Evaluation Of Oil Stock

Characterization Factors
There are several correlations between yield and
the aromaticity and paraffinicity of crude oils,
but the two most widely used are the UOP or
Watson ‘‘characterization factor’’ (KW) and the
U.S. Bureau of Mines ‘‘correlation index’’ (CI).
This method is for calculating the UOP
Characterization Factor of petroleum oils from
API gravity and distillation data.
The UOP Characterization Factor, commonly
called KUOP, is indicative of the general origin
and nature of a petroleum stock.
 Evaluation Of Oil Stock
Watson characterization factor:

SG: Specific Gravity at 15C (60 F)

Tb: mean average boiling point (R) (MeABP)
The Watson characterization factor ranges from less
than 10 for highly aromatic materials to almost 15 for
highly paraffinic compounds.
Crude oils show a narrower range of KW and vary
from 10.5 for a highly naphthenic crude to 12.9 for a
paraffinic base crude.
 Evaluation Of Oil Stock
Mean Average Boiling Point (R) (MeABP)
Given the ASTM D86 distillation the VABP can be calculated as the average of the
five boiling temperatures at 10, 30, 50, 70 and 90 percent distilled.

Where all temperatures are in F

The MeABP is calculated using the following equation:

 Problem

Calculate the MeABP of the petroleum fraction . If the API

gravity of this fraction is 62, calculate the Watson’s
characterization factor.
Evaluation Of Oil Stock
 Evaluation Of Oil Stock
UOP characterization factor:
Kuop has the same expression as Kw, but Tb transfer to
Volume average boiling point (VABP)
Additional notes related to the application of the above
characterization factors:
• Aromatics would have lower KUOP
• The use of boiling point indicates a relationship to the
interactive forces between the molecules.
• The use of specific gravity relates to how tightly the
molecules are packed (i.e. density)
 Evaluation Of Oil Stock
correlation index (CI).
The correlation index is useful in evaluating individual
fractions from crude oils. The CI scale is based upon
straight-chain paraffins having a CI value of 0 and
benzene having a CI value of 100. The CI values are not
quantitative, but the lower the CI value, the greater the
concentrations of paraffin hydrocarbons in the fraction;
and the higher the CI value, the greater the
concentrations of naphthenes and aromatics.
 Thermophysical Properties Calculation
1. Molecular Weight

Any material or energy balance calculations would certainly require the

estimation of molecular weight of a petroleum fraction.

Experimentally, the average molecular weight can be determined by

several methods, such as freezing point depression osmometry, or gel
permeation chromatography.

Most oil fractions have molecular weights in the range of 100–700.

Prediction of the molecular weight of petroleum fractions is achieved

through the following equation (Pedersen et al., 1989):
 where M is the molecular weight of the petroleum fraction,
Tb is the mean average boiling point of the petroleum fraction in K,
and SG is the specific gravity, 60 F/60 F.

2. Viscosity
The following equations can be used to calculate the liquid viscosities of
petroleum fractions at atmospheric pressure and at temperatures of 37.8
C (100 F) and 98.9 C (210 F) (Pedersen et al., 1989):
Saybolt universal second used for oils with flowing time up to 5600 seconds machine oil
Saybolt Furol seconds When the flowing time surpasses 5600 seconds, Saybolt Furol seconds (SFS
should be used instead of Saybolt universal seconds. Saybolt Furol seconds is measured with a
controlled temperature of 50 degC
3. Refractive Index
The refractive index is a readily measured property that can be used as
an input parameter for other correlations.

It is defined as the speed of light in vacuum with respect to the speed of

light in the medium.

Since refractive indices of petroleum fractions are not always known, it is

important to predict the refractive index.

The following equation may be used:

where a, b, c, d, e, and f are the constants varying with molecular weight
range (Table 3.4),

n is the refractive index at 20 C (68 F),

I is the Huang characterization parameter at 20 C (68 F),

Tb is the mean average boiling point, in degrees Rankin,

M is the molecular weight of petroleum fractions, and

SG is the specific gravity of petroleum fraction, 60 F/60 F.

 Evaluation Of Oil Stock

The following equations are used to predict the fractional composition of

paraffins, naphthenes and aromatics (PNA) contained in both light and heavy
petroleum fractions. The viscosity, specific gravity and refractive index of the
desired fraction are used as input parameters. For heavy fractions (M> 200):
 Evaluation Of Oil Stock
where a, b, c, d, e, f, g, h, and i are the constants varying with molecular weight range as
given in Table; xp, xn, and xa are the mole fraction of paraffins, naphthenes, and
aromatics, respectively; Ri is the refractivity intercept as given by the equation below

where n = refractive index at 20C (68F) and 1 atmosphere, d is the liquid density at
20C (68F) and 1 atmosphere in grams per cubic centimetre,VGC is the viscosity
gravity constant as given by equations below.

