Fuels and Combustion

Instructor: Dr. Tamal Ghosh, Chemistry Department, MNNIT

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 Fuels: Few General aspects

Fuels:

• Fuels are substances that produce useful energy when it

undergoes a chemical or nuclear reaction.
• Fuel such as coal, wood, Petroleum, or gas provides energy
when burned.
• Compounds in the body such as glucose are broken down
into simpler compounds to provide energy for metabolic
processes.
• Some radioactive substances, such as plutonium and
uranium provide energy by undergoing nuclear fission or
lighter nuclei undergo fusion.

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 Fuels: Few General aspects
• A chemical fuel is any compound that has stored energy. This
energy is captured in chemical bonds through processes such
as photosynthesis and respiration.

• Energy is released during oxidation. The most common form of

oxidation is the direct reaction of a fuel with oxygen through
combustion. Wood, petroleum, coal, and any number of other
fuels have energy-rich chemical bonds created using the
energy from the Sun, which is released when the fuel is burned
(i.e., the release of chemical energy).

• Chemical fuels are mainly fossil fuels that are useful reserve of
fuels and are therefore used extensively to satisfy the demands
of an energy-dependent civilization.

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 Fuels: Few General aspects

• All combustible substances are not fuels, e.g. though

diamond is also combustible substance but economically it is
not viable to burn a piece of diamond for making a cup of
coffee.

• Therefore, fuel can be defined as any combustible substance

which upon proper ignition gives large amount of energy
which can be utilized economically for doing purposeful work.

• Similarly, if any material having large amount of sulphur may

be burned to get energy but it will produce large amount of
harmful gases and therefore can not be a fuel.

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 Classification of Fuels

The chemical fuels can be put into two basic groups.

1. Primary or Natural fuels. e.g., Wood, Peat, Lignite, Bituminous

coal, Crude oil, Natural gas etc.

2. Secondary or Derived fuels. e.g., Coke, Charcoal, Gasoline,

Diesel, Water gas, Shift gas etc.

These can be further classified into solid, liquid and gaseous

fuels.

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 Characteristics of a Good Fuel

• The fuel selected must be suitable for the purpose.

• The fuel should have high calorific value.

• The fuel should be cheap and readily available.

• It should possess a moderate ignition temperature. Too high

temperature causes difficulty in kindling while too low ignition
temperatures may cause safety problems during storage,
transport and usage.

• The supply position of the fuel must be reliable.

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 Characteristics of a Good Fuel

• The velocity of combustion should be moderate.

• The fuel should have reasonable flexibility and control.

• The fuel should be such that safe and clean operation is

ensured. Too much smoke and obnoxious odors are not
desirable.

• It should be safe, convenient and economical for storage and

transport.

• It should have low moisture content.

• In case of solid fuel, the ash content should be less and the
size should be uniform.

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 Calorific Values of Fuels

• Calorific values represent the amount of heat produced during

combustion of fuels. People use calorific values to determine
how efficient and effective fuels are, looking for fuels with high
calorific values to use in energy generation.

• Determination of calorific value is done inside a device called

calorimeter.

• During the determination of calorific values, a set amount of the

object being studied is burned in controlled conditions, and the
products of combustion are measured to find out how much
heat was released during combustion.

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 Units of calorific values

The resulting calorific value is expressed in:

• energy/mole of fuel (kJ/mol)

• energy/mass of fuel ( cal/g or kcal/Kg)

• energy/volume of fuel (cal/cm3 or kcal/m3)

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 Types of Calorific value

• Two different measures can be used. Gross calorific

value, also known as higher heating value (GCV/HCV)
assumes that water produced during combustion
remains in a liquid form.

• Lower heating value or Net calorific value (NCV/LCV) is

calculated under the assumption that water produced
turns into vapor.

• These two different values are used to determine how

calorific values apply in the real world with different types
of systems.

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 Higher calorific value (HCV)

• HCV is determined by bringing all the products of

combustion back to the original pre-combustion
temperature, and in particular, condensing any vapor
produced. Such measurements often use a temperature
of 25°C.

• The higher heating value takes into account the energy

released as the latent heat of condensation of steam in
the combustion products. In other words, HCV assumes
all the water component is in liquid state at the end of
combustion.

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 Definitions

• Higher calorific value (HCV) = It is the total heat liberated in KJ

or Kcal by the complete combustion of 1 unit mass or 1 unit
volume of fuel and the products of combustion are brought
back to room temperature (25°C).

• Lower calorific value (LCV) = It is the total heat liberated in KJ

or Kcal by the complete combustion of 1 unit mass or 1 unit
volume of fuel and the products of combustion are allowed to
escape. It is the difference of Higher calorific value (HCV) and
latent heat evolved by condensation of water vapors.

• LCV= GCV- Latent Heat of Steam Condensation

• LCV=GCV-(0.09Hx587)
• Where H=% of Hydrogen in the fuel.

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 Lower calorific value (LCV)

• The quantity known as lower heating value Net calorific value

(NCV) or lower calorific value (LCV)) is determined by
subtracting the heat of condensation of the water vapor from
the higher calorific value (HCV).

