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BRAZILIAN JOURNAL OF PETROLEUM AND GAS
ISSN 1982-0593
ATOLINI, T. M.; RIBEIRO, P. R. VAPOR-LIQUID MIXTURE BEHAVIOR AT HIGH TEMPERATURES AND PRESSURES : A REVIEW DIRECTED TO DRILLING ENGINEERING.
Brazilian Journal of Petroleum and Gas. v. 1, n. 2, p. 123-130, 2007.
VAPOR-LIQUID MIXTURE BEHAVIOR AT HIGH TEMPERATURES AND

PRESSURES : A REVIEW DIRECTED TO DRILLING ENGINEERING
1
T. M. Atolini*, 1P. R. Ribeiro
State University of Campinas, Mechanical Engineering Faculty, Department of Petroleum Engineering
* To whom all correspondence should be addressed.

Address: DEP/FEM/UNICAMP, P.O. Box 6122, Campinas, SP, Brazil, CEP 13083-970
Telephone number: +55 11 3289-4999
E-mail: tarcila@dep.fem.unicamp.br
Abstract. This work involves the discussion about the thermodynamic behavior of
vapor-liquid mixtures at wellbore conditions (high pressure and temperature - HPHT),
found in drilling operations in Santos Basin, Brazil. A literature review on the
interaction of gases with organic fluids used in drilling operations and analysis of the
thermodynamic properties of these vapor-liquid mixtures were done with the purpose of
providing comprehensive knowledge on how the problem should be approached under
supercritical conditions. Among other property changes, solubility enhancement is
highlighted (which impairs the detection of occasional kicks, causing drastic
consequences due to unsuccessful well control operations). There is a limited amount of
phase equilibrium data for supercritical solvents and high molecular weight n-alkanes. It
is important, therefore, to increase the pressure and temperature range to study the
mixture behavior above critical conditions. This is accounted for in this article, which
also discusses the drawbacks associated with the extrapolation of measured data in order
to represent supercritical behavior.
Keywords: supercritical fluids; solubility; drilling; high pressure and high temperature
1. INTRODUCTION
Brazilian oil and gas potential reserves are
mostly concentrated under the seabed.
Petrobras, the main national gas and oil
company, concentrates 80% of their production
in offshore basins, 63% of which correspond to
deep and ultra-deep waters. The potential to be
explored in these areas reaches 79% of all
Brazilian reserves (Salis, 2005). The Brazilian
oil prospection in the sea began with the
activities in the Campos Basin, at the same
time as the first developments in other coastal
parts of the country. In effect, 57% of the total
area corresponds to water layers between 400
and 3000 meters in depth, whilst the average
distance between the bottom of the sea and the
reservoir is 4,500 meters. In 2005, the company
surpassed the Brazilian record in deep-water
drilling, with a well that reached 6,915 meters
below the seabed. The well was drilled in the
BMS-10 block, in the Santos Basin, located
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200 km from the southern coast of the State of

Rio de Janeiro.
One of the difficulties and consequent
technological advances inherent to the
exploration of oil under these conditions refers
to the drilling fluids, due to the high solubility
of gas in synthetic and oil-based fluids, which
are more commonly used by oil industries.
Contamination of drilling fluids with formation
gases is a very dangerous situation if not
properly controlled, with the possibility of
damaging equipment and negatively affecting
the environment and, above all, peoples lives.
The proper understanding of the gas-liquid
mixtures behavior is essential to appropriate
planning and implementation of the safety
procedures that must be carried out in order to
force the circulation of gases out of the well in
a more controlled way. High pressure and high
temperature (HPHT) conditions involve more
serious risks because, above the critical
123

pressure of the mixture, the solubility becomes

infinite [Brunner, 1994]. In a pressurecomposition diagram, as the one shown in
Figure 1, this phenomenon happens in the
supercritical region, indicated by the shaded
area.
This review examines the studies on the
solubility of gases in fluids when subjected to
high pressures and temperatures.
2. LITERATURE REVIEW
In the 1980s, significant contributions had
been given on measurements of phase behavior
of oil-based fluids, with reports on studies
focusing on the solubility of gas in diesel oil, a
fluid which was widely used at the time.
Thomas et al. (1982) and O'Bryans et al.
(1988) worked within the main fluid and
pressure ranges used in the oil industry on that
time. Perhaps for that reason, there is a gap
with respect to research developed at the
beginning of the 1990s. Due to environmental
concerns, conventional oil-based fluids were
replaced with synthetic oils, which are less
aggressive to the environment and feature
better physical and chemical properties for
drilling operations. This stimulated further
research at the end of the 1990s.
2.1. The Critical Point
One of the first reports on the solubility of
gas in oil at high pressures was presented by
Thomas et al. (1982), who described the effects
of the gas solubility on the properties of oil-
Figure 1. Generic P-x diagram.
124
Figure 2. Methane solubility in iesel n2

(Thomas et al., 1982).
based drilling fluids. The authors performed the

simulation of methane solubility in diesel n 2
using the Redlich-Kwong equation of state. The
results, presented in Figure 2, demonstrate that
the model provides unlimited solubility above a
given pressure for each isotherm.
In 1998, Lima presented some results which
were similar to those reported by Thomas et al.
(1982), involving tests conducted in Brazil, for
a study of synthetic drilling fluids, as shown in
Figure 3. Limas results were obtained by
extrapolation of experimental data obtained at
pressures up to 1800 psi, with a commercial
PVT simulator that employed the SoaveRedlich-Kwong equation of state. In his work,
measurements of saturation pressures were
taken for gas-oil ratios from 9 through 53 stdm std / std-m, which were used to adjust and
calibrate the simulator and extrapolate to
pressures up to 7600 psi, as shown in Figure 3.
Figure 3. Methane solubility in synthetic oil (Lima,

1998).

According to Thomas et al. (1982), the

limiting pressure that must be applied in order
to promote unlimited solubility is called the
critical pressure, while in the investigation by
Lima (1998), this was called the miscibility
pressure. By performing a thermodynamic
analysis of Figures 2 and 3, it can be concluded
that the vertical pressure lines in Figure 2 and
the horizontal pressure lines in Figure 3 are
representations of saturation pressure curves for
mixtures at constant temperature, since they
define the boundaries of the single-phase
region for each mixture. Based on this
reasoning, and remembering that in a P-x
diagram the point of highest pressure is
necessarily the critical point of the mixture, as
discussed in section 1, we can conclude that at
the highest pressures, in both plots, the mixture
is in a supercritical state, where complete
miscibility occurs. Thomas et al. (1982) were
correct when suggesting that the limit pressure
is the critical pressure. We can even say that in
that region the characteristics of the mixture
can gradually vary from liquid to gas with
increasing amounts of methane (Brunner,
1994).
Ester - 70C
Ester - 90 C
250
200
Solubility (cm /cm )
300
2.2. The Temperature Effect

OBryan et al. (1988) investigated the effect
of temperature on the solubility, using samples
of Mentor 28 oil. They measured the solubility
of methane at three temperatures and concluded
that the solubility decreases with increasing
temperature, as can be seen in Figure 4.
However, according to Figure 2, Thomas et al.
(1988) effectively prove that the solubility
Figure 4. Solubility of methane in Mentor 28 oil at

311 K, 366 K and 422 K (OBryan et al., 1988).
increases with increasing temperature, contrary

to the observations of OBryan and co-workers.
This discrepancy is due to the characteristics of
solubility of a low-volatility component in a
supercritical solvent, that is, at high pressures
the solubility increases with temperature, and at
low pressures the solubility decreases with
temperature (Brunner, 1994). Indeed, until
2800 psia, the maximum pressure checked by
OBryan et al., the variation of solubility with
temperature is not noticed for the isotherms at
311 K (38C), 366 K (93C) and 422 K
(149C) in Figure 2. For these temperatures,
N-Paraffin - 70 C
N-Paraffin - 90 C
150
100
50
0
0
10
20
30
40
50
60
Pressure (MPa)
Figure 5. Solubility of methane in n-paraffins and esters (Silva, 2004).
125

Saturation Pressure (MPa)
90
Peng-Robinson Eq. - 50 C
75
60
45
30
15
Limit of estudied molar
0
15
35
55
75
95
Molar fraction of Methane
Figure 6. Data computing (Winprop) for the saturation pressure of methane

in n-paraffin (Silva, 2004).
the isotherms merge up to 5000 psi, impairing

any attempt to determine how the solubility
varies with temperature in that region.
However, above 5000 psi, the solubility
increases with increasing temperature.
Further insight about the effect of
temperature on solubility is provided by Silva
(2004). The author examined the solubility of
methane in n-paraffins (C14 predominantly)
and esters (methyl linoleate predominantly) at
70C and 90C, and concluded that, within the
range studied, the results showed small
temperature influence on the solubility of gas
in the oil (see Figure 5). To extend this study,
Silva (2004) modeled the phase behavior with
the help of the Winprop (2004) software,
estimating the saturation pressure for different
molar fractions of methane in n-paraffin and
temperatures ranging between 50C and 150C.
The results are resumed in Figure 6, which also

shows that the variation due to temperature is
only significant at very high methane molar
fractions.
2.3. Mathematical Models
In order to understand the process of
dissolution of gases in drilling fluids,
particularly in the conditions of pressure and
temperature inside the borehole, mathematical
models based on equations of state have been
developed. These models are applied to
simulate the behavior of the mixture under
certain conditions of pressure and gas
concentration, under which it would not be
possible to acquire experimental data due to the
limitations of the PVT equipments. Thus,
works that employed this methodology and a
discussion of their reliability are presented
Figure 7. Phase equilibria for methane-diesel oil systems at 311.15 K

(Thomas et al., 1982).
126

below.
Besides the simulation of the solubility of
methane in diesel n 2, Thomas et al. (1982)
performed experimental measurements of
bubble pressure for nine compositions of
methane / diesel, at 311 K (38C). The authors
compared their results using the RedlichKwong equation of state to predict the phase
behavior and proposed adjustments to
minimize deviations on the description. Figure
7 presents the experimental results and the
modeling performed.
This plot refers to two modeling procedures:
(i) fitting the experimental data with ARKES
(Adjusted Redlich-Kwong Equation of State)
and (ii) applying the ARKES modeling based
on the composition and properties of the
components of the gas-liquid mixture. Both
procedures are questionable when the modeling
results are extrapolated beyond the measured
data, particularly in regions close to the critical
zone (inflection of the saturation pressure
curve). Note that the difference in predicting
the critical point between the two modeling
procedures has a magnitude of 40%.
Marteau et al. (1997) examined the risks of
relying on modeling results when approaching
the critical region. The experimental apparatus
that they used was a PVT cell that operates at
pressures up to 200 MPa, coupled with a gauge
to determine the composition of the in-situ
phases based on infrared absorption. This highprecision equipment allowed obtaining many
points of the phase diagram, the bubble and
dew point curves and the critical region. The
researchers generated experimental results for
the phase equilibrium of methane-hexane and
methane-benzene in regions very close to the
critical point of the mixture, as can be seen in
Figures 8 and 9. Using the Peng-Robinson
equation of state associated with the group
contribution method developed by Abdoul and
Peneloux (1991), the authors tried to fit the
data. As observed in Figures 8 and 9, at regions
distant form the critical point, both models
provided good predictions for the pressures, but
near the critical point both models did not
present satisfactory results compared to the
experimental data.
Figure 8. Vapor-liquid equilibrium for methanehexane at 323 K (Marteau et al., 1997).
Berthezene et al. (1999) investigated the

PVT behavior of gases at 363 K in four
different oils: diesel, mineral, olefin and
vegetal ester. Their measurements of saturation
pressure were conducted at pressures up to 35
MPa and these results were used to adjust the
Peng-Robinson equation of state. The modeling
Figure 9. Vapor-liquid equilibrium for methanebenzene at 323 K (Marteau et al., 1997).
127

Figure 10. Phase envelope for methane with 4 oil bases, measured
and calculated at 363 K (Berthezene et al., 1999).
of the phase behavior, Figure 10, shows good

agreement with experimental data. As shown in
Figure 10, in the range of moderate pressures,
up to 35 MPa, the solubility behavior of the
tested oils is comparable. The high pressure
conditions have been extrapolated, which
predicts the critical points for the mineral oil,
olefin and diesel between 50 and 70 MPa. For
the ester, there is no prediction of critical point
at pressures lower than 100 MPa and 363 K,
according to the modeling. One of the features
that differentiate the three traditional oils
(diesel, mineral and olefin) from the ester is
that in the first group there are only
hydrocarbon molecules, and in the second there
is an ester group, which enhances the polarity
of the compound, possibly reducing the total
solubility.
In order to confirm the findings of
Berthezene et al. (1999), Bureau et al. (2002)
conducted experiments on solubility, at
pressures up to 100 MPa, using an ester which
was similar to that used by Berthezene et al.
(1999) at the same temperature (363 K). The
authors drew the reader's attention to the
importance of understanding the value of the
critical point in the prediction of gas kicks,
since above this pressure the solubility
becomes infinite. On the other hand, in their
work Bureau et al. (2002) tried to ascribe the
128
highest dew point pressure as an indication of

the position of the critical point. However, up
to 100 MPa, it was only possible to measure
bubble points, which confirms that there is no
critical point below this pressure, as previously
indicated by extrapolations of Berthezene et al.
(1999). The results by Bureau et al. (2002) are
presented in Figure 11.
Bureau et al. (2002) also repeated the
experiment at 423 K and identified the dew
point at 80 MPa, but reported on some
difficulty because of the low visibility of the
gas-liquid interface caused by working in a
region very close to the critical point.
There are many factors that make it difficult
to predict the phase behavior near the critical
point region. The limitations of the equipment
may be one of these factors, but what Bureau et
al. (2002) reported is related to the fact that
intrinsic properties of gas and liquid are
identical (density, viscosity, index of refraction,
etc.) on the critical region. In this point there is
no gas-liquid interface, hampering the phases
identification.
The properties of the solvent in the critical
region are different from their properties as
liquid or gas, away from this region. Here, the
properties vary dramatically with small
changes in pressure and temperature, producing

Figure 11. Methane solubility in ester at 363 K Experimental and calculated data (Bureau et al., 2002).
different effects on the neighboring state

conditions (Brunner, 1994).
The physical-chemical properties of a
supercritical fluid are intermediate to those of
gases or liquids, which are often overlapped,
such as the high solvation power of a liquid and
the low viscosity of a gas. The density of a
supercritical fluid is higher than that of a given
gas and very close to that of a liquid sample.
There is a direct relationship between the
density of a supercritical fluid and its solvation
power, which, due to its high compressibility,
is extremely dependent on pressure.
Besides the experimental research on the
phase behavior of binary mixtures, Bureau et
al. (2002) made the modeling of their results
through three equations of state combined with
three mixing rules. The results of these
modeling are shown in Figure 11. Divergent
modeling results are clearly evident, both
between each distinct model and the
experimental data.
In view of all this, we would like to point
out that the attempt to predict the behavior of
gas-liquid mixtures based on extrapolations of
equations of state and fitted mathematical
models does not lead to reliable results. For
example, Berthezene et al. (1999) concluded
that there is no critical point below 100 MPa

for ester, but the authors themselves
commented on the risk of relying on
extrapolation results.
3. CONCLUSIONS
It was shown through the works presented
here that the effect of temperature on the
solubility behavior of gas-liquid mixtures is
perceptible only at high pressures and high gas
concentrations. Under these conditions, the
solubility
increases
with
increasing
temperature, although subtle analysis in the
region of low pressure (OBryan et al., 1988)
shows that the low solubility pressure decreases
with increasing temperature. This behavior is
characteristic of hydrocarbon mixtures with
low volatility in supercritical solvents.
The equipment limitations are an example of
the difficulty in predicting the phase behavior
in the region near the critical point, because it
is the region of highest pressure of the phase
envelope. The main limiting factor is related to
the fact that in the critical region the intrinsic
properties of gas and liquid are identical
(density, viscosity, index of refraction, etc.) and
the gas-liquid interface disappears.
129

The discussion on the published results in

the literature indicates the need to obtain
experimental data in wider ranges of pressure
and temperature, in order to characterize HPHT
conditions. The use of extrapolated results,
based on thermodynamic modeling, is not a
reliable practice, particularly when predicting
the properties of fluids in the critical region.
This could be further corroborated by analyzing
the works by Marteau et al. (1997) and Bureau
et al. (2002).
ACKNOWLEDGEMENTS
The authors are grateful to PETROBRAS
and FINEP / CT-PETRO for the continuous
financial support to our research group on
wellbore hydraulics and control during drilling
operations.
The laboratorial research facilities were
provided by the Department of Petroleum
Engineering of the State University of
Campinas (UNICAMP, Brazil).
REFERENCES
ABDOUL, W.; PENNELOUX A. Fluid
Phase Equilibria, 68 (1991) 47.
BERTHEZENE, N.; HEMPTINNE, J. C.
DE; AUDIBERT, A.; ALGILLIER, J. F.
Methane Solubility in Synthetic Oil-Based
Drilling Muds. Journal of Petroleum
Science and Engineering, 23, p. 71-81,
1999.
BRUNNER, G. Gas extraction An
Introduction to Fundamentals of
130
Supercritical Fluids and the Application

to Separation Processes, Germany, 1994.
BUREAU, N.; HEMPTINNE, J. C. DE;
AUDIBERT, A.; HERZHAFT, B.
Interactions Between Drilling Fluid and
Reservoir Fluid. SPE Annual Technical
Conference and Exhibition. San Antonio,
Texas. 29 Sep. 2 Oct. 2002.
LIMA, H. R. A Dynamic Model of Well
Hydraulics in Deepwater Riserless
Drilling Operations Using Synthetic
Based Drilling Fluids, Texas: Texas
A&M University, Dissertation (PhD),
1998.
MARTEAU, PH.; OBRIOT, J.; BARREAU,
A.; RUFFIER-MERAY, V.; BEHAR, E.
Experimental Determination of Phase
Behavior of Binary Mixtures: MethaneHexane and Methane-Benzene. Fluid
Phase Equilibria, 129, p. 285-305, 1997.
OBRYAN, P.L.; BOURGOYNE, JR. A. T.;
MONGER, T.G.; KOPCSO, D.P. An
Experimental Study of Gas Solubility in
Oil-Based Drilling Fluids. SPE Drilling
Engineering, March 1988.
SILVA, C.T. Study of the Solubility of
Methane in Organic Liquids used in the
Drilling Fluids formulation. Dissertation
(Master). Campinas: State University of
Campinas, 2004. (In Portuguese)
THOMAS, D. C., LEA JR., J. F. AND
TUREK, E. A. Gas Solubility in Oil-Based
Drilling Fluids: Effects on Kick Detection.
57th ATCE of the Society of Petroleum
Engineers, New Orleans, LA, Sept. 26-29.
1982.

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BRAZILIAN JOURNAL OF PETROLEUM AND GAS

VAPOR-LIQUID MIXTURE BEHAVIOR AT HIGH TEMPERATURES AND

T. M. Atolini*, 1P. R. Ribeiro

State University of Campinas, Mechanical Engineering Faculty, Department of Petroleum Engineering

* To whom all correspondence should be addressed.

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200 km from the southern coast of the State of

BRAZILIAN JOURNAL OF PETROLEUM AND GAS

pressure of the mixture, the solubility becomes

Figure 1. Generic P-x diagram.

Figure 2. Methane solubility in iesel n2

based drilling fluids. The authors performed the

Figure 3. Methane solubility in synthetic oil (Lima,

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BRAZILIAN JOURNAL OF PETROLEUM AND GAS

According to Thomas et al. (1982), the

Solubility (cm /cm )

2.2. The Temperature Effect

Figure 4. Solubility of methane in Mentor 28 oil at

increases with increasing temperature, contrary

Figure 5. Solubility of methane in n-paraffins and esters (Silva, 2004).

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BRAZILIAN JOURNAL OF PETROLEUM AND GAS

Saturation Pressure (MPa)

Limit of estudied molar

Molar fraction of Methane

Figure 6. Data computing (Winprop) for the saturation pressure of methane

the isotherms merge up to 5000 psi, impairing

The results are resumed in Figure 6, which also

Figure 7. Phase equilibria for methane-diesel oil systems at 311.15 K

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BRAZILIAN JOURNAL OF PETROLEUM AND GAS

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Figure 8. Vapor-liquid equilibrium for methanehexane at 323 K (Marteau et al., 1997).

Berthezene et al. (1999) investigated the

Figure 9. Vapor-liquid equilibrium for methanebenzene at 323 K (Marteau et al., 1997).

BRAZILIAN JOURNAL OF PETROLEUM AND GAS

of the phase behavior, Figure 10, shows good

highest dew point pressure as an indication of

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BRAZILIAN JOURNAL OF PETROLEUM AND GAS

different effects on the neighboring state

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that there is no critical point below 100 MPa

BRAZILIAN JOURNAL OF PETROLEUM AND GAS

The discussion on the published results in

Supercritical Fluids and the Application

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