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org/jced Article

New Design of the High-Pressure Optical Cell for Vapor−Liquid

Equilibrium Measurements. Supercritical Binary Mixture (Propane/
n‑Butane) + Acetophenone
Vener F. Khairutdinov, Farid M. Gumerov, Farizan R. Gabitov, Zufar I. Zaripov, Ilnar Sh. Khabriev,
Talgat R. Akhmetzyanov, and Ilmutdin M. Abdulagatov*

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ABSTRACT: A new design of the high-pressure and high-temperature optical

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cell has been developed for precise measurements of the vapor−liquid equilibrium
(VLE) properties of multicomponent mixtures at pressures up to 50 MPa and at
temperatures from room to 450.15 K. The present design of the VLE optical cell
allows avoidance of the separation of the binary system out of the sampler (in the
sampling tube) and accurate determination of the concentrations of the coexisting
phases without disturbing the phase equilibrium conditions during the high-
pressure sampling procedure (thermodynamically consistent PTxy data). A
sufficiently large volume (117 cm3) of the measuring cell allows extraction of a
relatively large sample volume (about 4.1 cm3) from the liquid and the vapor
phase independently without breaking the phase equilibrium (PT) conditions
during the sampling procedure from each phase. This allows a considerable
increase of the accuracy of the concentration determination of the equilibrium
phases using the gravimetric method, especially the vapor phase. The gravimetric sampling method provides a precise analysis of the
coexisting phase concentrations without using expensive chromatographic columns, which are not always suitable for the analysis of
various complex multicomponent mixtures. The accuracy, reliability, and correct operation of the new design of the high-pressure
VLE cell was verified by measuring the phase equilibrium properties of pure (propane) and the binary (propane + n-butane) mixture
with well-known VLE properties. Also, the method was applied for the new, previously unexplored, ternary mixture of supercritical
solvent (0.527 propane + 0.473 n-butane) + acetophenone. The values of the critical parameters for the ternary mixture have been
estimated from the experimental VLE data near the critical point. The combined expanded uncertainty of the temperature, pressure,
and concentration measurements at 0.95 confidence level with a coverage factor of k = 2 is estimated to be 0.15 K, 0.0022, and 0.03,
respectively.

1. INTRODUCTION
Study of the high-pressure vapor−liquid equilibrium (VLE)
(PTxy) properties of multicomponent mixtures has many
industrial applications, for example, in the oil and natural gas
industry, geothermal energy production processes, storage and
transportation of fluids, enhanced oil recovery (EOR), and
miscible displacement of heavy hydrocarbons from under-
ground reservoirs, etc. Accurate and comprehensive exper-
imental VLE data are essential in process engineering to help
more effective optimization of the design (to reduce the
overdesign) and operation of equipment units and to achieve
more effective optimization of oil pipeline networks and
processing equipment. For example, VLE properties are
required for the design of separation operations, which are
essential parts of a chemical plant. Most chemical processes
operate at high-pressures and high-temperatures (distillation,
absorption, etc.). Also, VLE at high-pressures are of interest in
geological exploration, such as in drilling for oil and natural gas
and geological processes deep below the earth’s crust, for
example, in oil reservoirs the fluids which coexist at high
pressures and temperatures are typically composed of light and
heavy hydrocarbons. Reliable information on the VLE proper-
ties of oil and geothermal reservoir fluids is very important for
modeling thermodynamic conditions of a production process.
VLE is one the most important characteristic of fluid mixtures
and determines their technological, operational, and consumer
properties. The sensitivity of design parameters to data
uncertainty has been discussed by several authors.1,45−47
Special Issue: Nontraditional Techniques for Meas-
urement of Phase Equilibria
Received: January 29, 2020
Accepted: June 8, 2020
Published: June 22, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.jced.0c00104

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Table 1. Description of the Samples of Propane, n-Butane, Acetophenone, and the Propane + n-Butane Mixture Used in This
Worka
chemical name CASRN water contentb
propane 74-98-6
n-butane 106-97-8
acetophenone 98-86-2
0.527 (propane) + 0.473 (n-butane)a
a
Expanded uncertainty in concentration of the propane + n-butane mixture determination is 0.0099 mole fraction of propane and 0.0077 mole
fraction of n-butane. bWater content was provided by the suppliers.
