Fuels & Combustion:

Liquid Fuels
January 2023

By Dr. K. C. Vora
Emeritus Professor, COEP
AICTE-INAE Distinguished Visiting Faculty
Chair, ASDC Expert Group on EV
Advisor, BAJA SAEINDIA
Former Sr. Deputy Director & Head ARAI Academy, ARAI, Pune.

With Prof Sagar Kadam, I C Engine Lab, COEP

01
 Contents
• Fuels & Combustion Course Outcome
• Fuels & Combustion Curriculum
• India’s Economic Profile / World & India’s Energy Basket
• Petroleum Production v/s Consumption
• Fuels & Classification
• Liquid Fuels
• Petroleum, Refining & Fraction
• Fuel Properties
• India’s Auto Fuel Policy (2003 & 2025)
• Fuels Quality Upgradation in Refineries
• Alternate Liquid Fuels
• Renewable Fuels
• Synthesis/Liquefication of Solid Fuels into Gasoline
• Conclusions
 ME 21012 Fuels and Combustion: COs

Course Outcomes (COs): At the end of the course student will be able to:

• Analyze the properties of fuels

• Compare the suitability of fuels utilization point of view.
• Evaluate the performance of an engine.
• Demonstrate stages of combustion in SI and CI engine
• Analyze the emission and performance of an engine.
 ME 21012 Fuels and Combustion: Curriculum
• Unit 1 (4 hrs)
• Characterization:
• Fuels - Types and Characteristics of Fuels, Fuels Analysis, Proximate and Ultimate Analysis,
Moisture Determination, Calorific Value, Gross & Net Calorific Values, Calorimetry,
DuLong’s Formula for CV Estimation, Flue gas Analysis.
• Unit 2 (6 hrs)
• Solid fuels:
• Coal Family, Properties, Calorific Value, DMMF, DAF and Bone Dry Basis, Ranking, Storage,
Washability, Coking & Caking Coals, Renewable Solid Fuels, Biomass, Wood Waste, Agro
Fuels, Manufactured Solid Fuels.
 Curriculum (Contd.)
• Liquid fuels:
• Sources, Petroleum Fractions, Classification, Refining, Properties of Liquid Fuels, Calorific Value,
Specific Gravity, Flash & Fire Point, Octane Number, Cetane Number etc, Alcohols, Liquefaction of
Solid Fuels
• Unit 3 (4 hrs)
• Gaseous fuels:
• Classification, Composition & Properties, Estimation of Calorific Value, Gas Calorimeter, Rich &
Lean Gas, Wobbe Index, Natural Gas, LPG, LNG, CNG, Methane, Producer Gas, Water Gas, Town
Gas, Coal Gasification, Gasification Efficiency, Biogas.
 Curriculum (Contd.)
• Unit 4 (2 hrs)
• Combustion:
• Combustion equations, stoichiometric A/F, enthalpy of formation, adiabatic flame temperature.
• Unit 5 (10 hrs)
• SI and CI Engine:
• Otto cycle, fuel supply system, stages of combustion in SI engines, abnormal combustion and knocking
in SI engines, factors affecting knocking, effects of knocking, control of knocking, combustion chambers
for SI engines Diesel cycle, fuel supply system, stages of combustion in C.I. Engines, delay period,
factors influencing delay period, diesel knock, control of diesel knock, types of combustion chamber.
• Unit 6 (10 hrs)
• Performance and Emission:
• Engine Performance and parameters, determination of IP, BP, FP, IMEP, BMEP, various efficiencies,
energy balance, performance of CI and SI engine. Exhaust after treatment, catalytic converters, exhaust
gas recirculation, emission control in engines, sources of SI and CI engine emission, Euro and Bharat
stage norms, Emission control methods in SI and CI engine.
 Curriculum (Contd.)
Text Books:
• Ganesan. V, “Internal Combustion Engines”, Tata McGraw Hill
• Mathur & Sharma, “A Course in Internal Combustion Engines”, Dhanapat Rai Publications.
• Samir Sarkar, “Fuels & Combustion”, 2nd Edition, Orient Longman, 1990
Reference Books:
• Edward E. Obert, “Internal Combustion Engines and Air Pollution”, Internal Edu. Pub, 1973
• Crouse W.H., “Automotive Mechanics”, McGraw Hill
• Heywood J., “I.C. Engines Fundamentals”, McGraw Hill publications
• Sharma SP, Mohan Chander, “Fuels & Combustion”, Tata McGraw Hill, 1984.
• Burns Stephen, “An Introduction to Combustion: Concepts & Applications”, 2012.
• Borman Gary, Ragland Kenneth, “ Combustion Engineering”, 1998.
• Pundir B P, “Engine Emission”, 2007.
India’s Economic Profile/
Energy Scenario
 India at a Glance
❖ 3rd Largest Economy of the World
❖ Skilled Human Capital
❖ Well Developed Capital Market
❖ Established Legal and Audit Systems
❖ Huge Untapped Natural Resources
❖ Huge Market Potential
 Economic Growth

Powered by Energy

Energy is a Key Enabler for Economic Growth

 India’s Growth Forecast

India is a fast-growing economy in the region

 World’s Energy Basket 2006-2030
2006
Primary Energy Consumption:
10880 MTOE

2030

Primary Energy
Consumption:
18040 MTOE
Source: BP Statistical Review of World
Energy 2006 & IEO-2006

MTOE(Million Tonnes of Oil Equivalent)

 India’s Energy Basket 2006-2030
2006
(Good to have diversity)
Primary Energy Consumption:
423.2 MTOE

2030

Primary Energy
Consumption: 812
MTOE
MTOE(Million Tonnes of Oil Equivalent) Source: BP Statistical Review of World Energy 2006 & IEO-2006
World’s Energy Basket 2015
India’s Energy Basket 2020
 Total Petroleum Production 2020
Total world petroleum
production in 2020
averaged 76,124,800
barrels per day.

Approximately 71%
came from the top ten
countries, and an
overlapping 36% came
from the thirteen
current OPEC members
Total Petroleum Consumption 2019
 Prevailing Conditions

Economics
• Rising oil prices Policies
• Resource scarcity • Emission Standards
• Limiting CO2 emission
• International
• International policies
politics Problems of
the 21st
Century
Society Environment
• Increasing traffic • Climate change
• Urbanisation • Pollutant emission
• Increasing • Global Warming
populations

Social change, resource depletion & urbanization

characterize the future of mobility
Hydrocarbon Sector - Operation Chain
Transportation
Drilling

Refining (Fractionation)

Refining (Secondary
Processing)

Products Transportation
 FUELS
• Fuel is a source of heat & energy

• Material that can be burned or otherwise consumed to produce heat &

energy. This includes our food.

• Fuels can be stored in Solid, Liquid or Gaseous forms, where

the carbon and hydrogen in fuel rapidly combine with oxygen in the air and
liberates heat, an exothermic reaction.

• Besides stored fuels, we have Solar, wind (acolian), nuclear, chemical

(batteries), tidal, biomass, fuel wood, peat, garbage, municipal wastes,
agri-residues, geothermal energy resources too.
 CLASSIFICATION OF FUELS
1. Primary fuels which occur in nature as such, e.g. coal, petroleum and natural gas.
2. Secondary fuels which are derived from the primary fuels, e.g. coke, gasoline, coal gas, etc.
Both primary and secondary fuels may be further classified based upon their physical state as
(i) solid fuels (ii) liquid fuels and (iii) gaseous fuels.
 Energy Usage
• Household Energy: Heating, cooling, cooking, lighting, appliances, etc.

• Transportation Energy: 2 Wheelers, 3 Wheelers, cars, truck, bus, plane,

train, ships, etc.

• Industrial Energy: Factories, industrial complexes, manufacturing units,

fertilizer production, R&D Division, trade, Gen sets, etc.

• Health, Education, Welfare & Events: Admin, water supply, sewage, trash
disposal, military forces, hospitals, schools, University, etc.:
 LIQUID FUELS
• Liquid fuels are combustible or energy-generating molecules that can be
harnessed to create mechanical energy, usually producing kinetic energy.

• Basically molecules of Hydrogen & Carbon.

• It is the fumes of liquid fuels that are flammable instead of the fluid.

• Most liquid fuels in widespread use are derived from fossil fuels; however,
there are several types, such as ethanol and biodiesel, which are also
categorized as a liquid fuel.

• Many liquid fuels play a primary role in transportation and the economy.
ADVANAGES & DISADVANTAGES OF LIQUID FUELS
Advantages:
•Higher calorific value per unit mass.
•Burn without ash, clinkers, etc.
•Controlling the combustion is easier.
•Transportation easier through pipes and stored indefinitely without loss.
•Loss of energy is comparatively lower.
•Require less furnace space for combustion.

Disadvantages:
•Cost of liquid fuel is much higher compared to solid fuel.
•Storage methods are costlier.
•Greater risk of fire hazards.
•Special burning equipment required for more efficient combustion.
Settler Activity: Solve the anagram
(rearrange the letters to make one word)

ICRUDE
CURE OLD
OIL
 PETROLEUM FUELS / CRUDE OIL
• Petroleum, also known as crude oil or oil, is a naturally occurring, yellowish-
black liquid found in geological formations beneath the Earth's surface.
• The average composition of crude oil is C =80 - 87 %, H =11-15%, S = 0.1 -3.5%,
(N +O) =0.1- 0.5%.
• It is commonly refined into various types of fuels.
• Components of petroleum are separated using a technique called fractional
distillation, i.e., separation of a liquid mixture into fractions differing in boiling
point by means of distillation, typically using a fractionating column.
• It consists of naturally occurring hydrocarbons of various molecular weights and
may contain miscellaneous organic compounds.[1]
• The name petroleum covers both naturally occurring unprocessed crude oil
and petroleum products that are made up of refined crude oil.
• A fossil fuel, petroleum is formed when large quantities of dead organisms,
mostly zooplankton and algae, are buried underneath sedimentary rock and
subjected to both intense heat and pressure.
PROCESS FOR FORMATION OF CRUDE OIL BENEATH ROCKS
Petroleum occurs in a Reservoir Rock which are sedimentary and have:

✓ fluid holding capacity (Porosity) and

✓ fluid transmitting capacity (Permeability).

