Thermodynamics 4

Characterization of C
7
+
Petroleum Fractions for Compositional Simulations, Colombia, Summer 2000

Author: Dr. Maria Barrufet - Summer, 2000 Page 1/38

Instructional Objectives
At the end of this module, the students should be able to
Understand the need for characterizing the heavy fraction for reservoir
simulation.
Use the correlations presented in class to determine critical pressures when
boiling point and specific gravity data are available
Use the correlations presented in class to determine critical temperatures of the
heavy fraction when boiling point and specific gravity data are available
Use the correlations presented in class to determine acentric factors of the heavy
fraction when boiling point and specific gravity data are available
Compare physical properties from various correlations
Be able to lump and characterize a hydrocarbon mixture (Gas Condensate
Example in class)
Be able to split and characterize the C
7
+
fraction of a mixture (Gas Condensate
Example in class).
7
+
Petroleum Fractions for
Compositional Simulations Generalized Phase Equilibria
Models

Fluid Characterization of the Hydrocarbon Plus Fraction ( C
7
+
): Gas Chromatography, True
Boiling Point Tests (TBP), Viscosity, and Specific Gravity.
Estimation Methods for Critical Properties. Characterization Factors.
Splitting and Lumping Schemes of Petroleum Fractions.
Applications to Reservoir Simulation. Group selection.
Tuning of Equations of State (EOS). Selection of regression variables. Limits of Tuned
Parameters. Model validation.
Improvement of EOS Volumetric Predictions by Volume Translation.
Building Fluid Models for Reservoir Simulation Using PVTi and Eclipse 300.

S t d din : MAB
7
+


Introduction
Nearly all naturally occurring hydrocarbon systems contain a quantity of heavy fractions
that are not well defined and are not mixtures of discretely identified components.
These heavy fractions are often lumped together and identified as the plus fraction, e.g.,
C
7
+
fraction. This fraction is composed of any molecules of the crude oil that have
boiling points higher than n-hexane.
A proper description of the physical properties of the plus fractions in hydrocarbon
mixtures is essential in performing reliable phase behavior calculations and
compositional modeling studies.
Frequently a distillation analysis or a chromatographic analysis is available for this
undefined fraction.

True Boiling Point Tests (TBP Tests)
Are used to characterize the oil with respect to the boiling points of its components. In
these tests, the oil is distilled and the temperature of the condensing vapor and the
volume of liquid formed are recorded. This information is then used to construct a
distillation curve of liquid volume percent distilled versus condensing temperature. The
condensing temperature of the vapor at any point in the test will be close to the boiling
of the material condensing at that point. For a pure substance, the boiling and
condensing temperature are exactly the same. For a crude oil the distilled cut will be a
mixture of components and average properties for the cut will be determined.
In the distillation process, the hydrocarbon plus fraction is subjected to a standardized
analytical distillation, first at atmospheric pressure, and then in a vacuum at a pressure
of 40 mm Hg. Usually the temperature is taken when the first droplet distills over. Ten
fractions (cuts) are then distilled off, the first one at 50
o
C and each successive one with
a boiling range of 25
o
C. For each distillation cut, the volume, specific gravity, and
molecular weight, among other measurements, are determined. Cuts obtained in this
manner are identified by the boiling-point ranges in which they were collected.
The following figure shows the equipment used for this type of tests.
7
+


Figure 1 - Equipment used for TBP tests.

The following table is an example of a distillation test with 11 cuts.

Component Ti Tf T mean V (cm3) ( V) V % Off
Hypo1 99 220 159.5 5.1 5.1 5.3
Hypo2 214 323 268.5 8.0 13.1 13.5
Hypo3 323 432 377.5 7.9 21.0 21.7
Hypo4 432 526 479 8.1 29.1 30.1
Hypo5 526 612 569 7.9 37.0 38.2
Hypo6 612 693 652.5 7.9 44.9 46.4
Hypo7 693 765 729 7.9 52.8 54.5
Hypo8 765 821 793 7.8 60.6 62.6
Hypo9 821 908 864.5 8.1 68.7 71.0
Hypo10 908 1010 959 5.2 73.9 76.3
Residual 1261.1692 22.9 96.8 100.0
Whole Oil 729
Residual Volume Left 22.9

Table 1 - Example of a distillation test with 11 cuts.

The boiling point of the residual it is unknown and it may be used as a tuning parameter.
One of the methods to estimate the boiling temperature of the residual is by using a
Watson characterization factor and the specific gravity of the residual.
7
+


TBP Distillation Curve
0
200
400
600
800
1000
1200
1400
0.0 20.0 40.0 60.0 80.0 100.0
Distilled Volume %
B
o
i
l
i
n
g

T
e
m
p
e
r
a
t
u
r
e

o
F
T initial
T final
T average

Figure 2 - TBP distillation curve.

Other physical properties such as molecular weight and specific gravity may also be
measured for the entire fraction or various cuts of it.

Average Boiling Points Used
Generally, there are five different methods of defining the normal boiling point for
petroleum fractions. These are:

Method 1: Volume Average Boiling Point (VABP)
This is defined by the following expression:

i
bi i
T v VABP (1)
where
7
+


T
bi
= boiling point of the distillation cut i,
o
R
v
i
= volume fraction of the distillation cut i

Method 2: Weight Average Boiling Point (WABP)
This is defined by the following expression:
i
bi i
T w WABP (2)
where w
i
= weight fraction of the distillation cut i

Method 3: Molar Average Boiling Point (MABP)
This is given by the following relationship:
i
bi i
T x MABP (3)
where x
i
= mole fraction of the distillation cut i

Method 4: Cubic Average Boiling Point (CABP)
This is defined as
3
3 / 1
1
]
1
i
bi i
T x CABP (4)

Method 5: Mean Average Boiling Point (MeanABP):
2
CABP MABP
MeanABP
+
(5)

These five expressions for calculating normal boiling points result do not differ
significantly from one another for narrow boiling petroleum fractions.

7
+


Key Physical Properties Required for Reservoir
Engineering
To use any of the thermodynamic property-prediction models, e.g., equation of state, to
predict the phase and volumetric behavior of hydrocarbon mixtures, one must be able to
provide the:
Critical temperature, T
c

Critical pressure, P
c

Critical volume, V
c

Critical compressibility factor, Z
c

Acentric factor,
Molecular weight, M
w

for both the defined and the undefined (heavy) fractions in the mixture.
Petroleum engineers are usually interested in the behavior of hydrocarbon mixtures
rather than pure components. However, the above characteristic constants of the pure
and of the hypothetical components are used to define and predict the physical
properties and the phase behavior of mixtures at any reservoir state.
The properties more easily measured are normal boiling points, specific gravities,
and/or molecular weights. Therefore existing correlations target these as the variables
used to back up the parameters needed for EOS simulations. (Tc, Pc, , etc)

Importance of the C
7
+
Fraction in Reservoir
Engineering
Most oil recovery processes are greatly influenced by the C
7
+
fraction. CO
2
injection for
miscible displacement is highly dependent upon the C
7
+
fraction but waterflooding
above the bubble point is insensitive except through the oil viscosity.
The C
7
+
fraction may greatly influence how fluids flow in the reservoir. Fluid viscosities
are based on volumetric fractions of the phases, which are determined by the phase
behavior, which is highly dependent upon the C
7
+
fraction. The fractional flow of each
7
+


phase is determined by the relative permeability and viscosity of each phase. The C
7
+

fraction is especially important for condensate flow calculations since the amount of
liquid dropout is strongly affected by the C
7
+
molecular weight and fraction.

Overview Of Generalized Correlations For Estimating
Physical Properties Of Hydrocarbon Fractions
Most correlations use the specific gravity and the normal boiling point Tb as correlation
parameters. Selecting proper values for these parameters is very important because
slight changes can cause significant variations in the predicted results.
The vast number of hydrocarbon compounds making up naturally occurring crude oil
have been grouped chemically into several series of compounds. Each series consists
of those compounds similar in their molecular make-up and characteristics. In general, it
is assumed that the heavy (undefined) hydrocarbon fractions are composed of three
hydrocarbon groups, namely:
Paraffins (P)
Naphthenes (N)
Aromatics (A)

The PNA content of the plus fraction of the undefined hydrocarbon fraction can be
estimated experimentally from a distillation analysis and/or a chromatographic analysis.

Riazi-Daubert
Riazi and Daubert (1980) developed a simple two-parameter equation for predicting the
physical properties of pure compounds and undefined hydrocarbon mixtures. The
proposed generalized empirical equation is based on the use of the normal boiling point
and the specific gravity as correlating parameters. The basic equation is:

c b
b
aT (6)

7
+


where Tb is the normal boiling point temperature expressed in degrees R and the
constants a, b, c, depend upon the physical property indicated by .

Property
Coefficients Percent Deviation
a b c Average Maximum
M
W
4.5673 x 10
-5
2.1962 - 1.0164 2.6 11.8
T
c
, R 2.42787 0.58848 0.3596 1.3 10.6
P
c
, psia 3.12281 - 2.3125 2.3201 3.1 9.3
V
c
ft
3
/ lbm 7.5214 x 10
-3
0.2896 - 0.7666 2.3 9.1
Table 2 - Correlation constants for Eq. (6).

The prediction accuracy is reasonable over the boiling point range of 100-850
o
F.
Later, in 1987, Riazi and Daubert (1987) modified their equation while maintaining its
simplicity while significantly improving its accuracy. Eq. (7) expresses the property as a
function of normal boiling point (Tb) and oil specific gravity at standard conditions (Form
1 in Table 3).

[ ] + +
b b
c b
b
fT e dT exp aT (7)

Eq. (8) expresses the property as a function of normal boiling point (Tb) and oil
molecular weight at standard conditions (Form 2 in Table 3).

[ ] + +
w w
c b
w
fM e dM exp aM (8)

The constants a to f for the two different functional forms of the correlation are tabulated
in Table 3, and depend upon the correlated property.

7
+


Form (1) Equation (7)
Property
Coefficient
Mw Tc (
o
R) Pc (psia) Vc (ft
3
/ lbm )
a 581.96 10.6443 6.162x10
6
6.233x10
-4

b 0.97476 0.81067 -0.4844 0.7506
c 6.51274 0.53691 4.0846 -1.2028
d 5.43076x10
-4
-5.1747x10
-4
-4.725x10
-3
-1.4679x10
-3

e 9.53384 -0.54444 -4.8014 -0.26404
f 1.11056x10
-3
3.5995x10
-4
3.1939x10
-3
1.095x10
-3

Form (2) Equation (8)
Property
Coefficient
Tc (
o
R) Pc (psia) Vc (ft
3
/ lbm ) Tb (
o
R)
a 544.4 4.5203x10
-4
1.206x10
-2
6.77857
b 0.2998 -0.8063 0.20378 0.401673
c 1.0555 1.6015 -1.3036 -1.58262
d -1.3478x10
-4
-1.8078x10
-4
-2.657x10
-3
3.77409x10
-3

e -0.61641 -0.3084 0.5287 2.984036
f 0.0 0.0 2.6012x10
-3
-4.25288x10
-3

Table 3 - Coefficients from Riazi and Daubert Correlations.

The limitations for using Riazi and Daubert correlations are that the molecular weight
should be in the range of 70-300 lb/lb-mol and the normal boiling point range: 80-650
o
F.

Lin-Chao Generalized Correlation
Lin and Chao expressed the physical properties of C
1
to C
20
n-alkanes by the following
generalized equation

7
+


( ) ( ) ( )
1
5
3
4
2
3 2 1
+ + + + Mw a Mw a Mw a Mw a a (9)

The constants a
1
to a
5
depend upon the property that is being correlated. Table 4
reports the values.

Property
C Tc (
o
R) ln (Pc) (psi) Tb (
o
R)
a
1
490.8546 6.753444 - 28.21536 0.66405 240.8976
a
2
7.055982 - 0.010182 2.209518 1.48130 x 10
-3
5.604282
a
3
- 0.02118708 2.51106 x 10
-5
17.943264 x10
-5
- 5.0702 x 10
-6
- 0.0127616
a
4
2.676222 x 10
-5
- 3.73775 x 10
-8
- 3.685356 x 10
-5
6.21414 x 10
-9
13.84353x 10
-6

a
5
- 4,100.202 3.50737 - 124.35894 - 8.45218 - 2,029.158
Table 4 - Values of the constants a
1
to a
5
.

Cavett's Correlations
Cavett (1962) proposed correlations for estimating the critical pressure and temperature
of hydrocarbon fractions. The correlations have received a wide acceptance in the
petroleum industry due to their reliability in extrapolating at conditions beyond those of
the data used in developing the correlations.
The proposed correlations were expressed analytically as functions of the normal
boiling point Tb and API gravity. Cavett proposed the following expressions for
estimating the critical temperature and pressure of petroleum fractions:

( )( ) ( ) ( )
2 2
6
2
5
3
4 3
2
2 1 0 b b b b b c
T API a T API a T a T API a T a T a a T
b
+ + + + + + (10)

( )( ) ( ) ( )
( )
2 2
7
2
6
2
5
3
4 3
2
2 1 0

ln
b
b b b b b c
T API b
T API b T API b T b T API b T b T b b P
b
+ + + + + + +
(11)

7
+


where the critical temperature (T
c
) is expressed in
o
R, the normal boiling point (T
c
) is in
o
F, and the critical pressure (P
c
) is in psia.

Table 5 lists the coefficients used in Eqs. (10) and (11).

Index a
i
b
i

0 768.07121 2.8290406
1 1.7133693 0.94120109 x 10
-3

2 - 0.0010834003 - 0.30474749 x 10
-5

3 - 0.0089212579 - 0.20876110 x 10
-4

4 0.38890584 x 10
-6
0.15184103 x 10
-8

5 0.53094920x10
-5
0.11047899 x10
-7

6 0.32711600 x 10
-7
- 0.48271599 x 10
-7

7 0 0.13949619 x 10
-9

Table 5 - Coefficients used in Cavetts correlations (Eqs. (10) and (11)).

Kesler-Lee Correlations
Kesler and Lee (1976) proposed a set of equations to estimate the critical temperature,
critical pressure, acentric factor, and molecular weight of petroleum fractions. The
equations, as expressed below; use specific gravity and boiling point in
o
R as input
parameters.

3 10
2
2 7
2
3
2
10 10
47227 0 648 3
4685 1
10
11857 0 2898 2
24244 0
0566 0
3634 8
b b
b c
T
1.6977
0.42019 T
. .
.
T
. .
.
.
. P

,
_
+ +
,
_
+
+
,
_

(12)

7
+


( ) ( )
b
b c
T
. . T . . . . T
5
10
26238 3 4669 0 1174 0 4244 0 1 811 7 341
+ + + + (13)

( ) ( )
( )
3
12
2
7
2
10 98 . 181
8828 . 1 02226 . 0 80882 . 0 1
10 79 720
3437 1
02058 . 0 77084 . 0 1 3287 . 3 6523 . 4 4 . 486 , 9 6 . 272 , 12
b b b b
b
T T T T
.
- .
T Mw
,
_
+ +
,
_
+ + +
(14)

The above equation was obtained by regression analysis using the available data on
molecular weights ranging from 60 to 650.

Acentric Factor
Defining the Watson characterization factor Kw and the reduced boiling point T
br
by the
following relationships.
( )
3 / 1
b
T
Kw
(15)
and
c b br
T T T / (16)
where Tb = boiling point,
o
R

Kesler and Lee proposed the following two expressions for calculating the acentric
factor,

For 8 . 0 >
br
T ,
( )
br
br
T
Kw
T Kw Kw
01063 . 0 408 . 1
359 . 8 007465 . 0 1352 . 0 904 . 7
2
+ + + (17)

and, for 8 . 0 <
br
T ,
7
+


( )
6
6
43577 . 0 ) ln( 4721 . 13 / 6878 . 15 2518 . 15
1693347 . 0 ) ln( 28862 . 1 / 09648 . 6 92714 . 5 696 . 14 / ln
br br br
br br br c
T T T
T T T P
+
+ +
(18)

Kesler and Lee stated that their equations for P
c
and T
c
provide values are nearly
identical with those from the API Data Book up to a boiling point of 1,200
o
F.
There are many other correlations worth mentioning, Whitson (1984) provides and
excellent review.

Edmister's Correlation
Edmister (1958) proposed a correlation for estimating the acentric factor , of pure
fluids and petroleum fractions. The equation, widely used in the petroleum industry,
requires boiling point, critical temperature, and critical pressure. The proposed
expression is given by the following relationship:
( )
( )
1
) 1 / 7
7 . 14 / log 3

b c
c
T T
P
(19)
with the temperatures expressed in degrees R.

Note that the acentric factor can be used as a tuning parameter in EOS simulations.

Katz-Firoozabadi Method
Katz and Firoozabadi (1978) presented a generalized set of physical properties for the
petroleum fractions C
6
through C
45
. The tabulated properties include the average boiling
point, specific gravity, and molecular weight. The authors' proposed tabulated
properties are based on the analysis of the physical properties of 26 condensates and
naturally occurring liquid hydrocarbons.
The following figures show the relationship among these properties according to Katz &
Firoozabadi relations.

7
+


Hydrocarbon Physical Properties (Katz & Firoozabadi)
0
400
800
1200
1600
0 250 500 750 1000 1250 1500
Molecular Weight
Tb
0.5
0.7
0.9
1.1
S
G
Tb(F) SG

Table 6 - Tb vs. molecular weight according to Katz & Firoozabadi relations.

Hydrocarbon Physical Properties (Kats & Firoozabadi)
0
400
800
1200
1600
0.6 0.7 0.8 0.9 1
Specific Gravity
T
b
,

M
w
Tb(F) Mw

Table 7 - Tb vs. specific gravity according to Katz & Firoozabadi relations.

The following figures illustrate the predicted values of of Tc, Pc, and as a function of
boiling point and specific gravities using Katz and Firoozabadi (1978). (See excel file
characterizations.xls)

7
+


Physical Properties of Normal Alkanes
0
400
800
1200
1600
0 200 400 600 800 1000 1200 1400
Tb (F)
T
c

,

P
c
0
0.5
1
1.5
2
2.5
A
c
e
n
t
r
i
c

F
a
c
t
o
r
Tc /F
Pc (psia)
w

Figure 3 - Predicted values of of Tc, Pc, and as a function of boiling point using Katz
and Firoozabadi (1978).

7
+


Physical Properties of Normal Alkanes
0
400
800
1200
1600
0.6 0.7 0.8 0.9 1
Specific Gravity
T
c

,

P
c
0
0.5
1
1.5
2
2.5
A
c
e
n
t
r
i
c

F
a
c
t
o
r
Tc /F
Pc (psia)
w

Figure 4 - Predicted values of of Tc, Pc, and as a function of specific gravity using
Katz and Firoozabadi (1978).

Willman-Teja Correlations
Willman and Teja (1987) proposed correlations for determining the critical temperature
and pressure of the undefined petroleum fraction. The empirical formulas are given by
using a nonlinear regression model to best match the critical properties data of Berman
et al. (1977) and Whitson (1980).

( ) [ ]
884540633 . 0
137242 . 0 25127 . 1 1
+ + n T T
b c
(20)

[ ][ ]
9265669 . 1
54285 . 0 873159 . 0 157759 . 184 , 1 0416805 . 339
+ + n n P
c
(21)

7
+


Splitting and Grouping Schemes of Petroleum
Fractions
Accurate phase behavior data of petroleum fluids is required since this has a profound
effect on reservoir simulation, particularly for gas condensates, highly volatile fluids, and
gas injection recovery.
Experimental PVT data is available, but often this is insufficient for the entire range of
pressures temperatures and compositions likely to occur in depletion or injection
scenarios.
A thermodynamic equation of state (EOS) can overcome the lack of measured data,
however the incomplete fluid description and limitations and the limitations of the cubic
EOS means that some type of calibration in the EOS parameters will be needed.
The uncertainty in the properties of the hydrocarbon plus fraction, which comprises a
significant portion of naturally occurring hydrocarbon fluids, provides at the same time
great flexibility for calibrating the EOS.
Normal boiling points and specific gravity of the C
7
+
fraction may be the only measured
data available. Other types of hydrocarbon analysis provide molecular weights.

In the absence of detailed analytical data for the plus fraction in a hydrocarbon mixture,
erroneous predictions and conclusions can result if the plus fraction is used directly as a
single component in the mixture phase behavior calculations. Numerous authors have
indicated that these errors can be substantially reduced by "splitting" or "breaking down"
the plus fraction into a manageable number of fractions pseudo-components) for
equation of state calculations.
The problem, then, is how to adequately split a C
7
+ fraction into a number of
pseudo-components characterized by:
Mole fractions
Molecular weights
Boiling Points
Specific gravities
7
+


These characterization properties, when properly combined, should match the
measured plus fraction properties; i.e., (Mw)
7
+
and ()
7
+
.

Splitting Schemes
Splitting schemes refer to the procedures of dividing the C
7
+
fraction into hydrocarbon
groups with a single carbon number (C
7
, C
8
, C
9
, etc.) and are described by the same
physical properties used for pure components.
Several authors have proposed different schemes for extending the molar distribution
behavior of C
7
+
, i.e., the molecular weight and the specific gravity. In general, the
proposed schemes are based on the observation that lighter systems such as
condensates usually exhibit exponential molar distribution, while heavier systems often
show left-skewed distributions. This behavior is shown schematically in the following
figure.

Mol ecul ar Wei ght
M
o
l
e

F
r
a
c
t
i
o
n

Di stri buti on Skewed to the Left
(heavy oi l s)
Exponenti onal Distri buti on
(Condensate Systems)

Figure 5 - Schematic of the distribution of lighter and heavier systems.

7
+


Splitting Constraints
Three important requirements should be satisfied when applying any splitting models.

First Constraint: The sum of the mole fractions of the individual pseudo-components is
equal to the mole fraction of C
7
+
.

+
+
N
i
C
i
z z
7
7
(22)

Second Constraint: The sum of the products of the mole fraction and the molecular
weight of the individual pseudo-components is equal to the product of the mole fraction
and molecular weight of C
7
+
.

+
+
+
7 7
7
C
N
i
C
i i
Mw z Mw z (23)

Third Constraint: The sum of the product of the mole fraction and molecular weight di-
vided by the specific gravity of each individual component is equal to that of C
7
+
+
+ +
+
7
7 7
7
C
C C
N
i
i
i i
Mw z
Mw z
(24)
Where
i = number of carbon atoms
N
+
= last hydrocarbon group in the C
7
+
with n carbon atoms, e.g., 20 +

It is assumed that the molecular weight and specific gravity of the C
7
+
are measured.

Several splitting schemes have been proposed recently. These schemes, as discussed
below, are used to predict the compositional distribution of the heavy plus fraction.

7
+


Katz's Splitting Method
Katz (1983) presented an easy-to-use graphical correlation for breaking down into
pseudo-components the C
7
+
fraction present in condensate systems. The method was
originated by studying the compositional behavior of six condensate systems using
detailed extended analyses. On semi-log scale, the mole percent of each constituent of
the C
7
+
fraction versus the carbon number in the fraction was plotted. The resulting
relationship can be conveniently expressed mathematically by the following expression:

) 25903 . 0 exp( 38205 . 1
7
n z z
n

+
(25)

This equation is repeatedly applied until the first splitting constraint is satisfied. The
molecular weight and specific gravity of the last pseudo-component can be calculated
from the second and third constraint, respectively.

Pedersen's Method
Pedersen et al. (1982) proposed that for naturally occurring hydrocarbon mixtures, an
exponential relationship exists between the mole fraction of a component and the
corresponding carbon number as follows,
1
]
1
B
A n
z
n
exp (26)
where A and B are constants.
For condensate and volatile oils, Pedersen and coworkers suggested that A and B can
be determined by a least squares fit to the molar distribution of the lighter fractions.
This equation can be used to calculate the molar content of each of the heavier
fractions by extrapolation. The classical three constraints are also imposed.

Whitson's Method
Whitson (1980) proposed that a probability function called the Three Parameter Gamma
Function can be used to model the molar distribution. Unlike the previous models, the
gamma function has the flexibility to describe a wider range of distributions by adjusting
7
+


its variance, which is left as an adjustable parameter. Whitson expressed this function in
the following form:
)! (
) exp( ) exp(
) (
1 1
0
7
j
Y Y Y Y
z
z
n
j
n n
j
n
j
n
+

+
+
+
+
+
(27)
where
z
7 +
= mole fraction of the heptanes-plus fraction
z
n
= mole fraction of the pseudo-component with a number of carbon atoms of
n
Using this equation the heptanes plus fraction with a mole fraction of z
7
+ can be divided
into several pseudo-components each with composition z
n
and molecular weight Mw
n
.

+
7
Mw
Mw Y
n n
(28)
where
= adjustable parameter
() = gamma function
= the lowest molecular weight expected to occur in the pseudo-component state. A
good approximation of is given by:
6 14 n (29)

The shape of the curve (exponential or left-skewed) representing the molar distribution
depends on the value of the adjustable parameter .
Whitson suggested that reasonable limits for are 0.5 to 3.0. For = 1, the distribution
is exponential. Values equaling less than one give accelerated exponential distributions,
while values greater than one yield left-skewed distributions.

7
+


Behrens and Sandler Splitting Scheme
Behrens and Sandler (1986) used semi-continuous thermodynamic distribution theory to
model the C
7
+
fraction for equation of state calculations. The authors suggested that the
C
7
+
fraction could be fully described with as few as TWO pseudo-components.
A semi-continuous fluid mixture is defined as one in which the mole fractions of some
components, such as C
1
through C
6
, have discrete values, while the concentrations of
others, (the unidentifiable components) such as C
7
+, are described by the continuous
distribution function F(I). This continuous distribution function F(I) describes the heavy
fractions according to the index I, selected to be a property such as boiling point, carbon
number, or molecular weight.
For a hydrocarbon system with k discrete components, the following relationship
applies:
0 . 1
7
1
+
+
z z
k
i
i
(30)

The mole fraction of C
7
+
in this equation is replaced with the selected distribution
function, to give
0 . 1 ) (
1
+
B
A
k
i
i
dI I F z (31)
where A and B are the beginning and upper cutoff limit of integration of the continuous
distribution).

The above molar distribution behavior is shown schematically in Figure 6. The
parameter A can be determined from the plot, or can be defaulted to

C
7
, i.e., A=7.

The value of the second parameter B ranges from 50 to infinity; i.e., 50 < B < ;
however, Behrens and Sandler pointed out that the exact choice of the cutoff is not
critical.

7
+


Continuous
Molar Distribution
Discrete
Property
P

Figure 6 - Molar distribution behavior according to Behrens and Sandler.

