Unit 1

Prepared by:
Janki Tailor

1
 Introduction

• Oil and natural gas are the important part of everyday life.

• It is playing a vital role in the industrialization and urbanization and

meeting basic needs of mankind through supplying energy for
domestic, industrial, transport sectors and as feedstocks for fertilizers,
synthetic fibre, synthetic rubber, polymers, intermediates, explosives,
agrochemical, dyes, paints etc.

2
Formation of Petroleum

3
 Formation of Petroleum

Kerogen : is the ultimate organic source material which is transformed into oil
4
 Migration of Petroleum

The transport of petroleum from the

source rock to the reservoir rocks is
called migration which occurs along
permeable carrier beds.

Accumulation of Petroleum

Petroleum accumulation refers to the

geological process in which oil and gas
are generated in a sedimentary basin,
migrated in the carrier layer, finally
filled into the trap, and accumulated to
form oil and gas reservoirs.
5
 History and Development of Petroleum Refinery in India
• The first oil deposits in India were discovered in 1889 near the town of Digboi in the state
of Assam.

• The Indian Petroleum refining sector has come a long way since crude oil was discovered
and the first refinery was set up at Digboi in 1901. Till 1947, that was the only refinery
with a capacity of 0.50 million metric tonnes per annum (MMTPA).

• The present Mumbai Refinery of HPCL was the first modern refinery to be set up after
independence by Esso in 1954, which was followed by setting up of refineries by other oil
majors, like Burmah Shell and Caltex in Mumbai (BPCL) and Visakhapatnam (HPCL).
Since then, refineries were established by the Government, Private Sector, Joint Venture.
6
History and Development of Petroleum Refinery in India

• Simple refinery configuration was adopted in 1950s, comprising crude oil distillation,
naphtha/ kerosene/ ATF treatment and catalytic reforming for upgrading naphtha to petrol,
with no secondary processing, low energy recoveries and high sulphur fuel oil as internal fuel.
The refineries established in the sixties by Govt. undertakings were based on processing of
indigenous crude oils of low sulfur origin available in North East and Gujarat basin. Indian
PSU refineries started adopting state-of-art modern technologies to upgrade the configuration
in line with the international trend and as per the product requirements and quality. Secondary
processing facilities like Fluid Catalytic Cracking (FCC) Units to upgrade low value streams
to high value middle distillates were installed in many of the refineries.

7
History and Development of Petroleum Refinery in India

• Configuration of Indian refineries further underwent a major change in late 1980s

and early 1990s. There was increased emphasis on maximization of middle
distillates as well as better stability of products, with configurations showing shift
from FCC towards Hydrocracking process and a combination of both. The first
hydrocracker in the country was commissioned in Gujarat refinery of IOCL in
1993. All new grassroots refineries started considering installation of
hydrocrackers. This led to marked increase in investment requirements for refinery
installations.

8
 History and Development of Petroleum Refinery in India

• Refinery configurations in late 1990s were dictated by the product quality up-
gradation due to environmental considerations. These include lead free
gasoline, low sulfur diesel, fuel oil and other improvement in properties along
with the ever increasing demand for middle distillates. The configurations
therefore were modified to include:
• Continuous Catalytic Reforming (CCR)
• Hydrocracker
• Hydrotreating / Hydro desulphurization facilities to generate low sulfur fuels
and fuel oil for internal use
• INDMAX Technology for LPG maximization
9
 Name Plate Capacity
Refinery Location Name of the Company
(MMTPA)*
PSU Refineries
1 Digboi - 1901 Indian Oil Corporation Ltd. 0.650
2 Guwahati – 1962 1.000
3 Barauni – 1964 6.000
4 Koyali – 1965 13.700
5 Bongaigaon – 1974 2.350
6 Haldia – 1975 8.000
7 Mathura – 1982 8.000
8 Panipat – 1998 15.000
9 Paradip - 2016 15.000
10 Manali – 1965 Chennai Petroleum Corporation Ltd. 10.500
11 Nagapattinam - 1993 0.000@
12 Mumbai – 1954 Hindustan Petroleum Corporation 7.500
13 Visakhapatnam – 1957 Ltd. 8.300
14 Mumbai – 1955 Bharat Petroleum Corporation Ltd. 12.000
15 Kochi - 1963 15.500
16 Numaligarh – 2000 Numaligarh Refinery Ltd. 3.000
17 Mangalore – 1996 Mangalore Refinery and 15.000
Petrochemicals Ltd.
18 Tatipaka, AP - 2001 Oil and Natural Gas Corporation Ltd. 0.066
Total 141.566
JV Refineries
19 Bina – 2011 Bharat Oman Refinery Ltd. 7.800
20 Bathinda - 2012 HPCL Mittal Energy Ltd. 11.300
Total 19.100
Private Sector Refineries
21 DTA-Jamnagar - 1999 Reliance Industries Ltd. 33.000
22 SEZ-Jamnagar - 2008 35.200
23 Vadinar - 2006 Nayara Energy (Formerly Essar 20.000
Oil Ltd.)
Total 88.200 10 Annum
MMTPA - Million Metric Tonnes Per
GRAND TOTAL 248.866
Major Problems of Petroleum Industry in India
• Shortage of petroleum crude
• Dependence of foreign countries
• Price hike
• Shortage of oil refining capacity
• Exploration of new reserves
• Technical problems
• Pollution
• Lack of market – determined pricing system

11
 Indian Scenario of crude oil consumption

• India’s crude oil consumption is expected to increase from 4.05

million barrels per day in 2022 to 7.2 MBPD in 2030

• In the 2023 – 2024 year, India imported 232.5 million metric tonnes of
crude oil. India’s main sources of crude oil imports are Iraq, Saudi
Arabia, Russia and the United Arab Emirates.

