CHARACTERIZATION

OF CRUDE
Ms. N. DEEPA PRIYA
Assistant Professor
Department of Chemical Engineeringg
Kongu Engineering College
Introduction
Petroleum is classified into mainly three types
– Paraffinic base – residue containing more than 5% paraffin's
– Naphthenic base – residue containing less than 5% paraffin's
– Mixed base – residue containing 2% - 5% paraffin's
The basis of classification begins with two chosen key fractions
■ Key fraction No.1 (Kerosene)
■ Has a boiling range of 250oC – 275oC at normal pressure
■ Key fraction No.2 (Lube)
■ Has a boiling range of 275oC – 300oC at a pressure of 40 mm Hg
■ When key fraction No. 1 has : 40 or more API gravity it is paraffinic, less than 33
API gravity, it is naphthenic and in the range of 33 – 40 API gravity, it is mixed
base
■ When key fraction No.2 has : 30 or more API gravity then it is paraffinic; less than
20 API gravity it is naphthenic and in the range of 33-40 API gravity it is mixed
base

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
 API (American Petroleum Institute)
gravity
■ A specific gravity scale developed by the American Petroleum
Institute (API) for measuring the relative density of various
petroleum liquids, expressed in degrees.

■ API gravity is graduated in degrees on a hydrometer instrument and

was designed so that most values would fall between 10° and 70°
API gravity.

■ If the API gravity is greater than 10, it is lighter and floats on water;
if less than 10, it is heavier and sinks.

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
 U.O.P. Characterization Factor (K)

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Ms. N. Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
 Correlation Index

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN 6
DISTILLATION
CHARACTERISTICS
CRUDE ASSAY ANALYSIS
■ Distillation characteristics of a crude are assessed by performing
preliminary distillation called “True Boiling Point Analysis” (TBP).
■ Information supplied by this distillation forms the basis of design of
distillation columns and thus represents the veridity of crude distillation
■ This test provides
– % quantum of fractions
– Base of crude
– Difficulties during operations.
■ Crude oil distillation curves
■ TBP curve
■ ASTM curve
■ EFV

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
1. TBP APPARATUS
■ T.B.P Analysis: also called (true boiling point distillation) it is a
standard batch distillation test for crude oil used to determine the
quality of products (petroleum cuts) and so to determine the value of
crude oil.
■ Stills developed by Peters and Podbielniak.
■ Less cost laboratory still which has
– Proper adjustments
– Controls whenever needed.
■ Consists of 10 to 12 stages.
■ Modern stills used to distill 2 litres of stock/charge.
■ Larger capacities of high boiling stocks are used for testing.

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Ms. N. Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
Process Description
 This type of distillation is commonly used due to the accuracy of the results obtained
by this method which is very close to that obtained via real distillation or industrial
distillation.
 In this distillation, there is a fractionation column located between the condenser and
the flask. In general, this type of distillation is carried out by two steps :
 firstly, under atmospheric pressure until 300°C (1% distilled very 2 min)
 secondly under vacuum pressure (to prevent cracking process and to reduce the
boiling point) at 40mmHg (1% distilled every 3 - 5 min)
 In this process, the vapour press. temp. is plotted vs. distilled(%) to get TBP curve

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
■ Distillation should proceed at constant rate.
■ High rate results in flooding and lower rate produces imperfect
fractionation.
■ Rate of distillation in beginning is very high but decreases with
increasing boiling point.
■ Good rate of distillation for atm. Condition is 1% distillation in 2
mins and under vacuum it is for 3 to 5 mins.
■ Vacuum distillation is used to prevent thermal degradation of high
boiling stocks.
■ High boiling stocks are prone to crack under a temperature of
370oC.
■ Vacuum distillation reduces the boiling point.

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN 12
ENGLER DISTILLATION
■ Also known as ASTM distillation.
■ It is a non fractionating distillation column.
■ Carried out with std. ASTM flasks of 100,200 and 500ml capacity.
■ Data is similar to TBP and whenever needed can be converted.
■ The standard test : ASTM 2892.
– The distillation apparatus consists of 15-18 theoretical plates.
– Reflux ratio = 5:1
– Atmospheric pressure for boiling points below 340 °C
– Vacuum pressure (1-10) mm Hg for the residue above 340 °C (
to avoid thermal cracking ).