Thermodynamic property uncertainties are costly, but some are
more costly than others.45 The effect of thermophysical
properties and their uncertainty on the optimization of design
and processing equipment is essential; for example,1,45−47 a 20%
error in density may result in a 16% error in equipment size or
cost. However, a 10% error in evaluating VLE data might lead to
10% and 200% errors in estimating the equipment and operation
costs in the cases of easy and hard separating mixtures,
respectively.47 VLE data are the most important resources for
the design and operation of separation units and reactors. Those
account for 40% to 70% of the equipment and operation cost of a
whole chemical plant.47
The complex interactions between dissimilar molecules in
multicomponent mixtures generate a wide variety of phase
behavior which is not observed in pure fluids. Phase behavior
(VLE), of the main heavy oil components under supercritical
extraction processes is key input to the development of the
technology for oil recovery. The supercritical fluids and heavy
reservoir hydrocarbons mixtures exhibit complex phase
behaviors during oil recovery processes which require a reliable
technique of VLE measurements. For example, the use of
supercritical extraction processes involving SC CO2 (heavy oil
recovery by SC CO2 injection,2−8 SC CO2 food processing
industry9−13) or SC CO2 sequestration processes,14−16 etc. In
recent years, separations with supercritical fluids (for example,
carbon dioxide) as a solvent have reached widespread attention
in various industrial applications such as food and oil processing,
biotechnology, and environmental control.2−13 The number of
applications using supercritical fluids is increasing constantly,
due to their unique properties17 and commercial signifi-
cance.2−16 In a number of our previous publications24−30 we
have studied aspects related to extractions of heavy hydro-
carbons from dry oil sludge, oil emulsions, and oil-bearing sand
by a supercritical binary mixture of propane + n-butane.
However, due to the lack of extensive, reliable, and precise VLE
data for the efficient design of separation units or the
development of new accurate methods for correlating and
predicting high-pressure phase equilibria, their widespread
commercial implementation is still limited. Thus, deeper
understanding of VLE (PTxy relations) in the multicomponent
systems containing supercritical fluids or fluid mixtures, can lead
to significant improvements of the supercritical technology
applications. Consequently, the success of industrial applica-
tions of the supercritical fluids depends on the accuracy of the
relevant phase equilibria (VLE) data.
A detailed review of equipment design for high-pressure
equilibria studies was reported by Fourie et al.18 (see also refs
19−22). For VLE studies Fourie et al.18 used classification of the
experimental methods proposed by Dimitrelis and Prausnitzs23
(see, also ref 18). They classified VLE measurement techniques
in two major groups, synthetic and analytical, depending on the
coexisting phase composition analysis. The synthetic method is
pubs.acs.org/jced Article
purity source
not found ≥0.9980 (NMR) Monitoring LLC (Moscow)
<0.0005 >0.9975 (NMR) Monitoring LLC (Moscow)
≤0.00005 ≥0.9980 (GC) ACROS Organics
not found UralOrgSynthesis LLC
just identifying a phase transition point, and no analyses of the
phase compositions are required. In the analytical method, in
contrast, accurate determination of the compositions of
coexisting equilibrium phases is required. Depending on the
sample movement through the measuring cell, there are two
major types of equipment such as static and dynamic
equilibrium cells. In the static method, a mixture is charged to
an equilibrium cell, immersed in a thermostat. Phase
equilibration is brought by vigorous stirring of the liquid
phase or, in some cell designs, by rocking the cell. After the
system comes to equilibrium, the pressure can be measured.