• India is the third largest consumer of crude oil in the world after USA
and China.
12
13
14
15
Composition of crude oil

Composition
of crude oil

Non -
Hydrocarbons
hydrocarbons

16
 Hydrocarbons

Paraffins Iso paraffins olefins Naphthene Aromatic

17
 Non
hydrocarbon

Sulfur Nitrogen Oxygen Naphthenic

Trace metals Salts
compounds compounds compounds acid

18
 Crude Oil Evaluation

• Petroleum is classified into mainly three types as:

1. Paraffinic base

2. Mixed base or intermediate base

3. Naphthenic base

19
20
 Crude
evaluation

Physical Thermal Electrical Optical

Properties Properties Properties Properties

1. Liquefaction and
solidification
1. Density 2. Volatility
1. Conductivity
2. Sulphur 3. Carbon residue
2. Dielectric strength
4. Specific heat 1. Refractive index
3. Viscosity 3. Electric loss and
5. Latent heat
4. Surface tension power factor 2. Optical activity
6. Enthalpy and heat
5. Metals content 4. Static
7. Thermal conductivity electrification
8. PVT relationship
9. Heat of combustion 21
 Density and API Gravity
• Density = Mass/Volume
• Specific gravity = Density of substance/density of reference substance
𝟏𝟏𝟏𝟏𝟏𝟏.𝟓𝟓
• 𝑨𝑨𝑨𝑨𝑨𝑨 𝒈𝒈𝒈𝒈𝒈𝒈𝒈𝒈𝒈𝒈𝒈𝒈𝒈𝒈 = − 𝟏𝟏𝟏𝟏𝟏𝟏. 𝟓𝟓
𝑺𝑺𝑺𝑺 (𝒂𝒂𝒂𝒂 𝟔𝟔𝟔𝟔℉)

• API = American Petroleum Institute

• For a blend, the API gravity is given as:
• (API)mix=(API)a * Wa+(API)b * Wb+ (API)c * Wc+ …..
• API a is API gravity of component A, W is the weight fraction of the mixture.

22
 Density and API Gravity

• The API gravity of a crude is influenced by the composition of the

oil.

• Crude oil characterized by high amount of dissolved gases, are less

dense thus, light in weight. And possess high API gravities.

• While denser crude oils of low amount of dissolved gases are

characterized by low API gravity values.

23
Classification of crude according to sp. Gr.
Crude Sp. Gr.
Light crude Less than 0.825
Medium crude Less than 0.875
Heavy crude Less than 1.00
Extra heavy crude Greater than 1.00

24
• Crude oil classified by API gravity according to distillate pressure as follow:

Light crudes API > 30

Medium crudes 30 >API >22
Heavy crudes API < 22

25
 UOP (Watson) Characterization Factor (kw)
• Since the early days of the petroleum industry, some physical properties of crude oil were
used to define characterization factors for classification of crude oil with respect to
hydrocarbon types .
• The Universal Oil Product (UOP) characterization factor or Watson ‘‘characterization
factor’’ of a hydrocarbon is defined by the following eq.
∛𝑇𝑇𝐵𝐵
𝐾𝐾𝑤𝑤 =
𝑆𝑆𝑆𝑆
• KW < 10 highly aromatic (A)

• KW =10- 11 naphthenic (N)

• KW = 11-12.9 paraffinic compounds (P)

26
 Correlation Index (CI)
• The U.S. Bureau of Mines Correlation Index (BMCI) or (CI) is useful for
characterization of crude oil fractions. CI is defined in terms of Mean Average
Boiling Point (Tb) and specific gravity (SG) at 60°F:
𝟒𝟒𝟒𝟒𝟒𝟒𝟒𝟒𝟒𝟒
• 𝑪𝑪𝑪𝑪 = + 𝟒𝟒𝟒𝟒𝟒𝟒. 𝟕𝟕 𝑺𝑺𝑺𝑺 − 𝟒𝟒𝟒𝟒𝟒𝟒. 𝟖𝟖
𝑻𝑻𝑩𝑩

• Where, TB= volume average boiling point (VABP) in degrees Kelvin

• SG=Sp. Gravity at 60 (oF)

• Using the CI values, crude oils can be classified as follows:

Paraffinic (P) CI<29.8

Naphthenic(N) CI<57.0

Aromatic(A) CI>75.0 27
 Viscosity gravity correlation (VGC)

10𝐺𝐺 −1.0752 log(𝑉𝑉−38)

• 𝑉𝑉𝑉𝑉𝑉𝑉 =
10 −log(𝑉𝑉×38)

• G is sp. Gravity and V is saybolt universal viscosity

• Paraffinic base: 0.80 – 0.83

• Intermediate base: 0.83 – 0.88

• Naphthenic base: 0.88 – 0.95

28
 Viscosity Index
• 𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉 𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 𝑉𝑉𝑉𝑉 = 100 × (𝐿𝐿 − 𝑈𝑈)/(𝐿𝐿 − 𝐻𝐻)

• L = viscosity at 100°F of reference oil with VI = 0

• H = viscosity at 100°F of reference oil with VI =100

• U = viscosity at 100°F of the base oil

• H = viscosity at 210°F of the base oil

• Naphthenic base oil have viscosity index between 40 and 80 with low pour point
while paraffinic base oil have higher viscosity index (>95) with high pour point.

29
 Viscosity Index
• The Viscosity Index (VI) is a unitless number that indicates how much a fluid's kinematic
viscosity changes with temperature. It is a critical property for lubricating oils.
•Higher VI = Better Viscosity Stability: A high VI means the lubricant maintains a
relatively stable viscosity over a wide temperature range. It thins out less at high
temperatures and thickens less at low temperatures.
•Lower VI = Greater Viscosity Change: A low VI means the lubricant's viscosity is highly
sensitive to temperature changes. It becomes very thin when hot and very thick when cold.
•Purpose: A high VI is desirable for applications (like engine oil) that operate across a wide
range of temperatures, from a cold start in winter to high running temperatures.
30
 Sulphur Content

1. Low sulfur crude oil (S content ≤ 0.5%) of the sulfur and it is called sweet crude oil

2. Sulfur petroleum (0.5% < S content < 2%) of the sulfur it is called intermediate.

3. High sulfur petroleum (S content ≥ 2%) it is called sour crude oil.

31
Boiling Point Curves

• ASTM (American Society for Testing and Materials) distillation or

TBP distillation characterize the volatility of petroleum fractions
and crude oils.

