Unit II

Subject: Petroleum Refining Technology

Faculty: Dr. Murali Pujari
 Crude oil
Crude oil is a complex mixture of hydrocarbons and may also contain some compounds like
sulfur, nitrogen, oxygen and traces of metals like Arsenic, vanadium, nickel, and others
Composition:
Element Composition (wt. %)
Carbon 84-87
Hydrogen 11-14
Sulphur 0-13
Oxygen 0-2
Nitrogen 0-0.6%
Metals 0-1000 ppm

 Colour is dark brown to bluish black or black

 Specific gravity of crude oil is 0.81-0.985
 Value of crude oil depends on Sulphur content

For Sweet crude (S<0.5 wt.%) and Sour crude (S˃0.5 wt.%)

Based on API (density):

API ˃31 Light crude

31≥API≥22 Medium crude
22˃API˃10 Heavy crude
 API gravity
  141.5
° 𝐴𝑃𝐼 = −131.5 Sp. gravity= density of oil/density of water
𝑠 . 𝑔 . 𝑎𝑡 15.6 o C

Sp. gravity API

Lighter crude has higher API. Water 1.0 10

While heavier crude has lower API. Gasoline 0.74 60
Generally crude oil API gravity is 20-45 Asphalt 0.99 11

Heavy crude 0.95 18

Light crude 0.84 36

West Texas Intermediate (WTI) crude oil has an API gravity of 40

Alaska Heavy crude oil has an API gravity of 8 to 14
 Classification of crude oil
Knowledge of the base is necessary as it depicts (although not fully) the usual property and can
adequately inform the refiners about the difficulties in processing

Crude oil

Paraffinic Mixed base Naphthenic

base or base
intermediate
 Crude oil evaluation
Based on Mallision classification if the residue
• Paraffinic base crude (containing more than 5% wax)
• Naphthenic base crude (containing less than 2% wax)
• Mixed base crude (containing 2 – 5 % wax)
 Crude oil evaluation
Based on U.S. Bureau of mines
i. The basis of classification begins with two chosen fractions, Key fraction no. 1 and
Key fraction no. 2.

ii. Key fraction no. 1 has boiling range of 250 - 275 ⁰C at atmospheric pressure.

iii. Key fraction no. 2 has boiling range of 275 – 300 ⁰C at 40 mm of Hg; 389 – 422 ⁰C
at 760 mm of Hg.

iv. The API (American Petroleum Institute) gravities of these fractions are found out
and the base of the crude is characterized.
• For Key fraction no. 1, 40 or more API gravity is paraffinic base, less than 33
API is naphthenic base, and 33 – 40 API is mixed based.
• For Key fraction no. 2, 30 or more API is paraffinic, less than 20 API is
naphthenic base, and 20 – 30 API is mixed based.
 Crude oil evaluation
(3) Based on U.O.P. Characterization factor.
• Also called, Watson Characterization factor
  (𝑇 𝐵) 1 /3 TB Mean average boiling point
𝐾= (MeABP) in ⁰R (Rankin)
𝑠 . 𝑔 . 𝑎𝑡 60 𝑜 𝐹

• For paraffinic base, K is equal to 12.5 or above.

• For naphthenic base, K is equal to 10 or less.

• For mixed base, K is between 10 and 12.5

 Crude oil evaluation
(4) Bureau of mines correlation index
• Also called, Correlation index (C.I.)

  48640 Mean average boiling point

𝐶 . 𝐼 .= + 473.7× 𝑠 . 𝑔 . − 456.8 (MeABP) in ⁰K (Kelvin)
𝑀𝑒𝐴𝐵𝑃

• For paraffinic base, C.I. < 15

• For naphthenic base, CI is greater than 50.

• For mixed base, CI is between 15 and 50

Compounds present in Crude oil
 Compounds

Asphaltenes
and resins
Paraffin Naphthene Aromatics
• Most abundant Metallic
• 2nd Most abundant
series. series. Inorganic compounds
impurities
Nitrogen
compounds
Olefins Sulfur
• Originally not present in crude oil. compounds
• But exist during crude oil processing.
Oxygen
compounds
 Paraffin
 Paraffin, aslo known as alkanes are Two
isomers
open chain saturated hydrocarbons General formula,
CnnH2n+2
2n+2
 Because of their structural difference,
these isomers have different properties.
Three
 Example: the presence of Iso paraffins in isomers
gasoline is essential for increasing the
octane number of gasoline.

 n-paraffins are poor anti-knocking

75
properties. isomers
for
 Example: Octane number of n- octane decane.
and Iso octane is 17 and 100, respective.
Contd…

Name No. of C atoms Mol. formula St. Formula No. of Isomers

Methane 1
Ethane 1
Propane 1
Butane 2
Pentane 3
Hexane 5
Heptane 9
Contd…
Name No. of C atoms Mol. formula St. Formula No. of Isomers

octane 18
nonane 35
decane 75
12 355
15 4347
18 60523
25 35,797,588
Properties of Paraffins:
Paraffins are stable not attacked by H2SO4 or other oxidizing agents

Higher paraffins are insoluble in water.

