Fluid Phase Equilibria, 29 (1986) 575-582 575

ElsevierSciencePublishersB.V.,Amsterdam-PPrintedinTheNetherlands

PREDICTION OF PROPERTIES OF PETROLEUM MIXTURES :

IMPROVEMENT IN RELIABILITY AND VALIDITY OF TUNED PARAMETERS

RAFIQUL GANI and AAGE FREDENSLUND

Instituttet for Kemiteknik,
Danmarks Tekniske Herjskole,
2800 Lyngby, Denmark

ABSTRACT
The val.idity, reliability and range of applicability of parame-
ters tuned for prediction of properties of petroleum mixtures con-
taining heavy hydrocarbons have been analyzed. The tuning policy
of Gani and Fredenslund ( 1985 ) has been applied to propose which
experimental data ( for example, constant mass expansion ) should
be applied in the parameter estimation problem. It is shown that
the parameters obtained from the tuning policy and adjusted to the
chosen experimental data, give good predictions in reasonable
ranges of temperature, pressure and composition. It is also found
that parameters tuned with the chosen experimental data for a part-
icular prediction problem ( for example, constant mass expansion )
are valid for simpler and some complex problems ( for example, com-
pressibility factors, dew points, bubble points, flash separations,
constant volume depletion experiments, etc. ).

INTRODUCTION
Prediction of properties of petroleum mixtures containing heavy
hydrocarbons may call for tuning of parameters of the equation of
state being used. The validity, reliability and range of applica-
bility of these tuned parameters depend on the application, the
type of mixture, and on the type and quality of experimental data
used. A serious constraint in case of prediction of properties of
petroleum mixtures is the availability of the desirable experimen-
tal data. Often, the reliability of the tuned parameters is ques-
tionable because of flaws in the data for tuning.
The objective of this work is to develop a set of criteria thro-
ugh which the reliability, validity and range of the adjusted para-

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576

meters can be defined. The results of Gani and Fredenslund (1985)

are used as the basis and their tuning policy will be used. Data
of seven gas condensates ( Pedersen et al. (1984a), (1984b), (1985a))
will be used for the purpose. Analysis of the results for different
combinations of experimental data, prediction problem, mixture type
and number and type of parameters to be adjusted will be made. The
objective of these analyses is to identify the most appropriate
experimental data to be used for tuning and the optimal number of
parameters to be tuned for a particular prediction problem and mix-
ture type. The Soave-Redlich-Kwong (SRK) equation of state ( Soave
(1972)) is used.

ANALYSIS OF PREDICTION RESULTS ( WITHOUT TUNING )

A thorough analysis of the results of different prediction prob-
lems and mixtures revealed certain characteristic trends as descri-
bed below. Global properties ( eg., 2, or V ) which represent sim-
ple prediction problems, usually are predicted to within +5 percent
accuracy. Bulk properties like bubble points and dew points which
in addition to global properties require individual property pre-
diction ( eg., fugacity coefficients ) and which represent semi-
complex problems, show high composition sensitivity of trace ele-
ments at low pressures. At high pressures, the sensitivity to para-
meters ( eg., Tc,Pc and w for each component and the binary inter-
action coefficients, k.. ) as well as composition are of equal imp-
ortance. Complex predigiion problems like single or multiple flash
( as in constant mass expansion or constant volume depletion ) usu-
ally have errors which increase with increasing pressure. The errors
related to the liquid phase are much greater than those related to
the vapor phase ( see Table 1 ). For many practical applications,
the vapor phase predictions are within the accuracy requirements.

SELECTION OF THE EXPERIMENTAL DATA FOR TUNING

Data such as those belonging to the true boiling point curvew,
densities and molecular weights of fractions and PNA analysis are
necessary for the characterization of the petroleum mixtures and
henceforth will not, in this work, be considered for tuning purp-
oses. As the individual component properties are extremely import-
ant for the solution of complex and semi-complex problems, experi-
mental data related to these properties need to be considered.Thus,
potentially any available data on bubble point, dew point, constant
mass expansion, constant volume depletion and single and multiple
flash separations can be used for adjusting/tuning of the parameters.
Since, usually, available data on bulk properties and single flash
separations do not cover a wide range of conditions, they are not
suitable for multiple parameter estimation problems. For tuning
with ( lumped ) data however, they may be considered. The choice
therefore lies between the multiple flash experimental processes
like constant mass expansion, constant volume depletion , and other
similar type of experiments. As the constant mass expansion experi-
ment is simpler, both from experimental and computational points of
view, these data ( if available ) are conveniently chosen for the
examples of this work.
The constant mass expansion data include, at different tempera-
tures and pressures, the methane composition in the vapor phase,
the compressibility factor of the vapor phase, the volume of the
condensed phase as a percentage of the dew point volume and the
volume of the vapor phase. From these data, the fraction of liquid
condensed ( in moles ) can be determined. As the analysis of the
results have shown that large errors in the prediction occur in the
liquid phase, these are the values ideally suited for the verifica-
tion of the estimated parameter values ( alongwith the known data ).

