Mushahid Ali, Minaam William, Raza Ur- Rehman, Muhammad Ali Hashmi,
Aneeq Ahmed,
Table of Contents
COAL TAR: .............................................................................................................................. 3
Types of Coal Tar: ................................................................................................................ 3
Low temperature tar: ........................................................................................................ 3
High temperature tar: ....................................................................................................... 3
Recovery of Tar:................................................................................................................... 3
Distillation of Tar: ................................................................................................................ 3
Uses of tar:.......................................................................................................................... 4
COAL TAR FUELS (C.T.F.): .......................................................................................................... 4
Uses of CTF: ........................................................................................................................ 5
Pitch Cresote Mixture (PCM): .................................................................................................... 5
Combustion Properties of Coal Tar Fuel (C.T.F.): ...................................................................... 6
KNOCK: .................................................................................................................................. 7
Reasons for knocking:........................................................................................................... 7
Effects of Knocking: .............................................................................................................. 7
OCTANE NUMBER:................................................................................................................... 7
Definition of Octane Number: ............................................................................................... 8
Determination of Octane Number:......................................................................................... 8
Octane number of Indian Petrol:............................................................................................ 8
Significance of Octane Number: ............................................................................................. 8
Limitation of Octane Number as a guide: ................................................................................ 8
Means to improve octane number: ........................................................................................ 8
Advantages of High Octane Number of Petrol: ........................................................................ 8
Anti-Knock Value: ................................................................................................................ 9
Lead Response:.................................................................................................................... 9
Octane Number of Blends: .................................................................................................... 9
CETANE NUMBER: ................................................................................................................... 9
Values of Cetane Number of Diesel: ....................................................................................... 9
Motor Fuel from Crude Oil: ..................................................................................................10
Production of Petrol (Gasoline) from Crude Oil: ......................................................................10
REQUISITE OF GOOD GASOLINE: ..............................................................................................11
Refining of Petrol: ...............................................................................................................12
Additives in Petrol (Gasoline): ..............................................................................................12
Aviation Gasoline: ...............................................................................................................12
1
DIESEL: ..................................................................................................................................13
Requisites of Good Diesel: ...................................................................................................13
FUEL OILS FROM PETROLEUM: .................................................................................................14
Properties of Fuel Oils: ........................................................................................................14
Analysis of Fuel Oil: .............................................................................................................15
Typical specification of Fuel Oil: ............................................................................................15
Combustion Characteristics of Fuel Oil: .................................................................................16
Recovery of Tar:
During the carbonization o fcoal in by-product coke oven, the tar vapors present in the coke
oven gas are separated by cooling it by ammoniacal liquor resulting in its condensation.
Remaining tar is separated in primary cooler and electrostatic tar precipitator thereby
recovering the bulk of tar present in the coke oven gas.
Distillation of Tar:
Tar contains around 1000 chemicals. Hence to recover some of these chemicals
economically and to produce better fuel, tar is distilled. The main fractions of tar (which are
recovered by distillation), their constituents, yield and boiling ranges are given in the
following table.
Fractions
Boiling range, o C
Yield
Light Oil
Upto 170 oC
2 4%
170 230 oC
5 7%
230 270 oC
15 25%
270 350 oC
Residue
14 17%
60 70%
Main constituents of
the fractions
Benzol, Naphtha and
Phenol
Phenol, naphthalene and
pyridine
Naphthalene and creosote
oil
Anthracene and wash oil
___
Uses of tar:
Tar is used as a furnace fuel. Its calorific value may be 8500 Kcal/Kg. Use of crude tar as a
fuel possesses a number of disadvantages viz.
The presence of volatile components which are lost on storage and which increase
the fire hazard.
The presence of water in tar which reduces the calorific value, causes corrosion and
its irregular combustion.
The presence of solid impurities such as a coke dust which may choke the burners
and pipelines.
Besides, the fact that tar is a storehouse of chemicals', its direct use as a fuel is discouraged.
Coal tar is also used as a binder for coal briquettes and for road making purposes.
coating of roof and pipeline for guarding against corrosion. Soft pitch having a softening
temperature of 30 oC can be used as liquid fuel after preheating.