• This treats any H2O formed as vapor. The energy released to

condense water, therefore, is not realized as heat.

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 Theoretical Calculation of Calorific Value
(Dulong’s Formula)

Constituent: H C S
HCV (kcal/kg) 34,500 8080 2240

• Oxygen is present in combined form with hydrogen in the

form of fixed hydrogen

• Amount of hydrogen available for combustion

= [(Total mass of hydrogen in fuel) - (fixed hydrogen)]
= (Total mass of hydrogen in fuel) – (1/8th mass of
oxygen in the fuel

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 Dulong’s formula

For calculation of calorific value:

1 O
• HCV = [8080 C + 34500 (H – ) + 2240 S] kcal/kg.
100 8
• Where, C, H, S and O are the percentages of each in the fuel.
Oxygen is assumed to be present in the combined state with
hydrogen as water.

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• LCV = [HCV − × H × 587] kcal/kg
100

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 Determination of Calorific Value

• Calorific Value of Fuel is determined by a device called

Calorimeter.
• For solid fuel and non-volatile liquid fuels, it is determined by
Bomb Calorimeter.
• For volatile liquid and gaseous fuels, it is determined by Gas
Calorimeter.

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 Characteristics of Bomb Calorimeters

• These measurements are obtained by burning a representative

sample in a high pressure oxygen atmosphere within a metal
pressure vessel or “bomb”.
• The energy released by this combustion is absorbed within the
calorimeter and the resulting temperature change within the
absorbing medium is noted.
• The heat of combustion of the sample is then calculated by
multiplying the temperature rise in the calorimeter by a
previously determined energy equivalent or heat capacity
determined from previous tests with a standardizing material.
• Corrections must be applied to adjust these values for any heat
transfer occurring in the calorimeter, as well as for any side
reactions which are unique to the bomb combustion process.

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Diagram of Bomb Calorimeters

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 Corrections in Bomb Calorimetric Determination

HCV = (W+w)(t2-t1)/ x kcal/kg

Where, W= water taken in the calorimeter
w= Water equivalent of calorimeter
t2 - t1= Rise in temperature of water
x = weight of sample
The specific heat of water is taken as 1cal/g/o C

• Fuse Wire Correction (Cf) - Fuse wire use to ignite the sample
will also produce some heat which should be subtracted from
the total heat.

• Cooling Correction (tc) - Some heat will be lost to the

surrounding with whatever precaution is taken, so that must be
determined and added to apparent rise in temperature.

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 Corrections in Bomb Calorimetric Determination

• Cooling Correction is therefore, determined by noting the rate and time

of cooling from higher to room temperature. If the rate of cooling is
degrees per minute and actual time taken is x minute, then
Cooling correction= X. dT, must be added to rise in temperature.

• Acid Correction (Ca) - Whatever nitrogen and sulfur is present in the

fuel will, upon combustion, be converted to oxides of sulfur and oxides
of nitrogen. The reaction will not stop here, due to prevailing condition
in the bomb these oxides will be converted to corresponding acid.
Since this conversion is an exothermic process, heat is evolved in the
system. Therefore, it must be subtracted from the overall heat.
S + O2 = SOx + H2O = H2SO4
N +O2 = NOx + H2O = HNO3

Therefore, the corrected equation will be:

(W+w)[(t2-t1)+tc] – (Ca+Cf)
HCV = x kcal/kg

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 Calorific value by Boy’s Gas Calorimeter

• It consists of a gas burner with an arrangement to

measure gas flow and pressure of the gas supplied to the
burner.
• A gas pressure regulator on the cylinder helps to provide
gas flow at lower pressure and dampens any pressure
fluctuations in flow.
• The burner burns inside a specially designed calorimeter
container containing a cooling coil with flowing water.
• The water is provided with a rotameter to measure flow of
cooling water.
• Two thermometers are provided, one at the inlet and one
at the outlet of the water flow through the coil.

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Boy’s Gas Calorimeter (internal view)

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 Calculation of Calorific Value:

W(t4-t3)
HCV = kcal/m3
V

where, W = Weight of water passed through calorimeter for time t, t3 and t4 are
the water inlet and outlet temperatures, respectively,
V = Volume of the fuel gas burned at a specific flow for time t.
No corrections are required for this determination as no (extra) fuel is used
for ignition.

LCV = HCV - (m’/V) x 587 kcal/m3

where, m’ = mass of steam condensed in time t,

m’/V = mass of water condensed per m3 of gas.

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 Solid Fuel: COAL

• Some of the important solid fuels are: Wood, Coal, Peat, Lignite and
Animal waste.

Coal Classification:
• Coal is classified into three major types namely anthracite, bituminous,
and lignite. However there is no clear demarcation between them and
coal is also further classified as semi- anthracite, semi-bituminous, and
sub-bituminous.

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 Solid Fuel: COAL

• Anthracite is the oldest coal from geological perspective. It is a

hard coal composed mainly of carbon with little volatile content
and practically no moisture.
• Lignite is the youngest coal from geological perspective. It is a
soft coal composed mainly of volatile matter and moisture
content with low fixed carbon. (Fixed carbon refers to carbon in
its free state, not combined with other elements.)
• Volatile matter refers to those combustible constituents of coal
that vaporize when coal is heated .The common coals used in
Indian industry are bituminous and sub- bituminous coal.