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN 13
ASTM method for Distillation of Petroleum Products at
atmospheric pressure

■ This test method covers the atmospheric distillation of petroleum

products using a laboratory batch distillation unit to determine
quantitatively the boiling range characteristics of such products as light
and middle distillates, aviation gasoline's, aviation turbine fuels, diesel
fuels, biodiesel blends up to 20 %, marine fuels, special petroleum spirits,
naphtha's, white spirits, kerosene’s, and Grades 1 and 2 burner fuels.
■ This test method is designed for the analysis of distillate fuels; it is not
applicable to products containing appreciable quantities of residual
material.
■ This test method provides an estimate of the yields of fractions of various
boiling ranges, and is therefore valuable in technical discussion of a
commercial natural.
■ This test method can be used for any petroleum product expect LPG ,
very light Napthas and fractions having initial boiling point above 400oC

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
Materials and Instruments:
1. Distillation Flasks.
2. Condenser and Condenser Bath.
3. Heater.
4. Thermometer.
5. Graduated cylinder.
6. Gasoline 100 Ml
Procedure :
■ A 100 mL of the Sample is added add to the
distillation flask .
■ Heat this flask in a regulated rate , so that a uniform
average rate of condensation in mL/min is maintained.
■ When the first drop appears at the lower end of the
condenser tube, the thermometer reading (vapour
temperature) is recorded, this temperature is the initial
boiling point (IBP).
■ We record the temperature at several Volume%
distilled up to the final boiling point (FBP) and
heating discontinued.
■ After flask cooled the volume of remaining liquids is
measured and recorded as the recovery.
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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
Equilibrium Flash Vaporization (EFV)
■ Is a single stage separation technique. Process in which a continuous liquid-mixture feed
stream is partly vaporized in a column or vessel, with continuous withdrawal of vapour
and liquid portions, the vapour and liquid in equilibrium. Also known as continuous
equilibrium vaporization; equilibrium distillation; flash distillation; simple continuous
distillation.
■ A liquid mixture feed is pumped through a heater to raise the temperature and enthalpy of
the mixture.
■ It then flows through a valve and the pressure is reduced, causing the liquid to partially
vaporize. Once the mixture enters a big enough volume (the "flash drum"), the liquid and
vapour separate. Because the vapour and liquid are in such close contact up until the
"flash" occurs, the product liquid and vapour phases approach equilibrium.
■ In continuous fractionation system such as TBP, contact between liquid and vapor exists.
In EFV, vapor is cohesive with liquid at some temperature. A sudden release of pressure
quickly flashes or separates the vapor from the mixture without rectification. By
successive flash vaporization stock can be distilled at different increasing temperatures.
■ In this type of distillation there is on fractionation column located between the condenser
and the flask. On the other hand, the raised vapour will not be fractionated in this process.
This distillation is used with fractions having short range of the boiling point.

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
HUMPEL DISTILLATION
■ Semi-fractionating type of distillation like Saybolt’s.
■ Used when TBP data is insufficient.
■ Different types of boiling point and functional values are

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
AVERAGE BOILING
POINT
 Volume average boiling point
■ It is based upon the boiling temperature of different cuts of the fraction.
■ Usually, cuts are chosen at regular intervals. For whole crude, it may be represented
as

■ If such data is not available then it may be defined as

where all percentage are in volumes.

■ If the fraction is boiling over a narrow range of temperature Then t50% may be
accepted as average boiling point.
(t10% means the temperature indicated when exactly 10% of the stock collected during
distillation)

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
WEIGHT AVERAGE:
In this case instead of volume , weight fraction is chosen for
evaluating boiling point .Thus

Where percentage calculation are based on weight.

MOLAL AVERAGE:
This is based upon boiling temperature at different mole fractions.

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
MEAN AVERAGE:
This is the temperature at which some physical properties like specific heat,
specific gravity etc., of a fraction are found out by taking the mean of temperature
levels.

mean average and average boiling point coincide for a blend of two components
and these are related to TBP slopes.
CUBIC AVERAGE:
Some properties like viscosity seem to be additive when Cubic average is taken in
to consideration , rather than mean average or molal average thus,

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN 22
Boiling point-pressure
■ For every liquid at equilibrium there is a definite vapor
pressure at definite temperature.
■ The vapor pressure increases with increase in temperature and
vice-versa.
■ When vapor pressure and temperature are plotted on a semi-
log paper a straight line relationship is revealed, this
relationship although may change from groups to groups like
alcohol, ketone, paraffins, aromatics etc.
■ Clausius-clapeyron equation can also be used where there is
data available on latent heat of vaporization.

