0263–8762/05/$30.00+0.

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# 2005 Institution of Chemical Engineers
www.icheme.org/journals Trans IChemE, Part A, February 2005
doi: 10.1205/cherd.03338 Chemical Engineering Research and Design, 83(A2): 160–166

SOME GUIDELINES FOR CHOOSING A CHARACTERIZATION

METHOD FOR PETROLEUM FRACTIONS IN
PROCESS SIMULATORS
H. A. ALADWANI and M. R. RIAZI

Chemical Engineering Department, Kuwait University, Safat, Kuwait

T
hermodynamic models are used to calculate physical properties of petroleum fluids
needed for process design and operation in petroleum related industries. Process simu-
lators used for design and operational purposes are usually equipped with as many as a
dozen of such thermodynamic models. The basic input parameters needed for use in these
thermodynamic models are critical constants, acentric factor and molecular weight. In this
paper, sensitivity of calculated properties from different characterization methods is demon-
strated. Most commonly used characterization methods have been reviewed and based on
evaluations with experimental data for various fluid mixtures recommendations are made
for use of an appropriate model for specific hydrocarbon systems.

Keywords: petroleum fluids; process simulators; thermodynamic models; characterization

scheme; selection method.

INTRODUCTION products such as naphtha, gasoline, kerosine, jet fuel, gas

Petroleum fluids are mainly mixtures of hydrocarbon
compounds in the form of liquid, gas or their mixtures.
Reservoir fluids produced from petroleum reservoirs con-
tain hydrocarbons from methane (CH4 shown as C1) to
very heavy hydrocarbons. Natural gas is an example of a
light reservoir fluid and black oil is example of a heavy
reservoir fluid. Hydrocarbon compounds in these fluids
are mainly from paraffinic, naphthenic and aromatic
families. Light petroleum fluids are rich in paraffins while
heavy petroleum fractions are richer in aromatic portion.
Properties of hydrocarbon mixtures depend on the type of
hydrocarbons in the mixture. The composition of reservoir
fluids is usually expressed in terms of mole fraction of pure
hydrocarbons from C1 to C5 (pentane), C6 group and C7þ.
In which C6 represents all hydrocarbons from paraffinic,
naphthic and aromatic groups with six carbon atoms
lumped as a single carbon number. The C7þ (heptane-
plus) fraction represents all hydrocarbons with seven
carbon atoms and heavier. From laboratory analysis,
usually molar mass and specific gravity of this fraction
are reported and are shown by M7þ and SG7þ, respectively.
For very heavy reservoir fluids, analysis of single carbon
number groups may continue to higher numbers, and
heavy part of the mixtures may be expressed in terms of
C20þ or C30þ . After separation of light gases from reservoir
fluids in field separators, crude oil is produced with nearly
no methane and little ethane in it. Crude oil is the feed to a
refinery where it is separated into various petroleum


Correspondence to: Dr M. R. Riazi, Chemical Engineering Department,
Kuwait University, PO Box 5969, Safat 13060, Kuwait.
E-mail: riazi@kuc01.kuniv.edu.kw
oil and residues. These products are also known as pet-
roleum fractions which differ from crude oils due to limited
boiling point range and carbon number. For example kero-
sines usually have carbon number range of C11 –C14 and
boiling point range of 205 –2558C. Further information
on the composition and chemistry of petroleum mixtures
are given by Speight (1998).
Production of petroleum and its refining require equipments
such as phase separators, distillation and absorption columns,
heat exchanges, reactors, pipelines, storage tanks, pumps and
mixers. Optimum design and operation of such units require
accurate values of certain thermodynamic and physical prop-
erties which include density, heat capacity, enthalpy, vapor
pressure, viscosity, thermal conductivity, diffusivity, surface
tension and fugacity (or equilibrium ratios). These thermo-
physical properties are calculated through thermodynamic
relations such as equations of state or generalized correlations
(Poling et al., 2000, API TDB, 1997). Such correlations
require certain input properties which include critical
temperature (Tc), critical pressure (Pc), critical volume (Vc),
acentric factor (v) and molecular weight (M) to convert a
molar property into weight based property. The critical con-
stants of petroleum mixtures needed for these correlations
are pseudocritical properties which cannot be measured.
Characterization of petroleum fractions involve methods
that use measurable properties such as boiling point (Tb)
and specific gravity (SG) to estimate mixtures critical proper-
ties or molecular weight needed in thermodynamic corre-
lations (Riazi, 2003).
Process simulators developed for design calculations
usually contain as many as dozen different characterization
methods for petroleum fractions (i.e., see HYSYS, 1996,
PRO/II, 1992). Selection of characterization method has