• Both are batch distillations, which differ mainly in the degree of

fractionation obtained during distillation.

32
TBP Distillation

33
 ASTM Distillation Methods
• ASTM Method D86: This method is used for the distillation of motor
gasolines, aviation gasolines, aviation turbine fuels, naphtha, kerosine, gas
oils, distillate fuel oils, and similar petroleum products. It is carried out at
atmospheric pressure. An exposed thermometer is used and temperatures
are reported.
• ASTM Method D1160: This method is used for heavy petroleum products
which can be vaporized partially or completely at a maximum liquid
temperature 750 F at absolute pressure down to 1 mmHg and condensed
as liquids at the pressure of the test. It is carried out at pressures between
1 mmHg and 760 mmHg. Temperatures are measured with a
thermocouple.
34
ASTM Distillation

35
Equilibrium Flash Vaporization

36
 Thermal Properties of Petroleum fraction
• Specific heat

• Heat of combustion

• Latent heat of vaporisation

• Latent heat of fusion

• Thermal expansion

• Spontaneous ignition temperatures

• Viscosity and viscosity index

• Viscosity – gravity constant

• Thermal conductivity

• Thermo viscosity 37
 Specific Heat
• Specific heat of petroleum fraction lies in the range of 0.3 to 0.85 and
depends upon temperature and gravity.
• Lighter fractions have higher values.
• With increasing density the specific heat decreases.
• Bureau standard formula:
1
• 𝑆𝑆𝑆𝑆. ℎ𝑒𝑒𝑒𝑒𝑒𝑒 = (0.4024 + 0.00081 𝑡𝑡)
𝜌𝜌
• With API gravity, temperature and characterisation factor (K) the specific
heat correlation is given below:
• 𝑆𝑆𝑆𝑆. ℎ𝑒𝑒𝑒𝑒𝑒𝑒 = [0.355 + 1280 °𝐴𝐴𝐴𝐴𝐴𝐴 10−6 + 503 + 1.17 × °𝐴𝐴𝐴𝐴𝐴𝐴 (32 +
1.8𝑡𝑡)10−6 ](0.05𝐾𝐾 + 0.41)
38
 Heat of Combustion

• Hydrogen is distinct for its heat of combustion (183.6 × 103 KJ/kg)

• Higher hydrogen content fractions will have more heat of combustion.

• In the order of paraffins to aromatics, the heat of combustion

decreases.

39
 Latent heat of vaporisation
• Latent heat for a fraction varies with the temperature at which
vaporisation takes place.
• This is commonly related to molecular weight, ° API and molal average
boiling point.
• Any two of the above parameters are sufficient to give latent heat of
vaporisation.
• Latent heat can also be converted from normal boiling point to any other
temperature up to critical condition.
• The relationship is expressed as
𝑇𝑇
𝐿𝐿 = 𝛾𝛾𝐿𝐿𝐵𝐵
𝑇𝑇𝐵𝐵
40
 Latent heat of fusion

• The heat of fusion is approximately fifty percent of latent heat of

vaporisation.

• For waxy distillates and waxes, the average latent heat of fusion may
be taken as 167 to 170 KJ per kg.

41
 Thermal expansion

• Like all liquids, petroleum fractions also suffer in loss of density due to
thermal expansion.

• Coefficient of expansion is very much required to find out the volume of

the container, which is exposed to frequent changes of temperature and this
is related to API gravity as given below:

42
43
 Spontaneous ignition temperatures
• The temperature at which a material can catch fire and burn continuously without the aid of external firing

agencies.

• Paraffins have less ignition temperatures and this precious property is regarded as most useful for the

performance of diesel fuels.

• Aromatics have high ignition temperature. In gasoline engines adiabatic compression of the mixture does not

raise the temperature to that extent, hence sparking is required for detonation.

• Gasoline engines this way differ form diesel engines.

• Ignition temperature remarkably decreases with increasing molecular weight of the series as well as with

oxygen content of molecule.

44
45
 Viscosity and viscosity index
• Viscosity is an important property of all lube oils.

• Lubrication assists in removing the frictional forces between two moving

bodies.

• Viscosity is defined as the force in dynes required to maintain 1 sq. cm plane,

with a unit velocity gradient from another similar plane separated by a
distance of 1 cm.

• The relative viscosity is the ratio of the viscosity to that of water at standard
temperature.
46
 Viscosity and viscosity index
• In all refinery operations instead of absolute viscosity kinematic
viscosity is used.

47
 Viscosity and viscosity index
• Lubricants are specified by another derived property namely viscosity
index, which indicates the variation characteristics of viscosity with
temperature.
• Dean and Davis had given the following formula:

48
The original VI scale was established by comparing an oil's performance to two reference
oils:
[Link] = 0 Reference Oil: A naphthenic-based oil that showed a large change in viscosity
with temperature.
[Link] = 100 Reference Oil: A paraffinic-based oil that showed a small change in viscosity
with temperature.

49
50
 Viscosity and viscosity index
• Walther’s equation:

• This describes the viscosity variation characteristics of an oil with

temperature.
• On the basis of this equation ASTM charts were prepared.
• This is essential when the pour point of oil is very high.
51
52
 Viscosity – Gravity constant
• This index of classification connects the viscosity and gravity of the sample
by the formula

• Where G is [Link]. At 15.6°C, V = SSU at 37.8° C

• Where the measurement of viscosity is not possible at 37.8° C an alternative
formula is used.

• Where V is at 98.9° C
53
 Viscosity – gravity constant

• Naphthenic oils have VGC 0.9 and above

• Paraffinic oils have 0.8

54
 Important product properties and test methods
• Distillation of crude yields number of cuts of varying boiling ranges.
• In the order of increasing boiling points, the main fractions from distillation
of crude, are

Gas/light – naphtha/ gasoline Solvents/fuels/motor spirits etc

Kerosene (light distillates) Jet fuels/illuminating oils/ heating
oils
Gas oils or middle distillates Diesel fuels, cat – cracking oils etc.
Heavy distillates Lubes/waxes/fuel oils etc
Residuum Asphalt, bitumen etc.