Paraffins upto 3 carbon atoms have tendency to form hydrates such as CH 4 7H2O, C2H6

7H2O and these offer clogging and corrosion difficulties.

Specific gravity of the series increases with M.Wt , but still have less specific gravity and
boiling point than aromatics.

Viscosity of paraffins is less but viscosity index is high in contrast to aromatics.

The smoke point of the paraffins is very high

Contd…
The pour point (freezing point) of paraffins is usually high and due to this paraffinic rich
crudes and products bring difficulties in storage.

Isoparaffins are more reactive than n-paraffins.

Isomers differ from n-paraffins by having slightly low boiling points, low pour points,
high viscosity and viscosity index.

High molecular weight >C20 may be of saturated or unsaturated nature decompose if

exposed to a tempt of above 370oC.

 Vacuum distillation is essential for distilling such boiling stocks to prevent them from
thermal degradation.
 Naphthenes
 Cyclo paraffin are saturated ring hydrocarbons

 General formula, CnH2n+2-2N

 Boiling point and densities of napthenes are

higher than alkanes having same number of
carbon atoms.

 Naphthenes, with 5 – 6 carbons atoms are

usually present in crude oil (good fuels).

 Multi-rings naphthene are present in heavier

part of crude oil (gas oil and lubricating oil).
 Aromatics
 Aromatics are unsaturated cyclic compounds with
one or more benzene rings
 General formula, CnH2n-6

 Light petroleum fractions contains mono-aromatics

and there presence increases octane number.

 Fused benzene ring (poly-nuclear aromatics) are

found in the heavier cuts.
 Their presence is undesirable because:
• Causes catalyst deactivation,
• Coke deposition during processing, and
• Environmental problems.
Contd…
Aromatics have high boiling points, low pour points, high octane numbers, high
viscosity, and low viscosity index.

Lighter aromatics (BTX) do not exceed even 5% of crudes of general nature.

 Olefins
 Also known as alkenes, they are unsaturated
hydrocarbons with carbon–carbon double or triple
bond.
 General formula, CnH2n
 Compounds containing C-C triple bonds are
known as alkynes

 They are more reactive than paraffins.

 The lightest alkenes are ethylene and

propylene which are important feedstocks for
the petrochemical industry
 They relatively unstable molecules which
oxidizes and polymerizes during storage.
 Resins
 It is dark coloured solids or semi-solid considered
as highly aromatic
 It contain one poly nuclear aromatic surrounded by
side chains of paraffins and small ring aromatics
with molecular weight between 500-1500

 Each poly nuclear aromatic may have S, N, O, V

and Ni etc.

 It produce colour to the products

 easily dissolve in crude oil sticky solid

 Asphaltenes
 These are sheets of poly nuclear aromatics
with 20 or more rings connected by
paraffinic and naphthenic chains

 Molecular Weight 5000-10000

 Hetero atoms distributed throughout

 Do not dissolve in crude oil and dispersed

as colloids in the crude

 Non volatile, black liquor

 Sulfur Compounds
 Sulfur content can vary from less than 0.1 % to
more than 7 % (w/w)

 Generally it falls in between 1 – 4 % (w/w).

 Occurs in different forms like free S, hydrogen

sulphide, mercaptans, and thiophenes etc.

 High sulfur content crude:

 Produces strong objectionable odor in gasoline and
kerosene fraction, There is no sharp dividing line between
 Corrosion, catalyst poison and air pollution sour and sweet crudes, but 0.5% sulfur
content is frequently used as the criterion.
 Oxygen Compounds
 Oxygen do not occur in free state either in
crudes or in fractions.

 Mostly less than 2 % weight in crude oil

 High oxygen content indicates:

 Can be in the form of alcohols, ethers,
carboxylic acid, phenolic compounds,
ketones, esters, and anhydrides,

 These compounds can cause crude to be

acidic leading to problems of corrosion
problem at various stages of processing.
 Nitrogen Compounds
 Nitrogen do not occur in free state either in
crudes or in fractions.

 Crude oil containing more than 0.25 % by

weight of nitrogen compounds requires
special attention.

 Nitrogen compounds are more stable and

are harder to remove.

 High nitrogen content crude causes:

 Causes catalyst poisoning, corrosion,
gum formation problems
 Metallic Compounds
 Metallic compounds may vary from few ppm to
1000 ppm

 Concentrations of metallic compounds must be

reduced to avoid operational problems and prevent
them from contaminating.
 They also corrosion and fouling.

 Even minute amount may affect the activity of

catalyst causing increased production of coke and
reduced gasoline yield.
 Crude oil Characterization
In this lecture we will discuss about various test for characterization of crude oil and its
product:

1. Fractionation
2. API gravity
3. Pour point
4. Viscosity
11. Reid vapor pressure
5. Refractive index
12. Water salt sediment
6. Freezing point
13. Molecular weight
7. Aniline point
8. Flash point
9. Octane number
10. Cetane number
11. Smoke point
 Fractionation
• Distillation of crude oils determines the yield of the products that can be obtained
from this crude oil when it is processed in a refinery.