160
 PETROLEUM FRACTIONS IN PROCESS SIMULATORS
significant impact on calculated physical properties which
in turn affect design calculations. Choosing a right charac-
terization method very much depends on the type of pet-
roleum fluid. Users of process simulators sometimes
select a method originally developed for specific hydro-
carbon fluids outside the range of their applications or it
may be used for systems containing nonhydrocarbons.
The other difficulty in selection of a characterization
method in a process simulator is what input data should
be used to obtain best output results. To address these
issues, in this paper some commonly used characterizations
methods are reviewed and necessary recommendations
are given for the most appropriate method for specific pet-
roleum fluids. This work is in conjunction with our previous
studies (Riazi et al., 2003, Riazi and Aladwani, 2003).
EFFECT OF A THERMODYNAMIC MODEL
ON UNIT DESIGN
Unit design is based on calculations from thermodynamic
models in a process simulator. For example, the minimum
number of trays in a distillation column which is required to
obtain a certain purity in the products may be calculated
from the Fenske equation (McCabe et al., 1985). The main
input data in this equation is relative volatility (a) which is
the ratio of equilibrium ratios of two key components in the
mixture. The main parameter in calculation of equilibrium
ratio is component vapor pressure. There are a number of ther-
modynamic correlations for calculation of vapor pressure.
Most widely used correlations (Lee and Kesler, 1975) methods
are based on the theory of corresponding states which requires
Tc, Pc and v as the input parameters (Poling et al., 2000). A
small error in calculation of one of these input parameters con-
tributes significantly in the error in the calculation of vapor
pressure. This is demonstrated in Figure 1 for the effect of
an error in Tc on vapor pressure of several pure hydrocarbons
calculated through Lee–Kesler correlation. Similarly an error
in calculation of relative volatility has an effect on the design
of distillation columns. This effect is greater at lower values of
a as shown in Figure 2. This figure is developed based on the
Fenske equation for calculation of minimum number of plates
Figure 1. Effect of error in critical temperature on the error in calculated
vapor pressure from Lee–Kesler correlation for n-alkane hydrocarbons.
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 160–166
161
Figure 2. Effect of error of the relative volatility, a, on the error of mini-
mum number of plates of a distillation column calculated from Fenske
equation.
in a distillation column:
ln½xD (1  xB )=xB (1  xD )
Nmin ¼ 1
ln (a)
where xD and xB are mole fractions of light component in the
distillate and bottom products, respectively. Since a is directly
proportional to vapor pressure, one can see the importance of
accuracy of calculation of Tc on design of a distillation tower.
As it is clear from Figure 1, when the error in Tc is only 21%,
the error in calculated vapor pressure is about 20%. However,
as shown in Figure 2 for a ¼ 1.3, just an error of 7% in the
value of a can cause a 100% error in the number of trays or
the length of the column. Error of 100% in column length
has major economical and operational problems for the related
industry (Dohrn and Pfohl, 2001). Effect of uncertainties in
thermodynamic properties on design of distillation columns
is also discussed by Peridis et al. (1993). Such error is inevita-
ble even with use of most sophisticated simulators once an
inappropriate method for calculation of Tc has been used.
Through an appropriate characterization method one can accu-
rately estimate the main input data for any thermodynamic
model. These data are usually Tc, Pc, Vc, v, M and ideal gas
properties. Various characterization methods for petroleum
fractions that are use usually used in different process simu-
lators are discussed below.
METHODS OF CALCULATION OF INPUT DATA
FOR THERMODYNAMIC MODELS
Characterization of petroleum fractions usually involves
use of measurable properties to calculate basic input
parameters for thermodynamic correlations. For narrow
boiling range (50 –608C) and light petroleum fractions