✓ Example: Sand, Sandstone, Grit, limestone, dolomite, etc.

The upward migration of the fluid from Reservoir Rock is prevented by an upper
stratum called cap rock like clay, shales, granite or marble, having low permeability.

The probable processes by which the degradation of source material takes place are:

✓ Anaerobic bacterial action

✓ Low temperature cracking in presence of clay and mineral catalysts
✓ Irradiation by radioactive material associated with sedimentary rocks.
 PETROLEUM CLASSIFICATION
Petroleum is classified into three types based on variation of chemical
nature of crude oil found in the earth:
i) Paraffinic-base type crude oil, which on distillation leaves a white
residue of solid paraffin wax: It contains saturated hydrocarbons
from CH4 to C35H72 and little amount of naphthalenes and
aromatics.
ii) Asphaltic-base type crude oil, which yields a black & lustrous
residue of asphalt: It contains mainly cycloparaffins or
naphthalenes with smaller amount of paraffins and aromatic
hydrocarbons.
iii) Mixed-base type crude oil, which yields a residue both wax &
asphalt: It contains both paraffinic and asphaltic hydrocarbons and
are generally in the form of semi-solid waxes.
Petroleum Refining: The Mother Industry

TRANSPORT

PETRO- PETROLEUM CHEMICALS

CHEMICALS REFINING & FERTILIZERS

ENERGY
What is Crude Oil & Crude Oil Refining?
• Crude oil, also known as black gold, is a thick, dark brown or greenish flammable liquid,
which is found in the upper strata of some regions of the Earth's crust
• It is a complex mixture of various hydrocarbons, (mainly, alkanes), along with trances of
other chemicals and compounds (e.g. Sulphur)
• When extracted from underground, it ranges in density from very light to very heavy and
in color, from yellow to black
• Crude oil can be categorized as either "sweet crude" (where the sulphur content less than
0.5%) or "sour crude" (where the sulphur content is at least 2.5%)

• Crude oil must undergo several separation

processes so that its components can be obtained
and used as fuels or converted to more valuable
products
• The process of transforming crude oil into finished
petroleum products (that the market demands) is
called crude oil refining.
An Oil Refinery
 Composition of Crude Petroleum
Mixture of different types of hydrocarbons

Paraffins CnH2n+2 normal straight chain

saturated compounds
Olefins CnH2n (mono-) single bonded straight chain
CnH2n (di-) double bonded straight chain
unsaturated compounds
Naphthenes CnH2n ring structure
saturated compound
Aromatics CnH2n-6 ring structure having benzene molecule
unsaturated compound
nitrogen sulfur
oxygen

metallic compounds – vanadium,

other contents iron, nickle, arsenic
So… What is Crude Oil?
Fill in the blanks

1. Crude Oil is a resource made of the remains of

that were alive millions of ago.

2. We for it and it from deep underground.

3. Many materials on which modern life depends are produced by crude oil, such
as ___________, lubricants, , detergents.

4. Crude Oil is made of lots of ____________ of different lengths. ______ _______

separates these.
So… What is Crude Oil?
Fill in the blanks

Crude Oil is a finite resource made of the remains of organisms that were alive
millions of years ago.

We drill for Crude Oil and extract it from deep underground.

Many useful materials on which modern life depends are produced by crude oil,
such as solvents, lubricants, polymers, detergents.

Crude Oil is made of lots of Hydrocarbon of different lengths. Fractional

Distillation separates these.
The Science
Game
Your category is…

Fractional Distillation
Starter:

Write a sentence about fractional

distillation

You have 2 minutes

Waiting for you to
write….
Is your answer is listed here?

It’s a branch of mathematics X

It’s made from water X

It produces crude oil X

Unfortunately, that’s not right. Let’s find out what is…

Well Done if your answer is listed here…

It’s used to break crude oil into useful products ✓

It happens in a fractionating tower ✓

The residue left (bitumen) is used for building roads ✓

It involves hydrocarbons ✓
 So… What is Fractional Distillation?
Fill in the blanks:
So… What is Fractional Distillation?
Fill in the blanks on your worksheet
1. is the process by which______ ___ is split
into different, more useful .

2. The can be to produce and

(feedstock) used in the industry.

3. The majority of _______ produced are hydrocarbon chains called

_______.
 So… What is Fractional Distillation?
Fill in the blanks:
So… What is Fractional Distillation?

Fractional distillation is the process by which crude oil is split into

different, more useful fractions.

The fractions can be processed to produce fuels and molecules

(feedstock) used in the petrochemical industry.

The majority of products produced are hydrocarbon chains called

alkanes.

(We mean fractions of crude oil, not fractions used in mathematics)

What are
crude oil
fractions?

Crude Oil

Fractions
A Fractional Distillation Column
 Fractional Distillation
In a fractionating column, the crude oil is heated to about 350 to 400°C in an iron
retort, whereby all volatile substances (except asphalt or coke) are 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 distances.
Each tray is provided with small chimney covered with a loose cap.

When the vapours of the oil go up in the fractionating column, they become
gradually cooler and get condensed at different heights of column.

The fractions have stronger intramolecular forces if they are longer chains, and
weaker if they are shorter chains.

This means that the shorter chains evaporate first and reach the top of the tower
where they condense, the longer chains stay towards the bottom of the tower.

The shorter the hydrocarbon chain, the lower the boiling point and viscosity, the
easier it flows and ignites.

The longer the hydrocarbon chain, the higher the boiling point and viscosity, it
flows and ignites less easily.
 Typical Products from Refinery

PRODUCTS
FUELS LUBES

LPG GASOLINE / NAPHTHA AUTOMOTIVE OILS RAIL-ROAD OILS

KERO / ATF DIESEL MARINE OILS INDUSTRIAL OILS

FUEL OIL BITUMEN

COKE GREASES

ATF: Aviation Turbine Fuel

 Different Different Exhaust
Automotive Fuels Constituents

Blending Formulation ?
Gasoline
Oxygenates
Olefins
Paraff./Napht.
Aromatics
Ö
L HC
+ Air Different Combustion NOx CO2
CO
C6H6 PAH
SO2 PM

Olefins
Aromatics
Different Naphtens
Crude Oils Paraffins Formulation ?
and Refineries
Diesel
* Source: www.awma.org/ACE2002/Forum/Topic3/walsh.ppt

47
 Crude Petroleum Refining
Separation of water (Cottrell's process)
 The crude oil from the oil well is an extremely stable emulsion of
oil and salt water. The crude oil is allowed to flow between two
highly charged electrodes, where colloidal water droplets coalesce
to form large drops, which is then separated out from the oil.

Removal of harmful impurities

 a) The presence of NaCI and MgCI in the crude oil can corrode the
refining equipment, hence these salts are removed by electrical
desalting and dehydration methods.
 b) The sulphur compounds present in the crude oil is removed by
treating oil with copper oxide, which results in the formation of
copper sulphide (solid), which is then removed by filtration.
 Crude Petroleum Refining
Thermal Cracking : Large hydrocarbon molecules are heated to a
high temperature and pressure, decomposing them to smaller
molecules – lower boiling point

Catalytic Cracking : A catalyst is used to decompose hydrocarbon

molecules at lower temperature and pressures than required for
Thermal cracking. The catalyst like aluminium silicate [Al2(SiO3)] or
alumina [A12O3] used in cracking gives higher yield and better
quality of gasoline. This process yields gasoline of improved anti-
knock property. It can be fixed bed or moving bed catalytic cracking.

Polymerization : A process of converting unsaturated olefins into

heavier and stable compounds
 Crude Petroleum Refining
Alkylation : In the presence of a catalyst, olefins combines with
iso-parafins to produce branched chain iso-parafins
Isomerisation : Isomers are produced having same chemical
formula but with different properties. 95% pure iso-parafins give
improved octane ratings in the range 93 – 107.
Reforming : Converts low anti-knock quality into high anti-knock
quality hydrocarbons
Blending : Method to obtain a product of desired quality by
mixing certain products in some suitable proportion
 Products of refining Process
fuel gas

propane / butane

light / heavy naptha

kerosene

light gas oil

heavy gas oil, lubricating oils

vacuum gas oils

tar, asphalt, coke, residue

Where is Gasoline & Diesel here?

 Products of refining Process
fuel gas

propane / butane

light / heavy naptha (Gasoline)

kerosene

light gas oil (diesel)

heavy gas oil, lubricating oils

vacuum gas oils

tar, asphalt, coke, residue
 Products of Refining Process
Sr Fraction Apprx BP Description Typical uses
No (OC)
Fuel gas -160 to - Natural gas is found dissolved in petroleum An alternative
44 under earth surface in oil and gas bearing Automotive fuel, refinery
areas. It is made up of paraffin compounds fuel
1
methane, a small amounts of propane,
ethane, butane and other light
hydrocarbons.
Propane - 40 Propane, butane and some other light An alternative
2 hydrocarbons after separation from natural Automotive fuel, cooking
gas, if stored under pressure, form liquid gas fuel
Butane -12 to 30 which is called liquid petroleum gas (LPG). Blended with motor
3 LPG is supplied in containers under gasoline to increase its
pressure above 10 bar. volatility
Light 0 to 150 Gasoline is the primary and lightest Major spark-ignition
Naptha product of this fraction. All materials boiling engine fuel,
4
upto 200 deg C is generally considered as Motor gasoline for
gasoline. It consists of more than 40 types catalytic forming
Heavy 150 to of hydrocarbons. Its specific gravity lies in Catalytic reforming fuel.
5 Naptha 200 the range of 0.7 to 0.78. This covers most Blended with light gas oil
of the fuels used for Spark-Ignition engines. to form jet fuels
 Products of Refining Process
Sr Fraction Apprx Description Typical uses
No BP
(OC)
Kerosene 200 to Kerosene is heavier than gasoline. Its Domestic – lamps &
6 300 specific gravity ranges from 0.78 to 0.85. stoves,
aviation fuels
Light gas 200 to Diesel oils lie between kerosene and Furnace fuel oil,
oil 315 lubricating oil. These cover a wide range Diesel fuel for
7
of specific gravity and boiling range. compression ignition
engines
Heavy gas 215 to It is similar to diesel fuel in specific gravity Industrial fuels, Feed for
oil 425 and distillation range but their composition catalytic cracking
8 varies in a range wider than diesel.
Lubricating These are made up of heavy distillate of For lubrication purposes
oils petroleum and residual oil.
Vacuum 425 to Feed for catalytic
9
gas oil 600 cracking
Pitch > 600 Tar and asphalt are solid or semi-solid Used as solid industrial
10 undistilled products of petroleum. fuel.
Petroleum coke.
Products of Refining Process: Lubs

Composition
Boiling
Sn. Name of the fractions of Hydrocarbons Uses
range (OC)
.