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN 23
THERMAL PROPERTIES
OF PETROLEUM
FRACTIONS
Thermal Properties

■Specific heat
■Heat of Combustion
■Latent Heat of Vaporisation
■Thermal Expansion
■Spontaneous Ignition Temperatures
■Viscosity and Viscosity Index
■Thermoviscosity

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Ms..N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
Specific Heat
■ Range – 0.3 to 0.85 kJ/kg ºC

■ Depends upon Temperature, Gravity and density

■ Lighter fractions have higher values

■ With increasing density the specific heat decreases

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
Correlations :

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
Heat of Combustion
■ The amount of heat released per unit mass or unit volume of a substance when
the substance is completely burned.
■ Higher hydrogen content fractions will be designed to have more heat of
combustion
■ Order of paraffins to aromatics, the heat of combustion decreases

Sherman-Kropff Relationship : (shows the relationship between heat content and

oAPI)

Heating Value kJ/kg =43,434 + 93.2( API-10)

■ The Wobbe Index (WI) or Wobbe number is an indicator of the

interchangeability of fuel gases such as natural gas, liquefied petroleum gas
(LPG), and town gas and is frequently defined in the specifications of gas
supply and transport utilities.
Wobbe No.=Heat of combustion/ √Sp.Gravity
For different manufactured gases like coal gas, SNG etc. Wobbe No. lies in the
range of 21.5 to 38.7
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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
 For Natural gas:
■ Low calorific value - 37.1-43.7
■ High calorific value - 43.4-52.4
■ LPG - 72.0-83.5

Gas modulus:
■ It is the term conveniently used to replace one gas to another (by
increasing the pressure at which it burns)

Gas modulus =P0.5 / Wobbe No.

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
 Latent Heat of Vaporisation
■ The amount of heat required to convert a substance from liquid to vapour
at a given saturation temperature and pressure is called latent heat of
vaporization
■ Latent Heat for a fraction varies with the T(or P)at which vaporisation
takes place. Related to molecular weight, API and molal average boiling
point. Any two of the above parameters are sufficient to give latent heat of
vaporization
■ Latent heat can also be converted to normal BP to any other Temperature
upto critical condition. This relationship is expressed as

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
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Latent Heat of Fusion
■ The heat energy required to convert either solid to liquid or
vice versa is called is called latent heat of fusion
■ The heat of fusion is approximately 50% of latent heat of
vaporisation
■ For waxy distillates and waxes ,the average latent heat of
fusion may be taken as 167 to 170kJ/kg

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 Thermal Expansion
■ Thermal expansion is the increase in volume of a material as its temperature is
increased, usually expressed as a fractional change in dimensions per unit
temperature change.
■ 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
Gravity range API Mean coefficient of expansion
(Change in volume for 1ºC)
0-14.9 0.00063
15-34.9 0.00072
35-50.9 0.00090
51-63.9 0.00108
64-78.9 0.00126
79-88.9 0.00144
89-93.9 0.00153
94-100 0.00162
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 Spontaneous Ignition Temperature
Definition: The Temperature at which a material can catch fire and burn
continuously without the aid of external firing agencies

■ Paraffins have less ignition temperatures

■ Aromatics have high ignition temperatures

■ This property is most useful for the performance of diesel fuels

■ In gasoline engines adiabatic compression of the mixture does not raise the
temperature to that extent, hence sparking is required for detonation . In this
way gasoline engines differ from diesel engines

■ Ignition T ↓ with ↑ molecular weight

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
 Viscosity and Viscosity Index
■ Viscosity: 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
■ Important property in all lube oils
■ Relative viscosity: Ratio of viscosity to that of water at standard temperature
■ In refineries, kinematic viscosity is used
■ Kinematic viscosity=absolute viscosity/ sp.gravity
■ U-tube, Fenske, Redwood, Engler give K.V only
■ Saybolt Universal Viscometre gives the time in seconds for 60cc sample efflux, through a
standard orifice at the given temperature and is expressed as Seconds Saybolt Universal(SSU)
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 above formula

L=viscosity of a reference oil of zero viscosity index at 37.8ºC
H=viscosity of a reference oil of 100 viscosity index at 37.8ºC
U=viscosity of test sample 37.8ºC

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■ Two std liquids L ad H are chosen
■ The starting viscosity of these samples is known by finding the viscosity of test sample at 98.9ºC
■ All the three samples have the same viscosity (V) at 98.9ºC
■ By substituting the values in the above equations , the V.I can be found out
■ Paraffin base oils have high V.I (100 for ref)
■ Napthene base oils are given the value 0 for ref
■ Higher V.I oils better in the viscosity –temperatures characteristics
■ Viscosity –Gravity Constant: This index of classification connects the viscosity and gravity of the
sample by the formula

Where ,
G=sp.gravity at 15.6ºC
V=SSU at 37.8ºC
where the measurement of viscosity is not possible at 37.8ºC an alternative formula is used
where V is at 98.9ºC

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 Thermo viscosity

■ Important for illuminating oils. Given by the relation

■ Thermoviscosity = 15 + 148 × kinematic viscosity
■ Frequently expressed in Ring number given as

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
 Reference :
‘Modern Petroleum Refining Processes’, Bhaskara Rao B. K.,
Fourth Edition

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN