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FUEL TECHNOLOGY:
Introduction to Liquid Fuels-Classification of Crude Oil-Fractional DistillationCracking (Thermal &Catalytic), Synthetic Petrol (Fischer-Tropschs & Bergius
Process) - Polymerization-Refining &Reforming Knocking Anti Knocking
Agents-Octane & Cetane Number.
LUBRICANTS:
Principle and functions of lubricants Types of lubrication and mechanism
Thick film or Hydrodynamic lubrication, Thin film lubrication, extreme
pressure lubrication. Classification and properties of lubricants Viscosity,
flash and fire points, cloud and pour points, aniline points, neutralization
number and mechanical strength.
INTRODUCTION TO LIQUID FUELS:
Petroleum or crude oil (petro=rock; ileum=oil) is a dark greenish brown viscous
oil found in earths crust. It is composed of straight chain hydrocarbons, cycloparaffins or naphthalenes, olefins and aromatic compounds together with small
amount of nitrogen, oxygen and sulphur.
The average composition is C=79.5 to 87.1 %; H=11.5to 14.8%, S=0.1 to 3.5%;
N+O=0.5%.
CLASSIFICATION OF PETROLEUM OR CRUDE OIL:
1. Paraffinic-base type crude is mainly consisting of saturated hydrocarbons from
C1-C35 and a little of naphthalenes and aromatics.
2. Asphaltic-base type crude is mainly cyclo paraffins with smaller amounts of
paraffins and aromatics.
3. Mixed- base type crude mainly contains both paraffinic and asphaltic
hydrocarbons and also semi-solid waxes.
REFINING OF PETROLEUM:
The crude oil is separated into various useful fractions by fractional distillation and
finally converted into desired specific products. This process is called Refining of
Petroleum. This process involves three steps,
Step-1: Separation of water (Cottrells
process): The crude oil from the oil well is an
extremely stable emulsion of oil and salt water.
This is passed through highly charged
electrodes. The Colloidal water droplets
coalesce to form large drops, which separate
out from the oil.
Step-2: Removal of harmful sulphur
compounds: this involves treating of oil with
copper oxide to form insoluble solid copper
sulphide, which is removed by filtration.
Step-3: Fractional distillation: The Petroleum
oil is then heated to about 400 0C in an Iron
retort, where by all volatile constituents, except
the residue (asphalt or coke) is evaporated. The
hot vapors are then passed up a fractionating Column which is a tall cylindrical
tower containing a number of horizontal stainless steel trays at short distance. Each
tray is provided with a small chimney covered with loose caps. As the vapors go up,
they become gradually cooler and fractional condensation takes place at different
heights of column. Higher boiling fraction condenses first; while the lower boiling
fractions turn-by-turn. Various fractional products are obtained as follows;
Name of fraction
Boiling rangeComposition
Uses
Below 30 0C
C1- C4
As domestic or
industrial fuel (L.P.G)
30-70 0C
C5-C7
As a solvent
40-120 0C
C5-C9
Naphtha
120-180 0C
C9-C10
Kerosene oil
180-250 0C
C10-C16
As an illuminant, jet
engine fuel
Diesel oil
250-320 0C
C10-C18
Heavy oil
320-400 0C
C17-C30
Uncondensed gas.
Petroleum ether
Gasoline or Petrol
Heavy oil on
refractionation gives:
As lubricant.
(a)Lubricating oil
(b)Petroleum jelly
As a lubricant
Or Vaseline
(c)Grease
(d) Paraffinic wax
Residue
Asphalt
Above 400 0C
Above C30
Tar
CRACKING:
Cracking is defined as the decomposition of higher hydrocarbon molecules in to
simpler low boiling hydrocarbons of lower molecular weight.
Decane (C10H22)
(B. p. = 36 0C
Cracking is usually takes place to cracks the Heavy oil to form Petrol or gasoline of
high quality and good yield than straight-chain petrol .There are two methods of
cracking.
