PETROLEUM

REFINERY

Thermophysical Properties of
Petroleum Fractions and Crude
Oils
 SARA Analysis
o The SARA analysis determines the content of saturate
aromatics, resins, and asphaltenes in crude oils, heavy cuts
and residues.
o This information is useful in refinery design and operation.
o The analysis is also preparative, meaning that the test
provides enough samples of four classes of compounds for
further testing and analysis by chemical analysis testing.
o The separation of these four classes of compounds is done
in different stages.
 Stages of SARA Analysis
1. Asphaltenes are precipitated by n-heptane.
2. The de-asphalted oil called maltenes is subjected to liquid
chromatography.
3. Liquid chromatography is similar in principle to gas chromatography
in that the compounds are eluted from a packed column by a carrier
liquid.
4. The saturated hydrocarbons are eluted by n-heptane, the aromatics
by a 2:1 volume mixture of n-heptane and toluene and the resins by
an equal volume mixture of dichloromethane, toluene and methanol.
5. The ASTM D4124 can be used in this case.
 Maltenes

n-heptane eluents toluene eluents Methanol/toluene eluents

 Contents of the Chapter
1. Introduction
2. Basic Input Data
3. Pseudo-Components
4. Thermophysical Properties Calculation
5. Estimation of Properties Related to Phase Changes
6. Calculating Properties Utilizing UNISIM Software
 Introduction
o Design and analysis of fractionation towers, heat
exchangers, and pumps require knowledge of the
thermodynamic and physical properties of the
petroleum fluids.
o Designing a crude distillation tower requires
knowledge on vapor–liquid distribution, and the
densities of the mixture.
o Heat exchanger design depends on enthalpies,
thermal conductivity, and viscosity of the flowing
streams.
 Introduction
o Due to the complexity of the composition of petroleum fractions and crude
oils, it is not possible to measure or calculate accurately all of these
properties.
o Calculation methods developed for pure hydrocarbons are not always
applicable.
o Therefore, over the years chemical and petroleum refining engineers have
developed special methods or correlations i.e., (British Petroleum method, Maxwell
Method, Edmister Method, 20% method) and experimental methods i.e., true boiling point apparatus,
to estimate the properties of petroleum fraction
reflux method, isoteniscope method
from easily measured properties like normal boiling point (NBP) and
specific gravity. And
 Introduction
oTraditionally these correlations are developed to be
simple to use, requiring minimum input data, and are
usually presented in graphical form.
oFor crude oils, mixture bulk properties cannot directly be
used to estimate the properties of the mixture.
Thermophysical Properties
 Basic Data Input
The characterization of petroleum fractions requires several measurable
laboratory properties:

1. Specific gravity (SG)

2. Boiling point curve (ASTM or true boiling point (TBP distillation)
3. Kinematic viscosity at 37.8oC (100oF) and 98.9oC (210oF) (v100, v210)
4. Refractive index (n)
5. Molecular weight (M)

With the exception of TBP distillation and molecular weight, these

properties can be readily measured in any petroleum characterization
laboratory.
 1. Specific Gravity

o Specific gravity for liquid oils is defined as:

at 1 atm (14.7 psia) and 15.6 C (60 F)

where ρoil is the oil density and ρwater is the water density.
o Since under the same conditions, most petroleum fractions are
lighter than water, i.e. ρoil ≤ 1
 API
o Another parameter for oil density is API gravity defined as:

o Heavy oils have low API and light oils have high API gravities.
o The density measurement of petroleum fractions and crude oils are
carried out using either a pycnometer or a Mettler/Parr
densitometer.
o The Mettler/Parr densitometer is based on density-dependent
frequency changes of an oscillating glass U-tube.
 Boiling Point Curves
o ASTM distillation / TBP
distillations characterize the
volatility of petroleum fractions
and crude oils.
o Both are batch distillations
which differ mainly in the
degree of fractionation obtained
during distillation.
ASTM Distillation
 ASTM Distillation
o 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 vapours.
o The fractions distilled are collected in a graduated cylinder.
o The temperature of the rising vapours is recorded at specific
interval of the collected distillates.
 ASTM Distillation
o This is essentially a batch distillation with one equilibrium stage and no
reflux and minimum separation of the components of the fractions.
o For gasoline, kerosene, gas oil, and similar light and middle distillates,
the ASTM D86, which is carried out at atmospheric pressure, is used.
o Heavy petroleum products, which tend to decompose in the ASTM D86
method but can be partially or completely vaporized at a maximum
temperature of 400oC (750 F) and pressures down to 1 mm Hg, are
distilled using the ASTM D1160 method.
o It is carried out at pressures between 1 and 760 mm Hg.
 ASTM Distillation
o The temperature at which the first drop of condensate is
collected is called the initial boiling point (IBP).
o The end point (EP) is the maximum vapour temperature when
almost the entire sample is distilled (above 95%).
o Boiling temperatures at sub-atmospheric pressures (less than
760 mm Hg) can be converted to NBPs (at 760 mm Hg).
 ASTM Distillation
o Minimum fractionation occurs in ASTM distillation, and
components in the mixture do not distill one by one in
the order of their boiling points, but rather as mixtures of
successively higher boiling points.
o because ASTM distillations are quickly conducted and
have been successfully automated, require only a small
sample, and are quite reproducible, they are widely used.
 True Boiling Point (TBP) Distillation
o True boiling point (TBP) distillation is a widely used batch
distillation process for the characterization of crude oils,
traditionally mainly for marketing and refining purposes.
o The TBP curve is obtained by plotting the cumulative mass or
volume distillation fraction with increasing temperature.
o The shape of these curves is dependent on the volatility of
components in a given crude oil.
o As such, these curves give a “footprint” of the composition of
crude oils.
 True Boiling Point (TBP) Distillation
o It is performed in columns with 15 theoretical plates or equilibrium
stages and a reflux ratio of 5.
o Rising vapors are condensed and collected either at a constant rate of
boiling points or a constant rate of the sample vaporized.
o Operation is at 760 mm Hg for boiling points below 400 oC (750 oF).
o For higher boiling point fractions, the distillation is conducted at
reduced pressures as low as 0.5 mm Hg.
o Results from vacuum operations are extrapolated to atmospheric
pressure.
o The high degree of fractionation in this test gives an accurate
component distribution (Perfect Separation).
 True Boiling Point (TBP) Distillation
o Because the degree of separation for a TBP distillation test is
much higher than that of the ASTM distillation test, its IBP is
lower and its EP is higher than those of the ASTM test.
o The TBP curve (a plot of the NBP versus the percent volume
of sample distilled) is usually used as a basis for the
characterization of crude oil or a petroleum product for the
purpose of design and analysis.
 Conversion between ASTM & TBP
Distillation
Since TBP distillation is both tedious and time-consuming in
comparison with the ASTM method, there has been an incentive
to develop a correlation to convert ASTM to TBP distillation
while at the same time achieving the benefit of the detailed
separation of TBP with the little effort of the ASTM distillation.

where a and b are constants varying with percent of liquid sample distilled.
TBP is true boiling point temperatures at 0, 10, 30, 50, 70, 90, and 95 volume
percent distilled, in degrees Rankin.
Conversion between ASTM & TBP
Distillation
Conversion between ASTM & TBP
Distillation
 Conversion between ASTM & TBP
Distillation

o The symbols T and T' stand for ASTM D86 and

TBP temperatures, respectively, both in F.
o The subscripts 0 and f stand for the initial and final
temperatures, respectively.
o The reported average error for this method is about
3oC (37.4oF).
Conversion between ASTM & TBP
Distillation
Numerical Problem
 Average Boiling Points
o Based on the distillation curve, five different average boiling points can
be estimated namely
1. Volume Average Boiling Point (VABP),
2. Molal Average Boiling Point (MABP),
3. Weight Average Boiling Point (WABP),
4. Cubic Average Boiling Point (CABP),
5. Mean Average Boiling Point (MeABP)
 Volume Average Boiling Point
(VABP)
o Among these, the volume average boiling point (VABP) and the mean
average boiling points (MeABP) are the most widely used in property
estimation and design.
o The MeABP is utilized in the definition of an important parameter, the
Watson characterization factor K given by

o where MeABP is in degrees Rankin

 Mean Average Boiling Point (MeABP)
o 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.

 Numerical Problem

Step 1: Determine VABP, SL and 

Step 2: Determine MeBP and SG
Step 3: Calculate Watson’s Characterization Factor