Measurement of the composition of the vapor phase is the most
important and difficult part of the static method. The total mass
of vapor in the cell is small, therefore, the vapor sample must be
extremely small in order that equilibrium not be markedly
disturbed on withdrawal of the sample. This leads to a large
uncertainty of the vapor phase concentration (y) determination
when using the gravimetric method. To avoid the problem, the
vapor compositions (y) can be determined indirectly, by
calculation, for example. Thus, sampling, sample homogeniza-
tion, analysis technique, and pressure- and temperature control
of the coexisting phases are the key aspects of the VLE
measurements. These are main differences of the available
methods and equipment for phase equilibrium measurements
various research laboratories. All methods have advantages and
disadvantages (see for example, Fourie et al.18). However, there
are no universal methods suitable for the study of phase
equilibrium for a wide variety of multicomponent mixtures.
In the present work we developed a new design of the high-
pressure VLE optical cell, which improved sampling and phase
composition analysis methods, sample homogenization, and
precise phase equilibrium control without disturbing phase-
equilibrium conditions during the sampling procedure. The
method and new design of the high-pressure optical cell was
applied to accurately measure the VLE properties (solubility) of
acetophenone in the supercritical binary solvent of (propane +
n-butane).
2. EXPERIMENTAL SECTION
2.1. Materials. The propane sample (CAS No. 74-98-6)
used in this work was supplied by chemical reagents production
company Monitoring LLC (Moscow, Russia). The purity of the
propane was 0.998 mass fraction. The n-butane sample (CAS
No. 106-97-8) with a purity of 0.9975 mass fraction was
provided by Monitoring LLC (Moscow). The acetophenone
sample (CAS No. 98-86-2) used in this work was supplied by
ACROS Organic Company (Germany). The purity of
acetophenone was 0.998 mass fraction. A ready to use mixed
propane + n-butane solvent with a fixed composition of 0.527
mole fraction of propane and 0.473 mole fraction of n-butane
was provided by UralOrgSynthesis LLC. Table 1 lists the
commercial sources, purities, water content, and analysis
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method of the samples used in the present work. No further
purification of the samples was attempted.
2.2. High-Pressure and High-Temperature VLE Appa-
ratus. For high-pressure and high-temperature phase equili-
brium (PTxy) measurements a new design of the VLE apparatus,
based on a static technique coupled with gravimetric analysis,
has been developed. The new design of the VLE apparatus
allows accurate measurements of the solubility of solid and
liquid solutes in supercritical pure or multicomponent solvents.
In the present work we are considering, as an example, the VLE
properties of the solute (solid or liquid) in a supercritical binary
mixture (solvent) in the static mode. A schematic diagram of the
experimental apparatus for high-pressure and high-temperature
VLE properties measurements is presented in Figure 1. The
Figure 1. Schematic diagram of the VLE property measurement
apparatus with high-pressure optical cell: (1) cylinder with solvent
mixture (propane+n-butane); (2) filter-dryer; (3) high-pressure pump;
(4) high-pressure optical cell; (5) copper jacket; (6) thermal insulation;
(7) valve for extracting sample from upper (gas) phase; (8) valve for
extracting sample from lower (liquid) phase; (9) sampler; (10)
thermostated bath; (11) valve.
experimental VLE apparatus consists of the following units: (1)
solvent (pure or mixture, in the present work we used propane +
n-butane mixture as a solvent) supply unit; (2) temperature
control unit; (3) pressure creating, regulating, and measuring
unit; (4) high-pressure optical cell; (5) evacuation (vacuuming)
system; (6) stirring mechanism; (7) sampling system (sampler);
and (8) analytical part.
The optical cell-4 (see Figure 1 and Figure 3 below) was
heated up to the desired experimental temperature using an
electrical heater. The voltage was regulated by laboratory
autotransformers PHO-250. For a smoother temperature
control and uniform heating of the measuring cell, a copper
jacket (5) was used. The measuring cell was completely isolated
using the thermal insulation material (6). From the cylinder (1),
the pure or mixture solvent (pure carbon dioxide or propane + n-
butane mixture) was supplied to the pump through the filter-
dryer (2). The pressure in the high-pressure optical cell (4) was
created using a plunger pump (3) (TharTechnology, Super-
critical-24). The pump has automatic control and pressure
maintenance system. The pump (3) generates a high pressure in
the following way. The working chambers of the pump (3) are
cooled by a refrigerator to −5 °C, which prevents the formation
of a gas plug. Pressure is pumped by alternately moving the
plungers and expelling the incoming liquid CO2 from the
pump’s working chamber. The maximum working pressure of
the pump is 50 MPa. Carbon dioxide discharge (flow rate) can
be adjusted from (1 to 50) g·min−1. The temperature range is
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from (219 to 505) K. The pressure on the valve depends on the
experimental temperature and pressure conditions.