55
 Gas
1. Natural gas

2. Associated gas

3. Dissolved gas

4. Casing head gas

5. Off gas from refinery

56
 Natural Gas
• Its name indicates that it is readily available in nature, almost as a finished
product.

• It contains varying proportions of methane.

• It may be accompanied by other dry gas fractions like ethane and propane
to a small extent.

• Some inert like CO2, N2, noble gases are also present.

• The proportion of methane ranges from 85% and goes up to 98%

57
 Associated gas
• This is obtained from oil reservoirs and this exists as a separate gas cap over
liquid phase.

• Though the gas mainly consists of methane and to some extent ethane and
propane, the proportions vary depending upon the reservoir conditions.

• When the gas phase is taken out, it may still contain some liquid
hydrocarbons mainly of volatile range like butane and pentane, which when
condensed are termed as natural gas liquids (NGL).
58
 Dissolved gas
• Gas may be present in the liquid hydrocarbons mainly in the dissolved
state depending upon the formation pressure.

• When the pressure is decreased, this dissolved gas comes out of the oil.

• It is fair to strip off such dissolved gas before crude is transported to

long distances by means of pipe lines or tankers.

• The remaining dissolved gas is first to come out of the distillation

column because of higher temperature than the surroundings.
59
 Casing Head gas
• Casing head gas is a type of natural gas that is found in liquid form with
crude oil.

• It is also more or less similar to natural gas but contains less % of methane
and high percentage of ethane and propane than natural gas.

• When the oil is produced, the casing head gas separates from it. This
happens either at the time of production or shortly after. It is a by product of
oil production.
60
 Refinery off gas
• In a refinery, gas is formed in cracking and reforming operations due to the
thermal degradation of liquid hydrocarbons.
• During stabilization of wild gasolines or processed gasolines, the gases are
vented.
• Thus the gas is mainly a mixture of saturates and unsaturates and quantity
is also not assessable.
• This forms a major source of heat energy for refinery, as well as feed stock
for petrochemicals.
• All the gases contain impurities like CO2, N2, mercaptans, H2S, water
vapour, suspended impurities etc.

61
 Refinery off gas

• Mixture of methane and ethane is called dry gas, while propane – butane
mixture is called wet gas.

• Wet gas is usually liquified and sold for commercial purposes.

• Butane is diverted to gasoline streams as a blending component, as butane

has more commercial value when blended with gasoline.

62
 Liquified Petroleum Gas (LPG)
• The gas that is vented from refinery distillation units, is processed and
conveniently stored after liquefaction.

• For domestic heating purposes, it is supplied in small cylinders 15 kg or 12

kg.

• This gas is known as liquified petroleum gas as it is stored in vapor liquid

mixture.

63
 Liquified Petroleum Gas (LPG)
• Reasons for popularity of LPG as popular kitchen aid

1. Ease of handling

2. Smokeless ness

3. Good and steady heating rates

64
 Liquified Petroleum Gas (LPG)
• Different types of mixtures resulting from propane – butane blends are sold
as LPG.
• Most important property of this fuel mixture is vapour pressure.
• Grades of LPG
1. Predominantly butanes
2. Butane – propane mixtures, mainly butanes
3. Butane – propane mixture (equal volumes)
4. Less butane – propane mixture
5. Butane – propane mixture (more propane)
6. Predominantly propane
65
 Important Test for LPG
• Reid vapor pressure test
• The apparatus will be discussed in gasoline section

66
 Gasoline
• Naphtha or gasoline (petrol as known in India)

• Next fraction to follow gas

• Volatile fraction and known as motor spirit

• Boiling point range: 37° C to 180° C

• Gasoline is a finished product, raw fraction is termed as naphtha or light boiling fraction

• Approx 40 type of gasoline

• 90% is consumed by automobile industry and the rest by aviation industry

• Two grades: Regular and premium, both either leaded or unleaded

67
 Tests for Gasoline

• ASTM distillation

• Reid vapor pressure

• Octane number

• Gum content

• Sulfur content

68
ASTM Distillation

69
 ASTM Distillation
• In this test 100 ml of sample is distilled in a standard flask at a uniform rate of 5 cc per minute.

• The distillate is condensed in a brass tube condenser, surrounded by a water bath kept at 0° C by
ice – water mixture.

• First drop from the condenser must be available in 5 to 10 minutes after heating started, at which
the recorded temperature is mentioned as initial boiling point (IBP) of the sample.

• The vapor temperature is recorded at each successive 10 cc distillate collected in a measuring

cylinder.

• The test continues in the same way till 95% of fraction is condensed.

• At this juncture, the heat intensity may be increased to obtain the maximum boiling point also
known as end point (EP)
70
 ASTM Distillation

• Fluctuation in temperature is common when last two or three ccs of

sample are distilled.

• When the bottom of the flask shows dryness, the temperature recorded
corresponds to final boiling point.

• The distillate collected shall not be less than 98% and the difference is
accounted as loss.

71
 ASTM Distillation

• ASTM distillation specifies the evaporation characteristics of gasoline.

• Accordingly gasoline fall mainly into 3 types:

• Type A, Type B and Type C

• In all these types 10%, 50% and 90% boiling point along with IBP and
FBP are mentioned.

72
ASTM Distillation

73
 ASTM Distillation
• Ease of starting is governed by IBP to 10% range boiling point.

• Lower IBPs are preferred for cold climates.

• A draw back of very low IBP is vapour locking of engine due to high
evaporation.

• Evaporation losses can also be related to vapour pressure.

• When gasoline tanks are filled up, the vapour that occupied the tank has to be
displaced and losses due to such kind of phenomenon are called ‘breathing
losses’ which are inevitable in all falling operations.
74
 ASTM Distillation
• With all these considerations, to ease of starting, winter gasolines and summer
gasolines are produced to satisfy the seasonal specifications.