the most commonly available data from laboratory measure-
ments are distillation data (boiling point, Tb) and specific
gravity (SG). Petroleum fractions can be considered light
(M  300, NC  22) or heavy (M . 300) as well as
narrow or wide. There is no sharp definition of light and
162 ALADWANI and RIAZI
heavy or narrow and wide fractions as these definitions vary
from one source to another. For heavier fractions (NC . 22)
where distillation data at atmospheric pressure are not avail-
able usually, viscosity or hydrocarbon type analysis are
measured. Kinematic viscosity at 1008F (15.58C) or at
2108F (98.98C) are reported for fractions which cannot be
distilled due to cracking. Hydrocarbon type usually is
expressed in terms of PNA composition which represents
volume (or weight)% of paraffins (P), naphthenes (N) and
aromatics (A). Other parameters that might be available
from laboratory measurements are molar mass (M), refrac-
tive index at 208C (n20), liquid density at 208C (d20) and
carbon to hydrogen weight ratio (C/H).
Over the past eight decades, dozens of different charac-
terization methods have been developed for estimation of
basic properties of petroleum fractions. Early correlations
in the 1930s (i.e., Watson and Nelson, 1933), 1940s and
1950s were mainly graphical, while from the 1960s analy-
tical correlations in the form of equations suitable for
computer use have been proposed. The best example of
graphical methods is the Winn nomograph (Winn, 1957).
Most of these correlations are empirical in nature and use
Tb and SG as input parameters to calculate Tc, Pc and M.
Most widely used methods are summarized below.
METHODS OF CALCULATION OF Tc and Pc:
Cavett (1962)
Cavett correlations for prediction of Tc and Pc are early
analytical correlations developed by the API group. They
used Tb and API specific gravity as input parameters.
These correlations are purely empitrical in nature.
Kesler and Lee (1976)
These correlations also referred as Lee– Kesler are in
terms of Tb and SG and are based on true critical properties
of pure hydrocarbons (up to C18), and calculated critical
constants from vapor-pressure data for heavier hydrocar-
bons up to boiling point of 5508C (NC  50 or M  700).
Correlations have been developed empirically and contain
as many as 14 numerical coefficients but are explicit in
terms of Tc and Pc and may also be applied to heavy
fractions with NC . 50.
Riazi and Daubert (1980)
A simple and generalized correlation was developed
based on cubic equations of state constants which has
three numerical coefficients. The structural format of corre-
lations were developed based on the theory of intermole-
cular forces while the coefficients were determined from
data. The equation has unique form for calculation of Tc,
Pc, Vc, M, n20 and d20. These equations are based on prop-
erties of pure hydrocarbons (from C5 to C20) and should be
applied to petroleum fractions with boiling point from
30– 3508C (100 –6508F). These equations were included
in the 1982 edition of the API-TDB. Recently, Jianzhong
(1998) re-examined these correlations and used extended
data base on more than 300 hydrocarbons to reported
slightly different coefficients based on density at 208C.
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 160–166
Sim and Daubert (1980)
These correlations are computerized version of Winn
(1957) graphical correlations. They were originally deve-
loped from Winn nomograph (Riazi, 1979) in a simple
form similar to Riazi – Daubert (1980) correlations with
same limitations. These correlations later were successfully
used by Sim and Daubert (1980) for phase equilibrium
calculations of petroleum fractions and usually are referred
as Winn or Sim –Daubert correlations.
Lin and Chao (1984)
Lin and Chao (LC) correlated Tc, ln(Pc), v, SG and Tb of
n-alkanes from C1 to C20 to molecular weight, M. These
properties for all other hydrocarbons having the same
value of M, were correlated to the difference in Tb and
SG of the substance of interest with that of n-alkane. There-
fore, LC correlations require three input parameters of Tb,
SG and M for each property. Each correlation for each
property contained as many as 33 numerical constants.
Twu (1984)
