I Iberoamerican Conference on Supercritical Fluids

PROSCIBA 2010

MEASUREMENTS OF MIXTURES WITH CARBON

DIOXIDE UNDER SUPERCRITICAL CONDITIONS
USING COMMERCIAL HIGH PRESSURE EQUIPMENT
Luis A. M. Rutledge, Luciana L. P. R. de Andrade, E.L. Moreno, I. Hovell, Krishnaswamy
Rajagopal*.
Universidade Federal do Rio de Janeiro, DEQ, Escola de Química, Laboratório de Termodinâmica e
Cinética Aplicada (LATCA),
Av. Horácio Macedo, 2030. Ed. Do Centro de Tecnologia, Bloco I – sala 122,
C.P. 68502, Cidade Universitária, CEP 21949-900, Rio de Janeiro – RJ, Brasil
Email: raja@eq.ufrj.br

Abstract. There is a growing interest in studying physical properties of binary

and multicomponent fluid mixtures with supercritical carbon dioxide (CO 2)
over an extended range of temperature and pressure. The estimation of
properties such as density, viscosity, saturation pressure, compressibility,
solubility and surface tension of mixtures is important in design, operation and
control as well as optimization of chemical processes especially in extractions,
separations, catalytic and enzymatic reactions. The phase behavior of binary
and multicomponent mixtures with supercritical CO2 is also important in the
production and refining petroleum where mixtures of paraffins, naphthenes
and aromatics with supercritical fluids are often encountered. Petroleum fluids
can present a complex phase behavior in the presence of CO 2, where two-
phase (VLE and LLE) and three phase regions (VLLE) might occur within
ranges of supercritical conditions of temperature and pressure.
The objective of this study is to develop an experimental methodology for
measuring the phase behavior of mixtures containing CO 2 in supercritical
regions, using commercial high-pressure equipment.

Keywords: sour gases, supercritical fluids, bubble point, PVT and equilibrium-phase.

1. Introduction
There is a growing interest in the use of supercritical fluid mixtures in a wide range of
chemical processes, including supercritical fluid extraction, McHugh (1986), water power
generation Beér, (2007) and Biodiesel production, Bunyakiat, et.al. (2006), high pressure
and supercritical state to complex mixtures Penedo et.al. (2009) just to name a few, and the
study of vapor-liquid equilibria is an important aspect of supercritical fluids behavior.
Many researchers have estimated, using analytical methods, the equilibrium phase’s
composition at high pressure and supercritical state to complex mixtures, but few
experimental data are available for the evaluation of multicomponent mixtures involving
CO2, especially at high concentrations and/or with heavy compounds. It is therefore
necessary to study experimentally the behavior and the thermodynamic properties of these
mixtures.
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In this work we evaluated vapor-liquid equilibrium experimental data of a standard

synthetic mixture of cyclohexane, n-hexadecane and CO2, the latter at high concentrations,
measured in a temperature range of 303.15 to 333.15 K and pressure range from 10 to 600
Bar, conditions similar to pre-salt reservoirs off the brazilian coast. Petroleum fluids can
present a complex phase behavior in the presence of CO 2, where two-phase (VLE and LLE)
and three phase regions (VLLE) might occur within ranges of supercritical conditions of
temperature and pressure. The objective of this study is to assess the effectiveness of the
procedure used to develop a methodology capable of producing experimental VLE data
(vapor-liquid equilibrium) and the thermodynamic properties of Pressure-Volume-
Temperature (PVT) systems in supercritical state and close that state.

2. Experimental Method
2.1 Experimental Apparatus
For this work we used PVT equipment developed by Schlumberger. The experiments
were carried out in a variable-volume vapor-liquid equilibrium cell consisting of a pyrex
cylinder closed at each end by stainless valves. The cell had an internal capacity of about
112 cm3. This cell is presented in Figure 1. To maintain the pressure system a high-pressure
positive displacement pump developed by Schlumberger. This pump is built and tested to
perform reliably, smoothly and safety to a maximum working pressure of up to 1378.951
Bar with a high precision in pumped volumes. The phase compositions were determined
with GC chromatographic analysis.

Fig. 1. Schematic Diagram of Equilibrium Cell.