• A light crude oil will produce higher amounts of gasoline than a heavier crude oil

• Different standard distillation tests can be performed on crude oil or petroleum

fractions. Usually the following methods are followed:
 ASTM (American Society for Testing and Materials) Distillation (ASTM D86)
 True boiling point distillation
 Fractionation
• ASTM Distillation (ASTM D86)

• ASTM distillation is carried out in a relatively simple

apparatus consisting of a flask holding the sample
connected to an inclined condenser, which condensed
the rising vapors.

• The fractions distilled are collected in a graduated

cylinder. The temperature of the rising vapors is
recorded at specific interval of the collected distillates.
This is essentially a batch distillation with one
equilibrium stage and no reflux and minimum
separation of the components of the fractions.
 Fractionation
• ASTM Distillation (ASTM D86)
• The temperature at which the first drop of condensate
is collected is called the initial boiling point (IBP).
• The end point (EP) is the maximum vapor
temperature when almost the entire sample is distilled
(above 95%).
• Minimum fractionation occurs in ASTM distillation,
and components in the mixture do not distil one by
one in the order of their boiling points, but rather as
mixtures of successively higher boiling points.

• Nevertheless, because ASTM distillations are quickly

conducted and have been successfully automated,
require only a small sample, and are widely used.
 Fractionation
• True boiling point distillation

• Data from TBP distillation provides more detailed • The high degree of fractionation in this test gives
characterization of the volatility of crude oil or an accurate component distribution.
petroleum fraction
• Because the degree of separation for a TBP
• It is performed in columns with 15 theoretical
distillation test is much higher than that of the
plates or equilibrium stages and a reflux ratio of 5.
ASTM distillation test, its IBP is lower and its
• Rising vapors are condensed and collected either at EP is higher than those of the ASTM test.
a constant rate of boiling points or constant rate of
the sample vaporized. • The TBP curve is usually used as a basis for the
characterization of crude oil or a petroleum
• Operation is at 760 mm Hg for boiling points product for the purpose of design and analysis.
below 400 ⁰C (750 ⁰F). For higher boiling point
fractions, the distillation is conducted at reduced
pressures as low as 0.5 mm Hg.
 Fractionation
• Conversion between ASTM distillation and TBP distillation
• Since TBP distillation is both tedious and time-consuming TBP is true boiling point temperatures at
in comparison with the ASTM method, there has been an 0, 10, 30, 50, 70, 90, and 95 volume
incentive to develop correlation to convert ASTM to TBP percent distilled, in degrees Rankin.
distillation while at the same time achieving the benefit of
the detailed separation of TBP with the little effort of the
ASTM distillation.
 
• The following equation suggested by Riazi and Daubert (1980)
and published by the API (1993) is used for the interconversion,
referred to as API method:

 𝑇𝐵𝑃=𝑎 × ( 𝑏
𝐴𝑆𝑇𝑀 𝐷 86 ) ASTM D86 is the observed ASTM
D86 temperatures at corresponding
where a and b are constants varying with percent of volume percent distilled, in
liquid sample distilled degrees Rankin.
 API gravity

The API gravity is also measured for various petroleum fractions. One of the
standard tests is ASTM D1298
 Pour point
• The pour point is defined as the lowest temperature at
which the sample will flow.

• It indicates how easy or difficult it is to pump the oil,

especially in cold weather.

• It also indicates the aromaticity or the paraffinity of

the crude oil or the fraction.
 A lower pour point means that the paraffin
content is low.
 Pour points for the whole crude and fractions
boiling above 232 ⁰C (450 ⁰F) are determined by
standard tests like ASTM D97.
 Freezing point
• Petroleum fractions are mostly liquids at ambient conditions.

• However, heavy oils contain heavy compounds such as waxes or asphaltenes.

• These compounds tend to solidify at low temperatures, thus restricting flow.

• The freezing point is the temperature at which crystals starts to form in hydrocarbon liquids
and then disappear when the liquid is heated. (Changes its phase)

• It is one of the important property specifications for kerosene and jet fuels due to the very
low temperatures encountered at high altitudes in jet planes.

• One of the standard tests is ASTM D4790 and ASTM D16.

 Flash point
• The flash point of a liquid hydrocarbon is the lowest temperature at which the sample must
be heated to produce a vapor/air mixture above the liquid fuel that is ignitable when
exposed to an open flame under specified test conditions

• It is an important specification for gasoline and naphtha related to safety in storage and
transport in high temperature environments

• Flash point indicates the fire and explosion potential of a fuel.

• A low flash point fuel is a higher fire hazard. In India flash point of diesel is kept around
50 – 55 ⁰C

• One of the standard tests is ASTM D1711, D09 and D1695.

 Fire point
• The fire point is the lowest temperature at which the vapor of the fuel will continue to burn
at least 5 seconds after ignition by an open flame of standard dimension

The ignition temperature (sometimes called the auto-ignition

temperature) is the minimum temperature at which the material
will ignite without an external source of ignition such as spark
or flame.
The method of measurement is given by ASTM E659
 Smoke point
• The smoke point is a test measures the burning
qualities of kerosene and jet fuel.
• It is defined as the maximum height in mm, of
a smokeless flame of fuel.
• High smoke point is essential for clean combustion.
• Smoke is contributed by aromatics.
• Naphthenes have good smoke and illuminating
characteristics and preferred in fuels.
• To improve the smoke point aromatics (tolerance
• However, the smoke point test is not
limit: 20%) should be either converted to
always a reliable criterion of combustion
naphthenes or should be completely removed. performance and should be used in
conjunction with other properties.
• One of the standard tests is ASTM D1322.
Smoke point
 Smoke volatility index
• Smoke point index is an important property of jet fuel.