TUNING PROCEDURE EMPLOYED

The tuning procedure has the following steps :
Step 1) characterize the given petroleum mixture by the method of
Pedersen et al. (1984b).
Step 2) perform the sensitivity analysis of Gani and Fredenslund
(1985) and establish the sensitivity type of the mixture.
Step 3) select the set of adjustable parameters most suitable for
tuning.
Step 4) obtain the best values of parameters which match the exper-
imental data ( in this case, constant mass expansion ).
A computer program consisting of two parts has been written. The
first part consists of steps 2 and 3. The second part consists of
step 4. A weighted least squares problem is solved in this part.
The second part allows the use of other experimental data ( for
example, bulk properties, constant volume depletion ) as well as
lumped data, that is, using for example, bulk property data and
constant mass expansion data in the same problem.
Choice of the data points
In this work, constant mass expansion data at three pressures,
one corresponding to the largest prediction error and the other two
 578

TABLE 1
Comparison of predictions for flash separation problems at
temperature = 121.6 K ( mixture 2, Gani and Fredenslund (1985)).

Properties Pressure = 362.2 atm. pressure = 171.5 atv.

liquid phase vapor phase liquid phase vapor phase
tuning no tuning tuning no tuning tuning no tuning tuning no tuning

component mole
fractions :
Methane 0.4843 0.5124 0.6885 0.6903 0.3464 0.3069 0.7012 0.7086
Pseudo, 0.0197 0.0603 0.0230 0.0225 0.0768 0.1459 0.0206 0.0160
Pseudo2 0.1969 0.0964 0.0063 0.0056 0.1908 0.1375 0.0002 0.0001
Phase fraction 0.0026 0.0130 0.9974 0.9870 0.0446 0.0652 0.9553 0.9348
Density (g/cc) 0.5980 0.5360 1.0120 1 .a340 0.6140 0.6010 0.8550 0.8900
Mol. weight 84.3000 61.6000 28.3000 28.0000 101.2000 92.4000 25.8000 2s.1000

1 : pseudocomponent with average carbon number of 8

2 : pseudocomponent with average carbon number of 20

TABLE 2
Summary of the results of the application of the proposed tuning
policy.

Mixture reference temperature pressure average prediction errors’( 8 )

l- a 402.15 48.0 1.42 1 .86 -7.90 - 6.53 26.08 92.67 1.34 0.72
437.0 15.3 60.2
2 a 394.15 70.8 6.91 7.40 -3.50 - 7.on 13.47 66.56 6.37 0.56
361.2 8.7 37.7
4 a 376.65 64.0 2.56 1.73 -6.10 -17.20 33.50 83.67 0.34 0.44
292.0 24.2 44.4

a : Gani and Fredenslund ( 1965 )

, : averageprediction error ( see table 1 )
, : the lower value obtained by excluding the high pressure end point
 579

at the upper and lower extreme points of the available data were
considered for all the parameter estimation problems ( except those
given in Table 4 ). Thus, the minimum data points necessary for any
prediction problem is three.
Number of parameters to tune
The tuning policy of Gani and Fredenslund (1985) identifies the
most sensitive parameters for a particular mixture type and predic-
tion problem. From experience, it has been found that three is the
largest number of parameters ( for a mixture characterized by eight
components, Pedersen et al. (1985a)) that need to be tuned. Trials
with more than three parameters did not improve the predictions
enough to justfy their inclusion.

RESULTS/DISCUSSION
Table 2 summerizes the results of the different applications of
the tuning policy. It can be seen that the predictions in the glo-
bal properties are generally improved, even though no global prop-
erty data were used here for the tuning of the parameters. The same
applies for the bulk properties predictions. This can be expl-
ained as follows : the constant mass expansion curve represents
data which are close to the dew points of the mixture. Hence, if
the parameters are 'tuned' to match this curve, then the 'tuned'
set of parameters may be expected to make better predictions for
dew points than the original set of parameters ( ie., predictions
made without tuning ).
The danger of tuning without a proper procedure has already been
pointed out by Pedersen et al. (1985b). The advantage of using the
proposed tuning policy is that the predictions for other problems
are improved ( eg., bubble points, dew points etc. ) even though
experimental data for these problems were not considered. Also, the
range for which these predictions are valid is the same as those
for the predictions of the other problems ( ie., both simpler and
more complex problems ) even though only data for complex problems
were used for the estimation of the parameters.
The results of Table 1 also show that single flash separation
predictions at low pressures are uneffected by the tuning procedure
and that the tuned parameters are valid for other complex predic-
tion problems ( eg., constant volume depletion process ). This is
to be expected since other complex prediction problems also require
individual component properties. Thus, with a single set of 'tuned'
parameters, different prediction problems can be solved over a
580

TABLE 3
Sensitivity index and estimated parameter values for four petroleum
mixtures.

