CO

2
Induced Asphaltene: a New Approach to Detect the
Deposition Onset
Noemi A. E. da Silva
a
, Victor R. da Rocha Oliveira
a
, Silvio Vieira de Melo
a
, Gloria M. N. Costa
a
*

a
Programa de Engenharia Industrial - Escola Politcnica Universidade Federal da Bahia, Rua Prof.
Aristides Novis, 2, Federao, 40210-630, Salvador, Bahia, Brazil.
* Corresponding author: gmeyberg@ufba.br Tel. +55-71-32839800 Fax +55-71-32839801

ABSTRACT

Carbon dioxide flooding has been used as a commercial process for enhanced oil recovery since the 1970s.
Significant amounts of residual oil can be recovered by this procedure. However, CO
2
flooding processes cause
many changes in flow and phase behavior of reservoir fluids and can significantly favor the precipitation of
asphaltenes, which is a serious and complex problem in all sections of the oil industry including oil production,
transportation and processing, and it causes a severe and detrimental impact on the oil production. Thus, it is of
vital importance to investigate under which conditions asphaltenes can deposit. In this paper a new approach is
presented which allows monitoring the CO
2
induced asphaltene deposition by varying the bubble pressure and
the oil density due to the CO
2
addition with a minimum of experimental data. It is shown that Hirschberg et al.
method [1] may be used for this purpose by performing several modifications regarding the characterization and
calculation of the solubility parameters of oil and asphaltene. Extensive testing with literature data allows
concluding that the proposed approach provides reasonable predictive results.

INTRODUCTION

Multiple contact miscible floods, involving the injection of relatively inexpensive gases into oil reservoirs,
represent one of the most cost effective enhanced oil recovery processes currently available. CO
2
miscible
flooding is among the most widely applied non-thermal enhanced oil recovery techniques
.
Among gas injection
processes,

CO
2
is preferred over hydrocarbon gases due to its low cost, high displacement efficiency, and the
potential for concomitant environmental benefits through its disposal in the petroleum reservoir. However, CO
2

flooding processes cause many changes in flow and phase behavior of the reservoir fluids and can significantly
favor the precipitation of asphaltenes. Asphaltenes refer to the heavy fraction of the petroleum mixture, which is
insoluble in some species, such as paraffins, but soluble in others, such as aromatics (benzene, toluene, etc.). The
precipitation of asphaltenes can be ascribed to changes in crude oil composition caused by addition of lower
boiling components as well as changes in temperature and pressure that affect the complex equilibrium keeping
the asphaltenes in solution or suspension. Asphaltenes are known to influence many of the process applied to oil
recovery operations and to crude oil refining [1]. There is a number of deposition models allowing the prediction
of asphaltene deposition under various parameters. The extended Flory-Huggins polymersolution theory [2] is
an example of such models where the maximum volume fraction of soluble asphaltene in crudes is obtained.
There is a method developed on the basis of the solubility model using the Flory-Huggins approach [1]. Further
modifications have been made to this approach. Others have used equation of state (EOS) for modeling
asphaltene deposition [3-5]. Continuous mixture modeling is another method which has been used to describe
asphaltene behavior in petroleum fluids, where asphaltenes are supposed to be dissolved in oil mixtures. Since
heavy organics have a wide molecular weight distribution, one may consider such components as a
heterogeneous polydisperse distribution [6,7]. A simple association model for asphaltene deposition based on a
chemical association theory was proposed in the literature [8]. Despite significant progress in theoretical and
experimental studies our understanding of asphaltene precipitation process is far from mature due to its
complexity.
The aim of this paper is to show that it is possible to use the traditional method [1] to provide a quantitative
description of deposited asphaltene by CO
2
injection with high accuracy and using a minimum number of
experimental data. However, it is necessary to perform several modifications in the oil characterization and in
the calculation of the solubility parameter of the oil and asphaltene as it is presented in this paper.

THERMODYNAMIC MODEL

The phenomenon of asphaltene precipitation is a very complex multicomponent process that involves a large
number of interactions at molecular and colloidal length scales. Consequently, the theoretical modeling for this
system is possible only by assuming simplified representations of crude oil. In this study a thermodynamic
model presented by Hirschberg et al. was used [1]. They developed a molecular thermodynamic model by
applying a modified FloryHuggins (FH) polymers theory [2] with a lumped compositional representation (two
or three components). Initially, a traditional approach using a cubic equation of state is used to analyze the
liquid-vapor behavior of the fluid, neglecting the possible effect of precipitated asphaltenes. In a second step
flocculation is taken into account as liquid-solid equilibrium. The asphaltene solution is considered as a two-
constituent system: the asphaltenes which may form a pure phase and the other constituents (including the
resins) which form the oil phase (the surrounding medium). The phase separation is calculated using the Flory-
Huggins model [2]. Therefore, the asphaltene molecules are considered as a monodispersed polymer. The
parameters which they used as input were the solubility parameter the molecular weight and the molar volume of
asphaltene. The volume fraction of asphaltene dissolved in oil was obtained by [1]:

( ) ( )
)
`

=
2
max
1 exp
L a
L
a
L
L
a
a
RT
V
V
V
V
V
o o |
(1)

where
a
| is the volume fraction of asphaltene in oil, the volume
L
V and the solubility parameter
L
o are the
properties of the liquid phase obtained from the calculated vapor/liquid split of the crude (or crude/solvent
mixture) at the conditions of pressure and temperature considered, and
a
o and
a
V are the same properties for
asphaltene.

The volume fraction of component i is defined as

m
i i
i
V
V x
= |
(2)

where
i
x is the mole fraction of component i,
i
V the molar volume of component i and
m
V the molar volume of
the mixture. The solubility parameter
m
o of the mixture is given by

i
i
i m
o | o

=
(3)

Calculating the
a
| and
L
| values, the weight fraction of dissolved asphaltene in oil
a
S can be obtained as
follows:

( )
a
a
a
L
L
a
a
a
a
a
V
MW
V
MW
V
MW
S
| |
|
+
=
1
(4)


where
L
MW and
a
MW are the molecular weight of the oil and asphaltene, respectively.
To model asphaltene precipitation in a reservoir fluid at certain T and P, the vapor-liquid equilibrium calculation
of the reservoir fluid is first performed using a cubic EOS to obtain the composition and fluid properties of the
liquid phase at equilibrium. To calculate the molar volume of liquid phase and the flash. the Soave-Redlich-
Kwong (SRK) EOS [9] was selected and detailed in Eq. (5) to Eq. (7).

) .(
) (
b V V
T a
b V
T R
P
+

=
(5)

where T is the temperature, P the pressure, V the molar volume, R the gas constant and a and b are mixture
specific parameters. The pure components parameters
i
a and
i
b are obtained from the critical temperature
ci
T ,the critical pressure
ci
P and the acentric factor
i
w
For mixtures the model parameters become composition dependent through the following mixing rules:

( ) ( )

=
i j
ij j i j i
K a a x x a 1 . . .
5 . 0
(6)

=
i
i i
b x b .
(7)

where
i
x is the component molar fraction and
ij
K
are the binary interaction parameters between components i
and j.

Characterization Procedure

In order to use an EOS it is necessary to know the critical temperature, Tc, the critical pressure Pc and acentric
factor w for each component in the mixture. For the True Boiling Point (TBP) fractions, which are pseudo
components covering from C7 and up, these three properties are not available. Therefore a characterization
procedure for the heavy hydrocarbon fraction (C7
+
) is required to calculate the critical temperature, the critical
pressure, and acentric factor. Furthermore, a lumping procedure is required to reduce the number of components.
In this study the boiling point calculations were performed with SPECS program (Technical University of
Denmark). The critical properties and the acentric factor of each TBP fraction are calculated by using the
Pedersen method [10]. To estimate the composition of the TBP residue, a logarithmic distribution of the mole
fraction x
i
versus carbon number of component (CN) or fraction i have been suggested by [11]. The used method
used to divide the components or TBP fractions into groups and the method used to lump the components into
groups are given in [12]

Calculation of Solubility Parameter
The most prevalent thermodynamic approach to describe the solubility of asphaltene has been the application of
the solubility parameter that can be estimated from

v
RT H A
= o
(8)

where H A is the enthalpy of vaporization at temperature T and v is the molar volume. In this work the
procedure for calculating the solubility parameter of oil and asphaltene developed by [13] was partially adopted.
Thus the first step is to calculate the enthalpy of vaporization of the component i at its normal boiling point in
(BTU/lb-mole).

( ) ( ) ( ) | |
bi bi Tbi i
T T H log 571 . 4 75 . 8 014 . 1 + = A
(9)


T
bi
is the normal boiling temperature of component i obtained by [14].

0 . 1 log
0 . 1 7
3

|
.
|

\
|

=
c
P w
u
u
(10)


where
ci bi
T T = u is the ratio of the normal boiling temperature
bi
T to the critical temperature
ci
T .

In order to correct the enthalpy of vaporization at a temperature T different from the normal boiling point, the
following equation is employed [15]:

( ) ( )
38 . 0
|
|
.
|

\
|

A = A
bi ci
ci
Tbi i T i
T T
T T
H H
(11)

where
ci
T and
bi
T correspond to the critical temperature and the normal boiling temperature of component i,
respectively.


RESULTS AND DISCUSSION

In this study of asphaltene precipitation under CO
2
injection five oils were selected from literature and the
relevant information concerning on their characteristics are displayed in Table 1.

Table 1 Composition and properties of crude oil samples*

Oil O1 O2 O3 O4 O5
Component Compositions (mol%)
N
2
0.13 0.69 0.96 0.96 2.07
CO
2
2.07 1.17 0.16 0.58 0.74
H
2
S 0.02 0.00 0.00 0.30 0.12
C
1
17.06 26.11 24.06 4.49 7.49
C
2
8.05 1.39 0.76 2.99 4.22
C
3
6.88 0.62 3.26 4.75 7.85
i-C
4
1.33 0.24 0.64 0.81 1.58
n-C
4
4.33 0.17 2.70 1.92 4.97
i-C
5
2.38 0.07 0.52 1.27 2.01
n-C
5
2.79 0.03 1.06 2.19 2.58
C
6
3.35 1.31 0.70 0.00 0.00
C
7
+
51.51 68.20 65.18 79.74 66.37
Asphaltene content (wt.%) 11.00 6.67 1.82 4.90 4.85
Reservoir temperature (K) 369 343 339 332.15 336
Bubble pressure at
reservoir temperature (atm)

74.15

88.82
73.23 28.52 48.56
Injection pressure (bar) 272.10 246.73 197.38 157.91 157.91
*Oil O1 [16]; Oil O2 [17]; Oil O3 [18]; Oils O4 and O5 [19]

Very important preliminary analysis consists of determining the oil bubble pressure as a function of CO
2
mole
fraction at the reservoir temperature by using the SRK equation of state. That is, from the bubble pressure fitting
at the reservoir temperature corresponding to the zero fraction of CO
2
addition, it is possible to calculate the
bubble pressure at any other CO
2
fraction. This step is important because by observing the bubble pressure
behavior it is possible to detect the exact CO
2
fraction at which asphaltene precipitation will occur. At the
selected injection pressure the asphaltene precipitation expected to occur at CO
2
fraction equal or greater than
the bubble pressure equal to the injection pressure. Figure 1 shows this behavior regarding all the selected oils. It
is of great importance to note that on the left side of the bubble pressure curve in Figure 1 there is no deposition
of asphaltene. The asphaltenes deposition can also be monitored by calculating the oil density on the injection
pressure at several CO
2
fractions as shown in Figure 2. When a sharp density variation occurs there has been a
phase change and thus asphaltenes deposition.


Figure 1. Phase diagram for mixture of O3 and O5 oils and CO
2
mixtures at 339 K and 336 K.


Figure 2. Calculated density versus CO
2
mole fraction for oil O1 and O2 at the temperature 369 K and 343 K.

To obtain the mass fraction of precipitated asphaltenes due to CO
2
addition we used the model of Hirschberg et
al. [1]. Therefore it is necessary to calculate the molar volume of the liquid phase, the molar volume of
asphaltene and solubility parameters of oil and asphaltene. Nevertheless the initial step consists on detailing
(characterization) the C7
+
fraction. It is an extremely important step, since from this characterization the
asphaltene representative components are selected.
Regardless of the characterization method employed the bubble pressure of the oil must always be monitored
and this is accomplished by the density of C7
+
fraction. It is estimated by trial and error and the correct value will
be achieved by comparing the calculated bubble pressure with (SRK) equation of state and its experimental
value at the reservoir temperature. Silva et al. [20] has shown the great influence exerted by the interaction
parameter k
ij
between methane and the heaviest fraction in the bubble pressure calculated by SRK equation of
state. The same importance exists in calculating the bubble pressure of a mixture containing oil and CO
2.

Another highlight: it is unknown the detailed asphaltene composition, so selecting the representative residue
components is one of the most critical steps of this work. Silva et al. [20] observed that the greater the number of
the selected components to represent the C7
+
fraction the closer the results of the calculated amount of
asphaltenes in oil are to the experimental values. The residue was considered to consist of 17 fractions in Silva et
al. [20] and also in this study. The key point is to determine which the cutoff point of the components
representing asphaltene is: this is the fractions that comprise the residue starting with the fraction having the
highest molecular weight; subsequent fractions are considered toward the decreasing molecular weight of each
fraction.

In summary:it is initially carried out the density of C7
+
fraction fitting and the corresponding breakdown with 17
subfractions. Next, to calculate the amount of asphaltene deposition as close as possible to the experimental
amount, there are some other variables susceptible to adjustment, which are: cutoff the residue fraction and the
binary interaction parameters. To determine the amount of asphaltenes in the oil due to CO
2
injection there are
two highly important parameters to be calculated: the solubility parameter of the oil and the asphaltene molar
volume. These parameters depend on two characteristics of the oils: the asphaltene content (wt.%) in the oil
before the CO
2
addition (main ) and C
1
mol fraction (secondary). With respect to these features there are some
different calculations aspects discussed below in details.

Let us consider initially the oils which contain greater amounts of asphaltenes and methane (O3 and O4 oils).
- Selection of an experimental data (the lowest amount of asphaltene precipitate preferentially) resulting in the
reference for fitting properties and also the new oil composition due to the corresponding CO
2
mol fraction;
- Binary interaction parameter estimation between methane and the heaviest component of the residue and the
flash calculation on the selected pressure. The flash calculation provides the liquid phase composition with
their respective critical properties and molecular weight of each fraction as well as the liquid phase molar
volume;
- Selection of the residue fraction as the lower limit of the asphaltenes (cutoff point);
- Solubility parameters obtained by Chung algorithm [13] and Hirschberg et al. method [1] provides the
volume fraction of dissolved asphaltene in oil by Eq. (1) and the weight fraction of dissolved asphaltene in
oil can be obtained with Eq. (5);
- The most suitable lower limit of asphaltene fraction is considered the one that supplies the lowest error
when compared with the experimental value. For other CO
2
mole fractions injected the following
parameters are retained: the asphaltene cutoff point, the binary interaction parameter and the same
difference between the oil and asphaltene solubility parameters.

Regarding to oils with a small amount of asphaltene (O3) the procedure is similar to the oils containing high
amounts of asphaltene and methane. The difference is that the asphaltene molar volume calculated at the fitting
point is kept constant at other CO
2
injections calculations. Also the calculation of oil solubility parameter is carry
out by a weighted average using oil and CO
2
mass fractions.

Concerning to oils with high amounts of asphaltene and small amounts of methane (O4 and O5) the following
steps must be noted:
-
The CO
2
fraction is selected such that the corresponding oil bubble pressure is nearest to the injection
pressure but there is no deposited asphaltene at this point
-
Binary interaction parameter estimation between the components of higher molar fraction allows the flash
calculation to be performed on the selected pressure and the cutoff point is found . The most suitable lower
limit of asphaltene fraction is considered the one that supplies the lowest error when compared with the
experimental value.
-
Another experimental point with great amount of deposited asphaltene is selected. The binary interaction
parameters and cutoff point already obtained on the previous step are used. A Hirschberg et al. [1] method
is applied keeping the same previous difference between the oil and asphaltene solubility parameters.
-
An optimum asphaltene molar volume is calculated such that it corresponds to a value equal to the
experimental asphaltene deposited. A linear relationship is considered involving these molar volumes and
the corresponding CO
2
mole fractions
-
For further injected CO
2
mole fractions the following parameters are held constant: the asphaltene cutoff
point, the binary interaction parameter and the difference between the oil and asphaltene solubility
parameters.

The simulations results of weight fraction of dissolved asphaltene in oil (S
a
) and comparisons with experimental
values from the literature for the five oils for which the composition and properties samples have already been
displayed in Table 1 are shown in Table 2.

Table 2. Comparison between the experimental and calculated dissolved asphaltene in oil due to CO2 injection

CO
2

injected
(mol %)
S
a

experimental
(wt.%)
S
a

calculated
(wt.%)

Error (%)
CO
2

injected
(mol %)
S
a

experimental
(wt.%)
S
a

calculated
(wt.%)

Error (%)
Oil O1 Oil O2
37.0* 9.67 9.62 0.45 47.7* 6.47 6.22 3.94
55.0 8.22 8.33 1.37 61.4 5.50 5.78 5.10
60.0 7.60 7.58 0.22 71.7 5.04 5.22 3.50
Oil O3 78.6 4.89 4.67 4.43
51.6* 1.76 1.73 1.85 Oil O4
63.8 1.59 1.56 1.73 54.9 3.22 2.45 23.95
71.6 1.50 1.36 9.29 65.3 2.19 1.93 11.84
80.2 1.40 1.06 23.98 75.0* 1.56 1.56 0.06
Oil O5
44.5 4.18 4.45 6.37
52.4 2.75 2.78 1.16
58.6 2.15 1.96 8.79
65.2* 1.37 1.37 0.06
*selected CO2 injected for fitting



Figure 3. Experimental versus calculated values of asphaltene dissolved in oil.



Figure 4. The predicted CO
2
effect on the amount of asphaltene deposition in Oil O1, at 272.10 atm and 269 K
and Oil O5, at 157.91 atm and 336 K.

A more extensive comparison can be seen in Figure 3. As it would be expected for oils O1, O2, O5 containing
higher amount of asphaltene in original oil, the prediction of asphaltene dissolved in oil is better. Using the
strategy previously detailed it is possible to calculate the amount of asphaltene deposited for several CO
2
mole
fractions different from those values obtained experimentally. The comparison between these values and the
experimental data are reported in Figure 4. It is important to note the quality of the simulation.

CONCLUSION

In this paper we proposed several modifications to the traditional method [1] and showed that it can be applied
successfully to provide a quantitative representation of deposited asphaltene due to CO
2
injection with high
accuracy and using a minimum amount of experimental data. The main modifications were made on the
calculation of the difference between solubility parameters of the oil and asphaltene and on the binary interaction
parameters. Furthermore, we can conclude that some steps are of critical importance in detecting asphaltene
precipitation by CO
2
injection, such as selecting the number of representative residue components and observing
bubble pressure behavior. Another remark concerns the slight difference between the procedures to calculate
dissolved asphaltene in oils with larger amounts of methane and oils with smaller amounts of methane, which
involves changes in binary interaction parameters and in the experimental data used as reference for fitting
properties.

RFERENCES

[1] HIRSCHBERG, A., DE JONG, L. N. J., SCHIPPER, B. A., MEYERS, J. G., Soc. Petrol. Eng. J., 1984, p.
283.
[2] FLORY, P. J., J. Chem. Phys., 10, 1942, p. 51.
[3] PAN, H., FIROOZABADI, A., SPE Annual Technical Conference and Exhibition - ACTE, 1996, Denver,
CO.
[4] NGHIEM, L. X., HASSAN, M. S., NUTAKKI, R., GEORGE, A. E. D., SPE Annual Technical Conference
and Exhibition - ACTE, 1993, Houston, TX.
[5] NGHIEM, L. X., COOMBE, D. A., ALI, S. M. F., SPE Annual Technical Conference and Exhibition -
ACTE, 1998, New Orleans, LA.
[6] MANSOORI, G. A., JIANG, T. S., KAWANAKA, S., Arabian J. Sci. Eng., 13, 1988, p. 17
[7] MANSOORI, G. A., JIANG, T. S., Proceedings of the 3
rd
European Conference on Enhanced Oil Recovery,
1985, Rome, Italy.
[8] VAFAIE-SEFTI, M., MOUSAVI-DEHGHANI, S. A. Fluid Phase Equilibria., 247, 2006, p. 182.
[9] SOAVE, G., Chem. Eng. Sci., 27, 1972, p. 1197
[10] PEDERSEN, K. S., THOMASSEN, P., FREDENSLUND, AA., New York: Taylor & Francis, 1989
[11] PEDERSEN, K. S., THOMASSEN, P., FREDENSLUND, AA., Ind. Chem. Process Des. Dev., 23, 1984c,
p. 163
[12] PEDERSEN, K. S., THOMASSEN, P., FREDENSLUND, AA., Ind. Chem. Process Des. Dev., 24, 1985, p.
948.
[13] CHUNG, F., SARATHI, P., JONES, R., Topical Report IIT Research Institute. National Institute for
Petroleum and Energy Research, 1991, Bartlesville.
[14] EDMISTER, W. C., Pet. Ref., 37, 1958, p. 173
[15] WATSON, K. M., Ind. Eng. Chem., 35, 1943, p. 398.
[16] NAKHLI, H., ALIZADEH, A., MOQADAM, M. S., AFSHARI, S., KHARRAT, R., GHAZANFARI, M.
H.. J. Petrol. Sci. Eng., 80, 2011, p. 61
[17] Z. YANG, C. -F. MA, X. -S. LIN, J.-T. YANG, T.-M. GUO., Fluid Phase Equilibria, 157, 1999, p. 143.
[18] HU, Y., LI, S., LIU, N., CHU, Y., PARK, S. J., ALI MANSOORI, G., GUO, T., Journal of Petroleum
Science and Engineering, 41, 2004, p. 169.
[19] SRIVASTAVA, R.K., SPEPF, 235, November 1990.
[20] SILVA, N. A. E., GOMES, U. S., OLIVEIRA, V. R. R. , COSTA, G. M. N., Journal of Petroleum Science
and Engineering, submitted.