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 The gradation of Indian coal based on its
calorific value

• Grade Calorific Value Range ( in kCal/kg)

• A Exceeding 6200

• B 5600 – 6200

• C 4940 – 5600

• D 4200 – 4940

• E 3360 – 4200

• F 2400 – 3360

• G 1300 – 2400
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 Composition of Coal

• Primary carbon
• Secondary Hydrogen
• Sulfur,
• Oxygen,
• Nitrogen

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Chemical structure of coal

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 COMMON COAL COMPOSITION

• Type of Coal %C %H %O %N %Moisture Heating Value (kcal/kg)

• Anthracite 92-95 3–4 2–3 0–2 1–4 7500–8000

• Bituminous 75–92 8–12 3–20 1–2 5–30 5000–8000

• Lignite 60–75 4–6 17–35 1–2 30–50 3000–4500

• Peat 45–60 3–7 20–45 1–3 70–90 <3000

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 Analysis of Coal

• There are two methods: Ultimate analysis and Proximate

analysis.
• The ultimate analysis determines all coal component elements,
solid or gaseous and the proximate analysis determines only
the fixed carbon, volatile matter, moisture and ash percentages.
• The ultimate analysis is determined in a properly equipped
laboratory by a skilled chemist, while proximate analysis can
be determined with a simple apparatus.
• It may be noted that proximate has no connection with the word
“approximate”.

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 Measurement of Moisture

• Loss in weight of coal caused by heating of coal sample for one

hour at 105 °C is the moisture content of coal.
• A known amount of finely powdered coal sample is kept in a
silica crucible and heated in a hot air oven at 105-110 °C for one
hour. There after the crucible is taken out, cooled in a
dessicator and weighed.
• The percentage of moisture is given by, % moisture in coal =
{loss in wt. of coal X 100}/ (weight of coal initially taken).

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 Measurement of Volatile Matter

• It is the loss in weight of moisture free powdered coal when

heated in a crucible fitted with cover in a muffle furnace at 925
°C for 7 minutes.
• % volatile matter ={ loss in wt. of moisture free coal X 100}/ (wt.
of moisture free coal taken)

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 Measurement of Ash

• It is the weight of residue obtained after burning a weighed

quantity of coal in an open crucible (i.e. in presence of air) at
750 °C in a muffle furnace till a constant weight is achieved.
• % ash in coal = {wt. of residue ash formed X 100} / (wt. of coal
initially taken)

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 Determination of Fixed Carbon

• It is determined indirectly by deducting the sum total of

moisture, Volatile matter, and ash percentage from 100.
• % fixed carbon in Coal = 100- (% moisture + % ash + %
volatile matter)
• Proximate Analysis indicates the percentage by weight of the
Fixed Carbon, Volatile matter, Ash, and Moisture Content in
coal. The amounts of fixed carbon and volatile combustible
matter directly contribute to the heating value of coal. Fixed
carbon acts as a main heat generator during burning. High
volatile matter content indicates easy ignition of fuel.

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Significance of Various Parameters in Proximate Analysis

(a) Fixed carbon:

Fixed carbon is the solid fuel left in the furnace after volatile
matter is distilled off. It consists mostly of carbon but also
contains some hydrogen, oxygen, sulphur and nitrogen not driven
off with the gases. Fixed carbon gives a rough estimate of heating
value of coal.

(b) Volatile Matter:

• Volatile matters are the methane, hydrocarbons, hydrogen and
carbon monoxide, and incombustible gases like carbon dioxide
and nitrogen found in coal. Thus, the volatile matter is an index
of the gaseous fuels present. Typical range of volatile matter is
20 to 35%.
• Proportionately increases flame length and helps in easier
ignition of coal.
• Sets minimum limit on the furnace height and volume.
• Influences secondary air requirement and distribution aspects.

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Significance of Various Parameters in Proximate Analysis
(c) Ash Content:
• Ash is an impurity that will not burn. Typical range is 5 to 40%
• Reduces handling and burning capacity.
• Increases handling costs.
• Affects combustion efficiency

(d) Moisture Content:

• Moisture replaces combustible matters. It decreases the heat
content per kg of coal. Typical range is 0.5 to 10%.
• Moisture Increases heat loss, due to evaporation and
superheating of vapour.
• Aids radiation heat transfer.

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 Ultimate Analysis

• The ultimate analysis indicates the various elemental chemical

constituents such as Carbon, Hydrogen, Oxygen, Sulphur, etc.
It is useful in determining the quantity of air required for
combustion and the volume and composition of the
combustion gases. This information is required for the
calculation of flame temperature and the flue duct design etc.

• Determination of total carbon, hydrogen, nitrogen, oxygen and

sulphur percentages in coal comprises its ultimate analysis.