Selecting the index I of the distribution function F(I) to be the carbon number n, Behrens
and Sandler proposed the following exponential form of F(I).
n
n D n F

exp ) ( ) ( (32)
with
A < n < B
where the parameter is given by solving the following expression
[ ]
( )
0
exp exp
exp 1

B A
B
n
B A
A C (33)
where
n
C is the average carbon number defined by the relationship:
[ ]
14
4
7
+
+
Mw
C
n
(34)

This equation can be solved for by successive substitutions or the Newton-Raphson
method, using an initial value of as:
7
+


A C
n

1
(35)

Substituting the distribution function yields

0 . 1 exp ) (
1
+
B
A
n
k
i
i
dn n D z (36)
or
+
B
A
n
dn n D z exp ) (
7
(37)

By a transformation of variables and changing the range of integration from A and B to 0
and c = (B-A) the equation becomes:

+
c
r
dr r D z
0
7
exp ) ( (38)

The authors applied the Gaussian quadrature numerical integration method with a
two-point integration to evaluate this equation as

+
2
1
7
) (
i
i i
w r D z (39)
where,
r
i
= roots for quadrature of integrals after variable transformation
w
i
= weighing factor of Gaussian quadrature at point i.

The following figure provides the values of r
i
and w
i
as a function of the Upper limit of
integration. For c > 10 these values remain essentially constant.
7
+


The weight factor w
2
is
1 2
1 w w (40)

Quadrature Points & Weights (Behrens & Sandler
Splitting
0
0.5
1
1.5
2
2.5
3
3.5
0 2 4 6 8 10
Upper Integration Limit (c)
r
2
0
0.2
0.4
0.6
0.8
1
r
1
,

W
e
i
g
h
t

(
w
1
)
r2 r1 w1

Figure 7 - Behrens and Sandler Roots and Weights for Two-point Integration

The computational sequences of the proposed method are summarized in the following
example.

Example (Given by Behrens and Sandier).
A heptanes-plus fraction in a crude oil system has a mole fraction of 0.4608 with a
molecular weight of 226. Using the Behrens and Sandler lumping scheme,
characterize the C
7
+ by two pseudo-components and calculate their mole fractions.
Solution.
7
+


Step 1.
Assuming the starting and ending carbon numbers to be C
7
and C
50
, calculate A and
B from
A = starting carbon number -
B = ending carbon number +

5 . 6 5 . 0 7 A
5 . 50 5 . 0 50 + B

Step 2.
Calculate the average carbon number
n
C from
[ ]
14
4
7
+
+
Mw
C
n

43 . 16
14
4 226
n
C

Step 3.
Solve equation for , to give
[ ]
( )
0
exp exp
exp 1

B A
B
n
B A
A C

A good initial guess is:
,
_

A C
n
1

0938967 . 0
7
+


Step 4.
Evaluate the range of integration c
c = (B-A)
13 . 4 0938967 . 0 ) 5 . 6 5 . 50 ( c

Step 5.
Find the weights and the integration points for c = 4.13 from excel file
(Characterizations.xls) or from the figure.
2267 . 0 7733 . 0
7733 . 0 4741 . 0
2 2
1 1

w r
w r

Step 6.
Find the equivalent pseudo-component carbon numbers n
1
& n
2
and mole fractions z
i
from the following expressions:
A
r
n +
1
1
& A
r
n +
2
2

+
7
1 1
z w z &
+
7
2 2
z w z

First pseudo-component
55 . 11 5 . 6
0938967 . 0
4741 . 0
1
+ n
3563 . 0 ) 4608 . 0 )( 7733 . 0 (
1
z

Second pseudo-component
7
+


08 . 33 5 . 6
0938967 . 0
4965 . 2
2
+ n
1045 . 0 ) 4608 . 0 )( 2267 . 0 (
2
z

The C
7
+
fraction is represented then by the following TWO pseudo-components:

Step 7.
Find the molecular weight of the individual pseudo-components from constraint
two.
Pseudo-
Component
Molecular
Weight
Carbon Number Mole Fraction
1 157.6572 C
11
.
55
0.3563
2 459.0724 C
33
.
08
0.1045

Step 8.
Assign the physical properties of the two pseudo-components according to
selected correlations. Satisfy the 3 lumping/splitting constraints.

Pseudo-
Component
n
T
b

(
o
R)
Mw
T
c

(
o
R)
P
c

(psia)

1 11.55 215.9 0.7315 154 1003.7 432.41 0.3167
2 33.08 647.9 0.8636 426 1425.23 202.60 0.7906

Lumping Schemes
Equation of state calculations are frequently burdened by the large number of
components necessary to describe the hydrocarbon mixture for accurate phase
7
+


behavior modeling. Often, the problem is either lumping together the many experimental
determined fractions, or modeling the hydrocarbon system when the only experimental
data available for the C
7
+
fraction are the molecular weight and specific gravity.

Generally, with a sufficiently large number of pseudo-components used in
characterizing the heavy fraction of a hydrocarbon mixture, a satisfactory prediction of
the PVT behavior by the equation of state can be obtained. However, in compositional
models, the cost and computing time can increase significantly with the increased
number of components in the system. Therefore, there are strict limitations on the
maximum number of components that can be used in compositional models and the
original components have to be lumped into a smaller number of new pseudo-
components.

The term lumpingor pseudoization then denotes the reduction in the number of
components used in equation of state calculations for reservoir fluids. This reduction is
accomplished by employing the concept of the pseudo-component. The pseudo-
component denotes a group of pure components lumped together and represented by a
single component.

There are several problems associated with regrouping the original components into a
smaller number without losing the predicting power of the equation of state. These
problems include:
How to select the groups of pure components to be represented by one
pseudo-component each.
How to determine (T
c
, P
c
, and ) for the new lumped pseudocomponents for
EOS use.

