Boling Point Curves

Prepared by:
Engr. Adeel ur Rehman
Assistant Professor
Department of Chemical Engineering
University of Karachi

 The first step in refinery is distillation in which the crude

oil separated into fractions according to its boiling point.
There are at least four types of distillation curves or ways
of relating vapor temperature and percentage vaporized.
a) True-boiling-point (T.B.P): (Fractional, run only on crude oil,
batch)
b) Equilibrium or Flash Vaporization (EFV).
c) ASTM or no fractionating distillation: (no fractional , run on
fractions)
d) Hempel: (Semi fractional).

Boiling Point Curves

 a) True-boiling-point (T.B.P): (Fractional, run only on

crude oil, batch) .
Distillation characteristics of a crude are assessed performing a
preliminary distillation called "True Boiling Point" analysis
(TBP). This test enlightens the refiners with all possible
information regarding the percentage quantum of fractions,
base of crude oil and the possible difficulties beset during
treatment operation etc.
True boiling point (TBP) and gravity-mid percent curves can
be developed from U.S Bureau of mines crude petroleum
analysis data sheet Fig. (1) which is reported in two portions:
The first is the portion of the distillation at atmospheric
pressure and up to 527 0F (275 0C) end point, the second at 40
mm Hg total pressure to 572 0F (300 0C) end point.
Boiling Point Curves

Boiling Point Curves

 b) Equilibrium or 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.
Boiling Point Curves

 c) ASTM or no fractionating distillation: (no

fractional , run on fractions) .
It is supposed to be like EFV, a non fractionating
distillation system, distinguishing itself as differential
distillation.
It is a simple distillation carried out with standard ASTM
flasks 100,200,500 ml flasks. The data obtained is similar
to TBP data

Boiling Point Curves

Condenser

Measuring
Cylinder

Engler
Flask

Heating
Source

ASTM Distillation Apparatus

d) 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.
Boiling Point Curves

 Minimum fractionation occurs in ASTM distillation, and

components in the mixture do not distil one by one in the
order of their boiling points, but rather as mixtures.
Nevertheless, because ASTM distillations are quickly
conducted and have been successfully automated, require
only a small sample, and are quite reproducible, they are
widely used.
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.
Boiling Point Curves

 The following equation suggested by Riazi and Daubert

(1980) and published by the API (1993) is used for the
inter conversion, referred to as API method:
TPB = a(ASTM D86)b
where a and b are constants varying with percent of
liquid sample distilled

Boiling Point Curves

 TBP is true boiling point temperatures at 0, 10, 30, 50,

70, 90, and 95 volume percent distilled, in degrees
Rankin.
ASTM D86 is the observed ASTM D86 temperatures at
corresponding volume percent distilled, in degrees
Rankin. Average error between the calculated and
measured TBP is in the range of 5 C (41 F).

Boiling Point Curves

10

 More recently, Daubert (1994) published a new method

for distillation curves interconversion using the following
equations:

95

90

95

Boiling Point Curves

90

11

 The symbols T and T stands for ASTM D86 and TBP

temperatures, respectively, both in F.
The subscripts 0 and f stand for the initial and final
temperatures, respectively.
The reported average error for this method is about 3 oC
(37.4 oF).

Boiling Point Curves

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Boiling Point Curves

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Boiling Point Curves

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Boiling Point Curves

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Probability Chart

Boiling Point Curves

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Boiling Point Curves

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Boiling Point Curves

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Boiling Point Curves

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Boiling Point Curves

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Boiling Point Curves

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Pseudo-Components
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.
Once these parameters are determined, the pseudo-components can be
treated as any defined component for the calculation of thermophysical and
thermodynamic property like enthalpy, entropy, and transport properties such
as viscosity, thermal conductivity and diffusivity.
Boiling Point Curves

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Breakup of TBP Curve into Pseudo-components

TBP cut point ranges are used to define pseudo-components with the
average temperature of the cut or the mid point NBP.
The number of such pseudo-components depends on the boiling point range
of the whole petroleum fraction.

Boiling Point Curves

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Boiling Point Curves

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Problem
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.

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Solution

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 The end point of the cut is 218.2 oC (425 oF)

and the IBP is -5.4 oC (22 oF). Therefore each
pseudo-component
has
a
temperature
interval of (218.2+ 5.4)/20 or 11.2 oC.
Then the curve can be cut as follows. The EBP
of the first cut is IBP + 11.2 oC or 5.8 oC. The
average boiling point for the first pseudocomponent is (5.4 + 5.8)/2 or 0.2 oC.
The vol% is 2.84 as read from the TBP curve.
The second cut has an end boiling point of 17
oC 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 11.4 oC.
Boiling Point Curves

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Boiling Point Curves

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