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2.2 Simulation Procedure

The choice of thermodynamic property package is one of the first steps in the simulation
process. In general the first criteria considered in the choice in type of property package is
governed by the use of Kay’s rule, Tr = T/Tci, where Tr is the reduced temperature and Tc
is the critical temperature. If the reduced temperature of any of the components in the
mixture under investigation is greater than 0.75 then the type of property package should be
an equation of state, EOS, Walas (1985). The reduced temperature for CO2 at 303.15 K is 1.
Therefore the property package type should be limited to EOS.
The Peng Robinson (PR) is the property package recommended for systems covering a
large range of conditions and rigorously describes the larger part of monophasic, biphasic
and triphasic systems with a high degree of efficiency and accuracy.
The methods based on state of equations used in this work were: Peng Robinson (PR),
Peng and Robinson (1976), Soave-Redlich-Kwong (SRK), Soave (1972), Sour PR,
(Rajagopal et al., 2009), Sour SRK, (Erbar et al., 1980), Peng Robinson Stryjek Vera
(PRSV), Stryjek and Vera (1986), Zudkevitch Joffee (ZJ), Zudkevitch and Joffee (1970).
These Equation State (EOS) are available in the process simulation program, UniSim
Design 370 R1, used in this work.

2.3 Experimental Procedure

Phase equilibria of mixtures were determined using a synthetic mixture composed of
cyclohexane, n-hexadecane and CO2. Before the PVT cell was filled with the mixture, the
cell and the tubing were evacuated for at least 40 minutes. After that a mixture of known
composition of cyclohexane (TEDIA, USA, above to 99%) and n-hexadecane (TEDIA,
USA, above to 99%) is injected in the cell. By weighing the syringe before and after the
injection, the amount of liquid injected in the PVT cell can be determined. Then, a known
amount of pure carbon dioxide is added in the mixture. The amount of CO2 added was
determined with a precision of ±0.011g. For this work three different compositions were
studied. A ternary mixture called M [1] with cyclohexane (1) + n-hexadecane (2) + CO2
(3), using the following masses m1= 8.64g m2= 9.96g, m3= 19.00g, and a second ternary
mixture called M [2] with the following mass composition m1= 9.29g, m2= 9.76g, m3=
9.32g and a third ternary mixture called M [3] using the following mass m1= 14.68g, m2=
6.29g, m3= 6.15g. Table 1 shows the experimental compositions employed for this study.

Table 1. Current Fraction Mole Compositions.

M [1] M [2] M [3]
Mixture
Mole Fraction
Cyclohexano 0.18 0.28 0.19
n-C16 0.08 0.12 0.42
CO2 0.75 0.60 0.40

The phase equilibrium has been studied at 303.15, 313.15, 323.15 and 333.15 K. The
phase transition resulting from pressure variations were studied by visualization through an
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optical device specially configured for this purpose. Other mixtures are under study to
analyze this system under super-critical conditions.
For each temperature, phase equilibrium measurements were made from the operating
pressure of the liquid-vapor biphasic system, of about 47.57 Bar, until the monophasic
equilibrium pressure. After reaching the equilibrium phase, the system is depressurized
slowly to determine the bubble point pressure at each equilibrium temperature. An aliquot
of gas and liquid phase of about 3 cm3 is removed and collected in a pycnometer for
chromatographic analysis.
The analysis of the gas aliquot is performed by transferring it to an Agilent gas
chromatograph, model 7890A, equipped with a capillary and a packing columns fitted with
FID and TCD detectors, specially configured for the CO 2 and hydrocarbons analysis. The
liquid phase analysis is carried out in other Agilent chromatograph, model 7890A with a
capillary column and FID detector.

3. Experimental and Simulation Results

The compatibility between the simulator and the experimental data for this asymmetric
ternary mixture was evaluated for the mixtures M[1], M[2] and M[3] at temperatures
between 303.15 and 333.15 K and pressures high enough to obtain monophasic conditions.
These conditions are more appropriate for an experimental pilot study and will help in the
exploration of the super-critical conditions of this ternary mixture close to the operating
temperature of the PVT equipment. The simulator uses the experimental temperature and
composition with each of the property packages.
Bubble point pressure measurements were made for all mixtures at each of the four
temperatures. The values for the bubble point pressures are reported in Table 2 where it can
be seen that the pressure of the bubble point increased in function of the temperature for
each composition.