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 Determination of Carbon and Hydrogen in coal

• A known amount of coal is burnt in a current of dry

oxygen thereby converting C and H of coal into CO2 and
H2O, respectively.
• The products of combustion are passed over weighed
tubes of anhydrous CaCl2 and KOH which absorbs H2O
and CO2, respectively.
• The increase in the weight of CaCl2 tube represents the
weight of water (H2O) formed while increase in the weight
of KOH tube represents the weight of CO2 formed.

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Fig.: Carbon and Hydrogen Determination

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 % of H and C calculations

• Let, wt. of coal sample taken= X

• Increase in the wt. of CaCl2 tube= Y
• Increase in the wt. of KOH tube = Z
• Amount of carbon in the coal sample =Z12/ 44

• % carbon in coal = 100x12Z/44X

• Similarly, amount of hydrogen in coal sample = 2Y/18

• % hydrogen in coal =100×2Y/18X

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 Determination of Nitrogen

• It is done by Kjeldahal‟s method.

• A known weight of powdered coal is heated with conc.
H2SO4 in presence of Potassium sulphate and
Copper/mercuric sulphate in a long necked flask, thereby
converting nitrogen of coal to ammonium sulphate. When
clear solution is obtained, it is treated with 50% NaOH
solution. The ammonia thus formed is distilled over and
absorbed in a known quantity of standard sulphuric acid
solution. The volume of unused H2SO4 is then determined
by titrating against standard NaOH solution. Thus, the
amount of acid neutralized by liberated ammonia is
determined.
• %of nitrogen in coal = {vol. of acid used x Normality x
1.4} / (wt. of coal taken)

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Fig.: Estimation of Nitrogen by Kjeldahl’s Method

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 Determination of Sulphur

• A known quantity of coal is heated with Eschka mixture (which

consists of 2 parts of MgO and 1 part of anhydrous Na2CO3) at
800˚C. After burning amount of sulphur present in the mix is
retained as oxides and it is precipated as sulphates.The
sulphate formed is precipitated as BaSO4 (by treating with
BaCl2).
• % of sulphur in coal = 100 x0. 1374 Y/X
• Where, X= weight of coal sample taken
• Y= Weight of BaSO4 precipitate formed

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 Determination of Oxygen

• It is deduced indirectly as follows:

• % of oxygen in coal = 100 – (% of C + H + N + S + Ash+ volatile

matter).

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 Petroleum

• Petroleum is an extremely complex mixture of hydrocarbons,

which can be separated into liquid (oil) and gas fractions.
Compared to coal, petroleum being a liquid is easier to
transport. It probably originated in marine sediments, in
contrast to the terrestrial origins of coal.
• Most plastics and other petrochemicals are made from
petroleum, along with almost all gasoline, diesel fuel, jet fuel,
heating oil, and lubricants. However, Earth's supply of
petroleum is limited.
• Because petroleum varies greatly in composition and
distribution throughout the world, elaborate systems of refining
and transport have been developed. Major oil fields or giant
petroleum fields are found primarily in the Middle East, North
and South America, and countries that made up the former
Soviet Union.

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 Crude oil
• Crude oil is the term for "unprocessed" oil, the stuff that comes
out of the ground. It is also known as petroleum.

• Crude oil is a fossil fuel, meaning that it was made naturally

from decaying plants and animals living in ancient seas
millions of years ago -- most places we can find crude oil were
once sea-beds.

• Crude oils vary in color, from clear to tar-black, and in viscosity,

from water to almost solid.

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 Crude Oil Components
• 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)

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 Hydrocarbons in crude oils
• The major classes of hydrocarbons in crude oils include:
• Paraffins, general formula: CnH2n+2 (n is a whole number,
usually from 1 to 20) straight- or branched-chain molecules can
be gasses or liquids at room temperature depending upon the
molecule examples: methane, ethane, propane, butane,
isobutane, pentane, hexane

• Aromatics, general formula: C6H5 - Y (Y is a longer, straight

molecule that connects to the benzene ring) ringed structures
with one or more rings, rings containing six carbon atoms, with
alternating double and single bonds between the carbons are
typically liquids examples: benzene, napthalene.

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 Hydrocarbons in crude oils
• Napthenes or Cycloalkanes, general formula: CnH2n (n is a
whole number usually from 1 to 20) ringed structures with one
or more rings, rings containing only single bonds between the
carbon atoms are typically liquids at room temperature
examples: Cyclohexane, methyl cyclopentane

• Other hydrocarbons: Alkenes, general formula: CnH2n (n is a

whole number, usually from 1 to 20) linear or branched chain
molecules containing one carbon-carbon double-bond can be
liquid or gas examples: ethylene, butene, isobutene. Dienes
and Alkynes, general formula: CnH2n-2 (n is a whole number,
usually from 1 to 20) linear or branched chain molecules
containing two carbon-carbon double-bonds can be liquid or
gas examples: acetylene, butadiens etc.