Used as lubricants
1. Lubricating oil - C17 to C20

Used in medicines and

2. Petroleum jelly (Vaseline) - - cosmetics

Paraffin wax - Used in candles, wax paper,

3. C20 to C28 boot polish, etc

4. Grease - - Used as lubricants.

Used for making roads, water

5. Asphalt or bitumen Above 400°C C30 and above proof roofing, etc
Fractions
What do you notice about these fractions?
Can you spot a pattern?
Can you write a method to predict how many hydrogens for a given number of carbons?

Molecule Formula
Propane C3H8
Kerosene C6H14
Petrol C13H25
Diesel C16H34
Check your prediction
(complete the table)

Molecule Carbons Formula

Methane C
Ethane C2
Propane C3
Butane C4
Pentane C5
Check your answers
The rule is CnH2n+2

These are known as Alkanes

Molecule Carbons Formula

Methane C CH4
Ethane C2 C2H6
Propane C3 C3H8
Butane C4 C4H10
Pentane C5 C5H12
Why is fractional distillation important?

Fractions are used for many purposes, but mostly,

hydrocarbons make very good fuels.
Quick Quiz
Which of these is more viscous?

a b
Which of these is more flammable?

a b
Which of these is has a lower boiling point?

a b
Which of these is a gas at room temperature?

a b
Which of these is a wax used in cosmetics?

a b
Which of these would travel highest in a
fractionating tower?

a b
Put these in the right order of size (S to L)?

Pentane
Methane
Butane
Ethane
Propane
Put these in the right order of size (S to L)?

Methane
Ethane
Propane
Butane
Pentane
 Fuel Properties

high energy density high thermal stability good fire safety

Low deposit forming tendency

good combustion quality

FUEL
low pollution tendency
compatibility with material

low toxicity easy handling, transportability,

easy on-board storage

Fuel must possess certain physical, chemical and combustion properties

to make it worthy for an I C Engine Combustion
 Fuel Properties: Calorific Value
Calorific value of a fuel is "the total quantity of heat liberated, when a unit mass (or
volume) of the fuel is burnt completely.“

Units of heat:
(1) 'Calorie' is the amount of heat required to raise the temperature of one gram of water
through one degree Centigrade (15-16°C).
one calorie is equal to approximately 4.2 (4.184) joules.
(‘Joule’ is the work done (energy transferred) on an object when a force of1 N acts on it
and moves it for a distance of 1 m in the direction of the force)
(2) "Kilocalorie" is equal to 1,000 calories. It may be defined as 'the quantity of heat
required to raise the temperature of one kilogram of water through one degree
Centigrade. Thus: 1 kcal = 1,000 cal
(3) "British Thermal unit" (B.T.U.) is defined as "the quantity of heat required to raise the
temperature of one pound of water through one degree Fahrenheit (60-61°F). This is the
English system unit.
1 B.T.U. = 252 cal = 0.252 kcal; 1 kcal = 3.968 or 4 B.T.U.

70
 Fuel Properties: HCV & LCV
Higher or gross calorific value:
 Usually, all fuels contain some hydrogen and when the calorific value of hydrogen-
containing fuel is determined experimentally, the hydrogen is converted into steam.
 If the products of combustion are condensed to the room temperature (15°C or 60°F),
the latent heat of condensation of steam also gets included in the measured heat,
which is then called "higher or gross calorific value".
 So, gross or higher calorific value (HCV) is "the total amount of heat produced, when
unit mass/volume of the fuel has been burnt completely and the products of
combustion have been cooled to room temperature"(i.e., 15°C or 60°F ).

Lower or net calorific value (LCV)

 In actual use of any fuel, the water vapour and moisture, etc., are not condensed and
escape as such along-with hot combustion gases. Hence, a lesser amount of heat is
available. So, net or lower calorific value (LCV) is "the net heat produced, when unit
mass /volume of the fuel is burnt completely and the products are permitted to
escape".
 Net calorific value= Gross calorific value - Latent heat of condensation of water vapour
produced = GCV - Mass of hydrogen per unit weight of the fuel burnt x 9 x Latent heat
of condensation of water vapour. 71
Fuel Properties: Dulong’s Formula for HCV & LCV

Dulong's formula for calorific value from the chemical composition of fuel is :

• HCV = 1/100 [8,080 C + 34,500 (H – O/8)+ 2,240 S] kcal/kg

• where C, H, O and S are the percentages of carbon, hydrogen, oxygen and sulphur
in the fuel respectively. In this formula, oxygen is assumed to be present in
combination with hydrogen as water, and

• LCV = [HCV - 9H/100 x 587] kcal/kg = [HCV - 0.09 H x 587] kcal/kg

• This is based on the fact that 1 part of H by mass gives 9 parts of H2O, and latent
heat of steam is 587 kcal/kg.

72
Theoretical calculation of calorific value
• Elements always combine in definite proportions to give. the products. For
example 12 gm of carbon combines with 32 gm of oxygen to give 44 gm of CO2
C + O2 CO2
12 32 44
• Similarly, 4 gm of hydrogen combines with 32 gm of oxygen to give 36 gm of H2O.
2 H2(g) + O(g) 2H2O(g)
4 32 36

• At STP (273 K, l atm) one mole of all gases occupy a volume of

22.4litres. Hence at S.T.P. 22.4 liters of CO2 will have a weight of 44 gm,
its molecular weight.

• Air contains 21 % of oxygen by volume and 23 % of oxygen by weight,

Hence 1 m3 of oxygen will be supplied by
1 x l00 = 4.76 m3 of air
21
• Similarly, 1 kg of oxygen will be supplied by
lxl00 = 4.35 kg of air.
23
73
• Molecular weight of air is 28.94 mol-1.

• Minimum oxygen required = (Theoretical O2 required) - (O2 present

in fuels).

• The mass of flue gas is calculated by balancing the carbon in the fuel
and the carbon in the flue gas.

• Minimum O2 required is calculated on the basis of complete

combustion of fuel. If as a result incomplete combustion or CO is
formed then O2 is calculated for the conversion of CO to CO2.

• If the fuel contains both O2 and H2, the amount of hydrogen and
oxygen may be present in the form of as H2O, which is a non-
combustible substance. The remaining available hydrogen takes part
in the combustion reaction.
2 H2(g) + O(g) 2H20

74
• 32 gm of oxygen combines with 4gm of hydrogen, Hence 1 part of hydrogen
combines with 8 parts of oxygen.

• Hence, theoretical amount of oxygen required for complete combustion of 1

kg of fuel is given by the equation,
{32/12 x C + 8[H – O/8] + S} kg

C, H and S are masses of carbon, Hydrogen and sulphur respectively per kg

of the fuel. Since 1 kg of air-contains 23%of oxygen by weight, the amount
of air required theoretically to burn 1 kg of fuel completely is given by
equation.
100/23 {32/12 x C + 8[H – O/8] + S} kg

75
• According to Dulong's formula, the theoretical calculation of calorific
value is,
1/100 [8080C + 34500 (H – O/8) + 2240S] Kcal/kg

• Where C, H, O and S represent the % of the corresponding elements in the

fuel. It is based on the assumption that the calorific value of C, H and S
are found to be 8080, 34500 and 2240 kcal, when 1 kg of the fuel is burnt
completely.

• However, all the oxygen in the fuel is assumed to be present in

combination with hydrogen in the ratio H:O as 1:8 by weight.

• NCV (or) LCV = [HCV – 9/100H x 587] kcal.kg

76
Theoretical calculation of minimum air requirement for combustion of a fuel

• Combustion is the process of burning any combustible substance in the presence of oxygen, which
liberates energy in the form of heat and light. For efficient combustion, it is essential that the fuel
must be brought into intimate contact with sufficient quantity of air or oxygen.

• The combustible substance usually present in fuels, which enter into the combustion, are mainly C,
H, S and O. But N, CO2 and ash are incombustible matters present in the fuel, do not take any
oxygen during combustion.

• For the complete combustion of a given quantity of fuel can be calculated by considering the
following point. Substances always combine in definite proportions, which are determined by the
molecular weights of the substances.

77
 i) Combustion of carbon
• C + O2 CO2
12 32 44 (by weight)

• 12 parts by weight-of carbon requires 32 parts by weight of oxygen for

complete combustion. 'C' parts by weight of carbon requires == 32 C /12 ==
2.67 C

• (H- 0/8) parts by weight of hydrogen requires = (H - O/8) X 32

4
= 8 (H- O/8)
ii) Combustion of hydrogen
• . When oxygen is present in the fuel, it always combines with hydrogen. The
combined hydrogen does not take part in combustion reaction. Therefore,
the quantity of combined hydrogen must be deduced from the total hydrogen
in the fuel.
2H2 + O2 2H2O
2 2 36 (by weight)

78
• 4 parts by weight of H2 requires 32 parts by weight O2 (or) 2 parts by
volume of H2 require 1 part by volume of O2
• There fore ‘H’ parts by weight of hydrogen require 32x H parts by weight
of O2. 4

iii) Combustion of carbon monoxide

• CO + ½ O CO2

• 28 16 (by weight)

• 1 0.5 (by volume)

• 1 volume of CO requires 0.5 volume of oxygen.

