Chapter 3

Thermophysical Properties of Petroleum

Fractions and Crude Oils

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Introduction
Design of Petroleum Refinery requires the knowledge of certain
Thermophysical properties
Thermodynamic properties Transport properties
- Enthalpy - Viscosity
- Heat capacity - Thermal conductivity
- Compressibility factors - Diffusivity
- Equilibrium K-values
- Flash curve

Physical properties
- Densities
- Volumes
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Introduction
• Crude oil has complex composition of petroleum fractions

• Calculation methods for pure hydrocarbons are not

applicable

• Correlations are developed to estimate the properties of

petroleum fractions

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Basic Input Data
Such correlations require basic input data from LAB
experiments:

1. Specific Gravity (SG)

2. Boiling Point Curve (ASTM or True Boiling Point
Distillation)
3. Kinematic viscosity (Ʋ100 , Ʋ210)
4. Refractive Index (n)
5. Molecular Weight (M)

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Specific Gravity (SG)

𝝆𝒐𝒊𝒍
𝑺𝑮𝒐𝒊𝒍 =
𝝆𝒘𝒂𝒕𝒆𝒓

ρoil is the oil density

ρwater is the water density

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Boiling Point Curve
For a crude oil or a petroleum fraction of unknown composition,
the boiling point may be presented by a curve of temperature
versus vol% (or fraction) of mixture vaporized.
There are several methods of measuring and reporting boiling
points curves of crude oil and petroleum fractions:
1 ASTM D 86 ***
2 True Boiling Point (TBP) ***
3 Simulated Distillation by GC (ASTM D 2887)
4 Equilibrium Flash Vaporization (EFV)
5 Distillation at Reduced Pressures (ASTM D 1160)
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ASTM
• There are many different types of
ASTM distillation methods for testing of
petroleum fractions
ASTM D 86 distillation data do not
represent actual boiling point of
components in a petroleum fraction.
ASTM D 1160 distillation data are
measured more accurately than ASTM D
86 since it is conducted at low pressure.
For this reason ASTM D 1160 curves are
closer to TBP curves at the same pressure
base.
True Boiling Point Distillation
• More detailed characterization of
petroleum fractions
• Performed in column with 15 plates
and reflux ratio of 5
• Higher degree of separation than
ASTM distillation
• IBP is Lower than that of ASTM
distillation
• FBP is higher than that of ASTM
distillation
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The IBP from TBP curve is less than the IBP
from ASTM D 86 curve, while the FBP of
TBP curve is higher than that of ASTM
curve. Therefore, the boiling range based on
ASTM D 86 is less than the actual true
boiling range.

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Conversion between ASTM & TBP Distillation
Both Temperatures are in Rankin
T(R)=(T(C)+273)*1.8 Or T(R) = (1.8T(C)+32)+460

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Pseudo-Components

1. Calculations involving crude oil and petroleum fractions

require composition of each process stream
2. Since the actual components are not known, petroleum
fractions are characterized as mixture of pseudo components
3. They are defined over boiling point range over the TBP
distillation curve.
4. Each pseudo-component corresponds to several unknown
actual compounds. 13
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Pseudo Components (Cont.)

5. Each pseudo-component is characterized by

– Normal Boiling Point (NBP, treated as MABP)
– Specific Gravity
– Molecular Weight

6. Once this parameters are characterized, Pseudo-component can be

treated as any defined component for the Thermophysical parameters
Calculations

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Breakup of TBP Curve to Pseudo-components

1. The following cut-points are reasonable for most refining calculations

TBP range is defined by (IBP-FBP)

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Breakup of TBP Curve to Pseudo-components
2. General Guideline for determining the number of Pseudo-
Components:
3. Divide the TBP curve into 20 pseudo-components. Calculate the liquid
volume percentage of each pseudo-component.

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Note that: TBP curve extends to 95 volume percent distilled only. To
Obtain the NBP of the final cuts, it has to be extrapolated to 100 %
distilled; by fitting polynomial curve using Excel and extrapolating it.
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Breakup of TBP Curve to Pseudo-components Using
Generalized form

The boiling point Tb is in Kelvin. xc is the cumulative weight, volume or mole fraction. Tb0
corresponds to the boiling point at xc = 0. Therefore, it should be equal or lower than the
IBP given in the assay data. The parameters A and B are obtained by fitting the equation
to available assay data. Since in this equation P∗ 1 as x∗ 1, an arbitrary point can
be added to the measured TBP data to limit the actual TBP end point. The same equation
can be used to fit data for molecular weight and specific gravity. The above generalized
equation can be converted to the following linear form:
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The fitting procedure is to calculate P*, knowing Tbo and plot Y versus X. This means the correlation
parameter R2 is calculated. If Tbo is not known, the value of Tbo is assumed and varied until a good fit is
obtained (R2 = 0.99). This fitting procedure can be easily done using the linear regression fit
of a Microsoft Excel spreadsheet. Tbo represents the initial boiling point. It can be estimated for cases
where Tbo is not available. Nonlinear regression of equation (3.8) is applied to find Tbo as well as A and B.

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Calculation of Pseudo-components SG
1. The K factor is assumed constant for all fractions, and equal to
its value for the whole Crude Oil.

2. For the pseudo-components; MABP = NBP in Ranking

3. Knowing K & NBP, SG can be obtained easily.

4. Knowing K = 11.94, calculate the API of the Pseudo-

components.
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Calculation of Pseudo-components
Molecular Weight

where M is the molecular weight of the petroleum fraction, T is

b

the mean average boiling point of the petroleum fraction in K,

and SG is the specific gravity, 60 0F/60 0F

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Refractive Index

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

speed of light in the medium.

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Molecular Type Composition of Petroleum
Fractions
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):

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Pseudo-critical Constants and Acentric Factors

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Generalized Equation for Thermophysical Properties
Riazi and Al-Sahhaf (1996) presented a method for the calculation of different properties

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Calculation of Enthalpy of Petroleum Fractions
Equations of state, such as the Soave–Redlich–Kwong
and the Peng–Robinson, are widely used in process simulation programs.
The Lee–Kessler generalized correlation (Kessler and Lee, 1976) has the
following expression for the compressibility factor:

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Estimation of Properties Related to Phase Changes

1. Cubic Equations of State

The Peng–Robinson (PR) equation is a cubic equation in volume
with the form:

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Estimation of Properties Related to Phase Changes

2. Vapour–liquid Equilibrium
The equilibrium Keq value for a component in a vapour–liquid
equilibrium system is given by

are called the fugacity coefficients of component i in the

liquidand vapour phase, respectively.

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