Thermophysical Properties of Petroleum

Fractions and Crude Oils

• A petroleum refinery is a collection of unit operations. knowledge of
the thermodynamics and physical properties of the petroleum fluids.
Designing a crude distillation tower requires knowledge on how
hydrocarbons in crude oil are distributed on each tray of the tower, that
is vapor–liquid distribution, and the densities of the mixture.
• characterization of petroleum fractions requires
several measurable laboratory properties:
 Specific Gravity
Boiling Point Curve (ASTM, TBP distillation)
Kinematic Viscosity, 100 and 200 oF.
 Boiling Point Curves
ASTM distillation or TBP distillations characterize the volatility of petroleum fractions
of crude oils. Both are batch distillation, degree of fractionation
• ASTM Distillation (D86): A batch • True Boiling Point Distillation
distillation with one equilibrium (D1160):
stage and no reflux and minimum Data from TBP distillation
separation of fractions, gasoline, provides more detailed
kerosene, distillates. The characterization of the volatility
temperature at which the first of crude oil or petroleum
drop of condensate is collected is fraction. It is performed in
called the initial boiling point columns with 15 theoretical
(IBP). The end point (EP) is the plates or equilibrium stages and a
maximum vapor temperature reflux ratio of 5.
when almost the entire sample is
distilled (above 95%).
 Cut points

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.
Consider the curve shown.
 Conversion ASTM data to TBP
API method: TBP = a(ASTM D86)b
where a and b are constants varying with percent of liquid sample distilled
as given in Table 3.2. TBP is true boiling point temperatures at 0, 10, 30,
50, 70, 90 and 95 volume percent distilled, T in Rankin.
Vol. % distil. a b
0 0.9167 1.0019
10 0.5277 1.0900
30 0.7429 1.0425
50 0.8920 1.0176
70 0.8705 1.0226
90 0.9490 1.0110
95 0.8008 1.0355
Example 3.1: A petroleum cut has the following
ASTM D86 Distillation data:
Volume % 0 10 30 50 70 90 95
distilled Applying API method:
Temperature, oC 36.5 54 77 101.5 131 171 186.5 IBP= 36.5 oC, = 65.7+492 = 557.7
Rankin
a= 0.9167, b=1.0019
Convert these data to TBP data TBP= 0.9167(557.7)^1.0019 = 517.4
using the API method of Riazi and
Daubert and Dauberts method. Plot
the results and compare.
Solution:
Application of the API method is
straightforward using
 Conversion Between ASTM and TBP using

•Daubert’s Method
1. Pre-selected volume percent are 0,10,30,50,70,90 and
95?, with corresponding boiling points as T0, T10, etc.
2. Calculate , , , , , .
3. Calculate , use table for A4 and B4 values
4. Use as starting temperature to find other values
Conversion between ASTM and TBP Distillation
ASTM Distillation
Table 1
Index, i
∆ 𝑇 2=𝑇 30 −𝑇 10 1 7.4012 0.6024
2 4.9004 0.7164
∆ 𝑇 3 =𝑇 50 −𝑇 30 3 3.0305 0.8008
4 0.8718 1.0258
∆ 𝑇 5=𝑇 70 −𝑇 50 5 2.5282 0.8200
6 3.0419 0.7750
∆ 𝑇 6 =𝑇 9 0 −𝑇 7 0 7 0.1180 1.6606

∆ 𝑇 7 =𝑇 𝑓 −𝑇 9 0
 Conversion between ASTM and TBP Distillation
′ ′ ′
∆ 𝑇 =𝑇 −𝑇
TBP Distillation
1 10 0
′ ′ ′ (eqn. 1)
∆ 𝑇 =𝑇 − 𝑇
2 30 10

′ ′ ′
∆ 𝑇 =𝑇 − 𝑇
3 50 30

′ ′ ′ (eqn. 2)
∆𝑇 5 =𝑇 70 −𝑇 50

′ ′ ′
∆ 𝑇 =𝑇
6 90 −𝑇 70

′ ′ ′
∆ 𝑇 =𝑇 − 𝑇
7 𝑓 90
Conversion between ASTM and TBP Distillation
• , Appl. Eqn. (2), to obtain
• From , i.e. ( ), Table 1, for and values, =0.8718,
=1.0258
We have already found , from given ASTM
distillation
• Hence, is calculated from after substituting.
• So on for all other temperatures.