Table1.2. Properties of Coal Tar Fuels (CTF)
Properties
Calorific Value, Kcal/Kg
Water content (volume
%) maximum
Ash content (weight %)
Softening point, oC
Flash Point
Sulfur Content (weight
%)
CTF 50
9150 to
9750
1
CTF
100
9150 to
9750
1
CTF
200
9000 to
9450
1
CTF
250
9000 to
9300
1
CTF
300
8900 to
9200
0.5
CTF
400
8750 to
9050
0.5
Nil
-60
Nil
-100
0.1
---
0.2
33.38
--
0.2
75.80
--
<1
<1
0.1
-1000 to
1500
<1
<1
<1
<1
Normally carbon content increases and hydrogen & oxygen content decreases in the series
CTF 50 to 400. C/H ratio increases from 11 to 16.5 in this series.
Uses of CTF:
Because of low sulfur content and high flame emissivity, it is one of the ideal fuels for
metallurgical furnaces. Besides, it is used for power generation, rotary kilns in calcination
and cement units and glass melting furnaces.
Calorific values (Kcal/Kg) of all the C.T.F. are lower than the corresponding petroleum
fuel oils.
Average carbon/hydrogen ratio for C.T.F. burns with a luminous flame which has a
high emissivity factor (0.6-0.9).
Higher emissivity factor of C.T.F. flame results in higher heat transfer rate by
radiation given by:
Q = CR (T14 __ T24)
Where, Q = radiation heat transfer rate Kcal/hour.m2
C = Steefan-Boltzman constant = 4.97 * 10-8 Kcal/hr.m2k4 = 5.67 * 10-8 W/m2.k4
E = Emissivity factor varies from 0.1 to 0.9
T1= Flame temperature of C.T.F., oK
T2= Temperature of the substance being heated, oK.
High emissivity factor implies higher heat transfer rate resulting in high thermal
efficiency of the furnace. Higher heat transfer rate means lesser time for heating a
substance i.e. higher production rate of the furnace.
C.T.F. (produced from high temperature carbonization tar) is aromatic in nature as
compared to paraffinic structure of fuel oils. Since the emissivity factor of aromatic
hydrocarbons are 25% higher than paraffins, the former has higher emissivity factor
and hence higher radiation heat transfer rate. Hence consumption (in kg) of C.T.F. is
10% less than petroleum fuel oil.
Sulfur content of C.T.F. is much lower (< 0.5%) than the corresponding petroleum
fuel oils (up to 4%). This makes it the most suitable for heating the metallurgical
furnaces like open hearth furnace, soaking pit, reheating furnace, annealing furnace
etc. as the high sulfur petroleum fuel oil causes the brittleness of steel slabs are
contaminated with sulfur.
Lighter C.T.F. can be atomized similar to petroleum fuel oil. Heavier C.T.F. are
difficult to atomize. Steam or compressed air is used for atomization of fuel. A
mixture of compressed air and steam are the most effective giving short, luminous
flame with a high heat release rate.
Because of low percentage of hydrogen (up to 6%) in C.T.F. (as compared to
upto12% in fuel oil), the difference between gross and net calorific value is less (up
to 325 Kcal/Kg) for C.T.F as compared to 625 Kcal/Kg for fuel oil. Because of less
difference, the heat losses due to hydrogen in fuel are much less in case of C.T.F. as
compared to fuel oil.
Theoretical air required for combustion of C.T.F. is bit less than that for fuel oil,
hence the volume of flue gas generated on combustion is less.
The dew point of flue gas generated by combustion of C.T.F. is lower compared to
that by fuel oil. Hence more waste heat recovery from flue gas is possible in case of
C.T.F. than fuel oil.
Specific heat of C.T.F. is 0.3-0.4 Kcal/KgoC. Higher specific heat improves fuel cooling
capacity (by high heat transfer rate) and reduces the heat transfer area.
Calorific value of C.T.F. is (9000 Kcal/Kg) less than that of corresponding fuel oil
(10000 Kcal/Kg).
ANTI-KNOCK VALUE
KNOCK:
When the fuel-air mixture undergoes very fast or intermittent combustion inside the combustion
chamber of an internal combustion engine, then a sort of rattling noise develops from the
combustion chamber (due to uneven, unsteady and uncontrollable combustion) which is called
knocking or detonation.
Effects of Knocking:
Knocking is an engine results in wear and tear of cylinder, piston and other engine parts.
Besides, it lowers the efficiency of the engine. Knocking reduces life of the engine.