The sampler (9) (see Figure 4, below), maintained in the
thermostated bath (10) (see also Figure 7, below), was used for
sampling from the liquid (8) and vapor (9) phases. Sampling
was carried out by connecting the sampler (9) and the optical
cell (4) through a half-turn ball valve (7) (see Figure 2), which
Figure 2. High-pressure half-turn ball valves with stamped body (Hy-
Lok).
facilitates quick sampling. A sampling valve is a half-turn ball
valve with a maximum working pressure of 41.4 MPa (Hy-Lok,
see Figure 2). To avoid possible removal of solute (n-
hexadecane or acetophenone in our case) from the vapor
phase during its release from the sampler (9), the particle trap
was mounted to the outlet valve of the sampler (9).
2.3. High-Pressure and High-Temperature Optical
Cell. The main part of the VLE apparatus (Figure 1) is a
high-pressure optical cell (4). The details of the optical cell
design is shown in Figure 3. The stainless steel-flanged sapphire
Figure 3. High-pressure optical cell with copper jacket: (1) body; (2)
copper jacket; (3) sapphire window; (4) sealing ring (rubber with
polyimide cover); (5) cell cap. All measurement numbers in
millimeters.
cell operates up to 50 MPa and at temperatures from room to
450.15 K. An optical cell (Figure 3) consists of sapphire
windows (3) installed between the cover and body (made from
stainless steel, 12X18H10T) of the apparatus. The working
volume of the cell is 117 cm3. The optical cell temperature was
measured using the chromel−alumel thermocouples. The
thermocouples were precalibrated using a 10 Ω reference
platinum resistance thermometer (PRT-10). The PRT-10 was
calibrated by the VNIIFTRI (Russian NIST, Moscow) against
the ITS-90 with an uncertainty of 2 mK. The uncertainty of
temperature and pressure measurements consists of (1) the
maximum instrumental uncertainty of pressure uP,ins = 0.025 bar
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and temperature uT,ins = 0.05 K, and (2) the deviation of
temperature and pressure due to thermostat temperature
fluctuation (uT,fluc = 0.03 K for temperature and uP,fluc due to
temperature instability). Therefore, the standard uncertainties
in the temperature u(T) and the pressure u(P) are
u(T ) = uT ,ins 2 + uT ,fluc 2 < 0.06 K
and
u(P) = uP ,ins 2 + uP ,fluc 2
They depend on experimental temperature and pressure
changes due to temperature instability.
The value of uP,fluc changes within the present experimental
conditions from 0.006 to 0.05. The maximal value of u(P) at the
temperature P and T conditions is about 0.056 bar (or maximal
uncertainty is 0.0011). Thus, the total combined expanded
uncertainty of temperature measurements (at 0.95 confidence
level, a coverage factor of k = 2) is 0.15 K (standard uncertainty
is 0.075 K). To measure the pressure in the optical cell, a
standard (reference) high precision dead weight pressure gauge
was used. The combined expanded uncertainty of the pressure
measurements (at 0.95 confidence level, a coverage factor of k =
2) is 0.0022 (standard uncertainty is 0.0011).
2.4. Sampling Procedure and Sample Analysis.
Accurate sampling under high-pressure and high-temperature
equilibrium conditions is a very important part of the VLE
measurements. The design and sampling procedure play an
important role in the VLE measurements and uncertainty of the
concentration measurements. For example, sampling through a
capillary tube (sampling tube, see Figure 4) can lead to a
Figure 4. Sampler for sampling from the liquid and vapor phases.
separation of the extracted sample inside the tube (before
reaching to the sampler), especially for mixtures containing low
and high volatility components, due to pressure drop (pressure
gradient) along the entire length of the sampling capillary tube.