The molecular weight and specific gravity of the lumped compound are determined by
reversed application of the constraints #1 and #2 defined in the splitting procedures.
General rules of thumb are:
Group components with similar critical properties
Group all components with smaller compositions (i.e. <1%)
7
+


Do not group light and heavy components
Proportion of every lumped group should be similar whenever possible

There are several unique published techniques which can be used to address the above
lumping problems; among those:
Lee et al. (1979)
Whitson (1981)
Mehra (1982)
Montel-Gouel (1984)
Schlijper (1984)
Behrens-Sandler (1986)
Gonzalez-Colonomos-Rusinek (1986)

Whitsons Lumping Scheme
Whitson (1980) proposed a regrouping scheme whereby the compositional distribution
of Lumping is the reversed problem the C
7
+ fraction is reduced to only a few Multiple-
Carbon-Number (MCN) groups. Whitson suggested that the number of MCN groups
necessary to describe the plus fraction is given by the following empirical rule:
[ ] ) log( 3 . 3 1 n N Int N
g
+ (41)
where:
N
g
= number of MCN groups
Int = Integer
N = number of carbon atoms of the last component in the hydrocarbon system
n =number of carbon atoms of the first component in the plus fraction

The integer function requires that the real expression evaluated inside the brackets be
rounded to the nearest integer

7
+


The molecular weights separating each MCN group are calculated from the following
expression:

I
n
N
g
n I
Mw
Mw
N
Mw Mw
1
1
]
1
,
_
1
1
]
1
ln
1
exp (42)
where:
Mw
N
= molecular weight of the last reported component in the extended analysis of the
plus fraction.
Mw
n
= molecular weight of the first hydrocarbon group in the extended analysis of the
plus fraction.
i = 1, 2,..., N
g

Molecular weight of hydrocarbon groups (molecular weight of C
7
-group, C
8
-group, etc.)
falling within the boundaries of these values are included in the i
th
MCN group.

Suggested Exercises
Suggested Exercise 1 - A heptanes plus fraction with a molecular weight of 203
and a specific gravity of 0.8125 presents a naturally occurring condensate system.
The reported mole fraction of the C
7
+
is 0.12.
Predict the molar distribution of the plus fraction by using Katz's
correlation
Characterize the last fraction in the predicted extended analysis in
terms of its physical and critical properties.

Suggested Exercise 2 - A crude oil system has the following composition:
7
+


Component Z
I

Cl 0.3100
C
2
0.1042
C
3
0.1187
C
4
0.0732
C
5
0.0441
C
6
0.0255
C
7
0.0571
C
8
0.0472
C
9
0.0246
C
10
0.0233
C
11
0.0212
C
12
0.0169
C
13
+ 0.1340
The molecular weight and specific gravity of C
13
+
are 325 and 0.842.
Calculate the appropriate number of pseudo-components necessary to
adequately represent the above components. Use:
Whitson's Lumping Method
Behrens-Sandler Method
Characterize the resulting pseudo-components.

Volume Translations to Improve Volumetric
Predictions from EOS
Cubic EOS such as SRK, (Soave-Redlich-Kwong) and PR (Peng-Robinson) give
satisfactory VLE predictions for all reservoir engineering applications. However,
7
+


volumetric predictions, particularly for the liquid phase can be quite poor. Good
predictions of both VLE and volumetric data was not possible until the volume
translation concept was developed.
Using VLE information from EOS and independent estimates of liquid densities (from
the many available correlations) may create inconsistencies in material balance
computations, such as negative saturations, "creation" of mass, negative
compressibilities, etc. The volume translation concept is a permissible transformation
that leaves the VLE unchanged.
Liquid and gas volumes can then be estimated with good accuracy by correcting the
volumes predicted from EOS using the proposed translating procedure from Peneloux
et.al (1982) (Fluid Phase Equilibria 8, 7-23 )

Equation of State Transforms by Volume Translations
Any EOS is a functional relationship relating pressure, volume, temperature and
composition.
( )
c
N t
n ,..., n , n , n , V , T f P
3 2 1
(43)
with N
c
being the number of different species (components) in the system.

The expression for the fugacity coefficient of component "i" using an integral in P is:
dP
P RT
V
ln
P
i
i

,
_

0
1
(44)

Where the partial molar volume of component "i" is defined and evaluated as:
i
n , P , T
i
V
n
nV
j
,
_
(45)

The equilibrium conditions for two phases labeled as v and l (vapor and liquid),
) x ,....., x , x , P , T (
x ) y ,....., y , y , P , T (
y
nc
l
i i nc
v
i i 2 1 2 1
(i = 1, 2, 3, ....nc) (46)

7
+


The proposed volume translation consists in defining a pseudo-volume according to:
+
c
N
i
i i i t
ps
t
V n c V V
1
(47)

The c
i
's are component characteristic constants.

Substituting this pseudovolume instead of the total volume into Eq. (43) yields a
pseudo EOS:
( )
c
N
ps
t
ps
n ,..., n , n , n , V , T f P
3 2 1
(48)

we can also define pseudo-partial molar volumes as
i i i
n , P , T
i
n , P , T
i
ps
t
ps
i
c V c
n
nV
n
V
V
j j
+ +
,
_
,
_
(49)
and pseudo-fugacity coefficients,
dP
P RT
V
ln
P ps
i
ps
i
,
_

0
1
(50)

Thus the pseudo EOS leads to equilibrium conditions given by.
) x ,....., x , x , P , T (
x ) y ,....., y , y , P , T (
y
nc
) l ( ps
i i nc
) v ( ps
i i 2 1 2 1
(i = 1, 2, 3, ....nc) (51)
or replacing Eq. (49) for the pseudo partial molar volume the expression in terms of the
true fugacity coefficients is
,
_
,
_
RT
P c
exp ) x ,....., x , x , P , T (
x
RT
P c
exp ) y ,....., y , y , P , T (
y
i
nc
l
i i
i
nc
v
i i 2 1 2 1
(52)

which is EXACTLY the same result given by the unmodified Eq. (46) .Thus, translations
along the volume axis according to Eq. (47) leave the predicted VLE conditions
unchanged.

