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Abstract: Critical pressure is one of the most important physical properties of the petroleum fractions, which
commonly considered in compositional modeling studies and phase behavior calculations. This paper presents a
comparison study among ten different correlations used to calculate the critical pressure of undefined petroleum
fractions. A new correlation was developed for calculating the critical pressure of petroleum fractions as a function of
the number of carbon atoms with an average error of 0.933977 % and correlation coefficient of 0.999585.
Keywords: Critical pressure, petroleum fractions, Compositional Modeling Studies, Phase Behavior Calculations.
INTRODUCTION
Katz and Firoozabadi [1] presented a generalized set of one must be able to provide the acentric factor, along with
physical properties for the petroleum fractions C6 through the critical temperature and critical pressure, for both the
C45. The tabulated properties include the critical defined and undefined (heavy) fractions in the mixture.
properties, average boiling point, specific gravity, and The problem of how to adequately characterize these
molecular weight. The authors generated these properties undefined plus fractions in terms of their critical properties
by analyzing the physical properties of 26 condensates and and acentric factors has been long recognized in the
crude oil samples. These generalized properties are given petroleum industry [3, 5].
in Table A-1. Riazi and Daubert [6] developed a simple two-parameter
Ahmed [2, 3] correlated Katz-Firoozabadi-tabulated equation for predicting the physical properties of pure
physical properties with the number of carbon atoms of the compounds and undefined hydrocarbon mixtures. The
fraction by using a regression model. The generalized proposed generalized empirical equation is based on the
equation has the following form: use of the molecular weight and specific gravity of the
Pc = a1 + a 2 n + a 3 n2 + a 4 n3 + a 5 n (1) undefined petroleum fraction as the correlating
parameters. Their mathematical expression has the
Where: following form:
a1 = 311.2361908 a 2 = −14.6869301 Pc = aMb γc EXP dM + eγ (2)
a 3 = 0.3287671
a 4 = −0.0027346 a 5 = 1690.9001135 Where:
a = 45203 b = −0.8063 c=
Undefined Petroleum Fractions 1.6015
Nearly all naturally occurring hydrocarbon systems d = −0.0018078 e = −0.3084
contain a quantity of heavy fractions that are not well Edmister [7] proposed a correlation for estimating the
defined and are not mixtures of discretely identified acentric factor of pure fluids and petroleum fractions. The
components. These heavy fractions are often lumped equation, widely used in the petroleum industry, requires
together and identified as the plus fraction, e.g., C7 boiling point, critical temperature, and critical pressure.
fraction [2, 4]. The proposed expression is given by the following
A proper description of the physical properties of the plus relationship:
fractions and other undefined petroleum fractions in 3 log pc 14.7
hydrocarbon mixtures is essential in performing reliable ω= −1 (3)
7 Tc Tb − 1
phase behavior calculations and compositional modeling
studies. Frequently, a distillation analysis or a The Edmister equation can be rearranged to solve for the
chromatographic analysis is available for this undefined critical pressure as follows:
fraction. Other physical properties, such as molecular 7
weight and specific gravity, may also be measured for the log pc = log 14.7 + ∗ ω+1
3
entire fraction or for various cuts of it [3, 5]. ∗ (Tc Tb ) − 1) (4)
To use any of the thermodynamic property-prediction
models, e.g., equations, of state, to predict the phase and Cavett [8] proposed correlations for estimating the critical
volumetric behavior of complex hydrocarbon mixtures, pressure of hydrocarbon fractions. The correlations
𝐶4 = −0.0000000373776 𝐶5 = 3.50737
Ei is the relative deviation in percent of an estimated value
Sancet [15] presented a correlation to estimate the critical from an experimental value and is defined by:
pressure from the molecular weight. This correlation has pc exp − pc cal
the following form: Ei = × 100
pc exp
𝑝𝑐 = 653 𝑒𝑥𝑝 −0.007427𝑀 + 82.82 (10)
i
and indicates the relative absolute deviation in percent The correlation coefficient lies between 0 and 1. A value
from the tabulated values. A lower value implies a better of 1 indicates a perfect correlation, whereas a value of 0
correlation. implies no correlation at all among the given independent
variables.
Standard Deviation
Standard deviation sx is a measure of dispersion and is Comparison of Correlations
expressed as:
n
Statistical Error Analysis
2
s x= Ei 2 /(n − 1) Average relative error, average absolute relative error,
i=1 standard deviation, and correlation coefficient were
computed for each correlation.
A lower value of standard deviation means a smaller
degree of scatter.
Table 1 presents the comparison of errors relative to the
experimental critical pressure calculated from two
Correlation Coefficient correlations. The correlation for critical pressure of this
The correlation coefficient, r, represents the degree of
study achieved the highest correlation coefficient accuracy
success in reducing the standard deviation by regression
of 0.999585, as presented in Table 2.
analysis. It is defined as:
Table 1 Comparison of critical pressure calculated by correlations from this study and others
Table 1 Cont.: Comparison of critical pressure calculated by correlations from this study and others
AARE, % SD R2
This study(sh4) 0.933977 1.317814 0.999585
Ahmed 3.475806 3.838117 0.991964
Reazi 16.22215 19.16977 0.946263
Lin 39.34908 47.73011 0.773554
Cavett 6.191865 7.612793 0.981904
Kesler 3.169919 3.518671 0.99421
Winn-Simm 11.5529 15.28577 0.962153
Edmister 0.322695 0.387337 0.999887
Watansiri 22.71815 27.04131769 0.910100284
Willman 2.809648 0.032314 0.996947
Sancet 15.12048 16.41881 0.896163
CONCLUSIONS REFERENCES
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Appendix 1:
Table A-1
C Tb SG K M Tc Pc 𝛚 Vc
6 607 0.69 12.27 84 923 483 0.25 0.06395
7 658 0.727 11.96 96 985 453 0.28 0.06289
8 702 0.749 11.87 107 1,036 419 0.312 0.06264
9 748 0.768 11.82 121 1,085 383 0.348 0.06258