PETROLEUM

REFINERY

Thermophysical Properties of
Petroleum Fractions and Crude
Oils
 Molecular Type Composition of Petroleum
Fractions
o Petroleum is composed of a variety of chemical compounds with widely
different chemical properties, mainly including non-polar saturated
hydrocarbons and aromatic hydrocarbons, and various types of heteroatom-
containing compounds, such as sulfides and thiophenes, basic and non-basic
nitrogen compounds, and oxygen compounds.
o However, it is a very challenging task for the molecular characterization of
petroleum, especially for heavy petroleum fractions, because petroleum is an
extremely complex organic mixture.
 Molecular Type Composition of Petroleum
Fractions
o The understanding of the chemical composition of petroleum at the molecular
level has made great progress due to the development of high-resolution mass
spectrometry (HRMS), such as
o Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS)
o Orbitrap MS

o Atmospheric soft ionization techniques such as

o Electrospray Ionization (ESI),
o Atmospheric Pressure Chemical Ionization (APCI),
o Atmospheric Pressure Photoionization (APPI)
o Laser Desorption Ionization (LDI) combined with HRMS
 Molecular Type Composition of Petroleum
Fractions
o The following equations are used to predict the fractional composition
of paraffins, naphthenes, and aromatics (PNA) contained in both light
and heavy petroleum fractions.
o The viscosity, specific gravity, and refractive index of the desired
fraction are used as input parameters. For heavy fractions (M> 200).
 Molecular Type Composition of Petroleum
Fractions
where
a, b, c, d, e, f, g, h, and i = The constants varying with molecular weight
range;
xp, xn, and xa = The mole fraction of paraffins, naphthenes, and
aromatics, respectively;
Ri = The refractivity intercept
Molecular Type Composition of Petroleum
Fractions
 Molecular Type Composition of Petroleum
Fractions
o The refractivity intercept is shown to represent a more constant relationship between
the densities and refractive indices of the members of an homologous series of
hydrocarbons than the usual equations for refractivity.
o Refractivity intercept, which is defined as refractive index minus one-half the
density, is not a new concept.

where

n = refractive index at 20oC (68oF) and 1 atm,

d = liquid density at 20 oC (68 oF) and 1 atmosphere in grams per cubic centimeter.

o It was originally developed in the US by Kurtz and Ward’ in 1936, and since then
several methods which employed its use in the compositional analysis of petroleum
fractions.
 Molecular Type Composition of Petroleum
Fractions
o The viscosity-gravity constant (VGC) is a useful function for the
approximate characterization of the viscous fractions of petroleum.
o It is relatively insensitive to molecular weight and is related to a fluids
composition as expressed in terms of certain structural elements.
o Values of VGC near 0.800 indicate samples of paraffinic character, while
values close to 1.00 indicate a preponderance of aromatic structures.
o Like other indicators of hydrocarbon composition, the VGC should not be
indiscriminately applied to residual oils, asphaltic materials, or samples
containing appreciable quantities of nonhydrocarbons.
 Molecular Type Composition of Petroleum
Fractions

where

SG = The specific gravity at 15.6 oC (60 oF)

V = The Saybolt universal viscosity at 37.8 or 98.9 oC (100 or 210 oF), in Saybolt universal seconds.
 Molecular Type Composition of Petroleum
Fractions
The Saybolt (SUS) universal viscosity (V ) is related to the kinematics viscosity
(n) in cSt by the relation:
Molecular Type Composition of Petroleum
Fractions
 Example
Calculate the paraffins, naphthenes and aromatic mole fraction for the crude
having the properties listed MeABP of 320 C and API gravity of 34.
Step I:
Convert temperature into kelvin
Step II:
141.5
𝐴𝑃𝐼 = − 131.5
𝑆𝐺
StepIII:

StepIV:
 Example
Step V:
 Example
Step VI:

Step VII:

Determine VGC for petroleum fraction depending upon the molecular weight (heavier or
lighter component)