(1)
(a)
(b)
(2)
(a)
FIXED BED CATALYTIC CRACKING: The oil vapors are heated in a preheater
to cracking temperatures and then forced through a catalyst chamber (clay mixed with
zirconium oxide) maintained at 425-460 0C and low pressure. The cracking takes
place and formation of gasoline and 2-4% carbon is formed and is observed by catalyst
bed. The vapors produced are then passed through a fractionating column, where
heavy oil fractions condense. The vapors are then passed through a cooler some gases
are condensed along with gasoline and uncondensed gases are move on. The gasoline
containing gases are passed through a stabilizer where dissolved gases separate out
and pure gasoline is obtained. The catalyst after 8-10 hours stops functioning due to
deposition of carbon black; this is reactivated by burning off deposited carbon.
SYNTHETIC METHODS FOR PRODUCTION OF PETROL:
POLYMERIZATION:
The gases obtained as a by-product from cracking of heavy oils, contains olefins and
alkanes. When this gaseous mixture is subjected to high pressure and temperature,
with or without the presence of catalyst, it polymerizes to form higher hydrocarbons,
resembling gasoline, called polymer gasoline.
CH3.CH=CH2
CH3.CH2.CH=CH2
Propene
Butene
5-methyl hexane-1
(b)
1.
FISCHERTROPSCHS PROCESS:
n CO + 2n H2
2. BERGIUS PROCESS:
In this process, low ash coal pulverized to fine powder is converted into a paste with
heavy oil and a catalyst nickel oleate is mixed with it. This mixture is sent to the
convertor maintained at 3500c and a pressure of 200-250 atmospheres, where it meets
the hydrogen gas. The hydrogen combines with carbon of the coal giving various
hydrocarbons from heavy oil to gasoline. Reaction carried for one hour.
The gases coming out of the convertor are passed into fractionators to get gasoline,
middle oil and heavy oil. The middle oil is subjected to hydrogenation in presence of
catalyst to produce gasoline. The heavy oil fraction is recycled to male paste with fresh
coal powder.
REFINING OF GASOLINE:
The gasoline obtained either by fractional distillation or synthesis contains
undesirable unsaturated straight-chain hydrocarbons and sulphur compounds. In
order to remove these, a process called refining is followed.
(a) The sulphur compounds are removed by treating gasoline with an alkaline
solution of sodium plum bite with controlled addition of sulphur. This process
is called sweetening and converts sulphur into disulphides. The lead sulphide is
removed by filtration and the disulphide is extracted with a suitable solvent.
2 RSH +Na2PbO2
Pb (SR)2
Pb (SR)2 +
PbS
+
Lead sulphide
2 NaoH
RSSR
disulphide
(b) Olefins and coloring matter of gasoline are removed by fullers earth, which
absorbs the olefins and coloring matter.
(c) After the refining add some inhibitors to retard the oxidation reactions to
improve quality of gasoline.
KNOCKING AND ANTI KNOCKING:
The ratio of the gaseous volume in the cylinder at the end of the suction stroke (intake
stroke) to the volume at the end of the compression stroke of the piston is known as
compression ratio. If the compression ratio is high then the efficiency of the internal
combustion engine is high. When the compression ratio is very high, the rate of
oxidation becomes so great that the last portion of the fuel air mixture gets ignited
instantaneously, producing an explosive violence, known as knocking. The knocking
results in loss of efficiency.
The tendency of fuel constituents to knock is:
Straight-chain paraffins > branched-chain paraffins > olefins > cyclo paraffins>
aromatics.
OCTANE RATING or OCTANE NUMBER:
It was introduced by Edger in 1872. It has been found that n-heptanes knocks very
badly and hence its anti-knock value has arbitrarily been given zero. On the other
hand, isooctane (2, 2, 4- tri methyl pentane) gives very little knocking, so its anti
knock value has been given as 100. Thus octane number of a gasoline (or any other
internal combustion engine fuel) is the percentage of isooctane in a mixture of
isooctane and n-heptanes, which matches the fuel under test in knocking
characteristics. It means, a 80-octane fuel is one which has the same combustion
characteristics as an 80:20 mixture of iso-octane and n-heptanes.