7
+


Not all forms of volume correction will preserve consistency. For example Lin and
Daubert (1980) (Ind. Eng. Chem. Process Des. Dev. 19, 51-59) correction which divides
volume by some factor does not preserve consistency.

Corrections for Soave-Redlich-Kwong EOS
The volume correction coefficient c
i
has been successfully correlated to the Rackett
compressibility factor Z
RAi
appearing in Spencer and Danner's (1973) correction of the
Rackett equation for saturated liquid volumes.

Z
RAi
is tabulated for most hydrocarbon species in the API Technical Data book Vol. II.
This set of notes includes part of that table for illustration purposes.

Many other correlating functions in terms of pseudo compressibility factors from other
sources have been tried for c
i
as well as similar corrections such as the shift factors

The first correction presented in Peneloux et.al (1982) paper (RSKc1) uses the following
relationship between c
i
and Z
RAi

( )
RAi
ci
ci
i
Z .
P
RT
. c
,
_
29441 0 40768 0 (53)

The second correction RSKc2 was obtained by substituting Z
Rai
in Eq. (53) for the
critical compressibility factors Z
ci
calculated from the experimental critical volumes.

The third correction RKSc3 was expressed in terms of the acentric factors was
( )
i
i
i
i
. .
Pc
RTc
. c +
,
_
0877 0 00385 0 40768 0 (54)

Variations of this volume translation concept developed by Peneloux-Rauzy and Freze
(PRF) are commonly used for others EOS as well in most reservoir engineering
packages.
7
+


The following figure shows the shift parameter used in the Peng Robinson EOS as a
function of molecular weight of the alkane hydrocarbon component.

Shift Factor for Normal Alkanes
0
200
400
600
0 50 100 150 200 250 300 350 400 450
Molecular Weight
P
c
,

V
c
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
S
h
i
f
t

F
a
c
t
o
r
Pc (psia) shift

Figure 8 - Shift factor for normal alkanes used in Peng-Robinson EOS

7
+


References
Ahmed, T., Cady, G., and Story, A., "A Generalized Correlation for Characterizing
the Hydrocarbon Heavy Fractions," Paper SPE 14266,presented at the 60th Annual
Technical Conference of the SPE, held in Las Vegas, September 22-25, 1985.
Behrens, R. and Sandler, S., "The Use of Semi-continuous Description to Model the
C
7
+
Fraction in Equation of State Calculation," Paper SPE/DOE 14925, presented at
the 5th Annual Symposium on EOR, held in Tulsa, Oklahoma, April 20-23, 1986.
Gonzalez, E., Colonomos, P., and Rusinek, I., "A New Approach for Characterizing
Oil Fractions and for Selecting Pseudo-Components of Hydrocarbons," Canadian
JPT, March-April 1986, pp. 78-84.

Hong, K. C., "Lumped-Component Characterization of Crude Oils for Compositional

Simulation," Paper SPE/DOE 10691, presented at the 3
rd
Joint Symposium on EOR,
held in Tulsa, Oklahoma April 4-7, 1982.

Hariu, 0. and Sage, R., "Crude Split Figured by Computer," Hydrocarbon Process.,
April 1969, pp.143-148.
Katz, D., "Overview of Phase Behavior of Oil and Gas Production," JPT, June 1983,
pp. 120-1214.
Lee, S., et al., "Experimental and Theoretical Studies on the Fluid Properties
Required for Simulation of Thermal Processes," Paper SPE 8393, presented at the
54th Annual Technical Conference of the SPE, held in Las Vegas, September 23-26,
1979.
Maddox, H. N. and Erbar, J. H., Gas Conditioning and Processing, Vol.3-Advanced
Techniques and Applications, Campbell Petroleum Series, Norman, Oklahoma,
1982.
Maddox, R. N. and Erbar, J. H., "Improve Predictions," Hydrocarbon Processing,
January, 1984, pp. 119-121.
Mehra, H., et al., "A Statistical Approach for Combining Reservoir Fluids into Pseudo
Components for Compositional Model Studies," Paper SPE 11201, presented at the
57th Annual Meeting of the SPE, New Or-leans, September 26-29, 1983.
7
+


Montel, F. and Gouel, P., "A New Lumping Scheme of Analytical Data for
Composition Studies," Paper SPE 13119, presented at the 59th Annual SPE
Technical Conference held in Houston, TX, September 16-19, 1984.
Pedersen, K., Thomassen, P., and Fredenslund, A., "Phase Equilibria and
Separation Processes," Report SEP 8207, Inst. for Kemiteknik, Denmark Tekniske
Hojskole (July 1982).
Schlijper, A. G., "Simulation of Compositional Process: The Use of Pseudo-
Components in Equation of State Calculations," Paper SPEI DOE 12633, presented
at the SPE/DOE 4th Symposium on EOR, held in Tulsa, Oklahoma, April 15-18,
1984.
Whitson, C., "Characterizing Hydrocarbon Plus Fractions," Paper EUR 183,
presented at the European Offshore Petroleum Conference held in London, October
21-24, 1980.

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Characterization of C

29441 0 40768 0 (53)

0877 0 00385 0 40768 0 (54)

Hong, K. C., "Lumped-Component Characterization of Crude Oils for Compositional

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