Twu’s correlations are rather complicated and are inter-
related to each other. His approach is similar to that of Lin
and Chao. Critical properties of n-alkanes are correlated to
boiling point and then the difference between properties of
a hydrocarbon and that of n-alkane is correlated to the
specific gravity. Twu’s correlations are applicable from
C1 to C100. For critical properties of hydrocarbons heavier
than C20, calculated values from vapor pressure data were
used in development of the correlations similar to Lee –
Kesler equations. The equations are not explicit and require
trial-and-error procedure, therefore, they are not suitable
for hand calculations.
API methods (1997)
These methods are based on Riazi –Daubert (1987a)
correlations. The methods in the API technical Data Book
have been repeatedly revised and updated since its first
edition in 1964 in which Cavett correlations were used.
In 1982 edition of the book, Riazi –Daubert (1980) were
adopted until 1988. After this date, the existing methods
were included in Chapter 4. These correlations are valid
for fractions with molecular weight in the range 70 – 300
(C5 – C22). Alternative methods, when refractive index is
available, are given by Riazi and Roomi (2001).
Pseudo-component method
In this method it is assumed that a fraction is a mixture
of three pseudo-components from n-paraffin (P), n-alkyl-
cyclopentane (N) and n-alkybenzne (A) groups. These
components have the same molecular weight or boiling
point as that of the fraction. The fraction critical properties
are calculated from the PNA composition and properties of
these components using simple Kay’s mixing rule. Riazi
and Al-Sahhaf (1995) have developed a generalized corre-
lation for properties of various homologous hydrocarbon
groups in terms of M which can be applied for hydrocar-
bons up to C50. Later Pan et al. (1997) have proposed a
modified form for the critical pressure and acentric factor
of n-alkylbenzenes. The pseudocompoent method is par-
ticularly useful for calculation of pseudocritical properties
 PETROLEUM FRACTIONS IN PROCESS SIMULATORS
of heavy petroleum fractions. In cases that the PNA compo-
sition is not available, it can be estimated from measurable
bulk properties such as density, refractive index and vis-
cosity as given by Riazi and Daubert (1986) which is
also included in the API TDB (1997).
Methods of calculation of M
Generally methods of calculation of M are very similar to
calculation of Tc and Pc from Tb and SG. The API-TDB is
based on a modified version of Riazi –Daubert correlations
and is given in Procedure 2B2.1 which is valid for fractions
with molecular weight in the range of 70– 700.
For heavy fractions in which boiling point cannot be
determined due to thermal cracking, an alternative
method was proposed by Riazi and Daubert (1987b) for
calculation of molecular weight from kinematic viscosities
at 100 and 2108F (37.8 and 98.98C) and specific gravity at
608F. This method is also included in the API-TDB (1997)
as Procedure 2B2.3. In cases that viscosity at only one
reference temperature is available an equation has been
proposed for calculation of viscosity at other temperature
using SG as an input parameter.
Lee –Kesler and Twu methods for calculation of M are
similar to their critical temperature correlations and use
Tb and SG as input parameters. The Twu method is not
explicit and require trial-and-error solution. Schneider
(1998) has published a good report on the effect of
choice of molecular weight correlation on errors associated
with calculated physical properties. This effect becomes
more important for heavier oils. He concludes that
estimation of molecular weight has a great impact on the
accuracy of calculated physical property and hence on
design calculations.
Methods of calculation of v
Acentric fractor (v) is used as a third parameter beside Tc
and Pc in generalized corresponding states correlations or
cubic equations of state for calculation of thermodynamic
properties. Accurate calculation of v requires accurate
values of Tc, Pc and vapor pressure at T ¼ 0.7 Tc . Vapor
pressure correlations are based on generalized correlations
using v as the third parameter. Once a vapor pressure
correlation is used to calculate atmospheric pressure at