• Rate of acceleration follows after the starting operation which is best judged by
the mid region boiling range (say 30 – 60 %)

• Rapid warm up is not very essential. It is generally influenced by prevailing

weather conditions.

• Warmup period is defined as the time required to develop fully the engine
power.
75
 ASTM Distillation
• 30 – 60 % boiling point range gives information on

a) Warm up period

b) Good evaporation

• If the range of boiling point is high, gasoline will not be evaporating

normally.

• If 90% boiling is high, then crank case dilution also increases as the fuel
is not volatile at the working conditions of carburretor.
76
Reid Vapour Pressure

Summer gasoline: Low RVP

Winter gasoline: High RVP
77
 Reid Vapour Pressure
• Vapour pressure of all volatile fractions is measured by the above apparatus
at (38° ± 0.1°C).
• The apparatus consists of two chambers. The lower chamber is in the form
of cylindrical bomb for holding test sample.
• Above this, there is air chamber, which is a hollow cylindrical space,
designed to possess four times the bomb volume.
• The top portion of the chamber is fitted with a bourdon gauge for pressure
indication.
• For the test, the bomb is first filled with the sample to the brim and
immediately the valve is closed and connected to the air chamber.
• The apparatus is now immersed in a water bath kept at 38° ± 0.1°C.
78
 Reid Vapour Pressure
• The maximum pressure indicated by the gauge is counted as the Reid
vapour pressure of the sample.

• LPG, gasoline, naphthas, jet fuels are tested like this.

• It is found that true vapour pressure in most of the cases is higher than the
indicated RVP, and the variation for different fractions is different.

• Relative expression ‘true vapor pressure to RVP’ for gasoline is in the range
of 1.03 to 1.45, while for crudes it goes up to 10.
79
 Octane Number
• Octane number is defined as percentage volume of i-octane (2,2,4 –
trimethyl pentane) in a mixture of i-octane and n-heptane that gives the
same knocking characteristics as the fuel under consideration.

• Knocking is due to untimely burning of fuel in a spark ignition engine,

which results in loss of power and sometimes it is powerful enough to
cause damage to engine parts.

80
 Octane number and engine
• Depending on a vehicle's engine design, octane plays a key role in engine
performance and measures the ability to resist auto-ignition, which is commonly
referred to as knock.

• As engine compression increases, so does the amount of power and efficiency

generated by a given amount of fuel. The higher the octane, the greater the fuel
can withstand compression and resist knock.

81
 Octane Number
• In United states,
• Prior to 1974, to increase octane number an additive tetra ethyl lead was
added, but due to environmental concerns in 1975 unleaded fuel was
introduced.
• Then refiner began to add methyl tertiary butyl ether (MTBE) to gasoline, it
was also stopped due to environmental concern.
• Then now 10 to 15% ethanol is added to gasoline to increase the octane
number in US.
82
 How does the octane level affect the vehicle
• Engines are designed to burn fuel in a controlled combustion. A flame starts at the
spark plug and burns throughout the cylinder until all of the fuel in the cylinder is
burned.

• In comparison, spontaneous combustion, also called auto-ignition, detonation,

or knock, happens when rising temperature and pressure from the primary
combustion causes unburned fuel to ignite. This uncontrolled secondary
combustion causes pressure in the cylinder to spike and causes the knock to occur.

83
84
 How is octane measured?
• The standard means of testing octane is with an octane testing engine. This test is similar to the way the
mass of an object can be determined by comparing it to objects (references) of known mass on a balance
scale. Primary Reference Fuels (PRF) of precisely known octane are formed by combining iso-octane,
heptane, and other well-known standards such as toluene. These PRFs are used to bracket a given fuel
sample to determine the pressure at which similar knock intensities are observed. This measurement is
taken by adjusting the octane engine's cylinder height, which changes the compression ratio/pressure in the
engine until the knocking reaches a specific intensity level.

• The (R+M)/2 you see on the label refers to the average of the research octane number (RON) and the motor
octane number (MON) ratings. To determine the RON, the fuel is tested under engine idle conditions with a
low air temperature and slow engine speed. To determine the MON the fuel is tested under the more
stressful conditions of higher air temperature and engine speed.
85
86
 Oxidation stability (Gum formation)
• Longer storage time

• Should not undergo any deleterious change under storage condition

• Free from deposits under discharge condition

• Deposits can cause choking in engine

• Gasoline manufactured by cracking processes contain unsaturated components

which may oxidise during storage and form undesirable oxidation products.

• An unstable gasoline undergoes oxidation and polymerisation under favourable

ambient conditions, forming gum, an resinous material.
87
 Oxidation stability (Gum formation)

• Gum formation appears to be the result of a chain reaction initiated by

radicals such as peroxides and catalysed by the presence of metals,
particularly copper, which might have been picked up during refining and
handling operations.

• By addition of small amount of antioxidant additives known as inhibitors,

this can be eliminated.

88
 Oxidation stability (Gum formation)

• Two types of gum

1. Existent gum (pre formed)

2. Potential gum (ultimate)

89
 Sulfur

• In addition to corrosiveness and pollution, sulfur compounds are

extremely harmful. More sulfur content may affect octane number.

• More TEL (tetra ethyl lead) is required if sulfur components are

present in gasoline.

90
 Sulfur
• The effect of sulfur on lead can be predicted by the relation given as:

91
 Additives for gasoline
• What is the need for additives in gasoline?
• Complete combustion of gasoline in engine is rare.
• Motor oils used for lubrication cause deposits in the combustion chamber. These
deposits enter the crank case of the engine to form lubricating oil sludges along
with unburnt gasoline.
• Effluent through positive crank case ventilation which causes deposits in the
delivery end of the carburettor.
• Hence additives are preferred to reduce the deposits as well as pollution.
92
 Additives for gasoline

• Anti icings and detergents

• Inhibitors for (a) corrosion (b) oxidation

• Combustion aids

• Anti – knocks

• Colours and dyes

93
 Anti – icings agents
• During cold and wet weather, spark ignition engine has a tendency to stall till the
combustion chamber is fairly warmed up.