79
 iv) Combustion of sulphur
• S + O2 SO2
32 32 (by weight)
1 1 (by volume)
• 1 volume of 'S' requires 1 volume of oxygen.

v) Combustion of methane
• CH4 + 2O2 CO2 + 2 H20
16 64 (by weight)
1 2 (by volume)

80
Problems For the calculation of Calorific value

• Calculate the gross and net calorific values of a coal sample having
the following composition C = 80%; H = 7%;O = 3%; S = 3.5%; N
= 2.5% and ash 4.4%

• Solution
(I) G.C.V = 1/100[8080*%C+34500(%H - %O/8)+2240*%S] kcal/kg
= 1/100[8080*80+34500(7 - 3/8)+2240*3.5] kcal/kg
= 8828.0 kcal/kg

(II) N.C.V = G.C.V – [0.09H*587] kcal/kg

= 8828 – [0.09*7*587] kcal/kg
= 8458.2 k cal/kg

81
Fuel Properties: Knocking in Gasoline Engines
• Knocking is a kind of explosion due to rapid pressure rise occurring in an IC engine.
• In a petrol engine, a mixture of gasoline vapour and air is compressed and ignited by
an electric spark. The products of oxidation reaction (combustion) increases the
pressure and pushes the piston down the cylinder.
• If the combustion proceeds in a regular way, there is no problem in knocking. But in
some cases, the rate of combustion (oxidation) will not be uniform due to unwanted
chemical constituents of gasoline. The rate of ignition of the fuel gradually increases
and the final portion of the fuel-air mixture gets ignited instantaneously producing an
explosive sound known as "Knocking".
• Knocking property of the fuel reduces the life & efficiency of engine. So, a good
gasoline should resist knocking.
• The knocking tendency of fuel hydrocarbons mainly depends on their chemical
structures. The knocking tendency decreases in the following order:
Straight chain paraffins> Branched chain paraffins> Cycloparaffins > Olefins > Aromatics.

82
Fuel Properties: Knocking in Gasoline Engines
Improvement of antiknock characteristics
 The octane number of gasoline can be improved by
(i) blending petrol of high octane number with petrol of low octane number, so
that the octane number of the latter can be improved.
(ii) the addition of anti-knock agents like Tetra-Ethyl Lead (TEL).

LEADED GASOLINE (ANTI-KNOCK AGENT)

• The anti-knock properties of a gasoline can be improved by the addition of

suitable additives. Tetraethyl lead (TEL) or (C2H5)4 Pb is an important additive
added to petrol. Thus, the fuel containing TEL is called leaded gasoline.

• TEL reduces the knocking tendency of hydrocarbon. Knocking follows a free

radical mechanism, leading to a chain growth which results in an explosion. If the
chains are terminated before their growth, knocking will cease. TEL decomposes
thermally to form ethyl free radicals, which combine with the growing free
radicals of knocking process and thus the chain growth is stopped.
83
 Fuel Properties: Knocking in Gasoline Engines
Disadvantages of using TEL:
• When the leaded gasoline is used as a fuel, the TEL is converted to lead oxide and metallic lead.
This lead, deposits on the spark plug and on cylinder walls which is harmful to engine life. To
avoid this, small amount of ethylene dibromide is added along with TEL. This ethylene
dibromide reacts with Pb and PbO to give volatile lead bromide, which goes out along with
exhaust gases.
• Such pollutants are not only emitted from gasoline additives, but also from battery factories
and non-ferrous smelters.
• Infants, children & Sr Citizens are especially susceptible.
• Lead pollution may lead to:
• nerve damage in fetuses and infants
• learning deficits
• lowered Intelligence Quota (IQ)
• Sterility
• neurological impairment, e.g. retardation and behavioral disorders.
Moreover, Lead is harmful to Aftertreatment Devices, where noble metal are used.

Alternatives to TEL:
Nowadays oxygenates, ethers & aromatic phosphates are used as antiknock agent because it
avoids lead pollution. 84
Fuel Properties: OCTANE NUMBER (or) OCTANE RATING in GASOLINE
• Octane number is introduced to express the knocking characteristics of Gasoline.
It has been found that n-heptane knocks very badly and hence, its anti-knock
value has been given zero. On the other hand, iso-octane gives very little
knocking and so, its anti-knock value has been given 100.

• Thus, octane number is defined as 'the percentage of iso-octane present in a

mixture of iso-octane and n-heptane.‘

• Iso-octane (Octane number = 100)

• CH3 – CH2 – CH2 – CH2 – CH2 – CH2 - CH3
• n - heptane (Octane number = 0)

85
Fuel Properties: CETANE NUMBER (or) CETANE RATING in DIESEL
• Cetane number is introduced to express the knocking characteristics of diesel. Cetane has
a very short ignition lag and hence its cetane number is taken as 100. On the other hand, 2-
methyl naphthalene has a long ignition lag and hence its cetane number is taken as zero.
• CH3 – (CH2)14 – CH3 CH
3

• n-cetane (hexa decane) (cetane number = 100)

• 2-methyl naphthalene (cetane number = 0)

• Thus, Cetane number is defined as "the percentage of hexa decane present in a mixture of
hexa decane and 2-methyl napthalene, which has the same ignition lag as the fuel under
test".
• The cetane number decreases in the following order:
n-alkanes > Cycloalkanes > alkenes >branched alkanes >aromatics

• The cetane number of a diesel oil can be increased by adding additives called dopes
Like Ethyl nitrate, Iso-amyl nitrate.
86
Driving Forces
for fuel quality requirements
Technology

mixture preparation
Legislation

(physical properties of fuel)

Ignition
(chemical properties of fuel)
combustion
(Chemical properties
of fuel)
 Diesel Engines
Fuel Economics
Cost & Availability High
of Fuel Specific power

Improved Highest Torque

Performance
Fuel & load carrying
economics capacity

High Fuel Economy

& Low Increased
maintenance cost engine life
Diesel Fuel Quality
parameters
viscosity
Properties
volatility affecting
mixture density
formation

Properties flash
affecting point
ignition
fire point

Cetane
number
Properties
affecting aromatic
combustion content
sulfur
content
 Diesel Fuel Properties
Cetane Flashpoint Viscosity Cloud Point Lubricity
Number ▪Measures the ▪A measurement of ▪Corresponds to the ▪The ability of a
temperature at the resistance to temperature at fluid to minimize
▪Measures the
which the vapors flow of a liquid which fuel first friction between,
readiness of a fuel
above the liquid can ▪Thicker the liquid, starts to crystallize and damage to,
to auto-ignite.
be ignited. higher the (forms a faint cloud surfaces in relative
▪ High cetane
▪Primarily used to viscosity in liquid) when motion under
number means the
determine whether ▪Water (lower cooled. loaded conditions.
fuel will ignite
a liquid is viscosity) vs. ▪Pour Point: ▪Diesel fuel
quickly at
flammable or Vegetable Oil temperature at injection
the conditions in
combustible (higher viscosity) which fuel thickens equipment relies
the engine (does
▪Generally any liquid ▪diesel fuel = 1.3 – and will not pour on the lubricating
not mean the
with a flash point 2.4 mm2/s ▪Cold Filter Plug properties of the
fuel is highly
below 38°C is ▪diesel fuel = 1.9 – Point (CFPP): The fuel.
flammable or
flammable. 4.1 mm2/s temperature at ▪Biodiesel has
explosive).
▪flash point for ▪Biodiesel = 4.0 – which fuel crystals shown higher
▪Most fuels have
diesel : ~52°C 6.2 mm2/s have agglomerated lubricity properties
cetane numbers
▪flash point for bio- Soybean based in sufficient than petroleum
between 40 and
diesel : > 130°C ▪biodiesel = 4.0 - amounts to cause a diesel
60.
4.5 mm2/s. test filter to plug.
 Diesel Fuel Properties
Influence of fuel properties on diesel performance
Parameter Change Influence
Cetane no CO, HC, NOx
BSFC
Density Smoke, power
HC,CO,PM

Viscosity Smoke

Aromatic Cetane no
content

Sulfur PM , SO2
content
Effect of Density on Diesel Emissions

➢Diesel fuel is supplied by the injection

pump on volumetric basis
➢Increase in fuel density increases injected
mass of fuel thus making an air-fuel mixture
richer
➢SOF in particulates increases with increase
in density.
Effect of Density on Diesel Emissions density

HC
CO
HC

CO
NOx

NOx
PM

PM

density
Effect of Viscosity on Diesel Emissions
Viscosity is a measure of fuel’s resistance to flow
Spray quality is influenced by the viscosity
• low viscosity allows bulk flow in pumping.
• low viscosity cause undue wear of injection system parts
• high viscosity is required for lubrication
• high viscosity may cause cold starting problem

Increase in viscosity cause –

• increase in smoke, unburnt HC, soot decrease in NOx
• little influence on SOF
Effect of Volatility on Diesel Emissions

Evaporation and mixing of diesel fuel with air is

essential for ignition and burning
Evaporation and burning occurs inside the combustion
chamber. Therefore, low volatility is OK for diesel
compared to gasoline
Low volatility helps less fuel boil-off from the injectors
during later part of expansion stroke, thus low HC
Flash and Fire point
Flash point is the temperature at which a flammable liquid produces a
mixture of its vapor and air, which would ignite to give a visible flash when
brought in contact with an open flame
Flash point > 65 deg C

Fire point is the temperature at which flash will sustain as steady flame
for at least five seconds

Flash and fire points indicate the temperature below which the
diesel fuel can be handled safely without fear or danger of fire.
Effect of Cetane No. on Diesel Emissions

Cetane number of diesel fuel is its ability to autoignite

Cetane number and ignition delay are inter-related. Increase
in cetane no. shortens ignition delay
Increase in cetane number cause –
• increased unburnt HC, PM (SOF)
• decreased soot and smoke
• NOx is relatively insensitive to change in cetane number
• reduced noise.
Effect of Cetane Number cetane
number
on Diesel Emissions

HC
CO
HC

CO
NOx

NOx
PM

PM

Cetane number
Effect of Aromatic Content
on Diesel Emissions

aromatic content varies inversely with cetane number

increase in aromatic content cause –
• considerably increased unburnt HC, PM (SOF), CO
• relatively less effect on NOx
Effect of Aromatic Content aromatic
content
on Diesel Emissions

HC
CO
HC

CO
NOx

NOx
PM

PM

Aromatic content
H/C ratio

H/C ratio flame temp NOx

Aromatics - H/C ratio

PAH - H/C ratio ………… NOx
Influence Of Diesel Properties On
Stages Of Combustion
injection evaporation Pre- Start of End of
combustion combustion combustion

density ✓ ✓ ✓
cetane ✓ ✓ ✓
no
volatility ✓ ✓ ✓ ✓ ✓
viscosity ✓
Global Demand for Refined Products
Future Issues Facing Refiners