normal boiling point, a correlation for calculation of v
can be derived in terms of three input parameters: Tc, Pc
and Tb. There are three correlations that have been derived
on this basis for calculation of v: 1) Edmister; 2) Lee –
Kesler; and 3) Korsten. Edmister correlation is the simplest
relation that is based on the Clasius – Clapyron equation
(Edmister and Lee, 1985) and it is usually used with the
Winn correlations for Tc and Pc. The Lee– Kesler corre-
lation (1975) is recommended in the API-TDB (1997)
and generally provides reliable values of v once accurate
values of Tc and Pc are used as the input parameters.
Korsten method (Korsten, 2000) is very similar to the
Edmister correlation with slight difference in the exponent
of Tb. This method has not been tested thoroughly for cal-
culation of thermodynamic properties. However, for pure
hydrocarbons the Korsten correlation gives results very
close to those of Lee – Kesler. Kesler and Lee (1976)
provided another correlation for calculation of acentric
factor of heavy petroleum fractions in terms of Watson
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 160–166
163
characterization factor. They recommended this method
for fractions with reduced boiling point greater than 0.8,
however, this method has not found wide application and
the Lee – Kesler (1975) method is used for all types of
fractions.
TREATMENT OF VARIOUS PETROLEUM FLUIDS
The above correlations have been developed based on
properties of pure hydrocarbons, single carbon number
groups (SCN) or narrow-boiling-range fractions. For mix-
tures calculated critical properties from the above methods
are pseudocritical properties. These pseudocritical proper-
ties are different from true critical properties which are
directly measurable in laboratory. For hydrocarbon mix-
tures calculated molecular weight represents an averaged
number molecular weight which can also be measured
directly.
Direct application of these correlations to wide-boiling-
range fractions lead to significant errors as a single value
cannot represent property of the whole mixture (Riazi and
Dabert, 1987c). These correlations cannot and should not
be directly applied to crude oils and reservoir fluids. For
such systems the mixture should be modeled by a number
of pseudocomponents through a distribution model as dis-
cussed by Riazi (1997). Once characterization parameters
for these pseudocomponents are determined then appropri-
ate correlations discussed above may be used to determine
Tc, Pc, v and M for each component. Finally an appropriate
mixing rule can be used to determine properties of the
whole mixture.
EVALUATION OF VARIOUS CHARACTERIZATION
METHODS
As discussed earlier, methods of prediction of critical
properties are based on pure hydrocarbon data. Experimen-
tal data on critical properties of hydrocarbons heavier than
C20 are not available due to the cracking of hydrocarbons
before their critical temperature. Therefore, various predic-
tive methods begin to deviate from each other when they
are applied to heavy hydrocarbons. This is demosntrated
in Figures 3 and 4 for Pc and v of n-alkylcyclopentanes,
respectively. Similar behaviors are observed for other prop-
erties such as Tc, Vc and M and for other types of hydro-
carbon families.
A summary of analytical comparisons between various
methods for estimation of critical properties of pure hydro-
carbons is given in Table 1. A similar evaluation for
methods of prediction of critical properties of more than
300 pure hydrocarbons with specific gravity up to 1.175
and boiling point up to 4188C is shown in Table 2 as
reported by Jianzhong (1998). Retzekas et al. (2002) pro-
posed a method based on group contriubution for prediction
of Tb, Tc and Pc of pure hydrocarbons using d20, M and
molecular structure. They compared their method for Tc
and Pc with another group contribution methods as well
as Riazi and Daubert (1980) methods with the coefficients
they obtained from their database. For some 170 data
points they reported AAD of 0.9 and 4.8% versus 1 and
2.7% from the group contribution method for Tc and Pc,
respectively. In the goup contribution methods, structure
of compounds must be known and these methods cannot
164 ALADWANI and RIAZI