• Formation of ice crystals begins when the ambient temperature is -5° C to 10 ° C,

at a relative humidity of 65%.

• During vaporisation of fuel in carburettor, there is a good temperature drop.

• These two result in formation of ice crystals.

• For the prevention of these formation, additives like glycols, mono ethers,
methanol, propanol are added.
94
 Detergents
• Where moving parts are present a timely lubrication is required.

• Carburettor detergents take care of smooth function of carburettor.

• For free piston movement, rapid erosion of deposits in combustion chamber,

lubricants and detergents are required.

• The deposits are mainly due to decomposition of lube oils and carbon formation
by frictional heat and combustion heat.

• Maleic anhydride, polyamines, poly isobutylenes, phenol epichlorohydrin –

amine products are some detergents
95
 Dyes and colours

• To identify to asses if there is any deterioration in gasoline during

storage.

• Pink colour is used for automobile gasoline

• Blue colour is added for aviation gasoline.

96
 Inhibitors (corrosion)
• Rust prevention during storage and transportation is essential.

• This is done by adding selective additives in products.

• These additives form a layer of coating on the metals and protect from
rusting.

• Ammonium sulfonates, organo phosphoric compounds

• Magnesium and silicon compounds are used for prevention of lead

corrosion.
97
 Inhibitors (oxidation)
• Oxidation may be accelerated by the presence of metallic impurities like copper
and its alloys unsaturates, they may react with atmospheric oxygen which leads to
gum formation due to free radical mechanism.

• Anti oxidants like phenols, cresols, phenylene diamines, alkyl amino phenols.

• Copper corrosion can be prevented by addition of disalicyledine and amino

propane.

• Without additives gasoline should not be stored for more than six months.

98
 Combustion aids

• The deposits in the combustion chambers often glow and cause the fuel to
burn untimely and contribute knocking.

• Boron compounds in small amounts can decrease the combustion deposits

and can also increase the effectiveness of anti knocking agents.

• Organo phosphorous compounds can also reduce surface ignition by

forming a refractory layer and preventing glows.

99
 Anti – knocking agents

• Tetraethyl lead is the most important additive of gasoline.

• Working mechanism

• Increases pollution due to oxides of nitrogen.

• Lead compounds accumulate in engine parts, for that dibromo methane

additive

• MTBE

100
101
 Naphtha
• These fractions are highly volatile and fall in the boiling range of motor spirit.

• Mostly used as solvents in paint, perfumery and other industries.

• Naphtha is not suitable for combustion, because of the rapid flame propagation,
resulting in explosions.

• Cuts boiling below 80 ° C are less used as solvents.

• Cuts in the range of 80 to 120 ° C are reformed to improve octane number and
goes as a blend into straight run gasoline.
102
 Naphtha as a solvent

• Almost water white in colour

• Non – corrosive nature

• High stability

• High solvent power

• Low boiling point

• Low acidity
103
 Kerosene

• Employed as fuel and illuminant

• Approximate boiling range 150 - 250° C

• Low in viscosity, stable, light in colour and free from smoky

ill smelling substances.

• Used as illuminating oil in domestic needs (in past)

104
 Test and properties of Kerosene

• Flash point and fire point

• Smoke point

• Volatility

• Sulfur content

• Aniline point
105
 Flash point
• Flash point is defined as the minimum temperature at which the vapours
from oil sample will give a momentary flash on application of a standard
flame under specific test conditions.

• Significance: it can predict the possible fire hazards during transportation,

storage and handling.

• The flash point of the marketable kerosene should be above 42° C.

106
Pensky – Martens Apparatus

107
108
• The test sample is filled up to the mark and the temperature of the oil
is slowly and uniformly raised at a rate of 3° C per minute.

• Occasional stirring is done.

• The spring handle is rotated at every 1 ° C raise in thermometer, till a

blush light flash is noticed.

109
• Abel flash meter is used for highly volatile samples less than 40° C.

• Pensky – Martens closed cup can be used for medium flash liquids

• High flash point liquid is to be tested in open cup flash meter.

110
 Fire Point

• This closely follows the flash point.

• The test is carried out in open cup rather than a closed one.

• Fire point temperature is noted when the oil vapours can burn
continuously for 5 seconds when tested in flash point apparatus and it
occurs after the flash point, by 3 - 4° C.

111
 Smoke Point
• Smoke point is an indication of clean burning quality of kerosene.

• Illumination depends upon the flame dimension although it is not related to flame height.

• Smoke point is defined as the maximum height of flame in millimetres at which the given
oil will burn without giving smoke.

• Different flame heights are obtained due to the presence of different components such as
paraffins, naphthenes and aromatics.

• Aromatics contribute smoke, so removal of aromatics increases the smoke point.

• In India, marketable kerosene should possess a smoke point 18 mm.

112
113
 Smoke point

• Smoke point may be predicted approximately by knowing the group composition

of oil

• Where P, N and A are % of paraffins, naphthenes and aromatics in the sample.

• Smoke point can not specify any illumination characteristics.

114
 Smoke point
• Luminosity number specifies the illumination characteristics of kerosene.

• This indicates luminosity of the flame and accompanying radiation problems in combustion
chambers.

• Smoke point apparatus with modification to include a photo electric cell can measure the flame
radiations.

• Luminosity number is expressed just like octane number.

• The constituents taken here are tetralin ( 0 luminosity number) and iso octane (100 luminosity
number)

• The blend of these two should match with the luminosity of fuel.
115
 Burning Quality Test
• This indicates the ability of kerosene to burn steadily and cleanly over a
long period.
• Kerosene is tested by burning in a standard wick lamp for a period of 24
hours, in a room free from air currents.
• The average rate of burning, change in shape of flame, the density of
chimney deposits are the prime factors by which the quality of kerosene is
assessed.
• A good quality kerosene (after burning for 16 hours) should present the
chimney as clean as possible (only slightly clouded) and the wick should
not have any appreciable hard incrustations with as large flames as in the
beginning.
116
 Burning Quality Test
• The continuity of the initial illumination over long periods in a lamp rests on the normal
flow of kerosene to wick end.