(Energy Efficiency
Improvement)
 Implications for Refiners
• Product balance shifts strongly towards diesel
• Configuration changes required to meet demand and handle
heavier crudes
• Potential over supply of gasoline
• CO2 reduction mandates
• Emerging Technologies for Secondary Processing
• Look for diversification opportunity in petrochemicals
• Energy efficiency a must
Specific Challenges in Indian Petroleum Refining
Industry / Technology Drivers
• Dismantling of APM (Administered Pricing Mechanism) /
Competitive Scenario
• Changing Products Demand Pattern
• Stringent Environmental Regulations
• Bottom of the Barrel Upgradation
• High crude price & deteriorating Crude Oil Quality
• Emergence of Natural Gas/ Alternative Fuels
India’s Auto Fuel Policy (2003)
 Background
GoI Constituted an Experts’ Committee under Chairmanship of Dr R A Mashelkar,
DG-CSIR in Sept.,2001 to Recommend an Auto Fuel Policy for the Country
including Major Cities with following Objectives :
➢ To Devise a Road map for its Implementation.
➢ To recommend Suitable Auto Fuels and Their Specifications Considering
Availability & Logistics of Fuel Supplies, Processing Economics of Auto Fuels,
Possibilities of Multi-Fuel Use in Different Categories of Vehicles.
➢ To recommend Attributes of Automobile Technologies, Fiscal Measures for
Ensuring Minimization of Social Cost of Meeting a Given Level of Environment
Quality and Institutional Mechanisms for Certification of Vehicles & Fuels.
➢ Also Recommending Monitoring & Enforcement Measures.
➢ Auto Fuel Policy Announced in Oct 2003.
➢ Investment Requirement Estimated ~ Rs 50,000- 60,000 Crores.
 Salient Contents of Auto Fuel Policy
Road Map for New Vehicles

•Road Map for Vehicular Emission Norms for New Vehicles(4-Wheelers)

•Road Map for Vehicular Emission Norms for New Vehicles(2&3-Wheelers)
•Road Map for Reducing Pollution from In-use Vehicles (For Entire Country)
•Road Map for Reducing Pollution from In-use Vehicles (For NCT-Delhi)
• Road Map for Reducing Pollution from In-use Vehicles (For 11 Cities)
•Bharat Stage-II Emission Norms.
•Euro-III Equivalent Emission Norms.
•Euro-IV Equivalent Emission Norms.
•Emission Norms & Deterioration Factors (DF) for 2&3-Wheelers.
•Indian Petrol & Diesel Specifications Required to Meet BS-II Emission Norms.
•Indian Petrol & Diesel Specifications Required to Meet Euro-III Equivalent Emission Norms
•Indian Petrol & Diesel Specifications Required to Meet Euro-IV Equivalent Emission Norms
•Proposed Specifications for CNG as Auto-Fuel in India.
•BIS Specs for Auto LPG ( IS 14861-2000).
Previous Emission Norms in India
Vehicle Category Existing Emission Effective date
norms
2W BS III / BS IV 1st April, 2010 /
1st April, 2016
3W BS III / BS IV 1st April, 2010 / 1st
April, 2016
4W ≤ 3.5T *BS III / BS IV 1st April, 2010

4W > 3.5T *BS III / BS IV 1st April, 2010

Agricultural Tractor / Stage IIA / CEV- 1st April, 2010

CEV stage III 1st April, 2011
From 1st April 2010 BS IV applicable to NCR+13 cities & BS III nationwide.
Today, it is applicable to around 50 cities.
From 1st April 2017 BSIV is applicable nationwide.
Present Emission Norms in India

Vehicle Proposed Emission Effective date

Category norms
2W BS VI 1st April, 2020
3W BS VI 1st April, 2020
4W ≤ 3.5T BS VI 1st April, 2020
4W > 3.5T BS VI 1st April, 2020
Agricultural Stage IV / Stage V 1st April, 2022
Tractor / CEV 1st April, 2024
 Road Map for Reducing Pollution
from In-use Vehicles
For the Entire Country

New PUC Checking System for All Categories of Vehicles

•To be put in place by 1 April, 2005.
Inspection & Maintenance (I&M) for All Categories of Vehicles
•To be put in place by 1 April, 2010.
Performance Checking System of Catalytic Converters and Conversion Kits
Installed in Vehicles.
•To be put in place by 1 April. 2007.
Augmentation of City Public Transport System
•Finalisation of plans by the State Governments / Local Authorities - Not later
than 1st April, 2005
 Indian Gasoline Specifications
S.No Characteristics Unit Bharat Stage II Bharat Stage III Bharat Stage IV
1 Density 15 0C Kg/m3 710–770 720–775 740–754
2 Distillation

a) Recovery up to 70 °C(E70) %Volume 10–45 10–45 10–45

b) Recovery up to 100 0 C (E100) %Volume 40–70 40–70 40–70
c) Recovery up to 180 0 C (E180) %Volume 90 - -
3
d) Recovery up to 150 0 C (E150) %Volume - 75min 75min
e) Final Boiling Point (FBP), Max °C 210 210 210
f) Residue Max %Volume 2 2 2

Research Octane Number (RON),

4 88 91 95
Min
Anti Knock Index (AKI)/ MON,
5 84 (AKI) 81 (MON) 85 (MON)
Min
6 Sulphur, Total, Max % mass 0.05 150 mg/Kg 10 mg/Kg
7 Lead Content(as Pb), Max g/l 0.013 0.005 0.005
Reid Vapour Pressure (RVP),
8 Kpa 35–60 60 60
Max
Benzene, Content, Max -
9 a) For Metros % Volume 3 1 1
b)For the rest 5
10 Olefin content, Max % Volume - 21 21
11 Aromatic Content, Max % Volume - 42 35<
Indian Diesel Specifications
S. No Characteristic BSII BSIII BSIV

1 Density Kg/m3 15 °C 820-800 820–845 833–837

2 Sulphur Content mg/kg max 350 50 10

48 51
3(a) Cetane Number minimum and / or 55
or and
3(b) Cetane Index
46 46

4 Polycyclic Aromatic Hydrocarbon - 11 6

5 Distillation
85
(a) Reco. Min. At 350 °C - -
95
(b) Reco. Min. At 370 °C - -
-
(c) 95%Vol Reco at 0 °C 360 345
Specifications for CNG as Auto-Fuel in India
IS 15918 : 2012
BIS Specs. for Auto LPG (IS 14861-2000)
S. No. Characteristics Requirement

(i) Vapour Pressure(gauge) @ 40oC., kPa

Min. 520*
Max. 1050
(ii) C5 Hydrocarbons & heavier,mol%,Max. 2.0
(iii) Dienes (as 1,3 Butadiene), mol%, Max. 0.5
(iv) Total Volatile Sulphur (after stanching),ppm,Max. 150
(v) Copper Strip Corrosion @ 40oC for 1 hour ,Max. Class 1
(vi) Hydrogen sulphide Pass test
(vii) Evaporation Residue , mg/kg , Max. 10.0
(viii) Free water content Nil**
(ix) Motor Octane Number (MON), Min. 88
(x) Odour Unpleasant &
Distinctive down to
20% Lower Explosive
Limit(LEL)***

*In Winter(1st Nov. to 15th Feb.), Vapour Pressure(gauge) @ 40oC requirement shall be minimum 700 kPa.
** Water content shall be determined at Refinery/ first dispatching location.
*** Product shall contain 20 ppm,min. Ethyl Mercaptan at first dispatching location
 Summary / Terms of Reference
➢ Report of Expert Committee of Govt. of India under Chairmanship of Shri Saumitra
Chaudhuri, Member Planning Commission - Prepared / Submitted (May 2014)
➢ Recommended Road-map for Auto Fuel Quality till 2025 for the Country (Taking into Account
Achievement under Auto Fuel Policy-2003)
➢ Recommended Suitable Mix of Automotive Fuels including NG and Its Specifications,
Considering Following:
a) Availability of Infrastructure and Logistics of Fuel Supplies,
b) Processing Economics of Auto Fuels, and
c) Improvement in Quality of Fuel vis-à-vis Improvement in Vehicle Engine
Technology
➢ Recommended Vehicular Emission Norms for Various Categories of Vehicles and Roadmap
for Their Implementation
➢ Recommended Use of Alternate Fuels to Minimise Impact on Environment
➢ Recommend Fiscal Measures for Funding Requisite Up-gradation of Oil Refineries, Logistics
and Removal of Inter-fuel Pricing Distortions
Summary / Status of Recommendations
of Auto Fuel Policy (2003)
Sl. No. Recommendations
BS-III/ BS-IV Auto Fuels
1
Use of CNG/ LPG in cities affected by high
2 vehicular population
Comprehensive programme for zero emission
vehicles to accelerate development of
3
alternative fuel vehicles (battery powered,
hydrogen and fuel cell)
Technologies for producing ethanol/bio fuels
4 from renewable energy sources and vehicles to
utilise these bio fuels
Replacement of existing PUC system to more
5
reliable computerised system
Inspection & Maintenance (I&M) system in 11
major cities and further extension throughout
6
the country
2015 Status
Coverage achieved is greater than
recommended
CNG extended to 60 cities; Auto LPG
expanded to ~ 350 cities having ~ 900
dispensing stations
Initiatives have been taken by MNRE, with
limited progress, while some initiatives have
also been taken by Department of Heavy
Industry
Minimum 5% ethanol blending has been
made mandatory, subject to availability of
ethanol
Computerized system may not have been
widely introduced across the country
- MORT&H and ARAI is looking into issues of
PUC and I&M - I&M model Centres to come
on PPP mode - End of life for vehicles is
being worked out
Summary / Status of Recommendations
of Auto Fuel Policy (2003) Contd.
Sl. No. Recommendations 2015 Status
OBD system for new vehicles in lieu of I&M OBD-II implemented in BS-IV vehicles
7
system from April 2013
Performance checking of catalytic converters and Not given effect to
8
conversion kits
Promoting public transport to improve urban road Some progress
9
traffic
Linking of vehicle insurance with Inspection and Not in place
10
Certification
Retrofitting old vehicles with new engines or Irregular
11 emission control devices. Developing incentives
for replacement of old polluting vehicle
System to check emission warranty of new Not ensured
12
vehicles
Random checking of CNG/ LPG kits, any other Irregular
13 emission control devices or retrofit engines for
emission performance
Notification of Fuel Economy Standards CO2 emission, fuel economy standards
14
for vehicles < 3500 kg has been notified.
Summary / Status of Recommendations
of Auto Fuel Policy (2003) Contd.

Sl. No. Recommendations 2015 Status

Levying higher motor vehicle tax on old Not in place
15
vehicles
Extending tank lorry locking system for Has been fully implemented
16
movement of products
Setting up of consumer pumps by transport Limited implementation through oil
17
companies operating public transport companies
Use of markers on commercial basis to Implemented but discontinued due to
18 detect and prevent adulteration circumvention. New markers under
development
Making oil companies accountable for Implemented
19 quality of fuels dispensed from their retail
outlets
Reporting of conversion of vehicles to CNG/ Not ensured
20
LPG to registering authority
 Salient Contents /Conclusions of Auto
Fuel Vision & Policy (2025)
• Present & Prospective Availability of BS IV & BS VI
Gasoline & Diesel
• Presently Not Enough BS IV Fuels Available for
Entire Country’s Needs
• Timely Completion of Ongoing Projects & Initiating
& Completing Some Others
• Significant Additional Investment Needed for BS VI
Automotive Fuels (Rs. 80,000 Crores)
 Salient Contents /Road Map of Auto Fuel
Vision & Policy (2025)
• Emission Norms for Passenger Cars, Light & Heavy Commercial & Goods
Vehicles Adapted from European Emission Norms for These Categories
• For 2 & 3 Wheelers Sizable Difference Between Euro IV & BS IV Norms
Proposed
• Gazette Notification Issued on 14th March 2014
• Transition to BS IV for Entire Country to be Completed by 1st April 2017
• Transition to BS VI for Entire Country to be Completed by 1st April 2020
• Encouragement for Use of Alternative Fuels (CNG, Auto LPG, Bio-diesel,
Electric / Hybrid Vehicles) Proposed
• Additional 50 Cities with BS IV Fuels by 2015 Over & Above 13 Cities
Covered in 2010 (Out of 50 Cities, 26 have already been Expanded)
Proposed BS VI Specifications for Motor
Spirit/Gasoline
Proposed BS VI Specifications for Motor
Spirit/Gasoline Contd.
Proposed BS VI Specifications for Diesel
Key Parameters: Comparison of Euro VI
and BS VI Gasoline Specifications
Key Parameters: Comparison of Euro VI
and BS VI Diesel Specifications
 Fuel Specification of Compressed Natural Gas
(CNG) for Automotive Purposes: IS 15958: 2012
Fuel Specification of Liquefied Petroleum Gas (LPG)
for Automotive Purposes: IS 14861: 2000
Proposed Conversion to BS VI by 1st April 2019
[Entire Country : 1st April,2020]
Investment Costs in Indian Refineries for Fuels’ Quality
Upgradation [Upto BH IV(Part)]
EMISSION NORMS INVESTMENT COST
(RS. IN CRORES)
INDIA 1996 TO INDIA 2000 9,500

INDIA 2000 TO BHARAT STAGE II 25,000

BHARAT STAGE II TO BHARAT STAGE III 11,000

BHARAT STAGE III TO BHARAT STAGE IV 18,500

TOTAL INVESTMENT 64,000

Source : CPCB Report on Fuel Quality by Dr Mukhopadhyay

 Investments Required by Indian
Refineries to Meet BS IV/VI Standards
 Technologies used in Indian Refineries for
Fuels quality Upgradation
ACID GAS SULPHUR PLANT TAIL
GAS TREATING
A
T LN
M ISOMERIZATION GASOLINE
T
HN
O REFORMER GASOLINE
W JET
Crude E JET/DIESEL
DIESEL
R JET/DIESEL
HGO HT

LVGO
V HCU
A LCO
C
T
O
W FCCG
HVGO GASOLINE
E VGO HT FCCU HDT
R
REFORMER JET/DIESEL HT
SR Coker / HCU/FCC
Visbreaker
LSFO
 Motor Spirit / Gasoline Quality Issues
▪ Lower Sulfur content
▪ Lower RVP
▪ Lower benzene & aromatics
▪ Lower olefin content
▪ Limited Oxygen content
• Environmental regulations on gasoline quality, which began with removal of lead from gasoline in the
seventies and eighties, were initiated in USA and then spread to other regions.
• Further regulations e.g. Clean Air Act Amendment (CAAA) sought to reduce ozone precursors.
• Following the world trend, the gasoline quality specification in India, too, has become very stringent. Newer
specifications on Sulfur, Benzene, aromatics and olefins are changing the face of refining industry gradually
and definitively.
• The production of gasoline meeting new specifications has been generally guided by Lead phase out, Lower
RVP, Benzene Content, Olefins Content, Oxygen Content & Sulfur Content.
 Major Technologies for Gasoline Production
Process Octane Sulfur Olefins Aromatics RVP Comments

FCC(Fluid 91-96 500- Upto Upto 40% High Requires S

catalytic 1500 45% for reduction & may
cracking) lower require olefin
olefins reduction in future
Reforming 89-102 Nil Nil 45-75% Requires Benzene
reduction & may
have aromatic
constraint
Isomerisation 85-91 Nil Nil Nil High Low cost Octane
improvement of LN
Alkylation 94-97 Nil Nil Nil Low Highest quality
gasoline
components
Etherification 114-118 Nil Nil Nil Low Constraints of max
oxygen content
spec
Technologies for Gasoline Pool Components
REFORMER

• Major technology for octane boost

• Constraints of Benzene and aromatic content
• Technological / operational change for overcoming the
constraints:
▪ Low pressure operation
▪ Change to CCR(Continuous Catalyst Regeneration) from
SR(Semi-Regenerative Catalytic Reformer)
▪ Pre-fractionation for Benzene Spec
▪ Integration with Isomerisation unit
▪ Option of extraction of Benzene (as a product) with the
choice of follow-up isomerisation
 Technologies for Gasoline
FCC (MAJOR TECHNOLOGY FOR MS)
•High Octane component
•Constraints of high S, olefins, high RVP for light olefins
•Technological/operational change for overcoming constraints:
➢Use of low ‘S’ crude, Hydrocracker bottom/ Hydrotreated feed for ‘S’ spec
➢Use of desulfurisation additives
➢Selective desulfurisation of FCC
➢Treatment of heart-cut of FCC in reformer
➢Use of FCC light olefins for production of TAME (additional RVP advantage)

FCC Fluid Catalyst Cracking

TAME: Tertiary-Amyl Methyl Ether
RVP: Reid Vapour Pressure
 Technologies for Gasoline
ISOMERISATION

▪ Ideal choice for upgrading light naphtha

▪ Popular due to simple and less expensive technology
▪ Used for saturation of benzene also
▪ Pt on Chlorinated alumina – most active catalyst
▪ Zeolite catalyst-based technology to be improved (more
activity required)
▪ Constraints of high RVP
 Technologies for Gasoline

ALKYLATION
• No unit in India yet (High LPG demand)
• Ideal Gasoline blend component
• Excellent for converting light olefins to MS grade
• Proven technology based upon HF / H2SO4 hazardous
• Solid acid-based process at development/demonstration stage
• Serious look-in expected in the scenario of NG replacing LPG.
 Benzene Management
▪ Feed fractionation and tuning of reformer
▪ Separation of benzene from refomate
▪ Hydrotreatment of a heart cut of reformate
➢ Low pressure hydrogenation
➢ Base metal catalyst or Noble metal catalyst (high Hydrogenation activity)
▪ Benzene saturation in Isom Unit
LN I
S Isomerate
Lt reformate
O M
C C
M S
HN R Saturated Lt
D Reformate P
U U Ben.
Sat O
Hy reformate O
L
 Sulfur Management
FCC gasoline - main source of ‘S’
FCC Feed Hydrotreatment
•High pressure and capital intensive
•May not be adequate
FCCG Desulfurisation
•Process for Selective Hydrotreatment
•Minimization of Octane loss
•Process for desulfurisation and simultaneous
octane gain
•Promotion of reactions like isomerisation
 FCCG Hydrodesulfurisation

Sulfur Reduction With Selective

Desulfurisation Catalyst

Corresponding Octane Loss

Major Parameters of Diesel Specifications
• Low sulfur

• Low aromatics / PAHs

• High cetane number

• Lower density

• Lower distillation end point

 Diesel Quality Issues
Future environmental regulations
demand reduction of sulfur to:
✓ Less than 10 ppm in diesel

For production of < 10 ppm ‘S’ diesel most

refractory ‘S’ compounds need to be removed:
✓ 4 or 6 MDBT, 4,6-DMDBT
✓ 3,6-DMDBT, 2,3-DMDBT
✓ 2,4,6-TMDBT
MDBT :Methyl Di-Benzo Thiophene
Technologies to Meet Diesel Specifications
High Pressure DHDT for Aromatic saturation and Cetane
improvement
➢Cetane increases with aromatic ring saturation
✓Maximum possible cetane improvement depends upon
feed quality
✓Selective opening of naphthenic ring can potentially give
additional cetane boost
➢Two stage unit with intermediate separation of liquid and
gases and Noble metal catalyst in second stage
➢Single stage units based upon non-noble metal catalysts
✓More popular due to tremendous activity increase
DHDT: Diesel Hydrotreating
Cetane Number for Different types of Compounds
 Diesel End Point Reduction
✓Reduction of 95% boiling point from 370oC to 360oC would
lead to loss of diesel yield
✓Heavy diesel, if processes in secondary processes, would load
the unit capacity and crack more towards lighter naphtha in
cracking units
✓Development / optimisation of catalyst systems in the existing
DHDS/DHDT units to convert this heavy diesel selectively to
lighter diesel would be most preferred solution.
Technologies for end Point Reduction
DHDT – MHC/Isom combination for end point reduction
➢ 95% boiling point has been reduced to 360oC
✓Adjusting the feed end point leads to yield loss

➢ Stacked bed of MHC catalyst or catalyst with isomerisation activity

can selectively convert the heavy end to diesel fraction
✓The cracking activity of MHC has to be finely adjusted for
restricting naphtha formation

✓Isomerisation catalyst has to be tolerant of S & N compounds

that would be present in the DHDS reactor.