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 Calorific Value
• The calorific value of coal varies considerably depending on
the ash, moisture content and the type of coal while calorific
value of fuel oils are much more consistent. The typical Gross
Calorific Values of some of the commonly used liquid fuels are
given below:
• Fuel Oil Gross Calorific Value (kCal/kg)
• Kerosene - 11,100
• Diesel Oil - 10,800
• Light Diesel oil (L.D.O) - 10,700
• Furnace Oil - 10,500
• Low Sulphur Heavy Stock (LSHS) - 10,600

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• Hydrocarbon chains derived from fossil fuels typified by the
petrochemical industry do not have the carboxylic acid ester
connection, and exist in many elaborate forms. For example
petrol may be a mixture of the following molecules:-

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 Refining of Crude Oil
• As mentioned previously, a barrel of crude oil has a mixture of
all sorts of hydrocarbons in it. Oil refining separates everything
into useful substances. Chemists use the following steps:

• The oldest and most common way to separate things into

various components (called fractions), is to do it using the
differences in boiling temperature. This process is called
fractional distillation. (Basically crude oil is heated up, let it
vaporize and then condense the vapor).

52
 Steps involved in Crude refining
• Corttell’s Process:- For removal of saltish water and emulsion.
In this the crude oil is passed between two highly charged
electrodes, which destroys the film and allows the water
droplets to collates to form bigger drops and separates out.

• Removal of Sulphur:- Suphur is removed by adding CuO in

calculated amount, where sulphur is precipitated as CuS and
filtered off.

• Then the crude oil is put to fractional distillation where various

fractions are separated depending on their boiling point.

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 Chemical processing
• Newer techniques use Chemical processing on some of the
fractions to make others, in a process called conversion.

• Chemical processing, for example, can break longer chains into

shorter ones. This allows a refinery to turn diesel fuel into
gasoline depending on the demand for gasoline.

• Refineries must treat the fractions to remove impurities.

54
 Chemical processing
• Refineries combine the various fractions (processed,
unprocessed) into mixtures to make desired products. For
example, different mixtures of chains can create gasolines with
different octane ratings.
• The crude oil distillation unit (CDU) is the first processing unit
in virtually all petroleum refineries.
• The CDU distills the incoming crude oil into various fractions of
different boiling ranges, each of which are then processed
further in the other refinery processing units.

55
Fractional Distillation Unit:

56
 Fractional distillation
• Different hydrocarbon chain lengths all have progressively
higher boiling points, so they can all be separated by
distillation.
• This is what happens in an oil refinery - in one part of the
process, crude oil is heated and the different chains are pulled
out by their vaporization temperatures.
• Each different chain length has a different property that makes
it useful in a different way.

57
 Fractions obtained by Fractional distillation
• Petroleum gas - used for heating, cooking, making plastics
• small alkanes (1 to 4 carbon atoms)
• commonly known by the names methane, ethane, propane,
butane
• boiling range = less than 104 degrees Fahrenheit / 40 degrees
Celsius
• often liquified under pressure to create LPG (liquified
petroleum gas)
• Naphtha or Ligroin - intermediate that will be further processed
to make gasoline
• mix of 5 to 9 carbon atom alkanes
• boiling range = 140 to 212 degrees Fahrenheit / 60 to 100
degrees Celsius.

58
 Fractions obtained by Fractional distillation
• Gasoline - motor fuel
• liquid
• mix of alkanes and cycloalkanes (5 to 12 carbon atoms)
• boiling range = 104 to 401 degrees Fahrenheit / 40 to 205
degrees Celsius
• Kerosene - fuel for jet engines and tractors; starting material
for making other products
• liquid
• mix of alkanes (10 to 18 carbons) and aromatics
• boiling range = 350 to 617 degrees Fahrenheit / 175 to 325
degrees Celsius.

59
 Fractions obtained by Fractional distillation
• Gas oil or Diesel distillate - used for diesel fuel and heating oil;
starting material for making other products
• liquid
• Alkanes containing 12 or more carbon atoms
• boiling range = 482 to 662 degrees Fahrenheit / 250 to 350
degrees Celsius.
• Lubricating oil - used for motor oil, grease, other lubricants
• liquid
• long chain (20 to 50 carbon atoms) alkanes, cycloalkanes,
aromatics
• boiling range = 572 to 700 degrees Fahrenheit / 300 to 370
degrees Celsius.

60
 Fractions obtained by Fractional distillation
• Heavy gas or Fuel oil - used for industrial fuel; starting material
for making other products
• liquid
• long chain (20 to 70 carbon atoms) alkanes, cycloalkanes,
aromatics
• boiling range = 700 to 1112 degrees Fahrenheit / 370 to 600
degrees Celsius.
• Residuals - coke, asphalt, tar, waxes; starting material for
making other products
• solid
• multiple-ringed compounds with 70 or more carbon atoms
• boiling range = greater than 1112 degrees Fahrenheit / 600
degrees Celsius.

61
 Typical crude oil distillation unit
• Below is a schematic flow diagram of a typical crude oil
distillation unit. The incoming crude oil is preheated by
exchanging heat with some of the hot, distilled fractions and
other streams. It is then desalted to remove inorganic salts
(primarily sodium chloride).