• Quantity of oil available at the tip of wick depends on the height of wick over liquid
surface, texture of wick and properties like viscosity and surface tension of oil.

• The surface tension of different oils (kerosene) may not vary much but the viscosity
varies.

• Stabilisation of flame is governed by viscosity.

• A good oil of 650 cc must burn at least for 120 hours.

117
 Sulfur content

• High sulfur content is harmful.

• When large amounts of such fuel is burnt, accumulation of these

oxides results, offering problems of corrosion and pollution.

• Maximum permissible amount of sulfur is 0.13% in kerosene.

118
 Aniline Point

• This test indicates qualitatively the amount of aromatics present in

kerosene.

• This method is fully discussed in diesel fuels.

119
 Diesel Fuels

• Boiling range: 250 - 320° C

• Two classes of diesel fuels:

• High speed diesels

• Low speed diesels

120
 Classification of diesel oils

Low speed Below 300 RPM For heavy loads at

constant speeds
Medium speed 300 – 1000 RPM Fairly heavy loads
moderately constant
speeds
High speed Above 1000 RPM Load and speed vary

121
Feature Low-Speed Medium-Speed High-Speed
RPM Range < 300 RPM 300 – 1,000 RPM > 1,000 RPM
Engine Cycle 2-Stroke 4-Stroke 4-Stroke
Typical Fuel Heavy Fuel Oil (HFO) Marine Diesel Oil (MDO) High-Speed Diesel (HSD)
Primary Use Large Cargo Ships Tugboats / Generators Trucks / Cars
Extremely Heavy /
Weight/Size Moderate Light / Compact
Massive

122
 Test recommended for diesel fuel

• Pour point

• Aniline point – diesel index (cetane number)

• Flash point

• Calorific value

• viscosity

123
 Pour Point
• The criteria of pour point fixation depends on two factors
• Climate conditions
• Storage and handling
• Fuel, at minimum ambient temperature must be free flowing.
• In India pour point is fixed at 5° C
• In Himalayan belt, where the climate tends to be at sub zero level, this may not be
satisfactory, so low pour point oils are essential.
• It is observed that at close approach of pour point, the viscosity increases very much, the
result of which is high pumping cost.
124
 Aniline Point
• Diesel fuels are mainly composed of paraffins but aromatics are also present in
that.

• Aromatics of this boiling range present in the fuel cause abnormal ignition delay.

• For this reason estimation of aromatics is essential.

• Aniline point can predict the aromatic content of oil and can predict the suitability
of oil.

• Aniline point is defined as the minimum temperature at which equal volumes of

anhydrous aniline and oil mix together.
125
 Diesel Index
• Diesel index is a derivative of aniline point and it is defined as

• Aniline being aromatic compound freely mixes with aromatics.

• Low aniline point indicates, low diesel index (high percentage of aromatics)

• Aniline point can also predict the amount of carbon present in the molecule
by the formula

126
• Diesel index is a measure of ignition quality of fuel.

• Diesel engine works on the principle of compression ignition.

• During compression adiabatically the air temperature reaches around 600° C, when the fuel in
finely atomised form is fed in, it instantaneously explodes.

• The temperature at which explosion takes place without the aid of fire is called self ignition
temperature.

• Self ignition temperature is low for paraffins while it is high for aromatics.

• Thus the fuel rich in aromatics burns later causing ignition delay and it gives rise to what is
known as diesel knock.

127
• For this reason all diesel fuels are processed to have a diesel index in
the range of 45 to 55.

• A high diesel index is also not desirable, as a fuel rich in aromatics

gives rise to better calorific value than paraffin rich fuel.

128
 Cetane number

• Cetane number is a corollary of Diesel index.

• It is defined as percentage volume of n – cetane in a mixture of n –

cetane and α - methyl naphthalene, which gives the same ignition
delay as the fuel under consideration.

129
 •High Aniline Point = High Paraffin content = Better Ignition (Higher Cetane Number).
•Low Aniline Point = High Aromatic content = Poor Ignition (Lower Cetane Number).

Characteristic High Aniline Point Low Aniline Point

Dominant Hydrocarbon Paraffins (Alkanes) Aromatics
Ignition Quality Excellent (Smooth) Poor (Engine Knock)
Effect on Rubber Gentle / Safe Likely to cause swelling/leaks
Diesel Index High Low

130
 Flash point

• It has no real significance on performance of fuel.

• Knowledge of this is required for safe handling and storage.

• In India flash point of diesel is kept around 50 - 55° C

131
 Calorific value

• High calorific value of the oil is desirable, but not at the expense of
diesel quality.

• A fuel having 41.83 KJ per gm calorific value is sufficient.

• Paraffins have high calorific value due to high hydrogen content, but
aromatics mainly contribute by bond dissociation.

132
 Viscosity

• Ease of starting depends on viscosity and ignition quality.

• At lower starting temperatures high cetane fuels are required.

133
 Diesel Additives
• Ignition accelerators are used for reducing the ignition delay.

• Oxygen donating substances like nitrates and nitrites of c7 – c8 acids, aldehydes,

ketones, ethers and peroxides are used.

• Inhibitors to stop gum formation are the same as gasoline.

• Pour point depressors are generally chlorinated paraffins are used to improve the cold
start performance of the engine.

• Anti – smoke additives like ethyl Lubrizol cause less smoke in the exhausts.

• Alkaline agents and ashless dispersant additives have been used to improve quality of
rail diesel.
134
 Lube Oils

• The principal source of lubricating oil is the fraction that is left after lighter
components, namely gasoline, kerosene, diesel oil during crude distillation.

• Lubes have a boiling point above 350°C and are obtained as the main
products from vacuum distillation units.

• Residuum, after precipitation of asphaltenes are known as bright stocks and

form a good source for lube oils.

135
 Composition of Lube oils

• Composed of paraffins, naphthene, aromatics and unsaturated bodies.

• The chief molecular structure of lubes is naphthene rings and aromatic

rings arranged in groups of as many as six with paraffinic side chains.

• The more such side chains the more paraffinic the oil is.

