B.E.

SEMESTER-I
ENGINEERING CHEMISTRY
UNIT (FUEL)

Dr. R. M. KHARATE
DEPATMENT OF
APPLED SCIENCES AND HUMANITIES
 FUEL
 Definition of Fuel
 Types of fuel
 Refining of petroleum
 Cracking of petroleum
 Types of cracking
 Knocking in IC engine
 Scale for knocking(Octane No.,Cetane No. )
 FUEL

 DEFINATION: Fuel is a combustible

substance which on burning in air gives
large amount of heat that can be use
economically for domestic and industrial
purposes.
 TYPES OF FUEL
FUEL

Natural(Primary) Artificial(Secondary)
Solid Wood,Peat, Coal Coke,Charcoal

Liquid Petroleum or crude oil Petrol,Kerosene,Diesel ,

Coal tar
Producer gas(CO+N2)
Gas Natural gas
Water gas(CO+H2)
Biogas
 CHARASTERISTICS OF GOOD FUEL
 IT SHOULD HAVE A VERY HIGH CALORIFIC VALUE
 IT SHOULD HAVE MODERATE IGNITION TEMPERATURE IF IT IS
LOW,STORE AND TRASPORT OF A FUEL WILL CAUSE PROBLEMS AND IF IT
TOO HIGH , IGNITION OF FUEL WILL REQUIRED MORE AMOUT OF HEAT
ENERGY
 IT SHOULD HAVE LOW MOISTURE CONTENT, AS IT DECREASES THE
CALORIFIC VALUE OF FUEL
 IT SHOULD HAVE LOW ASH CONTENT THE HIGH CONTENT OF ASH
DECREASES THE CALORIFIC VALUE IT ALSO CAUSES EXTRA
EXPENDITURE ON ITS STORAGE TRANSPORT AND DISPOSAL IT ALSO
CREATS AIR AND WATER POLLUTION
 VELOCITY OF COMBUSTION SHOULD BE MODERATE
 PRODUCTS OF COMBUSTION SHOULD NOT POLLUTE THE ATMOSPHERE
 THE FUEL SHOULD BE AVAILABLE ON LARGE SCALE AND LOW COST
 THE COMBUSTION SHOULD BE EASILY CONTROLLABLE
 IT SHOULD PRODUCE LESS AMOUNT OF SMOKE
 IT SHOULD NOT UNDERGO SPONTANEOUS COMBUSTION
 ANALYSIS OF COAL

1. PROXIMATE ANALYSIS OF COAL

% MOISTURE

% VOLATILE MATTER

% ASH

% OF FIXED CARBON
 ANALYSIS OF COAL

2. ULTIMATE ANALYSIS OF COAL

% CARBON

% HYDROGEN

% NITROGEN

% SULPHUR

% ASH

% OXYGEN
 FUEL(PETROLEUM)
What is Petroleum?
• Crude Oil

• Natural Gas
ESTIMATION OF C AND H
ESTIMATION OF N BY KJELDAHL’S METHOD
 ESTIMATION OF S

O2 BaCl2
S H2SO4 BaSO4 (Ba = 137 , S = 32 , O = 16)
32 233
FUEL(PETROLEUM)

Oil and Gas Supply More Than 60%

of World Energy Consumed

Oil (39%) Gas (23%)

Coal (24%) Nuclear (6%)
Hydroelectric (7%) Renewables (1%)

Source: EIA, Annual Energy Review, 2002

 COMPOSITION OF PETROLEUM
  On average, crude oils are made of the
following elements or compounds:
 Carbon - 84%
 Hydrogen - 14%
 Sulfur - 1 to 3% (hydrogen sulfide, sulfides,
disulfides, elemental sulfur)
 Nitrogen - less than 1% (basic compounds with
amine groups)
 Oxygen - less than 1% (found in organic
compounds such as carbon dioxide, phenols,
ketones, carboxylic acids)
 Metals - less than 1% (nickel, iron, vanadium,
copper, arsenic)
 Salts - less than 1% (sodium chloride, magnesium
chloride, calcium chloride
 REFINING OF PETROLEUM
How do we refine it?