Diesel Hydrodesulfurization (DHDS) / Hydrotreating (DHDT),MHC:Mild Hydrocracking

Use of Hybrid Catalysts for end Point Reduction

Feed
Mild hydrocracking
(MHC) for selective
HDS / HDT MHC cracking of heavy
CATALYST CATALYST end diesel, resulting
Product in End Point
Reduction
Feed
Isomerization of n-
HDS / HDT SELECTIVE paraffins for end
CATALYST ISOM CATALYST point reduction of
Product
diesel
Reduction of Diesel end Point with Hybrid
Catalyst (HDS / HDT + MHC)
Temp HDS/HDT+MHC = 345/360 deg C
16 15
Temp HDS/HDT+MHC= 345/375 deg C
Decrease in T95, deg C
14 Temp HDS/HDT+MHC= 345/380 deg C
Temp HDS/HDT+MHC= 345/390 deg C
12
Operating conditions 10
9.5
10 Press LHS H2/HC ratio
(bar) V (Nm3/m3)
8 (hr-1)
49 1.5 566
6 DELTA NAPTHA YIELD ~ + 2 wt%
4
2
2

0
(HDS/HDT + MHC) CATALYST
Reduction of Diesel end Point with Hybrid Catalyst
(HDS / HDT + ISOM)
Decrease in Increase in
Catalyst End Point Naphtha Yield (127
ºC-)
(ºC) (wt%)
HDS / HDT + ISOM1 4 2
HDS / HDT + ISOM2 8 3

Operating conditions
Temp Press LHSV H2/HC
(ºC) (bar) (hr-1) ratio
(Nm3/m3)
350 49 1.0 400
Ultra-low Sulfur Diesel Alternate Processes

Present hydrotreating processes are expensive for

desulfurization in the ultra low range due to:

➢ Higher consumption of H2
➢ Relatively large catalyst requirement
➢ Potentially high pressure systems

Cost effective alternate technologies are needed.

 Adsorption
Typical Reactive Adsorption based process (INDSORD)
✓ Feed stream is contacted with specially designed adsorbent in a hydrogen
environment
✓ The ‘S’ is removed from the sulfur compound by
✓ Cleavage of the C-S bond and adsorbed on the adsorbent
✓ The Adsorbent is regenerated by oxidation of ‘S’ to SO2 in presence of
air/nitrogen mixture
 INDSORD Process
Mechanism of Adsorption & Regeneration
+H
2

O2
Process Units Installed for Fuel Quality Improvements
Reasons to Consider Alternative Fuels
E
• Energy • Economy
• Environment
E E

• Energy Independence – produced from domestic sources.

• Emissions – some alternative fuels reduce vehicular emissions.
• Economy – some alternative fuels offer the potential to lower the
operating cost as well as running cost.
Existing & Emerging Technologies
❖Alternate fuels currently in use
• CNG
• LPG
• Alcohol

❖Emerging engine technologies & fuels

• Bio-fuels (Bio-Diesel, Bio-Butanol)
• Hydrogen
• Electric & Hybrid vehicles
• Fuel cells
Status/RoadMap of Alternate Liquid Fuels: Alcohol
Ethanol:

Methanol:
• NITI Aayog’s ‘Methanol Economy’ aims at 15% methanol blending in gasoline and 20%
DME (Di-methyl Ether, a derivative of methanol) in LPG for cooking gas.

Cost:
• Methanol is cheaper than Ethanol and Ethanol is cheaper than Gasoline.
Launch of E-20 Fuel by Hon’ble Prime Minister of India
Flex Fuel Policy to be Announced Soon in 2022
 Advantages of Alcohol as fuel
• Highly biodegradable.

• Can be generated from domestic sources – renewable.

• Promoter of rural economy.

• Contains 35% oxygen by weight, better cleaning than gasoline.

• Contains 80% lesser gum-forming compounds than gasoline.

• High Octane Fuel – better anti knock tendency.

• High Flame Speed – retard spark mechanism.

• When alcohols are burned, it forms more moles of exhaust gases, which gives higher pressure and more power in the expansion stroke.

• High LH – cooler intake process – increase vol eff - more power output.

• 10% ethanol blends reduce CO and HC emissions better than any other reformulated gasoline blend by as much as 25%. But slightly
high NOX (case study)

• Reduces CO2 level.

• Less NOx emissions – low flame temperature.

• Low sulphur content in the fuel.

 Disadvantages of Alcohol as fuel
• Drop in octane value – after water contamination, phase separation.
• Decreased shelf life of gasoline (blends).
• Alcohols have a low CV (almost half). Almost twice as much alcohol as gasoline must be burned to give the same energy output.
• Combustion of alcohols produce more aldehydes in the exhaust.
• It is corrosive on copper, brass, Aluminium, rubber and many plastics.
• Poor cold starting ability due to low vapour pressure and evaporation.
• Have poor ignition characteristics in general.
• Invisible flames – smokeless.
• Danger of storage tank flammability.
• Lower energy density than gasoline.
• Deposits and fouling are some effects of ethanol on fuel injection equipment.
• Leads to increased engine wear and tear due to low lubricity.
• Lower exhaust temperature take longer time to light off the catalyst.
• Possibility of vapour lock at high temperature. Ethanol increases overall fuel vapour pressure
• Sustained availability of ethanol is difficult.
• Higher ethanol blends require engine/vehicle modifications.
Properties of Gasoline and Alcohol Fuels

Air-
Energy Specific Heat of
Fuel Fuel RON MON
Density Energy Vaporization
Ratio
14.6 2.9 MJ/kg 0.36 MJ/kg 91-99 81-89
Gasoline 32 MJ/L
air
29.2 11.2 3.2 MJ/kg 0.43 MJ/kg 96 78
Butanol
MJ/L air
19.6 9.0 3.0 MJ/kg 0.92 MJ/kg 129 102
Ethanol
MJ/L air
6.5 3.1 MJ/kg 1.2 MJ/kg 136 104
Methanol 16 MJ/L
air
Properties of Gasoline, Diesel and Alcohol Fuels
Property Methyl Ethyl Alcohol Gasoline (C5- Diesel
Alcohol C12) BSVI (BSVI)
Specific gravity at 15OC 0.79 0.79 0.72-0.77 0.82-0.86
Latent heat of Vaporization (kJ/kg) 1110 900 400 600
Stoichiometric A/F Ratio (Lambda) 6.45 9.0 14.6 14.6
Low Calorific value (KJ/Kg) 19740 26880 48100 44100
Mixture heating value, (KJ/Kg of air) for 3070 2970 2930 -
stoichiometric mixture
Ignition limits (A/F) 2.15-12.8 3.5-17 8-18 20 - 80
Self Ignition Temperature (OC) 574 557 335 220
Octane Number (MON) 92 89 81 / 85 -
Cetane Number 3 8 15 51
Flammability limit (% in air) 7.3 to 36 4.3 to 19
Vapour pressure at 58OC 0.32 0.21 0.8
Flash Point (OC) 12 to 20 -45 to -13 35
Water Solubility 79 0
Laminar Flame Speed (cm/s) 39 33
Reid vapour Pressure (kPa) 17 60
Values would vary depending on the composition from source to source
 Alcohol Blends
• E5 and E10 are blends of ethanol and
gasoline – the number after “E” indicates
the percentage of ethanol.
• E85 is ethanol-gasoline blend fuel
containing 51-83% ethanol (vary according to
ASTM 5798). Also known as Flex Fuel.

• Low level blend

• Upto 5% can be used as oxygenate (as per IS2796:2000
specifications for motor gasoline)
• Upto 10% volume alcohol blend for gasoline vehicles.
• High level blend
• Containing 10 – 85% vol alcohol blend for gasoline vehicle.
• Upto 15% alcohol for diesel blend.
• Generally recommended 5 – 7.7 % for optimum emission
performance.
 Raw material for bioethanol production
▪ It is a well defined
molecule
▪ Clear liquid

▪ Made by fermentation of
sugar.
CO2 Cycle of Ethanol production from Sugarcane
 Ethanol Formula
C2H5OH
Freezing Boiling
Density Flash Point
point Point

0.79 Kg/l -114OC 78OC 13OC

C2H5OH(g) + 3O2(g) + (3*3.76)N2 (g)-------→ 2CO2(g) + 3H2O (l) + (3*3.76)N2(g)

• Ethanol is volatile, flammable and colorless chemical compound and has strong odor.
• Burns with smokeless blue flame which is not always visible in normal light.
• Biodegradable fuel additive.
• It is clean burning, high octane fuel and a versatile solvent.
• Mixes easily with water. Or ethanol molecules absorb water (moisture).
• Alcohols are water soluble, attract and absorb water/moisture, solvent, cleaner, drying
agent, de-greaser and many more…
• Ethanol-gasoline blends contain 10% of ethanol is known as “Gasohol”.
• Blend of ethanol with diesel is known as “e-diesel”.
Standards for Ethanol ASTM
United States Specification D4806-98
Denatured Ethanol Fuel for Blending with Gasoline for Use as Automotive Spark-Ignition
Engine Fuel
Specifications Value Test Method
Ethanol, (vol %) @ 15.56OC 92.1% min ASTM D 5501
Methanol, (vol % )@ 15.56OC 0.5% max ASTM D 5501
Solvent – washed gum (mg/100ml) 5.0 max ASTM D 381
Denaturant content (vol%) 1.96 – 2.5 min Calculated
5.0 max
Inorganic chloride content, mass ppm,(mg/L) 10 (8) ASTM D 7319 or 7328

Copper content (mg/kg) 0.1 max ASTM D 1688

Acidity (acetic acid) mass% ( mg/L) 0.007 , (56) ASTM D 1613
pH 6.5 - 9.0 ASTM D 6423
Sulphur, (mass ppm) 30 max ASTM D 2622, D 3120
Suplhate (mass ppm) 4 max ASTM D 7318, D 7319
Appearance Visibly free of suspended or Determined at indoor ambient
precipitated contaminants (clear & temperature.
bright)
 International Ethanol Blend Reference Fuel
Country Unleaded Petrol (Petrol + Alcohol mixture)