Premature separation of the sample can be avoided by using
special designs that provide the pressure drop only at the end of
the capillary next to the sampler or chromatographic system for
analysis. To solve the problem, Galicia-Luna et al.31 used a short
microcapillary entering the main capillary which reduces the
cross-sectional area at the end of the capillary. In the present
work we used a needle with a small coning angle inserted into the
sampling capillary, which allows changing the area of the annular
gap by screwing it on or off from the capillary. The needle and
capillary tube are connected by a screw pair with a small thread
pitch. This avoids separation of the binary system inside the
tubes and complete separation in the sampler.32 Compared to
using a short microcapillary31 entering the main capillary, in our
case there is the possibility of changing the annular gap area,
which makes it possible to use this design and sampler for the
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study of various types of binary systems (for example, mixtures
with low and high volatility components, light and heavy
hydrocarbons mixtures, or solid and SC solvent, for example,
etc., i.e., any type of complex solute and solvent mixtures). This
is one of the differences between our method and conventional
ones.
For sampling, a sampler (9) (Figure 1) with a volume of 4.1
cm3 was used. Design of the sampler is shown in Figure 4.
In the present method the sampling and extract analysis
procedures have been performed as follows. Schematic
representation of the sampling procedure is shown in Figure 5.
Figure 5. Schematic diagram of the sampling procedure.
Sampling was carried out by connecting the sampler (9) and the
optical cell (4) through a half-turn ball valve (7), which
facilitates quick sampling (see Figure 1). The extracted sample
in the sampler (9) is the mixture (propane−n-butane + solute
mixture) or pure fluid (SC CO2, for example) as a solvent and
the second component under study as a solute (for example, n-
hexadecane or acetophenone in our case). The separation of the
extracted sample into gaseous (propane−n-butane mixture
solvent) and solid or liquid components (test fluid, n-
hexadecane or acetophenone) was carried out by cooling the
sampler (9) to 293 K. At this condition the test fluid (n-
hexadecane or acetophenone) dissolved previously in the
propane−butane mixture, is precipitating, i.e., the extracted
sample separates into the heavy (condensable, n-hexadecane or
acetophenone) and light (noncondensable, propane + n-butane
mixture) components.
The separating procedure of the extracted sample into the
vapor and liquid phases was implemented at a temperature of
293 K because below 291.23 K n-hexadecane and acetophenone
are starting crystallize (the crystallization temperature of
acetophenone is 292.85 K). In the case when we have other
solutes with different crystallization temperatures, the separa-
tion can be performed at other temperatures depending on the
properties of pure solutes. The same method and sampler (9)
were used (Figure 1) for sampling from the liquid and gas phases
(see Figure 5). The sampler alternately connects to the top or
bottom part of the optical cell depending on the sample being
taken. The connection scheme of the sampler is shown in Figure
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5. Details of the sampler’s throttle unit design are shown in
Figure 6.
Figure 6. Sampler’s throttle assembly.
For each particular case, the sampler (9) temperature can be
adjusted using the air thermostat-10 (Binder M115, Figure 7).
Figure 7. Air thermostat (Binder M115).
The temperature inside the thermostat was maintained uniform
within 0.03 K. Air was used as a thermostatting media. The
maximum operating temperature of the thermostat was 573 K.
