions like benzene, butadiene andaldehydes were much less than with gasoline.
Natural gas can replace diesel fuel in heavy-duty
engines with the addition of a spark ignition
system. Engines operate at J = 0.7 giving low in-
cylinder temperatures and hence low NOx.
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Natural Gas in Engines
Heavy-duty natural gas engines are designed tomeet low emission vehicle (LEV) emissionstandards without a catalytic converter and willmeet ULEV emission standards with a catalytic
converter. For heavy-duty applications, dual fuel operation
is attractive, for buses, locomotives, ships,compressors and generators. They are operatedlean to reduce NO
x. However, at light loads, the
lean combustion conditions will degrade thecombustion process increasing HC and COemissions.
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Component Percentage
Hydrogen 20
Carbon Monoxide 19.5
Carbon Dioxide 12.5
Methane 2
Nitrogen 46
Octane Number 100-105
Lower Heating Value 6.7 MJ/m3
Typical Composition of Producer gas
Energy density of stoichiometric fuel-air mixture:
Producer gas: 2.5 MJ/m3
Gasoline-air: 3.5 MJ/m3
Diesel-air: 3.3 MJ/m3
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Types of Liquid Fuels
Liquid Hydrocarbon fuels may be
1. Paraffins: straight chain compounds like methane,ethane, propane, etc. or branched chain compounds(isomers) like iso-butane, iso-heptane (like 2,2,3 tri-
methyl butane or triptane) and iso-octane (like 2,2,4tri-methyl pentane).
2. Olefins: Open chain unsaturated hydrocarbons with adouble bond like ethene or propylene which also havestraight and branched chain compounds.
3. Diolefins: These are olefins with 2 double bonds.
Both types of olefins produce gum when reacted withoxygen which can block fuel filters.
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Types of Liquid Fuels
(Continued)4. Alkynes: Unsaturated hydrocarbons with a
triple bond. A typical example is acetylene orethyne.
5. Napthenes or Cycloparaffins: Have samegeneral formula as monoolefins but aresaturated compounds with a ring structure.Examples are cyclopropane, cyclobutane etc.
6. Aromatics: Ring structured unsaturated
hydrocarbons with double bonds but morestable than the parafffinc double bondhydrocarbons. Examples are benzene,toluene, naphthalenes, and anthracenes.
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General Formulas for Organic
Compounds found in Crude Oil
Family Formula Structure
Paraffins (alkane) CnH2n+2 Straight andBranched
Paraffins (alkene) CnH2n Straight andBranched
Paraffins (alkyne) CnH2n-2 Straight andBranched
Naphthenes(cyclanes)
CnH2n Ring
Aromatics
(Benzenes)CnH2n-6 Ring
Aromatics
(naphthalene)C
nH2n-12Ring
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Composition of typical crude oil
Carbon: 80-89%
Hydrogen: 12-14%
Nitrogen: 0.3-1.0%Sulfur: 0.3-3.0%
Oxygen: 2.0-3.0%
Plus oxygenated compounds like phenols,fatty acids, ketones and metallic elements
like vanadium and nickel.
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Typical Refinery Products
Product Boiling Range, oC
Liquefied Petroleum Gas -40 to 0
Motor Gasoline 30-200
Kerosene, jet fuel (ATF) 170-270
Diesel Fuel 180-340
Furnace Oil 180-340
Lube Oils 340-540Residual Fuel 340-650
Asphalt 540+
Petroleum Coke Solid
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Refinery processes
1. Distillation: Continuous, Atmospheric,and Vacuum.
2. Cracking: Thermal, Catalytic and Hydro.
3. Reforming: Thermal, Catalytic and Hydro
4. Polymerization
5. Alkylation
6. Isomerization
7. Hydrogenation
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ADDITIVES USED FOR GASOLINE1. Anti-knock Additive: Required to eliminate knock.
2. Deposit-modifiers: Used to modify the chemical character of combustionchamber deposits and so reduce surface ignition and spark plug fouling.They are usually a phosphorus or boron compound.
3. Anti-oxidants: Used to reduce gum formation and decomposition of the leadcompounds. They are usually an amine.
4. Detergents: Used to prevent deposits in the carburetor and manifold. Theyare usually an alkyl amine phosphate.
5. Lubricants: Used to lubricate valve guides and upper cylinder regions. Theyare usually light mineral oils.
6. Metal de-activators: Used to destroy the catalytic activity of traces ofcopper. They are usually amine derivatives.
7. Anti-rust Agents: Used to prevent rust and corrosion due to moisture in theair. They are usually fatty acid amines, sulfonates, or alkyl phosphates.