OCTANE NUMBER:
Octane number expressed the anti-knocking characteristics of petrol. Normal heptane (a
constituent of petrol) when burnt in a petrol engine knocks it very badly i.e., the anti-knock
value of n-heptane is very poor and it is assigned an octane number equal to zero. On the
other hand, iso-octane (also a constituent of petrol) has got very good anti-knock
characteristics, hence it is assigned on octane number of 100.
7
Anti-Knock Value:
Anti-knock value of the hydrocarbons present in petrol increases with increase in the
compactness of the molecules, cyclic structure and double bond. Thus butane has an octane
number of 90 whereas heptane has 0.
Anti-knock value i.e., octane number increases in the order paraffins olefine
naphthenes iso-paraffins aromatics. It means that aromatics have highest anti-knock
value whereas paraffins have lowest anti-knock value (hence octane number). So, presence
of maximum quantity of aromatic and minimum quantity of paraffins is desirable in petrol.
In case of paraffins and olefins, anti-knock value (i.e., octane number) decreases with
increasing chain length.
In case of naphthenes, the larger the size of the ring and the length of the side chain, the
lower is the anti-knock value.
In case of aromatics, side chain addition up to 3 carbon atoms length improves the octane
number, but afterwards, the octane number decreases in proportion to the length of the
longest chain.
Lead Response:
The response of gasoline to the addition of tetra ethyl lead [(C2H5)4 Pb] for increasing its
octane number is different for different for different categories of hydrocarbons. The order
of decreasing effect of TEL addition (called lead response) is paraffins naphthenes
olefins aromatics. Alcohols, sulfur compounds and lubricating oils respond negatively.
CETANE NUMBER:
Cetane number is the measure of knocking in a diesel engine. Cetane (C 16H34) has a very
short ignition delay hence its cetane number is taken as 100 whereas alpha
methylnaphthalene (C11H10) has a very large ignition delay hence its cetane number is taken
as 0.
The cetane number of a diesel is defined as the percentage of cetane (by volume) in a
mixture of cetane and alpha methyl naphthalene which has same ignition delay as the diesel
under test.
11
Characteristic
Color, visual
Octane Number (Research Method),
Min.
Lead Content
a) as lead, g/l, Max.
Distillation
a) Initial Boiling Point
b) Recovery up to 70oC, percent
by volume, Min.
c) Recovery up to 125oC,
percent by volume, Min.
d) Recovery up to 180oC,
percent by volume, Min.
e) Final boiling point, oC, Max.
f) Residue, percent by volume,
Max.
Reid vapor pressure at 38oC,
Kg/cm2, Max.
Sulfur, total, percent by weight,
Max.
Residue on evaporation, mg/100 ml,
79 Octane
Gasoline
Orange
79
83 Octane
Gasoline
Orange
83
93 Octane
Gasoline
Red
93
0.42
0.56
0.80
-10
-10
-10
50
50
50
90
90
90
215
2
215
2
215
2
0.70
0.70
0.70
0.25
0.25
0.25
4
11
Max.
Oxidation stability, minutes, Min.
Copper-strip corrosion for 3 hours at
50 oC
360
Not worse than
No. 1
360
360
Not worse than
No.1
--
--
--
Density at 15 oC
Refining of Petrol:
The crude petrol is refined by treating with sulfuric acid to remove sulfur compounds
present in it (the process is called 'sweetening' of petrol). It is then passes through a bed of
fuller's earth to remove its color, which is due to the presence of gum in it. Finally, the
dissolved gases in it are driven off by a process called stabilization. Tetraethyl lead or other
additives are then added to increase the octane number (if the need be) or to inhibit the
gum formation before the petrol is ready for use.
Aviation Gasoline:
Petrol used in the airplanes has comparatively higher volatility and higher octane number
(>100) than motor gasoline. Though higher proportion of TEL (4.6 c.c/U.S. gallon) is added in
aviation gasoline, other additives are lesser in number and quantity. The main components
of aviation gasoline are iso-paraffin alkylates and aromatic reformates.
A typical specification of aviation gasoline is tabulated below in the table:
Table3.2. Typical Specification of Aviation Gasoline
S.No.
1.
2.
3.
4.
5.
6.
7.
8.
9.
Patameters
Reid vapor pressure at 37.8 oC (100oF)
Freezing point, maximum
Performance number
Aromatic content, minimum
Diesel index, minimum
Net calorific value, minimum
Total sufur, maximum
Tetra ethyl lead
Oxidation stability (16 hours ageing)
Units
Kg/cm2
o
C
-% by volume
-Kcal/Kg
% by weight
mg/liter
Value
0.385-0.490
60
130-145
5
75-90
10390-10500
0.05
Nil
12
10.