At low temperatures (cooling the sampler (9)), the mixture of
n-hexadecane and acetophenone dissolved in propane + n-
butane is precipitating into solid or liquid phases (depending on
the sampler’s temperature, (273 or 293) K). We experimentally
found that the procedure of separation of the mixtures
(propane/n-butane) + n-hexadecane and (propane/n-butane)
+ acetophenone into (propane/n-butane) gas phase and liquid
n-hexadecane and acetophenone at a temperature of 293 K is
most optimal. At this temperature the (propane + n-butane)
mixture transforms into the gas phase. As a result, n-hexadecane
and acetophenone are completely separating from the solvent
(propane+n-butane mixture). We also experimentally observed
that the separation at temperatures of (273, 288, and 293) K
does not affect the determination of the n-hexadecane and
acetophenone concentrations. Moreover, the separation below
273 K causes some condensation of water from the air absorbed
on the sampler’s walls. This introduces an additional uncertainty
in the n-hexadecane and acetophenone concentrations deter-
mination. For this reason, cooling the sampler (9) to very low
temperatures (below 273 K) is not applicable in this case. Thus,
in the present study we have assumed that the vapor fraction
removed from an extracted sample does not contain n-
hexadecane or acetophenone. This assumption was additionally
verified by chromatographic analyses of both the separated
liquid and vapor phases. Chromatographic analysis of the
propane−n-butane mixture was carried out on a Chromos GC-
1000 chromatograph using a thermal conductivity detector. The
length of the chromatographic column was 6 m, internal
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diameter was 3 mm, 30% pentaerythritoltetrabutyrate on
diatomite 0.16−0.20 mm. The carrier gas velocity was 30
cm3/min. The volume of the launched sample is 6 cm3. It has
been found that the concentration differences are within the
experimental uncertainty.
2.5. Equilibrium Phase Composition Determination. In
the present method, when analyzing liquid and vapor phase
samples taken from an optical cell at equilibrium condition, only
the gravimetric method was used. However, in order to verify the
correctness of the gravimetric method we used independent
chromatographic tests. The equilibrium phase concentration
measurement procedure was carried out as follows. Before
sampling, the sampler (9) (Figure 1) was preliminarily weighed
using a Vibra electronic balance with an uncertainty of 0.001 g.
The mass of the propane + n-butane mixture in the sampler (9)
was calculated as the difference between the full and the empty
sampler after releasing the vapor phase (see the example in what
follows). Analogously, the mass of the solute (n-hexadecane or
acetophenone) was calculated as the difference between the
mass of sample remaining in the sampler after releasing the
vapor phase and empty sampler (9). Thus, the solubility of the
solute (n-hexadecane or acetophenone) in the binary propane +
n-butane mixture solvent can be obtained as
msol
Msol
y= mC3 + C4 msol
+
MC3 + C4 Msol (1)
where msol is the mass of the dissolved solute (n-hexadecane or
acetophenone) in the supercritical propane + n-butane mixture;
Msol is the molar mass of pure solute (n-hexadecane or
acetophenone), mC3+C4 is the mass of the propane + n-butane
mixture and MC3+C4 is the molar mass of the mixture given
concentration of x = 0.473 of n-butane. To verify the accuracy
and reliability of the present gravimetric method of coexisting
phase concentration measurements, an additional chromato-
graphic analysis of the extracted samples was performed.
Chromatographic analysis confirmed the gravimetric results by
determining the presence of traces of each component in the
separated propane + n-butane and in n-hexadecane (or
acetophtnone) samples. This additionally verifies the reliability
and accuracy of the gravimetric method of the equilibrium phase
concentration analysis used in the present work. Therefore,
chromatographic analysis is not required for the present method,
and the vapor and liquid phase concentrations can be
determined directly.
The measurement procedure was carried out as follows. In
this method, unlike that often used conventional techniques, the
sampling from the gas and liquid phases is performed separately
at different P and T conditions. This allows reliability and
thermodynamic consistency between the (P,T) and concen-
tration (x,y) measurements. After a quick sampling from one of
the equilibrium phases (gas or liquid using valves 7 and 8,
respectively, Figure 1) at the given T and P experimental
condition, the phase equilibrium concentration and pressure in
the system shift. Therefore, the next sampling from the other
phase, at the same thermodynamic conditions (at the same T
and P) becomes impossible in this method. The next
equilibrium phase concentration measurements were performed
at different P and T conditions. Consequently, the next sampling
was performed after stirring the sample and reaching equilibrium
conditions at other T and P conditions. For convenience, the
phases (liquid or gas) were analyzed separately, at different T
and P conditions. This approach, different to other existing
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methods, allows an accurate measurement of the phase Table 2. VLE Experimental Data in a Ternary Propane + n-
compositions (x,y) corresponding to the exact (not disturbed Butane + Acetophenone Mixture at (403 and 423) Ka
as with other methods) equilibrium P and T conditions.