Table 1. Evaluation of various methods for prediction of critical properties

of pure hydrocarbons from C5 to C22.

% error

Method Tc Pc Vc

API 0.5 2.7 2.4

Twu 0.6 3.9 3.8
Kesler–Lee 0.7 4.0 —
Cavett 3.0 5.5 —
Winn (Sim–Daubert) 1.0 4.5 —
Riazi–Daubert 1.0 3.1 3.2
Lin and Chao 1.0 4.5 —


Data on critical properties of 150 hydrocarbons from C5 to C22 from
different families reported in API-TDB were used for the evaluation
process.



The method of Riazi and Daubert (1987) is used.

Figure 3. Critical pressure of n-alkylcyclopentane predicted from various

methods.
be conveniently applied to undefiend petroleum mixtures of
unknown structure. In this work only methods that require
bulk properties and can be applied to undefined mixtures
as included in process simulators are studied. One can see
that evaluations reported in different sources vary according
to the database used in such evaluations. The pseudocompo-
nent method of Riazi and Al-Sahhaf (1995) which estimates
critical properties of homologous families predict critical
properties of pure compounds from C5 to C20 with average
errors of 0.3, 0.8 and 0.6% for Tc, Pc and Vc, respectively.
Acentric factor of pure compounds can be estimated from
Lee – Kesler, Edmister and pseudocomponent methods by
1.2, 3.3 and 1%, respectively. The true importance of these
methods can be observed in their ability to predict thermo-
dynamic properties of petroleum fractions.
Calculation of thermodynamic and physical properties
of petroleum fractions through equations of states or corre-
sponding states correlations require pseudocritical properties
that cannot be measured for such mixtures. However,
molecular weight of petroleum fractions can be directly
measured. Evaluation of various methods for prediction of
molecular weight of more than 600 fractions is given in
Table 3. The API method for estimation of molecular
weight of petroleum fractions gives lowest error and is
recommended to be used for the range of 70–700. For
heavy fractions in which boiling points are not available, Pro-
cedure 2B2.3 in the API Data Book may used. This method
which is based on Riazi and Daubert (1987c) method gives
average error of 3% for the molecular weight range of 200–
800. A similar method given in ASTM D-2502 (ASTM,
2002) is based on Hirschler method (Hirschler, 1946) which
gives average deviation of 7% for 160 fractions. As shown
by Schneider (1998), choice of selection of method of predic-
tion of molecular weight has a major effect on design calcu-
lations of petroleum related units.
For petroleum fractions or heavy hydrocarbons in which
direct evaluation of critical properties is not possible,
predictive methods may be evaluated indirectly through
prediction of measurable properties such as enthalpy,
viscosity, surface tension, etc. Lenoir and Hipkin (1973)
have reported a set of data on enthalpies of eight petroleum
fractions. This data set was used for evaluation of various
characterization methods. Another property that was used
for evaluation of various characterization methods of
petroleum fractions was interfacial tension (IFT). Summary
of results for enthalpy and IFT predictions is given in Table 4.
Results shown in Table 4 indicate that for some properties
such as IFT, the choice of characterization has a major impact
on calculated values. Petroleum fluids evaluated in this

Table 2. Evaluation of various methods for prediction of critical properties

of some 300 pure hydrocarbons from C5 to C25.

% error

Method Tc Pc Vc

Twu 0.74 3.43 4.3

Kesler–Lee 0.92 8.32 —
Riazi–Daubert 0.76 4.05 4.78
Jianzhong et al. (1998) 0.68 3.79 2.89


Data on critical properties of 300 hydrocarbons from C5 to C25 from
different families were used for the evaluation process as reported by
Jianzhong et al. (1998). The method of Jianzhong et al. (1998) is similar
Figure 4. Acentric factor of n-alkylcyclopentane predicted from various to Riazi and Daubert (1980) using density at 208C instead of specific
methods. gravity at 15.58C.

Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 160–166
 PETROLEUM FRACTIONS IN PROCESS SIMULATORS 165

Table 3. Evaluation of several methods for prediction of molecular weight fluids and are included in available simulators for PVT proper-
of undefined petroleum fractions.
ties of reservoir fluids. The 1980 Riazi–Daubert correlations for
Absolute deviation %

Tc and Pc, were generally used and recommended by various
researchers for light fractions (M , 300, carbon number
Method AAD% MAD% ,C22). Yu et al. (1989) used 12 different correlations to charac-
terize the C7þ plus fraction of several samples of reservoir
API 4.0 18.7
Twu 5.1 16.1 fluids. Based on the results presented on gas phase composition,
Kesler–Lee 8.4 28.2 GOR and saturation pressure, methods of Riazi and Daubert
Winn 5.3 25.9 (1980), Twu and Sim–Daubert (Winn) correlations showed
API procedure 2B2.3

2.8 15.8 better predictions. Whitson (1984) made a good analysis of
ASTM D2502

6.8 27.9
correlations for the critical properties and their effects on


Number of data points: 650; Ranges of data: M 70–700, Tb 300 –850, characterization of C7þ of reservoir fluids and suggested the
SG 0.63–0.97. use of Riazi and Daubert for petroleum cuts up to C25 . For
Data sources: Riazi and Daubert (1986, 1987a, b, c) and Riazi and Roomi fractions heavier than C25, he recommended the use of
(2001).



Based on 160 data for peroleum fractions with M from 200 to 800 Kesler–Lee or Twu. Pan et al. (1997) used Riazi and
without boiling point. Al-Sahhaf (1995) methods for calculation of critical properties
of heavy hydrocarbons in their model for calculation of proper-
ties of reservoir fluids. The main focus of this work is character-
Table 4. Evaluation of several characterization methods on prediction of ization methods used in process simulators for process design
enthalpy and interfacial tension of petroleum fractions.
and not for phase behavior calculation of reservoir fluids.
Abs. dev. % Abs. dev. for Choice of characterization methods for PVT properties
Method for enthalpy, kJ/kg interfacial tension and phase behavior of reservoir fluids has been discussed else-
where (Riazi and Aladwani, 2003) and is outside of the objec-
Pseudocomponent 6.2 5.7
API-TDB (1997) 6.3 6 tive of this work.
Kesler and Lee (1976) for 6.4 19 Selection of a right characterization method for pet-
Tc, Pc and M roleum fluid of interest has a good effect on calculated
Lee and Kesler (1975) for v properties and subsequent design calculations. It is up to
Twu (1994) 6.8 13
the users of process simulators to decide which characteri-