MIXtUrP reference parameter sensitivity estimated

identification index parameter
( kij )
i j

1 a 3 8 - 2.94 0.075
3 7 - 1.53 -0.250
2 a 3 8 -41.38 0.125
3 7 -21.43 -0.750
4 a -17.14 -0.010
4 a 3 8 - 4.85 0.025
3 7 - 3.00 -0.400
3 6 - 2.00 -0.300
6 a 3 a - 3.02 0.050
3 I - 1.53 -0.400
3 6 - 0.92 -0.200

a : Gani and Fredenslund ( 1985 )

t : Estimated value corresponds to table 5 of
reference a.

TABLE 4
Comparison of predictions with parameters tuned with different
experimental data.

Mixture parameters experimental data points prediction of fraction condensed

in single PT flash at T = 376.65 K
number type number type pressure calculated experimental
(atm) VdllJSZ VdlW

4 3 k.. 3 CME 276.80 1.825 0.380

11
222.80 4.363 3.410
101.40 9.646 7.540
3 k.. 2+1+2 CHE+De” pt.+ 276.80 1.894 0.380
11 cw
222.80 4.564 3.410
107.40 9.621 7.540
2*1 kij+Tc B 3 CME 276.80 0.534 0.380
222.80 4.269 1.410
107.40 9.385 7.540

CHE : cwstant mass expansion

CM : constant volume depletion
 581

wide range of conditions. At the same time, predictions at low

pressures can be expected to remain uneffected.
Table 3 lists the derivative values ( to be called 'sensitivity
index' ) of the parameters tuned and their final adjusted values
for four gas condensates. In all cases, it can be seen that the
parameter with the largest sensitivity index has a positive value
and the others have negative values. Of the negative values, the
parameter with the second largest sensitivity index has the larger
value. Also, it can be seen that if the sensitivity indices are
greater than 10.0 or less than 1.0 ( absolute ), the parameter
values ( the negative or the larger positive or both ) are close
to their limiting values. For the positive number, the limiting
value is +0.4 and for the negative number, it is -0.75. Also, the
ratio of the sensitivity indices has importance. If all the indices
are close to each other, the parameter values will be close to each
other and more difficult to adjust. It was found from computations
that the positive parameter is sensitive to large values and the
large values for the negative parameters were not as critical.
Also, the large value indicate problems where timing of parameters,
although feasible, is not easy. In this table, component 3 is
methane and components 6,7 and 8 are the three heaviest pseudocom-
ponents in the characterized mixture.
Table 4 shows the prediction results for lumped parameter estima-
tion problems. In the first two cases, data for different exper-
iments ( dew point, constant mass expansion and constant volume
depletion ) were used to estimate the three parameters ( binary
interaction coefficients ) of mixture 4 ( see Table 3 ). In the
last case, for the same mixture, two binary interaction coeffici-
ents and one true component property ( Tc of the heaviest pseuao-
component ) were estimated with data from one type of experiment
only ( but different data, ie., compositions and volume of liquid
per dew point volume ). The prediction results correspond to single
flash problems whose data were not considered for the estimation
problem. It should be noted that although the predictions were
satisfactory for all cases, quite different parameter values were
obtained for the three cases.

CONCLUSIONS
A mathematical approach to the tuning parameters for the pre-
diction of properties of petroleum mixtures has been developed. By
identifying the best set of parameters to tune and the best set of
experimental data to use, the procedure allows the prediction of
properties over a wide range of conditions. Thus, for a particular
petroleum mixture, a set of tuned parameters having an 'acceptable'
range of validity and reliability are provided. Furthermore, the
proposed policy provides important insights in the choice of data
points, number of parameters to tune, the final values of the tuned
parameters and the degree of difficulty of the tuning problem.

ACKNOWLEDGEMENTS
The authors wish to thank Karen S. Pedersen for fruitful dis-
cussions, use of her computer programs and interest in the work.

NOMENCLATURE
critical pressure, atm
pC
critical temperature, K
*C
V volume, cc/gmole
z compressibility factor
k binary interaction coefficient
ij
w acentric factor

REFERENCES
Gani, R. and Aa. Fredenslund, 1985, Thermodynamics of Petroleum
Mixtures Containing Heavy Hydrocarbobs: Development of a Tuning
Policy, submitted to I&EC, Process Des. and Develop.
Pedersen, K.S., Thomassen and Aa. Fredenslund, 1984a, Thermodyna-
mics of Petroleum Mixtures Containing Heavy Hydrocarbons,
Part 1: Phase Envelope Calculations Using the SRK Equation of
State, I&EC, Process Des. and Develop., 23: 163 - 170
ibid, 198433, Part 2: Flash and PVT Calculations Using the SRK
Equation of State, I&EC, Process Des. and Develop., 23: 566-573.
ibid, 1985a, Part 3: Efficient Flash Calculation Procedures Using
the SRK Equation of State, I&EC, Process Des. and Develop., 24:
948 - 954.
Pedersen, K.S., P. Thomassen and Aa. Fredenslund, 1985b, On the
Dangers of Tuning Equation of State Parameters, ACS National
Meeting, Miami, USA.
Soave, G., 1972, Equilibrium Constants from the Modified
Redlich-Kwong Equation of State, Chem.Eng.Sci., 27: 1197 - 1203.