• Naphthenic crudes give more rings with less side chains.

• Normal paraffins in this range are usually waxy in nature and have to be
separated for maintaining free flow of oil.
136
 Classification of lube oils
• Machine and engine oils
• Compounded oils
• Turbine oils
• Cold test oils
• Transformer oils
• Colour oils
• Corrosive oils

137
 Machine oils and engine oils

• These are all high viscosity index oils as they have to serve under varying
temperatures.
• Medium viscosity oils are suitable for most of the industrial applications.
• Low viscosity index oils are suitable for compression ignition engines
• Air craft engines require a very high viscosity index oils.
• Straight, premium, heavy duty
• Marine grade oils are produced in our country as blends from indegenous
and imported oils.
• Aviation oils are also special grade oils not produced in India.
138
• HVI oils for planes, high speed operations

• MVI oils for petrol, diesel and stationary vehicles

• LVI oils for light equipment

139
 Compounded oils

• These are lube oils mixed with animal or vegetable oils.

• These oils exhibit more wettability characteristics which makes them

suitable for steam engines, compressors and quenching and tempering
operations.

140
 Turbine oils

• High speed machinery, such as steam turbine, electric motors should

have emulsion free oils.

• Extreme stability is required for such oils.

141
 Cold test oils

• These oils are mainly used in refrigeration and hydraulic systems,

specially designed for arctic climates.

• Pour point is the important thing compared to all other properties.

142
 Colour oils
• These are industrial oils used in textiles, food and paper industries.

143
 Corrosive oils

• Some oils are blended with corrosive ingredients.

• These are used in cutting, shaping of metals.

• Heavy duty oils and extreme pressure lubes are of this category.

144
 Test for lube oil

• Flash point

• Pour point

• Viscosity and viscosity index

• Oxidation stability

• Carbon residue

145
 Carbon Residue
• The propensity of cracking is indicated by carbon residue of the oil.
• Heavy oils being delicate to high temperatures, have a tendency to crack,
with deposition of carbon.
• Lube oils are often subjected to such hazardous temperatures.
• The amount of carbon formed during cracking does ultimately provide an
idea of usability of oil at high temperatures.
• This test is conducted by two methods
• Conradson method
• Ramsbottom method

146
 Conradson method
• A sample of 10 gms is taken into a silica crucible and heated out of contact with
air.

• The set up provides the necessary precautions, such that the oil is thermally
decomposed out of contact with air.

• The decomposition is brought by means of high heating rates.

• As the heating continues fumes appear at the chimney top.

• The fumes are burned and heating rate is adjusted such that the burning sustains,
but the flame is never allowed to cross the bridge of the chimney.
147
148
• After burning of the fumes further heating is continued.

• Afterwards, the set is cooled and the silica crucible is weighed to get
the weight of carbon deposited.

• Expressed in percentage gives Conradson carbon residue.

149
 Ramsbottom method
• In this method the sample is carefully fed into a glass bulb which has a
capillary end.
• The bulb is kept into a heating bath kept at 550° C.
• The sample is allowed to decompose for 20 minutes.
• After heating is over the bulb is cooled and weighed to find the carbon
formed.
• Amount of material to be taken is inversely proportional to coking tendency
of the oil.
• Best quality of oil give less carbon residue under serviceable conditions.
• Conradson carbon residue of this should not exceed 0.2 to 1.0% .
• Paraffin oils give less carbon residue compared to naphthenic oils. 150
 Oxidation stability

• This test reveals the deterioration characteristics of oil on oxidation.

• Oils are generally in contact with air and hot surfaces thus oxidation is
inescapable.

• Higher paraffins are easily oxidised compared to naphthene and aromatics.

• Major amount of lube oil is paraffin, which is more prone to oxidation.

• In the laboratory the test is conducted by passing air at a rate of 15 liter per
hour through a sample of 40 ml kept at 200° C for 6 hrs.
151
• Second oxidation period for another 6 hrs at the identical conditions
for the same sample is carried out.

• After oxidation periods are over, the sample is cooled and its viscosity
and carbon residue are found out and compared with the original
sample.

152
 Bitumen
• Bitumen is the residual product obtained from crude distillation unit.
• It is essentially solid at room temperature and has got very high
viscosity.
• Asphalt is usually a mixture of bitumen in oil, containing much mineral
matter.
• Bitumen natural deposits are available; famous Trinidad pitch lake is
such a deposit.
• Bitumen obtained from the distillation column is poor in qualities.
• Most of the bitumen is used in high way constructions, waterproofing
and coatings works.
153
 Test for bitumen

• Softening point

• Penetration index

154
 Softening point (35 to 70°C)
• Bitumen being amorphous does not melt sharply.
• The softening point is found out by the Ball and Ring Test.
• Bitumen is first melted and casted into discs of two numbers in standard rings.
• A steel ball weighing (3.5±0.05) gms (dia 9.53 mm) is kept on each casted disc of
bitumen.
• The whole stand carrying these two discs with balls is immersed in a water or glycol
bath.
• As the heating proceeds, softening occurs.
• The temperature at which the sample detaches from the die and falls, indicates its
softening point.
• Two samples from such rings are supposed to fall within a difference of 5 seconds.
• Higher the softening point the better is consistency of bitumen.
155
156
 Penetration Index
• The hardness or penetration quality of bitumen is assessed by this test.

• A standard needle is allowed to penetrate under a load of 100 gms through a

sample kept at 25°C for 5 sec.

• Distance travelled under those conditions indicates the consistency of sample.

• The distance (easily) travelled would naturally depend upon its load, and
softening point.

• More penetration index naturally impairs the surface applications, where hardness
is sole criteria.
157
158
 Ductility
• Bitumen must possess good ductility, when it is used in surface application.

• The ductility is measured by ductilometer.

• Ductility is a measure of the capacity of bitumen to elongate or stretch.

• This test is carried out by pulling a test piece of bitumen of standard

dimensions at a uniform rate (5 cm/min) keeping sample at 25° C.

• Higher capacity for elongation indicates that the sample is having a high
ductility.
159