REFINERY

The process in which crude oil is separated in to various

useful fractions having different boiling points by
fractional distillation.
FRACTIONAL DISTILATION OF PETROLEUM
 CRACKING OF PETROLEUM

Cracking is defined as the process of decomposition of

the higher molecular weight hydrocarbon having high
boiling point to the low molecular weight hydrocarbon
having low boiling point.
eg. C10H22 Cracking C5H12 + C5H10
n-Pentane n-Pentene
Decane
B.P.= 1740C B.P.=360C B.P.=360C

1. Higher hydrocarbons are converted to lower hydrocarbons.

2. Saturated hydrocarbons are converted to unsaturated
hydrocarbons.
 TYPES OF CRACKING

Thermal cracking Catalytic cracking

Vapour phase
Liquid phase Vapour phase catalytic cracking
thermal cracking thermal cracking
(500-600 0C,100Kg./cm2) (600-700 0C,20Kg./cm2)

Fixed bed Moving bed (fluid)

catalytic cracking catalytic cracking
FIXED BED CATALYTIC CRACKING
MOVING(FLUID) BED CATALYTIC CRACKING
 ADVANTAGES OF CATALYTIC CRACKING
OVER THERMAL CRACKING
• uses a catalyst
• lower temperature
• lower pressure
• more flexible
• different reaction mechanisms ionic vs. free radical
• High thermal efficiency
• Good integration of cracking and regeneration
• High yields of gasoline and other distillates
• Low gas yields
• High product selectivity
• Low n-alkane yields
• High octane number
• Chain-branching and high yield of C4 olefins
• High yields of aromatics
KNOCKING IN I.C. ENGINE

I.C. ENGINE

S.I. ENGINE C. I .ENGINE

PETROL DIESEL
 KNOCKING IN I. C .ENGINE
Reasons for knocking
1.The rate of oxidation is so great that mixture
detonates producing sound called as engine knock
2.Rate of oxidation of hydrocarbon molecules depend
upon the number of C-atoms in chain and structure
of molecule and temperature.
3.Temperature depends upon compression ratio.
v1 v2
Compression ratio= v2 v1
After ignition
Before ignition
STROKE 1: (INTAKE)
The downward moving piston sucks a mixture of air
and
 petrol into the cylinder.

PETROL
ENGINE
STROKE 2: (COMPRESSION)
The piston moves up, compressing the gas mixture. This is
where a low octane fuel might ignite and cause knocking.

PETROL ENGINE
STROKE 3: (POWER)
Just before the piston reaches the top of the cylinder a
spark from the spark plug explodes the gas mixture.
 pushes the piston down and drives the crank shaft
This
round.
.

PETROL ENGINE
STROKE 4: (EXHAUST)
The piston moves up and pushes the gases out through
the exhaust valve. As the piston moves down, it pulls more

fuel/air mixture in to begin the cycle again

PETROL ENGINE
 CHEMICAL STRUCTURE AND KNOCKING

 The tendency of knocking depends upon the nature

of fuel and air-fuel ratio.
 Knocking tendency of different constituents of
petrol are in following order.
Straight chain alkanes > branched chain alkanes >
alkenes > naphthalenes > aromatic hydrocarbons
 SCALE FOR KNOCKING IN PETROL ENGINE
(OCTANE NO.)
 A value used to indicate the resistance
of a fuel to knock. Octane numbers are
based on a scale on which isooctane is
100 (minimum knock) and heptane is 0
(bad knock).

2,2,4-trimethylpentane(C8H18)
n – Heptane(C7H16) (Iso-octane)
OCTANE NO.= (0) OCTANE NO.= (100)
 ANTIKNOCKING AGENTS

1.Tetraethyl lead(Pb(CH2CH3)4 )
2.Methyl tertiary butyl ether(MTBE)CH3)3C-O-CH3
3.Methylcyclopentadienyl manganese tricarbonyl
C9H7MnO3
(CH3CH2)4Pb + 13 O2 → 8 CO2 + 10 H2O + Pb

Pb + CH2 Br PbBr2 + CH2

Lead
Lead Bromide
CH2 Br CH2
Ethylene bromide Ethylene
WORKING OF DIESEL ENGINE
COMPRESSION IGNITION

P and T of air
2
P= 40 Kg/cm
T= 500-600 OC

2
70 Kg/cm
 SCALE FOR KNOCKING IN DIESEL ENGINE
(CETANE NO.)