8. Anti-icing Agents: Used to prevent the freezing of gasoline from water in thefuel and throttle plate icing from moisture in the air. Methanol is added to
gasoline to absorb water- and so prevent ice from forming in the fuel linebetween the tank and carburetor. Isopropyl alcohol or a surface action agent(orsurfactant) like ammonia salts or phosphates is added to prevent icefrom forming or adhering to the throttle plate. The alcohol acts by loweringthe freezing point of the condensate. The surface-action additive forms afilm on the metal, which discourages adhesion of ice. Some of the surface-action additives also have detergent qualities.
9. Dye: Added to identify the lead compound in the fuel. Lead-free gasoline is
transparent and is usually called white petrol".
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DESIRED CHARACTERISTICS OF GASOLINE1. KNOCK CHARACTERISTICS. The measure for knock characteristics for a
spark ignition engine fuel is the octane rating. The fuel should have anoctane rating to suit the engine requirements.
2. VOLAT
ILITY
.T
here are four aspects of volatility for a spark ignition enginefuel. These are:
(a) Starting and Warm up Characteristics. If the fuel or a portion of it has alow boiling point, the engine will start readily.
(b) Vapor lock and Hot Start and Idling Characteristics. The fuel should havea low vapor pressure at the existing fuel line temperatures to avoidvaporization of the fuel in the fuel lines and the carburetor float-bowl.This will help in eliminating the problem of stoppage or reduction in theflow of liquid fuel.
(c) Running Performance or Normal Acceleration. In general, the fuel withthe lowest distillation temperature is the best.
(d) Crankcase Dilution. The dilution of the lubricating oil may occur whenthe fuel condenses or fails to vaporize in the engine. A low distillationtemperature range is desirable.
(e) Other Factors.T
his includes factors like carburetor icing, evaporationloss and fire hazard.
3. GUM AND VARNISH DEPOSITS. The fuel should not deposit either gum orvarnish in the engine.
4. CORROSION. The fuel and the products of its combustion should be non-corrosive.
5. COST. The fuel should be inexpensive; its price must be competitive.
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VOLATILITY
Volatility is "the temperature at which a given
air-vapor mixture is formed when under
equilibrium conditions at a pressure of one
atmosphere, when a given percentage of thefuel is evaporated".
According to this definition, one gasoline is more
volatile than another for any given percentage
evaporated, if it forms the given air-vapormixture at a lower temperature.
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A simple test for volatility
A flask containing 100 ml of fuel is heated. The vapors arecondensed. The temperatures are recorded when thefirst drop falls into a graduated cylinder, then dropscontaining 5, 10, 15 per cent etc. are condensed. Since
the fuel contains many hydrocarbons, the boilingtemperature continuously rises as evaporation proceeds.
At the end of the test, a limiting end point temperaturewill be reached. A residue will condense in the flaskafter cooling. However, some fuel would have been lost
(called loss) which is assumed to be due to the mostvolatile part of the fuel. Thus we get a correctedASTMdistillation curve, where the loss appears at the start andthe residue at the end of the curve.
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Equivalent AirDistillation (EAD)
CurvesWhile in the ASTM test procedure, the fuel isevaporated in the presence of its own vapor, inthe actual engine manifold, the fuel isevaporated in the presence of air. An Equivalent
Air Distillation (EAD) process has to be followedto test the fuel under simulated engineconditions. The test has to ensure that the fuelvaporization process will reach a state ofconstancy or equilibrium. In fact, the length of
the actual engine intake manifold and the highflow velocities obtained therein would result innon-equilibrium conditions to prevail.
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Start Up Limits of Flammability of air-gasoline vapor
mixture are 6:1 to 20:1 by weight. Rich mixture is used to ensure greater mass of
fuel available as vapor.
Engine should start in 10 revolutions. Air-vapor
mixture for successful start is given by log10 (AV) = 1.301 2/n
where n is the number of revolutions
For n = 10, AV = 12.62
If 5% (AV=20) fuel evaporates it will start. For safestart it is 7.9% (AV=12.62). For sure start it is16.7% (AV=6).
Fuel with low 10% temperature (T10) would start
easily in cold weather.
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Start Up (Continued)It is found that percent distilling below 70oC
influences ease of cold start: the greater thepercentage, the more readily the start.
Table III Effect of percentage distilled below 70oC (ASTMTest D86) on lowest starting temperature.
---------------------------------------------------------------------------------Percentage distilled Lowest ambient
below 70oC(vol.%) temperature for acceptable start, oC
---------------------------------------------------------------------------------
30 -17.825 -12.2
15 - 6.7
10 -1.1
---------------------------------------------------------------------------------
W U
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Warm Up
Length of warm up depends on number of
factors.The higher the percentage distilling below
100oC, the faster the warm up
The lower the temperature at 50% point(T50), the faster the warm up.