Brazil With 22± 1 % ethanol

With 4.7 – 5.3 % ethanol ( E5) – EURO V

European With 9.0 – 10% ethanol ( E10)– EURO VI
Union With 83 – 85 % ethanol ( E85)– EURO V for FFV
Ethanol ( ED95)– Ethanol min 92.4% - EURO V/VI

US –
With 9.8 – 10.2% ethanol ( E10)
California

With 14.6 – 15% ethanol ( E15) – Proposed

US – Federal
With 83 – 85 % ethanol ( E85) - for FFV

Japan With 9– 10% ethanol ( E10)

In 2022, ethanol blending in the country is 10% and is

INDIA
expected to be 20% by 2025.
GAIN Report June 2017
Ethanol Storage Regulation
Ethanol Safety Standard
 Material Compatibility of Ethanol
• Ethanol has more water content and acetic acid, which is water soluble. Hence it will corrode
certain metal components.
• Recommended metals which can be used with ethanol are carbon steel, stainless steel.
• Mg, Zn, Cu, brass are not recommended.
• Al can be used provided ethanol must be pure, or else Al should be coated with nickel. Or must
be protected by other means.
• Teflon and nylon are compatible with ethanol.
• Equipment used for transportation and dispensing of ethanol must be compatible to avoid fuel
contamination and component breakdown.
‡ Caused by ionic impurity
General ‡ Chloride ion, acetic acids

Ethanol Wet ‡ Caused by azeotropic water

Corrosion ‡ Oxidizes most metals

Dry ‡ Mg, Pb, Al are susceptible

to chemical attack
 Status of Alternate Liquid Fuels: Butanol

July 14 to August 15, 2005 was the first run on 100% Butanol, demonstrating to the
public that there is an alcohol made from corn that replaces gas right now if we had it.
The sooner we start making ButylFuel™ the sooner you will see it in your tank, go down
the road - and stop Global Warming. The ’92 Buick Park Avenue got 24 miles per gallon
on butanol with no modifications-normally gas is 22 mpg. That is a 9 % increase.
In ten states, Butanol reduced Hydrocarbons by 95%, Carbon monoxide to 0.01%, Oxides
of Nitrogen by 37%, this in a 13 year old car with 60,000 original miles. It runs great up
hill and across the deserts.
Butanol is an alcohol that replaces gasoline !
BioButanol™ is made from anything that grows on the planet
Butanol can be blended in any percentage with gasoline with increase in performance.
 Renewable Fuels Strategy
Generation 1
• Vegetable oils and greases to diesel, gasoline and jet fuel.

Generation 2
• Lignocellulosic biomass to fuels
• Algal oils to fuels
 Biodiesel: Advantages
• It is Renewable, Sustainable.
• Biodiesel contains fewer aromatic hydrocarbon:
benzofluoranthene:56% reduction, Benzopyrenes:71%
reduction.
• Biodiesel reduces emissions of CO by approx 50% and
CO2 by 78% on a net lifecycle basis.
• It is biodegradable and non-toxic posing no threat to
human health.
• It has high cetane rating than diesel (avg over 50).
• High lubricity, even in blends as low as 1+2%.
• Domestically produced.
• Reduces Nox in boilers and home heating.
 Biodiesel: Disadvantages
• Its storage for long period is not suitable for engine operation.
• It becomes gel in cold weather.
• It has water content (hygroscopic).
• It degrades rubber.
• It has higher Nox emissions (10%).
• It decreases Horsepower of an engine by approx 15-20 %.

EFFECTS ON ENGINE SEALS, GASKETS & HOSES

• Bio diesel has strong solvent properties Natural rubber and soft
plastics especially vulnerable
• Problem substantially reduced for the B20 blend
• The only hose and gasket material that is truly resistant to
biodiesel is Viton.
 Why Jatropha seeds…?
➢High Oil Content (35-40%).
➢Grows under sub tropical conditions and
low fertility land.
➢High potential as a energy plant.
➢No need of intensive water supply.
➢Non-Edible.
➢The Majority of oil is present in Kernels.
 Biodiesel Production Technology
Vegetable Oil

Methanol
Transesterification
NaOH/KOH +

Crude Biodiesel
Crude Glycerin Biodiesel
Methanol
Recovery Refining
Glycerin
Refining
Glycerin
Patent: A Home Appliance for Production of Bio Diesel,
Patent No. 301915 dated 5th Oct 2018
Biomass
Belt

Dehuller

Control
Reactor Panel

Expeller
Cake
Output Oil
Pump

Beaker Filtration Biodiesel

unit Output
Case Study – Biodiesel Production
EXPERIMENTAL SETUP

Reactor Manual Expeller Motorized Expeller

Transesterification Process
 Transesterification is the process of exchanging the
organic group R″ of an ester with the organic group
R′ of an alcohol.
 These reactions are often catalysed by the addition
of an acid or base catalyst. The reaction can also be
accomplished with the help of enzymes.

Catalyst
50 – 60OC

Alcohol Bio-Oil Glycerol Bio-Diesel

 Biodiesel Properties
DIESEL ASTM D975 BIODIESEL B100- ASTM D6751 EUROPEAN EN 14214
Property LIMITS ASTM Method LIMITS LIMITS
Flash point 52 min D93 130 °C min 101OC
Water & Sediment 0.050 max D2709 0.050% vol. max -
Kinematic Viscosity,
1.9-4.1 mm2/sec D445 1.9-6.0 mm2/sec. 3.5-5.0 mm2/s
40 °C
Sulfated Ash 0.50 max D874 0.020% mass max 0.02% mass
Sulfur 0.05% mass max D5453 0.05% mass max 10.0 mg/kg
Copper Strip
No 3 max D130 No. 3 max class 1 - EN ISO 2160
Corrosion
Cetane 40 min D613 47 min 51 min
Oxygen by wt (%) 0 - 11 -
Location & season Location & season Location & season
Cloud Point D2500
dependant dependant dependant
Carbon Residue,
0.35 max (% vol) D4530 0.050% mass max -
100% Sample
Acid Number - D664 0.80 mg KOH/gm max 0.50 mg KOH/g
Free Glycerin - D6584 0.020% mass max 0.02% wt
Total Glycerin - D6584 0.240% mass max 0.25% wt
Specific Gravity - D287 Not Required 0.86-0.90
Biodiesel Blend

Govt has notified B-100 as an automotive fuel

in CMVR vide GSR 915 (E)
Status of Alternate Liquid Fuels: Biodiesel
ADVANTAGES:

• Miscible with any Diesel Fuel and in any proportion

• Fuel quality Improvements

• High Cetane No ~ 65
• Low Sulfur content. 0-200 ppm
• High Flash point >1000c
• Better Lubricity 325 micron on HFRR
(High Frequency Reciprocating Rig) (460 micron)

• Exhaust Emissions PM 25-50%

• Bio degradable, ideal for use in fragile areas e.g. nature reserves,
bodies of water, etc.
Green Diesel Fuel Properties

FAME:Fatty acid methyl ester

 Alternate / Bio-Refinery Concept

Bio-Mass
Coal / Coke Gasification Syn-Gas
Pet Residue

Clean / Green Fuel Parafins/ Wax

F-TSynthesis
(Diesel) Hydroprocessng

..Contd
Alternate / Bio-Refinery Concept

Bio-Mass Pyrolysis Pyrolysed Liquid

Existing Crude
Oil Refinery

Coal Liquefaction Liquid Product

 Synthesis/Liquefication
of Solid Fuels into Gasoline
• The gasoline obtained from the fractional distillation of crude
petroleum oil is not enough to meet the requirement of the
present community due to vast increase of automobiles.
• Hence an alternate source need of finding out to manufacture
synthetic gasoline.
• Synthetic gasoline can be manufactured by the process of
hydrogenation of coal. The preparation of liquid fuels from
solid coal is called hydrogenation of coal.
• Gasoline is synthesised by the following methods:
1. Fischer- Tropsch process.
2. Bergius process.

195
 Synthesis of Gasoline: Fischer- Tropsch Process
In this process, coal is first converted into coke. Then water gas is produced by the
action of steam over red hot coke. It is mixed with hydrogen and the mixture is
compressed to 5-25 atmospheres. The compressed gases are then led through a
converter which is maintained at a temperature of 200-300°C.
The converter is provided with a suitable catalyst consisting of a mixture of 100 parts
cobalt, 5 parts thoria, 8 parts magnesia and 200 parts kieselguhr. A mixture of
saturated and unsaturated hydrocarbons occurs as a result of polymerization.
• n CO + 2 n H2 CnH2n + n H2O

• n CO + (2 n + 1) H2 CnH2n+2 + n H2O
The reactions are strongly exothermic. Hence, the hot
out coming gaseous mixture is led to a cooler where a
liquid resembling crude oil is obtained. The crude oil
thus obtained is then fractionated to yield gasoline and
high boiling heavy oil. The heavy oil is used for cracking
to get more gasoline

196
 Synthesis of Gasoline: Bergius Process
This method was developed by Bergius in Germany during the First World War. The low ash coal is
finely powdered and made into a paste with heavy oil and then a catalyst (composed of tin or nickel
oleate) is incorporated. The whole mixture is heated with hydrogen at 450°C and under a pressure 200-
250 atm for about 1.5 hours, during which hydrogen combines with coal to form saturated
hydrocarbons, which decompose at prevailing high temperature and pressure to yield low-boiling liquid
hydrocarbons.

The issuing gases (from the reaction vessel) are led

to condenser, where a liquid resembling crude oil is
obtained, which is then fractionated to get:
(i) gasoline, (ii) middle oil, and (iii) heavy oil.
The latter is used again for making paste with fresh
coal dust.
The middle oil is hydrogenated in vapour-phase in
presence of a solid catalyst to yields more gasoline.
The yields of gasoline in about 60% of the coal dust
used.

197
 Conclusions
➢ Challenging scenario - both in Indian Petroleum
refining & Automobile Industry: No single solution
for sustainable Environment and Profitability
➢ Environmental regulations, Deteriorating crude
quality and Higher cost, Tougher Competition …
Liquid Hydrocarbons to remain the major fuel
➢ Innovative approach & novel cost-effective
technologies through continuous R&D efforts:
Conversion of challenges into opportunities
Continuous Technological Breakthroughs and ‘Out-of-Box
Thinking’ – Necessary for sustaining green environment
and profitability