ANTI-KNOCKING AGENTS:
The octane number of fuels can be raised by the addition of some anti-knocking
materials like tetra ethyl lead, (C2H5)4Pb or TEL and diethyl telluride, (C2H5)2Te. During
combustion, the added tetra ethyl lead is converted into lead oxide (PbO). They
combine with hydrocarbons producing free radicals which slow down the explosive
combustion. Thus the anti-knocking characteristics of the fuel are considerably
increased. The lead oxide after combustion is reduced to metallic lead and is harmful
to engine life, therefore a small amount of ethylene dibromide, C 2H4Br2 is added to
convert lead into lead bromide and remove it along with the exhaust gases. Recently
new anti-knock agents which are safe and completely volatile are used rather than
TEL.
CETANE NUMBER:
In a diesel engine, the fuel is not ignited by a spark but the compression of air
increases the pressure and temperature and the incoming fuel should ignite below
compression temperature to have as short an induction lag as possible. This means
that the hydrocarbon molecules in a diesel fuel should be as far as possible the
straight chain ones with minimum admixture of aromatic and side chain
hydrocarbon molecules.
The suitability of a diesel fuel is determined by its cetane value, which is the
percentage of hexadecane (cetane) in a mixture of hexadecane and 2-methyl
naphthalene, which has the same ignition characteristics as the diesel fuel in
question. The cetane number of a diesel fuel can be raised by the addition of small
quantity of certain pre-ignition dopes like ethyl nitrite, isoamyl nitrite, acetone
peroxide etc.
2-Methyl naphthalene (Cetane No. = 0)
n-Hexadecane (Cetane No. = 100)
Ignition quality order among hydrocarbon constituents of a diesel fuel is as follows:
n-alkanes naphthalenes alkenes branched alkanes aromatics
Thus, hydrocarbons which are poor gasoline fuels are quite good diesel fuels.
PRINCIPLE OF LUBRICATION:
All material surfaces, no matter how smooth they are, show many irregularities in the
form of peaks (or asperities) and valleys, which are large when considered on a
molecular scale (see figure below). When two solid surfaces are pressed over each
other a real contact between these surfaces occurs only at a limited number of
asperities i.e. peaks of the upper surface are in contact with peaks of the lower
surface.
Even under small loads, the local pressure at the asperities may be sufficiently
great to cause appreciable deformation in ductile metals. This causes the formation of
welded junctions between the asperities. It is these junction areas that carry the entire
load between the two surfaces. Thus the real or true area of contact is only a small
fraction of the apparent contact area between the two surfaces.
In all type of machines, the surfaces of moving (or) sliding (or) rolling parts rub
against each other. Due to mutual rubbing of one part against another, a resistance is
offered to their moment. This resistance is known as friction. Friction causes a lot of
wear and tear of surfaces of moving parts, and large amounts of energy are dissipated
in the form of heat, thereby causing loss in the efficiency of machine. Moreover, the
moving parts get heated up damaged and even some times results in seizure (welding
of melted surface peaks).
Any substance introduced between two moving/sliding surfaces with a view
to reduce the frictional resistance between them is known as a lubricant. This process
is called as lubrication.
FUNCTIONS OF LUBRICANT:
1.
It reduces surface deformation, wear and tear
2.
Reduces loss of energy in the form of heat
3.
Acts as a coolant.
4.
Reduces waste of energy, so efficiency of machine is enhanced.
5.
Reduces expansion of metal by local frictional heat.
6.
Reduces the maintenance and running cost of the machine.
7.
Avoids the unsmooth relative motion of the moving parts.
8.
In the ICE (Internal Combustion Engine) it acts as a seal (between piston and
cylinder)
And also prevent the leakage of gases under high pressure from the cylinder.
MECHANISM OF LUBRICATION:
There are mainly three types of mechanism by which lubrication is done.