Based on a test, in a car at 0oC:
1. Fuel with 42% distilled at 100oC warm updistance was 4.3 km.
2. Fuel with 60% distilled at 100oC warm up
distance was 2.5 km.
W U
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Warm UpWith full choke at (cold) starting, fuel supply is 10
times that needed for normal running.
At warm up, fuel consumption is double thatrequired for fully warmed up engine.
To reduce warming up period we would need
(1) heating of the intake with quick choke off. This
affects drivability or(2) use fuel with increased volatility.
A more volatile fuel will
(1) be easier to start from cold,
(2) give faster warm up,(3) consume less fuel, and
(4) give lower exhaust emissions during earlyphase of engine operation.
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Normal Running
High distillation temperature (low volatility)causes less fuel to evaporate gives poor
distribution. Requires over-fuelling. Gives
more power but fuel consumption is high.
Low distillation temperature (high volatility)
gives better mixing; may even superheat the
fuel vapor. But vapor displaces the air and
reduces volumetric efficiency and gives less
power. This is similar to using gaseous fuel.
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Acceleration
Fuel lag due to sudden acceleration
Requires an acceleration pump to give aricher mixture or use of a high volatility
fuel. May require manifold heating to avoid
use of the acceleration pump.
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R id
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Reid vapor pressure
The vapor lock tendencies of a gasoline are
directly related to the front-end volatility, that
is, 0 to 50% of the ASTM curve (Taylor
specifies 10% only). The Reid Vapor
Pressure (RVP), which is a direct measureof the vapor pressure, is a reliable indicator
of the vapor lock tendency. Gasoline
specifications usually place an upper limit on
vapor pressure, the limit depending upon
type of service and climatic conditions
expected in service.
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Reid vapor pressure
The Reid Vapor Pressure depends upon the
vapor-liquid (V/L) ratio. The V/L ratio is defined
as the equilibrium volume of vapor at a given
temperature and pressure, per unit volume ofliquid, supplied at that temperature.
The higher the RVP, the more volatile the
gasoline.
For Indian fuels it is 35 to 70 kN/m2.
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Reid vapor pressure
For a single constituent fuel, the vapor-liquid ratio is amulti-valued one since the extent of vaporization doesnot change the vapor-pressure at a fixed temperature.On the other hand, for the usual multi-constituent fuels,
the vapor pressure depends on the extent ofvaporization. Thus, if the vapor volume is made larger,the vapor decreases. Hence for commercial gasoline,specifying a temperature and a pressure also specifies adefinite vapor-liquid ratio.
The Reid method specifies a V/L ratio of 4 and atemperature of 100oF or about 38oC.
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Vapor-locking Tendency
Four Equations to measure this:
1. Vapor Forming Index: (ASTM Standards on PetroleumProducts, Part 17):
VFI = RVP + 2 (slope of ASTM 10% point)
2. Front End Volatility Index :FEVI = RVP + 0.13(percent evaporated at 70oC ASTMdistillation curve)
3. General Motors Vapor Pressure:
Vapor Pressure Measured at a V/L of 25, at 100oF
(approximately 38oC)4. Modified General Motors Vapor Pressure:
Vapor Pressure Measured at a V/L of 25, at 55oC.
V l k b li i t d b f l
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Vapor lock can be eliminated by fuel
system design that achieves the
following conditions:1. Fuel handling with minimum temperature rise: fuel lines,
pumps, carburetors, etc., must be located away from theheat of the engine and exhaust. Insulating gaskets arerequired for mounting the pump and carburetor.
2. Minimum pumping requirement from the pump to thecarburetor: the pump should be amply over-sized or ofadequate capacity so that the presence of vapor will notreduce the flow demanded by the engine.
3. Minimum fuel line elevation and cross-sectional area
changes.4. There must be proper flow of air through and past the
fuel system by adequate design of the fan and ventilationlouvers.
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Hot Start and Idling
Percolation: This is due to fuel being forced
through the main jet when pressure in the
float bowl increases due to restriction in
the venting.
It will cause (hot) starting problems because
a very rich mixture enters the engine. It
may be due to high volatility of the fuel.Idling will be rough.
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The drivability index (DI)
DI = 1.5T10 + 3T50 + T90
The lower this value, the more volatile thefuel, and the better the drivability,
particularly in cold weather after a cold
start.
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Crankcase Dilution
Condensation of vapor on the cylinder walls
or the presence of liquid fuel in the air will
result in mixing of the fuel with the
lubricating oil.