The Saybolt (SUS) universal viscosity (V ) is related to the kinematics viscosity (ν)
in cSt by the relation:
Evaluation Of Oil Stock
 Evaluation Of Oil Stock
Calculate the paraffins, naphthenes and aromatic mole fraction for the
crude which has a MeABP of 320C and API gravity of 34.
Solution:
SG = 0.855 then d = 0.855 g/cm3, n = 1.481 then Ri = 1.0535
M = 257.1 which can be considered heavy fraction n100 =5.777 cSt
then VGC = 0.8348 By substituting the constants for the heavy
fraction, Ri and VGC

xp = 0.789;
xn = 0.164 and
xa = 0.046
Evaluation Of Oil Stock
Evaluation Of Oil Stock
Problem
 Evaluation Of Oil Stock
The Bureau of Mines analysis is reported in two parts:
the first is the portion of the distillation performed at
atmospheric pressure and up to 527°F (275°C) end
point, the second at 40 mmHg total pressure to 572°F
(300°C) end point.
The portion of the distillation at reduced pressure is
necessary to prevent excessive pot temperatures,
which cause cracking of the crude oil.
The distillation temperatures reported in the analysis
must be corrected to 760 mmHg pressure. Generally,
those reported in the atmospheric distillation section
need not be corrected, but if carried out at high
elevations it may also
CH-406 : Evaluation Of Oil Stock
CH-406 : Evaluation Of Oil Stock
 Evaluation Of Oil Stock
The distillation temperatures at 40 mmHg pressure
can be converted to 760 mmHg by use of charts developed by Esso Research and
Engineering Company [6]. Figure 3.6 shows the relationships between boiling
temperatures at 40 mmHg and 760 mmHg pressure.
The 572°F (300°C) end point at 40 mmHg pressure corresponds to 790°F
(421°C) at 760 mmHg. Refinery crude oil distillation practices take overhead
streams with end points from 950 to 1050°F (510 to 566°C) at 760 mmHg. Estimates
of the shape of the TBP curve above 790°F (421°C) can be obtained by
plotting the distillation temperature versus percentage distilled on probability
graph paper and extrapolating to 1100°F (593°C) [11]. (See Fig. 3.7.) The data
points above 790°F (421°C) can be transferred to the TBP curve.
The gravity mid-percent curve is plotted on the same chart with the TBP
curve. The gravity should be plotted on the average volume percent of the fraction,
as the gravity is the average of the gravities from the first to the last drops
in the fraction. For narrow cuts, a straight-line relationship can be assumed and
the gravity used as that of the mid-percent of the fraction.
Smooth curves are drawn for both the TBP and gravity mid-percent curves.
Figure 3.8 illustrates these curves for the crude oil reported in Figure 3.5.
PP-407 : Basic Definitions and Correlations
 Evaluation Of Oil Stock
Cut Point:
A cut point is defined as that temperature on
the whole crude TBP curve that represents
the limits (upper and lower) of a fraction to
be produced.
 Pseudo-Components
Calculations involving crude oil and petroleum fractions require the
composition of each process stream.

Since most of the actual components are not known, the petroleum
fractions are characterized as a mixture of discrete pseudo-components
with defined boiling point ranges or cut points on the TBP distillation
curve.

Each pseudo-component corresponds to several unknown actual

compounds (e.g. paraffins, naphthenes and aromatics) which boil in a
given temperature range.

Usually each pseudo-component is characterized by an average normal

boiling point, specific gravity and molecular weight.
 CH-406 : Evaluation Of Oil Stock
Pseudo Components
Crude oil and its fractions are not expressed in
terms of pure components, but as ‘cuts’
expressed between a range of boiling points.
These ‘cuts’ are further defined by splitting them
into smaller sections and treating those sections
as though they were pure components. As such,
each of these components will have precise
properties such as specific gravity, viscosity,
mole weight, pour point, etc. These components
are referred to as pseudo components and are
defined in terms of their mid boiling point.
Evaluation Of Oil Stock
Divide the TBP curve of the petroleum cut as calculated from API method
into 20 pseudo-components. Calculate the liquid volume percentage of
each pseudo-component.
 Pseudo-components

Solution:
The TBP curve extends to 95 volume percent distilled only. In order to obtain the average
boiling point of the last cuts, the curve is extrapolated to the final point of the distillation
(100%) by fitting the curve to a suitable polynomial function and extrapolating the results.
 Pseudo-components