62
Flow diagram of a typical crude oil distillation unit

63
Distillation columns in an oil refinery

64
 Chemical Processing
• One fraction can be changed into another by one of three
methods:

• breaking large hydrocarbons into smaller pieces (cracking)

• combining smaller pieces to make larger ones (unification)

• rearranging various pieces to make desired hydrocarbons

(alteration)

65
 Cracking
• In petroleum geology and chemistry, cracking is the process
whereby complex organic molecules such as kerogens or
heavy hydrocarbons are broken down into simpler molecules
such as light hydrocarbons, by the breaking of carbon-carbon
bonds in the precursors.

• The rate of cracking and the end products are strongly

dependent on the temperature and presence of catalysts.

• Cracking is the breakdown of a large alkane into smaller, more

useful alkanes and alkenes. Simply put, hydrocarbon cracking
is the process of breaking long-chain hydrocarbons into short
ones.

66
 Cracking
• In plain language, the fluid catalytic cracking process breaks
large hydrocarbon molecules into smaller molecules by
contacting them with powdered catalyst at a high temperature
and moderate pressure which first vaporizes the hydrocarbons
and then breaks them.
• The cracking reactions occur in the vapor phase and start
immediately when the feedstock is vaporized in the catalyst
riser.

• Cracking can be achieved by two processes:

• Thermal Cracking Process.
• Catalytic Cracking Process.

67
Diagrammatic Example of the catalytic cracking of
petroleum hydrocarbons

68
 Thermal cracking
• The first thermal cracking method, the Shukhov cracking
process, was invented by Russian engineer Vladimir Shukhov.

• Modern high-pressure thermal cracking operates at absolute

pressures of about 7,000 kPa.
• An overall process of disproportionation can be observed,
where "light", hydrogen-rich products are formed at the
expense of heavier molecules which condense and are
depleted of hydrogen.

• The actual reaction is known as homolytic fission and

produces alkenes, which are the basis for the economically
important production of polymers.

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 Mechanism of Thermal Cracking
• A large number of chemical reactions take place during steam
cracking, most of them based on free radicals. Computer
simulations aimed at modeling what takes place during steam
cracking have included hundreds or even thousands of
reactions in their models. The main reactions that take place
include:
• Initiation reactions, where a single molecule breaks apart into
two free radicals.
• In steam cracking, initiation usually involves breaking a
chemical bond between two carbon atoms, rather than the
bond between a carbon and a hydrogen atom.
• CH3CH3 → 2 CH3•
• Hydrogen abstraction occurs where a free radical removes a
hydrogen atom from another molecule, turning the second
molecule into a free radical.
• CH3• + CH3CH3 → CH4 + CH3CH2•

70
 Mechanism of Thermal Cracking
• Radical decomposition occurs where a free radical breaks apart into
two molecules, one an alkene, the other a free radical. This is the
process that results in the alkene products of steam cracking.
• CH3CH2• → CH2=CH2 + H•
• Radical addition, the reverse of radical decomposition, occurs where a
radical reacts with an alkene to form a single, larger free radical. These
processes are involved in forming the aromatic products as a result
when heavier feed stocks are used.
• CH3CH2• + CH2=CH2 → CH3CH2CH2CH2•
• Termination reactions occur when two free radicals react with each
other to produce products that are not free radicals. Two common
forms of termination are recombination, where the two radicals
combine to form one larger molecule, and disproportionation, where
one radical transfers a hydrogen atom to the other, giving an alkene
and an alkane.
• CH3• + CH3CH2• → CH3CH2CH3
• CH3CH2• + CH3CH2• → CH2=CH2 + CH3CH3

71
 Example of cracking of butane CH3-CH2-CH2-CH3

• 1st possibility (48%): breaking is done on the CH3-CH2 bond.

CH3* / *CH2-CH2-CH3
• After a certain number of steps, we will obtain an alkane and an
alkene: CH4 + CH2=CH-CH3

• 2nd possibility (38%): breaking is done on the CH2-CH2 bond.

CH3-CH2* / *CH2-CH3
• After a certain number of steps, we will obtain an alkane and an
alkene from different types: CH3-CH3 + CH2=CH2

• 3rd possibility (14%): breaking of a C-H bond

• After a certain number of steps, we will obtain an alkene and
hydrogen gas:
• CH2=CH-CH2-CH3 + H2
• this is very useful since the catalyst can be recycled.
72
 Fluid catalytic cracking (FCC)
• FCC is the most important conversion process used in
petroleum refineries.
• It is widely used to convert the high-boiling, high-molecular
weight hydrocarbon fractions of petroleum crude oils to more
valuable gasoline, olefinic gases, and other products.
• Cracking of petroleum hydrocarbons was originally done by
thermal cracking, which has been almost completely replaced
by catalytic cracking because it produces more gasoline with a
higher octane rating.
• It also produces byproduct gases that are more olefinic, and
hence more valuable, than those produced by thermal cracking.

73
 Fluid catalytic cracking
• The feedstock to an FCC is usually that portion of the crude oil
that has an initial boiling point of 340 °C or higher at
atmospheric pressure and an average molecular weight
ranging from about 200 to 600 or higher. This portion of crude
oil is often referred to as heavy gas oil.
• The FCC process vaporizes and breaks the long-chain
molecules of the high-boiling hydrocarbon liquids into much
shorter molecules by contacting the feedstock, at high
temperature and moderate pressure, with a fluidized powdered
catalyst.
• Initial process implementations were based on low activity
alumina catalyst and a reactor where the catalyst particles were
suspended in a rising flow of feed hydrocarbons in a fluidized
bed.

74
 Catalytic cracking
• A modern FCC catalyst has four major components: crystalline
zeolite, matrix, binder, and filler.
• Zeolite is the primary active component and can range from
about 15 to 50 weight percent of the catalyst.
• The zeolite used in FCC catalysts is referred to as faujasite or
as Type Y and is composed of silica and alumina tetrahedra
with each tetrahedron having either an aluminum or a silicon
atom at the center and four oxygen atoms at the corners.
• It is a molecular sieve with a distinctive lattice structure that
allows only a certain size range of hydrocarbon molecules to
enter the lattice.
• In general, the zeolite does not allow molecules larger than 8 to
10 nm (i.e., 80 to 90 angstroms) to enter the lattice.

75
 Catalytic cracking
• The gasoline produced in the FCC unit has an elevated octane
rating but is less chemically stable compared to other gasoline
components due to its olefinic profile.
• Olefins in gasoline are responsible for the formation of
polymeric deposits in storage tanks, fuel ducts and injectors.
• The FCC LPG is an important source of C3-C4 olefins and
isobutane that are essential feeds for the alkylation process
and the production of polymers such as polypropylene.

76
Fluid Catalytic Cracking unit

77
 Mechanism of catalytic Cracking
• The catalytic cracking process involves the presence of acid
catalysts (usually solid acids such as silica-alumina and
zeolites) which promote a heterolytic (asymmetric) breakage of
bonds yielding pairs of ions of opposite charges, usually a
carbocation and the very unstable hydride anion.
• Carbon-localized free radicals and cations are both highly
unstable and undergo processes of chain rearrangement, C-C
scission in position beta as in cracking, and intra- and
intermolecular hydrogen transfer or hydride transfer.
• The catalytic sites in the zeolite are strong acids (equivalent to
90% sulfuric acid) and provide most of the catalytic activity.
The acidic sites are provided by the alumina tetrahedra.
• The aluminum atom at the center of each alumina tetrahedra is
at a +3 oxidation state surrounded by four oxygen atoms at the
corners which are shared by the neighboring tetrahedra.

78
 Mechanism of catalytic Cracking
• Thus, the net charge of the alumina tetrahedra is -1 which is
balanced by a sodium ion during the production of the catalyst.
• The sodium ion is later replaced by an ammonium ion, which is
vaporized when the catalyst is subsequently dried, resulting in
the formation of Lewis and Brønsted acidic sites.
• In some FCC catalysts, the Brønsted sites may be later
replaced by rare earth metals such as cerium and lanthanum to
provide alternative activity and stability levels.

79
 Example of Mechanism

Cn─CH2─CH2─CH2─CH2─CH3→ Cn─CH+─CH2─CH2─CH2─CH3
• LA + LAH-
• ↓
•
+
• Cn-CH=CH2 + CH2-CH2-CH3 + LAH-
• ↓
•
• CH3-CH2-CH3 + LA

80
Fixed bed catalytic cracking

81
Moving bed type catalytic cracking

82
 Major products
• Liquified petroleum gas (LPG)
• Gasoline (also known as petrol)
• Naphtha
• Kerosene and related jet aircraft fuels
• Diesel fuel
• Fuel oils
• Lubricating oils
• Paraffin wax
• Asphalt and tar

83
Schematic flow diagram of a typical oil refinery

84
 Refining of Gasoline

• The straight run gasoline obtained from fractionation or by

synthesis contains some undesirable unsaturated straight
chain HC and some sulphur compounds.
• The straight chain hydrocarbons get oxidized and polymerized,
causing gum formation.
• The sulphur compounds leads to corrosion of internal
combustion engine.

85
 Refining of Gasoline
• The following steps are involved in refining process of
gasoline:
• Removal of Sulphur compounds: The sulphur compounds are
removed by:
• Treating gasoline with alkaline solution of sodium plumbite
with controlled addition of sulphur. This process is known as
Sweetening or Doctors process.
• 2RSH + Na2PbO2 → Pb(SR)2 + 2NaOH
• Pb(SR)2 + S → PbS ↓ + RSSR
(removed by solvent
extraction)

86
 Refining of Gasoline
• Removal of coloring matter: coloring matters of gasoline
are removed by:
percolating gasoline through Fuller's earth in a column
which preferentially absorbs the coloring matter.
• Addition of Inhibiters: Certain inhibiters are
added to slow down the oxidation reaction,
thereby increasing the storage and
transport properties of gasoline.

87
 Reforming of Gasoline

• Reforming is process of bringing structural change in the

gasoline molecule to enhance their octane rating. This can be
done by two ways:
– Thermal Reforming.
– Catalytic Reforming.
• In modern refineries generally it is carried out by catalytic
reforming process. This process yields better fuel and is more
advantageous than thermal reforming.