The upper portion of the distillation curve
must be low to ensure that all the fuel will
vaporize.Crankcase ventilation will reduce dilution.
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Carburetor Icing
This is due to condensation of the water
vapor in the air on to the throttle plate.
Can be reduced by using manifold heating
or by use of additives.
Volatility also plays an important role here.
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Evaporative Loss
The lower the 10% temperature (T10) thehigher the loss. Loss is greater from a tankthat has less fuel. The loss from a tank
full was 60% more than from a tank thatwas full.
This is also a pollution hazard.
Can be controlled by venting the tank into acharcoal canister which adsorbs anddesorbs fuel vapors.
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Fire Hazard
The explosive range for gasoline vapor is
between 65oC and 20oC.
Gasoline vapor gives a highly combustible
atmosphere in a closed space.
Fires develop a great intensity almost
immediately.
A fuel of higher volatility is a greater fire
hazard.
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Calorific Value and Volatility
Motor gasoline is sold by volume, so a fuel
of high calorific value per unit volume is
necessary.
Now kJ/m3 = (kJ/kg)(kg/m3)
Thus the fuel must have high density and
it means a lower volatility. But we have
seen that it must be volatile also.
Hence a compromise is necessary.
Summary of Volatility Characteristics and
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Front end Middle range Rear end
10-30% 50-70% 90%
Engine Problem:Cold starting Prime Insignificant Insignificant
Evaporation loss Prime Insignificant Insignificant
Vapor lock Prime Intermediate Insignificant
Hot starting Prime Intermediate Insignificant
Hot idle Prime Intermediate Insignificant
Carburetor icing Intermediate Prime InsignificantWarm up Insignificant Prime Intermediate
Acceleration Insignificant Prime Intermediate
Oil dilution Insignificant Insignificant Prime
Cleanliness Insignificant Insignificant Prime
Calorific value Insignificant Insignificant Prime
Summary of Volatility Characteristics and
Effects
The table gives a summary of the various aspects of volatility
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GUM DEPOSITS
Reactive hydrocarbons and impurities in the fuel have atendency, especially when stored during long periods athigh ambient temperatures, to deteriorate due tooxidation and form viscous liquids and solids, which are
referred to as gum.This can also occur when used in the engine.
These gums can seriously influence the performance of thegasoline.
Mainly due to presence of olefins and diolefins in the fuel.
Require hydrogen treatment or use of anti-oxidant additives
Problems Associated with Gum Formation
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Problems Associated with Gum Formation
1. Sticking of intake valves, piston rings, and automaticchokes, also fuel lines and filters.
2. Carbon deposits in the engine and gum deposits in themanifold; the latter could build up to a sufficient degree toreduce volumetric efficiency.
3. Clogging of carburetor jets and also cause sluggish
operation of the carburetor linkages.4. Lacquering of the valve stems, cylinders, and pistons.Lacquer is the name assigned to varnish-appearing residuethat the gum leaves when exposed to high temperatures. Ifthe gum is inflamed, it is reduced to a residue of carbon.
This carbon, lacquer, and gum deposits, all result from gumin the liquid fuel.
5. High sludge levels in storage tanks, cloudy gasoline anddeposits in various parts of an engine fuel system that cangive rise to vehicle malfunctions.
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CORROSION
Corrosion in the fuel system of a vehicle can lead to severeproblems.
1. Leaks can develop in automobile fuel tanks
2. Particles of rust can block fuel lines, filters and critical
carburetor orifices such as jets.3. Small amounts of water and dissolved air promote
corrosion of ferrous parts of the fuel system.
4. In addition, alcohols such as methanol or ethanol,present as blend components, can attack many non-ferrous parts, as well as increase the dissolved watercontent of the gasoline.
Major Cause of Corrosion
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Major Cause of Corrosion
The major cause of corrosion in fuels is the presence of sulfur.
Hydrocarbons may contain free sulfur, hydrogen sulfide, and
other sulfur compounds.Free sulfur and hydrogen sulfide in the fuel can corrode fuel
lines, carburetors, and fuel injection pumps.
Sulfur in all forms in the fuel, will form sulfurous and sulfuric aciddue to combustion with oxygen, and the presence of water, atlow temperatures.
Though a large portion of the exhaust gases escape through theexhaust pipe, the gases trapped in the clearance volume(residual gases) contain sulfur dioxide at the appropriatetemperatures to form sulfurous acid.
The sulfur dioxide may combine with other substances to formproducts that cause engine wear. The presence of sulfur inthe fuel can reduce its self-ignition temperature therebypromoting knock in the spark ignition engine.
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