Aromatic hydrocarbons> naphthalenes > alkenes

branched chain alkanes > Straight chain alkanes
CH3

CH3(CH2)14CH3
Cetane(C16H34)
-Methyl naphthalene(C11H10)
CETANE NO.= (100) CETANE NO.= (0)
Cetane number test:
In this method a standard reference fuel is used in a
test cylinder. The most widely used reference fuel is a
mixture of cetane and alpha-methyl-naphthalene.
Cetane has an extremely high ignition quality (ignites
quickly) and is rated for the test at 100. Alpha methyl-
naphthalene has a very low ignition quality (is difficult
to ignite) and is rated for the test at 0.
To increase the cetane number of diesel the additives
like acetylene ethyl nitrate acetone diethylether are
added in diesel as a preignition fuel
DIFFERENCE BETWEEN OCTANE NO AND CETANE NO
LUBRICANTS
CLASIFICATION OF LUBRICANTS
CLASIFICATION OF LUBRICANTS
 MECHANISM OF LUBRICATION

FLUID FILM OR THICK FILM OR HYDRODYNAMIC LUBRICATION

 MECHANISM OF LUBRICATION

THIN FILM OR BOUNDARY LUBRICATION

REDWOOD VISCOMETER NO. 1/2 PROPERTIES OF LUBRICATNTS

VISCOSITY AND
VISCOSITY INDEX
 PROPERTIES OF LUBRICATNTS

FLASH POINT AND FIRE POINT

PENSKY MARTEN’S FLASH POINT APPARATUS

PROPERTIES OF LUBRICATNTS

CARBON RESIDUE

CONRADSON’S APPARATUS
 PROPERTIES OF LUBRICATNTS

CLOUD POINT AND POUR POINT

CLOUD POINT AND POUR POINT APPARATUS

 POLYMERS
CLASSIFICATION OF POLYMERS
CLASSIFICATION OF POLYMERS ON THE BASIS OF STRUCTURE
 INDIVIDUAL POLYMERS
POLYVINYL CHLORIDE (PVC)
 INDIVIDUAL POLYMERS

TYPES OF POLYVINYL CHLORIDE (PVC)

 INDIVIDUAL POLYMERS

POLYTETRAFLUROETHYLENE (PTFE)
 INDIVIDUAL POLYMERS

PHENOL-FORMALDEHYDE
RESIN (BAKELITE)
INDIVIDUAL POLYMERS

PHENOL-FORMALDEHYDE RESIN
(BAKELITE)
RUBBERS OR ELASTOMERS
RUBBERS OR ELASTOMERS

VALCANIZATION OR RECOMPOUNDING
OR CURING OF RUBBER
 SYNTHETIC RUBBERS

STYRENE RUBBER (GR-S OR BUNA-S ORSBR OR BSR)

 SYNTHETIC RUBBERS

NITRILE RUBBER (GR-A OR BUNA-N OR BUTADIENE-ACRILONITRILE RUBBER

SYNTHETIC RUBBERS

BUTYL RUBBER
STEREO-REGULER POLYMER
ENVIRONMENTAL CHEMISTRY
ENVIRONMENTAL CHEMISTRY
ENVIRONMENTAL SEGMENTS
GREEN HOUSE EFFECT (J. FOURIER 1827)
ACID RAIN
CONSEQUENCES OF ACID RAIN
OZONE DEPLETION
OZONE DEPLETION
CONTROL OF AIR POLLUTION
CYCLONE SEPARATOR
ELECTROSTATIC PRECIPITATOR
FABRIC FILTER (BAG HOUSE)
CYCLONE SCRUBBER