The end point of the cut is 218.2 o C (425oF) and the IBP is -5.4oC
(22oF). Therefore each pseudo-component has a temperature
interval of (218.2+ 5.4)/20 or 11.2oC. Then the curve can be cut
as follows. The EBP of the first cut is IBP = 11.2oC or 5.8oC. The
average boiling point for the first pseudo-component is (-5.4 +
5.8)/2 or 0.2oC. The vol% is 2.84 as read from the TBP curve. The
second cut has an end boiling point of 17oC and an end volume
percent of 6.19.
Therefore, the vol% of this cut is 6.19 - 2.84 or 3.36 vol%. .The
average boiling point for the second cut is (17 + 5.8) /2 or 11.4oC.
Pseudo-components
 Evaluation Of Oil Stock

Mid boiling point components

For these pseudo-components, the average boiling
point can be estimated as either mid-boiling
point or mid-percentage boiling point. The TBP
curve is divided into an arbitrary number of
pseudo-components or narrow boiling cuts. 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.
 Evaluation Of Oil Stock
Mid boiling point components
In compiling the assay narrow boiling fractions
and are analyzed to determine their properties.
These are then plotted against the mid boiling
point of these fractions to produce a smooth
correlation curve. To apply these curves for a
particular calculation it is necessary to divide the
TBP curve of the crude, or fractions of the crude,
into mid boiling point components.
CH-406 : Evaluation Of Oil Stock
 Evaluation Of Oil Stock

Mid Per Cent Curves

Distillation is a means of arranging of
chemical compounds in order of their
boiling points. The properties such as color,
specific gravity, and viscosity are found to
be different for each drop or fraction of the
material distilled. The rate at which these
properties change from drop to drop may
plot as mid per cent curves.
 Evaluation Of Oil Stock
In reality, the specific gravity or viscosity of a
fraction is an average of the properties of the
many drops that constitute the fraction. If each
drop is equally different from the last drop and
from the succeeding one, then the drop that
distills at exactly half of the fraction has the
same property as the average of all the drops.
The arithmetical average of the properties of
these small fractions is the property of the total
or large fraction, or even the entire sample.
These properties are termed as Additive
properties.
 Evaluation Of Oil Stock
Integral- averaging by adding together the
properties of a series of short fractions and
dividing by number of fractions can not be used
on properties that are not additive.
Specific gravity (not API gravity) is an example of
an additive property, e. g. 10 volumes of an oil of
specific gravity 0.8 when mixed with an equal
volume of 0.9 specific gravity oil yields a mixture
that has a specific gravity 0.85.
 Evaluation Of Oil Stock

Additive Properties Non additive Properties

Boiling Point (T.B.P) API Gravity
Vapor Pressure Viscosity
Specific Gravity Color
Aniline Point Flash Point
Sulfur Content
Hydrogen/Carbon ratio
 Evaluation Of Oil Stock
Use of Gravity Mid percent curve :(Pg 106
Nelson)
Example1: Compute the spg of a 41.4 API
(0.8183 spg) mixed base crude oil from the spg
mid percent curve.
Evaluation Of Oil Stock
Evaluation Of Oil Stock
Evaluation Of Oil Stock
Evaluation Of Oil Stock
EFV curve is used to define temperature/pressure conditions in
distillation.
Yield Curve
Equilibrium Flash Vaporization (EFV).
The feed material is heated as it flows
continuously through a heating coil. As vapor is
formed it kept cohesively with liquid at some
temperature and a sudden release of pressure
quickly flashes or separates the vapor from the
mixture without any rectification. By successive
flash evaporation like this the stock can be
progressively distilled at different increasing
temperatures. a curve of percentage vaporized
vs. temperature may be plotted.
 Evaluation Of Oil Stock
Hempel: (Semi fractional).
It is considered as a semi-fractionating type of
distillation like Saybolt 's, Where TBP data is
insufficient , this can be used.
 Evaluation Of Oil Stock
Estimation of EFV Distillation Curve
1. Estimate of t 50% of ASTM/ TBP using:
 Basic Definitions and Correlations
2. Estimate the 10 to 70% slope of ASTM/TBP by
using the fig. above

i.e

3. Use Fig. (5) to convert slope (ASTM/TBP) to

slope of EFV
Evaluation Of Oil Stock
Evaluation Of Oil Stock
 Evaluation Of Oil Stock

Estimation of EFV Distillation Curve

A- Estimation of the straight line EFV curve:
1. Estimate of t 50% of ASTM/ TBP
2. Estimate the 10 to 70% slope of ASTM/TBP using
Slope ( ASTM / TBP ) =(𝑡70 − 𝑡10)/60
3. Use Fig. (5) to convert slope (ASTM/TBP) to slope of
EFV
4. Estimate t 50% of EFV from Fig. ( 4 )
t 50 %EFV = (DRL -FRL)
5. Draw a straight line through t50% EFV with slop of
EFV.
6. t 0% ( bubble point ) = t 50 % EFV - slope*(50) EFV
7 . t 100% (dew point) = t 50 %EFV + slope*(50) EFV
Evaluation Of Oil Stock