• Sometimes instead of expressing the quality of jet fuel by

smoke point alone, it is express in terms of smoke volatility
index defined as,

Smoke volatility index =smoke point + 0.42 (% distilled at 204 ⁰C)

 Aniline point
• The lowest temperature at which an equal volume mixture of the petroleum and aniline
are miscible
• Since aniline is an aromatic compound, a petroleum fractions with high aromatic content
will be miscible in aniline at ambient conditions.
• However, if the oil has more paraffins, it will require a higher temperature and thus
higher aniline point in order to be miscible in aniline.

• This property is important for the specifications of diesel fuels. It is measured by ASTM
D611.
 Refractive index
• The refractive index is the ratio of the velocity of light in a vacuum to the velocity of light
in the oil.

• This parameter is used as a characterization parameter for petroleum fraction composition

• It is measured according to ASTM D1218

 Reid vapor pressure
• Reid vapor pressure (RVP) is a common measure of the volatility of gasoline and other
petroleum products.
• The Reid vapor pressure (RVP) of a product is the vapor pressure determined in a volume
of air four times the liquid volume at 37.8 ⁰C (100 ⁰F).

• This property measures the vapor-lock tendency of a motor gasoline in which excessive
vapors are produced in the fuel line causing interruption of the supply of liquid fuel to the
engine.

• It also indicates the explosion and evaporation hazards of the fuel. One of the standard
tests is ASTM D323.

• High levels of vaporization are desirable for winter starting and operation and lower levels
are desirable to avoid vapor lock during summer heat
 Reid vapor pressure
• Fuel cannot be pumped when there is vapor in the fuel line (summer) and winter starting will
be more difficult when liquid gasoline in the combustion chambers has not vaporized.

• Thus, oil refineries manipulate the Reid Vapor Pressure seasonally specifically to maintain
gasoline engine reliability.
 Knocking
 Octane number is the measure of anti-knocking tendency of gasoline fuels, in spark
ignition engines.

 Octane number is the percentage of iso-octane in a mixture of iso-octane and n-

heptane

 Octane number is determined by measuring the knocking value compared to

knocking of a mixture of n-heptane and Iso-octane.

 Higher the octane number, more the resistance to auto-ignition during compression
and prior the spark ignition
 Octane number
• Pure n-heptane is assigned a value of zero
octane while isooctane is assigned 100
octane.
• Two octane tests can be performed for
gasoline:
• Motor octane number (MON)
• Research octane number (RON)
• The motor octane number (MON) indicates
engine performance at highway conditions
with high speeds (900 rpm).
• The research octane number is indicative of
low-speed city driving (600 rpm).
• The posted octane number (PON) is the
arithmetic average of MON and RON.
• One of the standard tests is ASTM D2700.
 Diesel index
• Diesel index is the measure of ignition
quality of fuel.
• Diesel engine works on the principle of
compression and ignition
• During compression of diesel engine, the
temperature of air reaches around 600 ⁰C,
when the fuel is fed in atomized form, it
explodes instantaneously.
• Self ignition temperature is low for
paraffins, while it is high for aromatics
(651 ⁰C for benzene).
• Thus fuel rich in aromatics burns later
causing ignition delay and it gives rise to
diesel knock.
• For this reason all diesel fuels have a diesel
index of around 45 to 55.

• The temperature at which this explosion

takes place without the aid of fire is called
self ignition temperature.
 Cetane number
• The cetane number measures the ability for Cetane no. Diesel index
auto ignition and is essentially the opposite
30 26
of the octane number.
35 34
• The cetane number is the percentage of pure 40 42
cetane (n-hexadecane) in a blend of cetane
and alpha methyl naphthalene which matches 45 49
the ignition quality of a diesel fuel sample. 50 56
55 64
• Higher the cetane number, the better is the
combustion quality. 60 72

• It is an indicator of the combustion speed of • This quality is specified for middle

diesel fuel and compression needed for
distillate fuels. One of the standard
ignition
tests is ASTM D976.
 Water, salt and sediments
Ranges from
• Crude oil contains small amounts of water, mineral salts and sediments
0.1 – 2.0 %

• Chlorides of magnesium, calcium and sodium are the most common salts

• The presence of salts causes problems in processing, such as corrosion, erosion and
plugging of equipment, and catalyst deactivation

• Sediments are solid material that are not soluble in the hydrocarbon or water and can be
comprised of sand, drilling mud, rock or minerals coming from erosion of metal pipes,
tanks and equipment

• One of the standard tests is ASTM D6470

 Viscosity
• The resistant to flow or the pumpability of the crude oil or petroleum fraction is indicated
by the viscosity

• More viscous oils create a greater pressure drop when they flow in pipes

• Viscosity measurements is expressed in terms of kinematic viscosity

• Kinematic viscosity is measured at 37.8 oC by ASTM D445 and by ASTM D446 at 99 oC

 Molecular Weight
• Most crude oils and petroleum fractions have average molecular weights from 100 to 500

• There are several methods for measuring the molecular weight, the most suitable method
is that based on freezing point depression
Product composition
 Low boiling products
• The classification low-boiling products encompasses the compounds which are in the gas
phase at ambient temperatures and pressures: methane, ethane, propane, butane, and the
corresponding olefins.

• Methane
 Used as refinery fuel
 can be used as a feedstock for hydrogen
production by pyrolytic cracking and
reaction with steam.
• Ethane
 Ethane (C2) can be used as refinery
fuel
 Feedstock to produce hydrogen or
ethylene, which are used in
petrochemical processes.

• Propane
 Propane (C3) is frequently used as a refinery fuel but is also sold as liquefied petroleum
gas (LPG),
 Low boiling products
• Butane
 Butane used as components of gasoline and in refinery processing as well as in LPG.

 Normal butane (nC4) has a lower vapor pressure than isobutane (iC4), and is usually
preferred for blending into gasoline to regulate its vapor pressure.

 Normal butane has a Reid vapor pressure (RVP) of 52 psi (358 kPa) as compared with
the 71 psi (490 kPa) RVP of isobutane, and more nC4 can be added to gasoline without
exceeding the RVP of the gasoline product.

 Normal butane is also used as a feedstock to isomerization units to form isobutane

 Low boiling products
• Butane
 Isobutane has its greatest value when used as a feedstock to alkylation units, where it is
reacted with unsaturated materials (propenes, butenes, and pentenes) to form high-
octane isoparaffin compounds in the gasoline boiling range.

 A significant amount of isobutane is converted to isobutylene which is reacted with

methanol to produce methyl tertiary butyl ether (MTBE).

 Butane–propane mixtures are also sold as LPG

Naphtha
Generic name given to lighter hydrocarbons boiling in the gasoline range.

Light distillate obtained from refining of crude oil

Naphtha are usually classified as light naphtha (fraction boils below 100oC),
intermediate naphtha (100-150oC), heavy naphtha(above 150oC).

Used as gasoline and feed stock for petrochemical and fertilizer industry.
Methods to produce naphtha
Naphtha is produced by atmospheric distillation of crude oil.

Cracked naphthas: Visbreaking, fluid catalytic cracking, hydrocracking, coking

Proper quality of naphthas can be achieved by dearomatising the napthta

Composition of naphtha depends on crude oil processed and the conversion process
employed.
 Gasoline
 Gasolines are complex mixtures of hydrocarbons • Blending
having typical boiling ranges from 100 to 400°F (38 • Light straight gasoline
to 205°C) as determined by the ASTM method. • Reformate gasoline
• Cracked gasoline
 Hydrocarbon range:C5-C10(mainly n-paraffins, iso • Polymer gasoline
• Alkylate, n-butane
paraffins, naphthenes and aromatic hydrocarbons) • MTBE (methyl tertiary
 Most refiners produce gasoline in two or three grades, • butyl ether), ETBE (ethyl
regular, midgrade, and premium, tertiary butyl ether), TAME
• Regular grade 85 < PON < 88 (tertiary amyl methyl ether)
• midgrade, 88 < PON < 90 • Ethanol.
• premium, PON > 90  The quantity of antiknock agents
 Components are blended to promote high antiknock added, and their costs, must be
quality, ease of starting, quick warm-up, low determined by making octane
tendency to vapor lock, and low engine deposits. blending calculations.
 Gasoline
 The vapor pressure [expressed as the Reid
vapor pressure (RVP)] of gasoline is a
compromise between a high RVP to
improve economics and engine starting
characteristics and a low RVP to prevent
vapor lock and reduce evaporation losses.
 As such, it changes with the season of the
year and varies between 7.2 psi (49.6 kPa) in
the summer and 13.5 psi (93.1 kPa) in the
winter.
 Butane has a high blending octane number
and is a very desirable component of
gasoline. So, refiners put as much in their
gasolines as vapor pressure limitations
permit.
 Iso-butane can be used for this purpose but it
is not as desirable because its higher vapor
pressure permits a lesser amount to be
incorporated into gasoline than n-butane.
 Gasoline
 Concern over the effects of hydrocarbon fuels
usage on the environment has caused changes
in environmental regulations which impact
gasoline and diesel fuel compositions.  Some aromatics and most olefins react
with components of the atmosphere to
 The main restrictions on diesel fuels limit produce visual pollutants.
sulfur and total aromatics contents
 Gasoline restrictions include not only sulfur and
total aromatics contents but also specific
compound limits (e.g., benzene), limits on
certain types of compounds (e.g., olefins),
maximum Reid vapor pressures, and also
minimum oxygen contents for areas with carbon
monoxide problems.
Composition of Gasoline

Light distillate, boiling range of 38-205oC.

Hydrocarbons ranging from C5 to C10.

Main types are: N-paraffins, iso or branched paraffins, cycloparaffins, aromatics and
olefins.

Prepared by mixing various components produced by refining processes.

Small quantities of additives are added.

Quality of gasoline depends on its hydrocarbon composition.

Properties of Gasoline
Quality is maintained by limiting and controlling specification characteristics .

Combustion quality is a primary performance indicator.

Combustion quality relates those properties which affect the ability of gasoline to
ignite properly.

Handling and storage characteristics is a function of volatility, fluidity,

contamination during refinement.
 Distillate fuels
• Distillate fuels can be divided into three types:
• Jet fuel or turbine fuels
• Diesel fuels
• Heating oils

These products are blended from a variety of refinery streams to meet the desired
specifications
Jet or Aviation turbine fuel
 Jet fuel is blended for use by both commercial aviation and military aircraft
 The primary source of jet fuel blending stocks is the straight-run kerosine fraction from
the atmospheric crude unit
 The stringent total aromatic and naphthalene content and smoke point specifications limit
the amount of cracked stocks
 For refineries with a hydrocracker, kerosine boiling range hydrocarbons from this unit
can also meet jet fuel specifications and is a major contributor to jet fuel production.
 For the refiner, it is more profitable to blend the kerosine fractions from the atmospheric
crude unit and the hydrocracker into jet fuel rather than other products
Contd…
Aviation fuels consist primarily of straight and branched alkanes and cycloalkanes.

Depending on the specific specification, the limit on aromatic hydrocarbons and

naphthenes are 20 to 25% and 3% of the total mixture

Contd…
Two basic types of jet fuels that are in general use are

Based on kerosene (kerosene-type jet fuel)

• Kerosene-type jet fuel (including Jet A and Jet A-1, JP-5 or JP-50) has a carbon
number distribution between about 8 and 16 (carbon atoms per molecule)
Based on gasoline (naphtha) (gasoline-type jet fuel)

• Naphtha-type jet fuel (JP-8), between about 5 and 15

• Naphtha jet fuel is produced primarily for the military purpose

• The major jet fuels used by the military are JP-4, JP-5, JP-6, JP-7, and JP-8.

• Safety consideration limits the commercial jet fuels to the narrower boiling range
products (177 - 288 oC)
 Jet fuel specifications
Property Jet A JP-8
Flash point minimum of 38 ⁰C minimum of 38 ⁰C

Smoke point minimum of 18 – 25 mm minimum of 20 – 25 mm

Aromatics limit (vol. %) 20 % 22 %

Napthalene limit (vol. %) 3% 3%
Freezing point – 40 ⁰C – 47 ⁰C

Sulfur content maximum of 0.3 % maximum of 0.3 %

Automotive Diesel Fuels
Volatility, ignition quality (expressed as cetane number or cetane index), viscosity,

sulfur content, percent aromatics, and cloud point are the important properties of

automotive diesel fuels.

No.1 diesel fuel ( super-diesel) is generally made from virgin or hydrocracked stocks

having cetane numbers above 45.

It is has a boiling range from 360 to 600 °F (182 to 320 °C) and is used in high-speed
engines in automobiles, trucks, and buses.
Contd…

No.2 diesel fuel has a wider boiling range than No. 1.


It usually contains cracked stocks and may be blended from naphtha, kerosene, and light cracked oils from

the coker and the fluid catalytic cracking unit.


Limiting specifications are flash point [125°F (52°C)], sulfur content (0.05% max.), distillation range,

cetane number or cetane index (minimum of 40), percent aromatics and cloud point
Contd…

The ignition properties of diesel fuels are expressed in terms of cetane number or cetane index


Cetane number is similar to octane number and is expressed as the volume percent of cetane in a

mixture with alpha-methyl-naphthalene


Cetane number is a function of mid–boiling point and gravity of the sample.


Cetane index is an indicator of the H/C ratio and also indirect indicator of the aromatic content of

the diesel fuel


Higher the H/C ratio, the better the burning characteristics (i.e., higher the smoke point and

higher the cetane index)

Contd…
 To improve air quality, more severe restrictions are placed on the sulfur and
aromatic contents of diesel fuels
 Lowering sulfur and aromatics contents specifications also lowers the particulate
emissions from diesel engines.
Contd…
• Railroad diesel fuel
• Railroad diesel engine fuel is one of the significant markets for diesel fuels.
• Railroad diesel fuels are similar to the heavier automotive diesel fuels but have
higher boiling ranges [up to 750°F (400°C)] and lower cetane numbers min of 30
 Distillate fuels
• Heating oil
• The fuel oils are mainly used in space heating and thus the market is quite high
specially in cold climates.

• The principal distillate fuel oils consist of No. 1 and No. 2 fuel oils.

• No. 1 fuel oil is very similar to kerosene, but generally has a higher pour point and end
point.

• No. 2 fuel oil is very similar to No. 2 diesel fuel, contains cracked stock, and is blended
from naphtha, kerosene, diesel, and cracked gas oils.
• Limiting specifications are sulfur content, pour point, distillation boiling range, and
flash point.
 A space heater is a device used to heat a single, small area;
 central heating is used to heat many connected areas, such
as the rooms of a house.
 Space heaters are powered by electricity or a burnable fuel,
such as natural gas, propane, fuel oil, or wood pellets.
 Residual fuel oil
• Residual fuel oil is the fuel oil that is manufactured from the distillation residuum, and
the term includes all residual fuel oils, including fuel oil obtained by visbreaking.

• It is mainly composed of vacuum residue.

• It sells for a very low price (historically about 70% of the price of crude from which it
is produced) and is considered a by-product.

• Critical specifications are viscosity and Sulfur content.

• Low Sulfur residues are in more demand in the market.

Kerosene
Kerosene (kerosine):also called paraffin or paraffin oil, is a flammable pale-yellow or
colorless oily liquid with a characteristic odor.

It is obtained from petroleum and used for burning in lamps, cooking stoves, and
domestic heaters or furnaces, as a fuel or fuel component for jet engines, and as a
solvent for greases and insecticides.

It is a medium oil distilling between 150 oC and 300 oC (HC: C9-C16).

Kerosene has a flash point of about 25 oC (77 oF) and is suitable for use as an
illuminant when burned in a wide lamp.
Kerosene Composition
Kerosene, because of its use as a burning oil, must be free of aromatic and
unsaturated hydrocarbons, as well as free of the more unpleasant sulfur
compounds.

The desirable constituents of kerosene are saturated hydrocarbons, and it is for

this reason that kerosene is manufactured as a straight-run fraction, not by a
cracking process.
 Lubricating oil
 lubricating oil is used to reduce friction and wear between
bearing metallic surfaces that are moving with respect to
each other, by separation of metallic surfaces by a film of
the oil.
 Lubricating oil is distinguished from other fractions of
crude oil by a high (> 400°C, > 750°F) boiling point
 Lubricating oil is composed of base oil plus the various
additives that are necessary to enable lubricating oil to meet
specifications.
• A high boiling point and low freezing point,
• viscosity,
• Thermal stability
• Corrosion prevention
• A high resistance to oxidation
Bitumen
Residue obtained from CDU.

Solid at room temperature. High viscosity.

Asphalt: mixture of bitumen in oil containing mineral matter.

Use: high way construction, water proofing coating

Asphalt
 Asphalt, also known as bitumen is a sticky, black, and highly
viscous liquid or semi-solid form of petroleum

 Asphalt are residue obtained from

petroleum after nondestructive distillation
and has removed all the volatile materials

High way construction, water proofing coating etc.

Petroleum coke
 Petroleum coke or simply, Petcoke is the coke that, is
derives from a final cracking process—a thermo-
based process that splits long chain hydrocarbons of
petroleum into shorter chains, which takes place in
units termed coker units.

 Carbon compounds formed from thermal conversion

of petroleum containing resins and asphaltenes are
called petroleum cokes.
 Used in electric power plants, cement
 Fuel grade coke contains about 85% carbon and 4% kilns, aluminum and steel plants
hydrogen. The balance is made up of sulphur,
nitrogen, oxygen, vanadium and nickel.
Evaluation of properties of crude oil
and its fractions
Whole crude TBP data (API gravity 36.3)

Volume % 5 10 20 30 40 50 60 70 80 85
TBP temperature (oF) 62 144 255 344 437 531 623 717 819 897

 Plot TBP and determine characterization factor (K), MW, and wt. for the crude oil
 Average Boiling Point

Volume Average Boiling Point (VABP):

OR

Weight Average Boiling Point (WABP):

Molal Average Boiling Point (MABP):

Cubic Average Boiling Point (CABP):

Where Xvol,i is volume fraction of compound i
Ti is boiling point of i

MeABP= VABP - Correction Factor

Slope of distillation curve:

 The petroleum fractions are ‘‘cuts’’ from the crude oil with specific boiling point range
and with special properties such as API gravity and viscosity.

 Each of these cuts can be further defined by dividing them into narrow boiling fractions,
called pseudo- (not real) components.
 For these pseudo-components, the average boiling point can be estimated as either mid-
boiling point or mid-percentage boiling point.
 The mid boiling point is the average between the IBP and the EP of that pseudo
component.

 The mid percentage boiling point is the temperature at the arithmetic average of the
volumes distilled at IBP and EP of that pseudo component.
Mid boiling point and Mid volume percentage:

N K D
T

10 30 70
Vol%
General procedure for evaluation of crude oil/fractions:

 From the crude distillation data, plot TBP curve

 Calculate the volume average boiling point (VABP)

 Calculate slope of the whole crude

 Convert VABP to mean average boiling point (MeABP) using the proper correction factor

 K found as a function of MeABP and API by use of graph.

K
Calculations:
Whole crude TBP data (API gravity 35)
Volume % 0 10 20 30 40 50 60 70 80
TBP temperature (oF) 75 200 300 385 470 550 625 715 825

i) Plot TBP and determine characterization factor (K), MW, and wt. for the crude oil

ii) Assuming K remains constant, calculate molecular weight, API and weight for the
following boiling range cuts
a) For the TBP range (IBP to 200 oF) calculate MeABP, API, M.W based on 100
barrels of whole crude
b) For the TBP range (200 -300 oF), repeat above step (a) and so on until the entire
crude range has been converted.
c) From these calculations, draw the curves Vol% vs. Wt.%, Mid Vol.% vs. Mol wt.,
API vs. Mid Vol.%
Refinery Configurations and Categories:
 It is useful to classify refineries by their processing capability for economic
analyses.