88
 Reforming of Gasoline
• Thermal Reforming:
• It is carried out at about 500-600˚C and a pressure of 85 atm. in
a reactor. To avoid decomposition of gasoline molecules
conditions are controlled by rapid quenching process by
spraying cold oils.
• There are certain disadvantages of this process, such as yield
is low and the quality of reformates is low as compared to
catalytic reforming.

89
 Catalytic reforming
• Catalytic reforming is a chemical process used to convert
petroleum refinery naphthas, typically having low octane
ratings, into high-octane liquid products called reformates
which are components of high-octane gasoline (also known as
high-octane petrol).
• Basically, the process re-arranges or re-structures the
hydrocarbon molecules in the naphtha feedstocks as well as
breaking some of the molecules into smaller molecules.

90
 Catalytic reforming
• The four major catalytic reforming reactions are:
• 1: The dehydrogenation of naphthenes to convert them into
aromatics as exemplified in the conversion ethylcyclohexane
(naphthene) to toluene (an aromatic), as shown below:

91
 Catalytic reforming
• 2: The isomerization of normal paraffins to isoparaffins as
exemplified in the conversion of normal octane to 2,5-
Dimethylhexane (an isoparaffin), as shown below:

92
 Catalytic reforming
• 3: The dehydrogenation and aromatization of paraffins to
aromatics (commonly called dehydrocyclization) as exemplified
in the conversion of normal heptane to toluene, as shown
below:

93
 Catalytic reforming
• 4: The hydrocracking of paraffins into smaller molecules as
exemplified by the cracking of normal heptane into isopentane
and ethane, as shown below:

94
 Catalytic reforming and mechanisms
• Most catalytic reforming catalysts contain platinum or rhenium
on a silica or silica-alumina support base, and some contain
both platinum and rhenium. Fresh catalyst is chlorinated prior
to use.

• The noble metals (platinum and rhenium) are considered to be

catalytic sites for the dehydrogenation reactions and the
chlorinated alumina provides the acid sites needed for
isomerization, cyclization and hydrocracking reactions.

95
 Catalytic Reforming Process
• The latest and most modern type of catalytic reformers are
called continuous catalyst regeneration reformers (CCR).
• Such units are characterized by continuous in-situ regeneration
of part of the catalyst in a special regenerator, and by
continuous addition of the regenerated catalyst to the
operating reactors.
• Many of the earliest catalytic reforming units (in the 1950s and
1960s) were non-regenerative in that they did not perform in
situ catalyst regeneration. Instead, when needed, the aged
catalyst was replaced by fresh catalyst.

96
Semi-regenerative catalytic reforming unit

97
 Knocking and Octane Rating
• For gasoline, the primary performance criterion is knock
resistance, defined by the fuel’s octane number.

• Engine knock is a condition where a fraction of the unburned

fuel mixture spontaneously ignites before it can be consumed
by the flame generated from the spark plug.

• The resulting mini-explosions can cause significant engine

damage. Engine knock has historically limited the performance
and efficiency of spark ignited engines, and much work has
been done to minimize knock through hardware modifications
and chemical upgrading of the fuel.

98
 Octane number (or rating)
• The octane number of a fuel is measured using a single cylinder,
variable compression ratio, knock testing engine. The
compression ratio of the engine is adjusted to give knock of a
standard intensity.
• The engine is then run using reference fuels which are mixtures of
n-heptane and iso-octane (2,2,4-trimethylpentane).
• The octane number of n-heptane is defined as 0 while that of iso-
octane is 100.
• The octane number of the test fuel is defined as the volume
percent of iso-octane in the reference fuel giving the same knock
as the test fuel. Because some fuels are more knock-resistant than
iso-octane, the definition has been extended to allow for octane
numbers higher than 100.
• Racing fuels, avgas, liquefied petroleum gas (LPG), and alcohol
fuels such as methanol may have octane ratings of 110 or
significantly higher.
• Typical "octane booster" gasoline additives include MTBE, ETBE,
isooctane and toluene.

99
 Chemical structure and Octane Rating
• Octane number of Molecule also depends on its structure. The
following rule in general helps in assigning the possible octane
number to different kind of molecules.
• 1. The knocking tendency decreases with increase in the
compactness of the molecules, double bonds and cyclic
structures.
• 2. In the normal paraffins the anti knocking properties
decreases with increase in the chain length of the hydrocarbon
chain. Thus for given molecules the order of anti knocking
character decreases in the order:
n-Butane (90) > n-Pentane (60) > n-Hexane(29)
> n-Heptane (0).
• 3. Aromatic hydrocarbon such as benzene and toluene have
higher octane rating than their alicyclic counter parts.

100
 Chemical structure and Octane Rating
4. Branched chain paraffins have higher anti knocking
characteristics than their normal counter isomer. Thus
resistance to knock increases with the number of branches
and their position.
• 2-Methyl Hexane Octane No.= 55
• 2,2-Dimethyl Pentane Octane No.= 80

5. Olefins have higher anti knocking characteristics than

corresponding parafins.
Butane ˂ Butene

Further it is noted that the anti knocking tendency increases

as the position of the double bond approaches center of the
chain.
But-1-ene ˂ But-2-ene

101