1. Thick-film or Fluid- film or hydrodynamic lubrication.
2. Thin film or Boundary lubrication.
3. Extreme pressure lubrication.
1. THICK FILM OR FLUID FILM OR HYDRODYNAMIC LUBRICATION:
For low load and high speed surfaces, thick film lubrication is used
(a)
(b)
(c)
(d)
(e)
(f)
(g)
In this, the moving surfaces are separated from each other by a thick film of
fluid (at least 1000 thick), so that direct surface to surface contact and
welding of junctions rarely occurs.
The lubricant film covers the irregularities of the moving surfaces and forms a
thick layer in between them. This consequently reduces wear.
The small friction (if any) occurs is only due to internal resistance between the
particles of the lubricant moving over each other.
In such a system friction depends on the thickness and viscosity of the
lubricant, the relative velocity and area of the moving surfaces.
The coefficient of friction is as low as 0.001 to 0.03 for fluid film lubricant
system.
Hydrodynamic friction occurs in the case of shaft running at a fair speed as well
as in well lubricant bearings, with not too high loads.
In a journal bearing a film of the lubricating oil covers the irregularities of shaft
as well as bearing surface and also the metal surfaces do not come into direct
contact with each other.
Eg. Delicate instruments, watches, guns, scientific instruments etc. are provided with
this type of Lubrication.
(h)
Fluid film lubrication is satisfactorily done by hydrocarbon oils.
(i)
Hydrocarbon oils are generally blended with selected long chain polymers in
order to maintain the viscosity of oil constant in all reasons of year.
(j)
2.
(d)
Graphite:
(i)
It is one of the most widely used solid lubricants. It is (i) soapy to touch (ii) Non
inflammable (ii) Not oxidized in air below 375 0 C (iv) In the absence of air, it is
used up to high temperature.
(ii)
Graphite is used either in powdered form or suspension (in oil or waterwith
help of emulsifying agent like tannin).
(iii)
When graphite is dispersed in oil, it is called oil dag and when it is dispersed in
water it is called aquadag. Oil dag is found particularly useful in Internal
Combustion Engines while aquadag is useful where a lubricant free from oil is
needed.
(iv)
Graphite is used as a solid lubricant at General machine shop works, Railway
track joints, Lathe machines tec.
Molybdenum disulphide (MoS2):
(a) It possess very low coefficient of friction
(b) Stable in air up to 400 0C
(c) It is used in powder form (or) along with solvents and greases
PROPERTIES OF LUBRICANTS:
Some of the properties of lubricating oils are
(a) Viscosity
(d) Cloud and pour point
(b) Flash and fire point
(e) Aniline point
(c) Mechanical stability
(f) Neutralization number
VISCOSITY:
It is the property of a liquid or fluid by virtue of which it offers resistance to its own
flow. The force per unit area required to maintain a unit velocity gradient between two
parallel layers is called coefficient of viscosity. The unit of viscosity is Poise. Viscosity
is the most important property of lubricating oil, because it is the main determinant of
the operating characteristics of the lubricant. Viscosity of good lubricating oil should
not change much with change in temperature.
MEASUREMENT OF VISCOSITY OF LUBRICATING OIL:
Many Instruments are available for measuring viscosity and are known as
viscometers. In a viscometer fixed volume of the liquid is allowed to flow, from a given
height, through a standard capillary tube under its own weight and the time of flow in
seconds is noted. The time in seconds is proportional to true viscosity.
Redwood viscometers (No.1 and No. 2) and Say bolt viscometers are used for
measuring the viscosity of lubricating oil. The essential difference between the two is
Red wood-2
15mm
3.8mm
Higher
viscous oil
MECHANICAL STABILITY:
To know the suitability of a
lubricant under conditions of very high
pressure, different mechanical tests are
carried out. One such test is four-ball
extreme-pressure lubrication test in
which the lubricant under test is poured
in a machine containing four balls. The
lower three balls is stationery while
upper ball is rotated. Load is gradually
increased and the balls are examined at
specific intervals for scale formation etc.
on them. If the lubricant is satisfactory it
will not form any scales otherwise the
heat generated may weld the balls and lead to scratches or scale formation. Thus, this
test enables us to determine the maximum load that can be carried safely by a
lubricant.