 Four general categories or configurations of refineries are

• Topping
• Hydroskimming
• Cracking
• Full conversion/complex
Topping
 A topping refinery is the simplest configuration

 The refinery processing scheme primarily consists of a crude unit making light
ends (C1–C4), naphtha, kerosene, and some diesel.
 The atmospheric residue from the crude unit is normally sold as fuel oil or an
intermediate
Topping

Simple topping refinery flowsheet

Topping
 Products from a topping refinery do not undergo much additional treatment

 Specifically, they do not undergo chemical processing to change their boiling

range (cracking, coking) or to improve the products characteristics (like reforming
or hydrotreating).
 Crude fed to a topping refinery is generally light, sweet material to get the most
value from the equipment. This limits crude options and flexibility.

 The limited process capabilities of this refinery, these facilities are usually found
in locations where environmental regulations are not strict, where there is a use
for the intermediates, or at oil field processing facilities to stabilize the crude.
Topping
 The advantages of topping refineries lie in their simplicity and low cost. It is
relatively easy to operate a crude column. Compared to more complex refineries,
these are cheap to build, with flexibility in size.

 The key disadvantages of topping are in the limited crude slate, products that will
not meet most environmental specifications and must be sold as intermediates,
and production of a lot of low value product (like fuel oil).

 This type of refinery is usually not economically viable in low margin periods
Hydroskimming Refinery
 The next most complex and capable refinery is the hydroskimming facility

 In this configuration, the diesel and lighter products from the crude unit are
processed to meet final product specifications. There is still no cracking involved.

 Products from a hydroskimming refinery could include light ends (C1–C4),

finished gasoline, finished jet fuel, and ultralow sulfur diesel.
 The light ends may also be upgraded to improve their value (e.g., isomerizing
butanes).
 This configuration gains some crude flexibility, but still wants a light crude. The
crude does not have to be sweet. It is still fairly inexpensive to build and easy to
Hydroskimming Refinery
 The key disadvantages of hydroskimming are that still are producing a lot of fuel
oil and are limited to relatively light crudes.

Simple hydroskimming refinery flowsheet

Cracking Refinery
 A cracking refinery begins to chew into the atmospheric resid to convert it to
more valuable products
 Compared to hydroskimming, a cracking refinery adds a vacuum tower and (a) a
fluid catalytic cracking (FCC) unit plus an alkylation unit or (b) a hydrocracker to
convert the vacuum gas oil. Some refineries may have both.

 Additional feed or product treating is needed to meet the most stringent

specifications, such as US Tier III gasoline.

 The vacuum resid is still sold as fuel oil (usually high sulfur) or made into asphalt
Cracking Refinery
 A cracking refinery with a high gasoline market will favor an FCC route

 In a diesel market, the cracking refinery would favor hydrocracking over FCC

 The advantages of a cracking refinery are greatly increased crude flexibility and
the production of more high-value products per barrel of crude

 To obtain the advantages, this type of refinery takes on greater operating complexity,
as well as higher capital and operating costs
Two possible configurations for a cracking refinery
Two possible configurations for a cracking refinery
Full conversion/complex refinery
 The final category for refinery configurations is the full-conversion/complex refinery
 The key feature distinguishing these facilities is the conversion of the remaining
vacuum resid to high-value products

 The refinery pretty much looks like a cracking refinery up to a point

 The key changes from the cracking refinery flowsheet are the addition of coking,
heavy oil cracking (like a resid FCC), deasphalting, and/or resid hydrocracking (like
LC-fining or H-oil)

 The first configuration would focus on a gasoline-driven market, whereas the

second sheet would apply more to a diesel-driven market.
Full conversion/complex refinery
 A full-conversion refinery has the greatest flexibility possible in crude slate and
seeks to make the maximum amount of high-value products from the crude charge
with a minimum of by-product.
 Because of their flexibility, these facilities can operate profitably through low margin
periods

 On the downside, these facilities cost significantly more than the other types of
refineries and add operating complexity

 There are still some by-products that are of low value, such as petroleum coke, that
must be managed
Two possible complex refinery configurations
Two possible complex refinery configurations
Video links for test methods:
1. ASTM Distillation test method: https://www.youtube.com/watch?v=xQ7LQMUTT4g
2. Reid vapour pressure Test-https://www.youtube.com/watch?v=LZmEglC-tKI
3. Octane test(Gasoline):https://www.youtube.com/watch?v=vL8Uj2CNWtI
4. Cetane test(Diesel):https://www.youtube.com/watch?v=WdQ4J-NFoU8
5. Flash & Fire point test:https://www.youtube.com/watch?v=yLtuDv3GzWo
6. Viscosity test(Lube oils):https://www.youtube.com/watch?v=iv_KvOFSqeY

7. Carbon residue test:https://www.youtube.com/watch?v=fApV3AXcAEA

8. Pour point test: https://www.youtube.com/watch?v=dO5gq-WPIqg
9. Smoke point test(Kerosene):https://www.youtube.com/watch?v=f-PRqAO22T8
10. Aniline point test:https://www.youtube.com/watch?v=GsmSPb4W46s
Thank You