Table 2. Bubble Point Pressure at Different Temperatures for Mixtures M [1], M [2], M [3].
Temperature, Bubble Point Pressure, Bar
K M [1] M [2] M [3]
303.15 58.95 52.54 50.68
313.15 70.33 55.85 66.88
323.15 85.49 72.19 67.22
333.15 96.53 88.25 86.24

Chromatographic analysis of the gas phase produced after the determination of the
bubble point at a pressure of 41.37 Bar (initial pressure of the experiment) showed that the
gas phase is formed of cyclohexane and CO2 and that the composition is mainly CO2,
around 90%. The composition of the gas phase did not change with temperature.
The absolute average percentage deviation (AA%D) between the experimental and
calculated bubble points is shown in Table 3.
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Table 3. Absolute Average Deviation between Experimental and

Simulated Bubble Point Pressures.
Pacote de Propriedades AA%D Bar
Peng Robinson (PR) 6.96
Soave-Redlich-Kwong (SRK) 8.48
Sour PR 7.10
Sour SRK 8.48
Peng Robinson Stryjek Vera (PRSV) 21.51
Zudkevitch-Joffee (ZJ) 10.00

Even though the Peng Robinson Equation of State (PR EOS) presented the smallest
deviation of the property packages examined it did not achieve accuracy within
experimental error, which is 1.72 Bar.
Figure 2 shows the experimental and simulated bubble point pressures using the PR and
SRK property packages for M [1]. The PR and SourPR property packages estimated bubble
point pressure values close to the experimental values for the temperature range studied. It
can be seen, in Figure 2 that the SRK bubble point pressure values increasingly deviate
with increasing temperature.
The mixture M [1] had a CO2 mole fraction content of 0.75.

140
120
Pressure, Bar

100
80
60 E xperimenta
40 l
SRK
20 PR
0
300 310 320 330 340
Temperature, K

Fig. 2. Experimental and Simulated Bubble Points pressures for M [1].

The simulation of the experimental bubble point pressures using the PR EOS was
reliable using the conditions of the experiment throughout the temperature range in these
sub-critical conditions. Table 4 contains the compositions used in this work, M [x], and the
proposed compositions, Px, and their respective critical pressure and corresponding critical
temperature values modelled using the Peng Robinson equation of state and default
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interaction parameters. The upper temperature limit of the PVT apparatus is 523.15 K
showing that the mixture composition should contain more than 0.75 mole fraction of CO 2.
The upper pressure limit of the PVT is 1030 Bar.

Table 4. Proposed compositions to study critical conditions of the ternary

mixture: CO2/C6/C16.
ID CO2 Cyclohexane n-C16 Pc, Bar T c, K
M [1] 0.75 0.18 0.08 193.2 510.15
M [2] 0.6 0.28 0.12 138.8 567.15
M [3] 0.395 0.185 0.419 61.3 674.15
P1 0.901 0.079 0.020 131.1 346.15
P2 0.884 0.092 0.024 152.9 362.15
P3 0.859 0.112 0.029 178.2 387.15
P4 0.820 0.143 0.037 196.0 424.15
P5 0.752 0.197 0.051 190.5 474.15
P6 0.603 0.315 0.082 143.6 539.15

The proposed compositions, Px are actually under experimental study.

5. Conclusions
Experimental data of the VLE of the synthetic mixture of cyclohexane + hexadecane +
CO2 were obtained for different temperatures and pressures, and compared with estimated
values using several EOS in order to choose an appropriate equation suitable for the study
of complex mixtures such as reservoir fluids. Three different compositions were evaluated
experimentally and the results were compared with simulated values using EOS methods.
The simulated bubble points were found to be close to the values obtained experimentally
using the Peng Robinson property package, although the difference between them were
larger than the experimental error.
The consistency of the results confirms the reliability of the apparatus, the technique
employed and simulation method used in this work for determining and predicting VLE. It
would thus be possible to study the supercritical region, using a process simulation program
to calculate the composition of this complex ternary mixture, in the PVT apparatus.

Acknowledgments
The authors acknowledge the financial support of
MCT/FINEP/CTPETRO/PETROBRAS under the convenio 01.06.1036.00 entitled,
“Distribuição do Gás Sulfídrico entre Óleos Pesados, Gás Liberado e a Água de Formação
nas Condições de Reservatório”. The authors thank CNPq for the scholarship “bolsa de
produtividade” awarded to Krishnaswamy Rajagopal. and FINEP/CNPq for DTI
scholarships awarded to Luciana L. P. R. Andrade, Ian Hovell e Luis Augusto Medeiros
Rutledge. The authors thank Jorge Pereira dos Santos for help making the experimental
measurements.
 I Iberoamerican Conference on Supercritical Fluids
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