Gum, maximum
Precipitate, maximum
I.B.P/F.B.P.
mg/100 ml
mg/100 ml
o
C
6
2
<75/170
DIESEL:
It is a straight run product of crude petroleum oil distillation obtained in between kerosene
and lubricating oil. Diesel obtained from paraffinic crude are the most suitable as higher
amount of paraffin present in it increases its cetane number. Diesel is also produced by
cracking of heavy fuel oil and vacuum distillation of atmospheric distillation residue.
Though the most desired components of diesel fuels are the straight run distillates from
paraffin and mixed base crude oils, these are often used as feedstock for gasoline
production via cracking. Since, there is some overlap in the boiling ranges of kerosene and
diesel fuel hence diesel is prepared from heavy distillates obtained from catalytic cracking
unit. Since, the distillates are rick in aromatics and iso-paraffins (having low cetane number),
additives are added to improve the cetane number of diesel fuel. The suitable volatility is
obtained by blending with light fraction. Residual oils are also used in significant proportions
in meeting large demand of diesel fuel.
Characteristic
Grade
Special
Grade A
38
38
Grade B
(LDO)
Light Diesel
Oil
66
2.0 to 7.5
2.0 to 7.5
2.0 to 7.5
0.20
0.20
1.50
42
45
90
40
43
90
----
Not worse
than No. 1
Not worse
than No. 1
0.05
0.05
0.25
0.05
0.01
Nil
0.50
1.0
6
6
0.05
0.01
Nil
0.50
1.0
0.10
0.02
Nil
-1.8
12 for winter
18 for summer
Propeties
Viscosity
Remarks
It should be low for its proper atomization through burner and low
pressure drop during pumping.
Pour point and freezing It should be low to permit easy flow in cold weather.
point
Sulfur content
Should be low to avoid corrosion, pungent odor and increase in
dew point of flue gases.
Sludge,
gummy Should be low to avoid chocking of pipelines, erosion of
material and ash
furnaces/engines and contamination of products.
14
Calorific value
Specific gravity
Flash point
Water content
Characteristic
Low
Viscosity
Flash point (Pensky-Martens) (closed), C,Min. 66
Kinematic viscosity, centistokes at 50oC, Max. 80
Water content, percent by volume, Max.
1.0
Ash, percent by wt., Max
0.1
Sulfur, total percent by wt., Max.
3.5
Sediment, percent by wt., Max.
0.25
Acidity, inorganic
nil
Grades
Medium
Viscosity
66
125
1.0
0.1
4.0
0.25
nil
High
Viscosity
66
370
1.0
0.1
4.5
0.25
nil
A typical specification of low sulfur heavy stock (LSHS) fuel oil produced at Barauni Refinery
is given in the following table:
Table3.5. Typical Specification of LSHS
Characteristics
Value
o
26
0.93
10000
60
66
1
0.1
1
15
Combustion of fuel oil take place initially in vapor state, hence atomization must be
sufficient to initiate combustion.
In case of heavy fuel oil, cracking of hydrocarbons takes place at the surface of
droplets of oil resulting in liberation of carbon particles which burn with a luminous
flame having higher emissivity factor, hence higher radioactive heat transfer
capacity.
Higher the aromatic content of fuel oil i.e. higher the carbon/hydrogen ratio, the
more luminous is the flame and higher the emissivity factor.
About 15 Kg air per Kg of fuel oil is required for complete combustion with low
excess air to the tune of 10% only.
The shape and size of flame affects thermal efficiency. Optimum flame can be
produced with fuel oil by suitable burner and combustion air control.
With 10% excess air (preheated to 200oC), the flame temperature obtained from fuel
oil is around 1700oC which will radiate energy at the rate of 1000000 Kcal/m3 of
combustion volume (e=0.5).
High amount of sulfur present in fuel oil leads to high dew point (up to 160 oC) of flue
gas. Hence the flue gas going out of chimney cannot be cooled below this
temperature otherwise SO2 and SO3 present in it will condense and corrode the
boiler parts, induced draught fan blades and chimney checker bricks etc.
Sodium and vanadium in the ash of fuel oil are corrosive and get deposited on the hot
pressure parts of boilers.
16