Enthalpy evaluation is based on Lenoir and Hipkin data set (1973) which zation method to select. No general guideline is given in
include 700 data points for 8 petroleum fractions. IFT evaluation is based on such simulators and users knowledge and experience is
8 petroleum fractions from Miqueu et al. (2001). The API methods are: the main guide for such selections. Although no concrete
Riazi and Daubert (1987a) for Tc, Pc and M and the Lee–Kesler method for v.
recommendation can be made for selection of right charac-
terization method, but based on evaluations and limitations
analysis are mainly petroleum products obtained from atmos- reported in this work or those by other researchers as
pheric distillation units with molecular weights less than 300. mentioned here, for each method some guidelines are rec-
For this group of fractions the API methods generally give ommended in Table 5. Such recommendations may vary
best results. The pseudocomponent method is equally accu- from one individual to another based on his/her experience
rate provided data on the PNA composition is available. and type of data used. However, one should be careful that
use of these methods outside of the ranges that they have
been recommended usually result in less accurate pre-
dictions of thermodynamic properties.
CONCLUSIONS AND RECOMMENDATIONS
Process simulators (i.e., HYSYS, 1996, PRO/II, 1992)
contain as many as a dozen different characterization
Table 5. Recommended methods for prediction of the basic pure properties
methods. These methods as discussed in this paper vary of hydrocarbons and narrow boiling range petroleum fractions.

in their limitations and applications. For example when
the API methods for Tc and Pc are used for very heavy frac- Property Range of M Method
tions (NC . 30) they give less accurate values than the M 70–700 API (1997)—Procedure 2B2.2
pseudocomponent or Kesler– Lee methods. 70–300 Riazi–Daubert (1980)
Most recent evaluations for critical properties of pure 200–800 API (1997) Procedure 2B2.3a
hydrocarbons was made by Jianzhong et al. (1998) which 70–700 Twu (1984)
followed the work of Voulgaris et al. (1991) for prediction Tc 70–300 API (1997)
70–700 Kesler– Lee (1976)
of physical properties of petroleum fractions and coal 70–800 Riazi et al. (1995)
liquids was given in Table 2. They correctly concluded Pc 70–300 API (1997)
that complexity of predictive correlations does not neces- 70–700 Kesler– Lee (1976)
sarily result in more accurate prediction. All these corre- 70–300 Riazi et al. (1995)
300–800 Pan–Firoozabadi–Fotland (1997)b
lations are developed based on properties of pure Vc 70–350 Riazi–Daubert (1980)
hydrocarbons, therefore, when they are applied to mixtures 30–700 Riazi et al. (1995)
which contain large quantities of hetroatoms such as sulfur v 70–300 Lee–Kesler (1975)
or nitrogen or contain nonhydrocarbon compounds, less 70–700 Riazi et al. (1995)
accurate results are obtained. 300–700 Pan–Firoozabadi–Fotland (1997)b
These characterization methods are also used by reservoir a
Only when boiling point is not available.
b
engineers in their calculations for phase behavior of reservoir Modified form of Riazi et al. (1995) pseudocomponent method.

Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 160–166
166 ALADWANI and RIAZI
NOMENCLATURE
API-TDB American Petroleum Institute—Technical Data Book
d20 density at 208C
M molecular weight
M7þ molecular weight of C7þ fraction
NC number of carbon atoms in a hydrocarbon compound
or group
Nmin minimum number of trays
n20 refractive index at 208C
Pc critical temperature
Tb boiling point
Tc critical temperature
SG specific gravity
SG7þ specific gravity of C7þ fraction
a relative volatility
v acentric factor
PNA paraffin –naphthene–aromatic content of a petroleum
fraction
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ACKNOWLEDGEMENT
This research is supported by the Research Administration of Kuwait
University under Project EC03-01.
The manuscript was received 1 September 2003 and accepted for
publication after revision 5 November 2004.