pressure P/ mole fraction of mole fraction of mole fraction of
Example of the Phase Concentration Determinations. To (MPa) acetophenone propane n-butane
determine the composition of each component, the sampler was
T = 403 K
weighed three times. When sampling from the liquid phase at a
Gas Phase
pressure of P = 4.9 MPa and temperature of T = 423 K, the
1.72 0.028 0.515 0.457
following values were obtained: (1) empty sampler weight = 2.60 0.013 0.523 0.464
194.009 g; (2) mass of a full sampler = 197.9367 g; (3) mass of 3.49 0.020 0.519 0.461
the sampler after releasing of the vapor phase = 195.8292 g. 4.04 0.044 0.507 0.449
Therefore, acetophenone mass (msol) = (sampler mass after Liquid Phase
vapor phase releasing) − (empty sampler mass) = 195.8292 − 2.05 0.649 0.186 0.165
194.009 = 1.8202 g. Gas mass (mC3+C4) = (mass of the full 3.17 0.385 0.326 0.289
sampler) − (mass of the sampler after vapor phase releasing) = 3.73 0.221 0.413 0.366
197.9367 − 195.8292 = 2.1075 g. Then the mole fraction of 4.02 0.127 0.462 0.411
acetophenone was calculated using eq 1 as T = 423 K
1.8202 Gas Phase
120.40 1.55 0.031 0.514 0.455
y= 2.1075 1.8202
= 0.267
+ 120.40 3.05 0.018 0.520 0.462
50.73 (2) 4.05 0.021 0.519 0.460
5.00 0.033 0.513 0.454
2.6. Uncertainty Evaluation. Uncertainty analysis is based Liquid Phase
on the working eq 1 for the method. We used the generally 2.48 0.706 0.156 0.138
accepted procedure of uncertainty analyses recommended in the 3.84 0.468 0.282 0.250
literature.46,48−51 Assuming that all of the input (measuring) 4.90 0.267 0.388 0.345
parameters Xi (msol, mC3+C4, T, P) in eq 1 are independent, the 5.14 0.186 0.431 0.383
2
variance of concentration (Y) is u(Y )2 = ∑i = 1
N
( ∂Y
∂X i
u(Xi) ), a
Standard uncertainties u are u(T) = 0.075 K; ur(P) = 0.001; ur(x) =
0.015; and ur(y) = 0.015.
where N = 4 (in our case) is the number of input parameters in
the working eq 1 and the combined standard uncertainty is the
square root of the variance (Y) (see refs 46 and 48−51). The
derivative ∂Y/∂Xi can be readily taken from eq 1, and u(Xi) is the system was evacuated using a vacuum pump (3). Next, the
standard uncertainty of the mass determination (well-known for optical cell (4) (Figures 1 and 3) was heated to the desired
the weighing method). The values of (∂x/∂P)T,y,mi, (∂x/∂T)P,y,mi, temperature and the propane + n-butane mixture was supplied
(∂y/∂P)T,y,mi, (∂y/∂T)P,y,mi were approximately estimated using into it using a high- pressure pump (3) (Figure 1) until the
the experimental data. We used Vibra brand scales with an required pressure was reached. The phase equilibrium study is
accuracy of 0.001 g. It is apparent that the uncertainty of required to identify the equilibrium condition before compo-
concentration determination in the present method depends on sition analyses is performed. How long it takes before
uncertainty of the weighing procedure, that is, on the mass of equilibrium condition is reached depends on the method of
dissolved solute (acetophenone, msol) and the mass of the stirring and operation conditions. In order to reach the
propane + n-butane mixture (mC3+C4). Table 2 provides the equilibrium condition in the two-phase (liquid+gas) system,
values of the calculated uncertainty for each experimental the sample propane/n-butane + solute (n-hexadecane or
condition (data points). On the one hand, the smaller is the acetophenone) mixture under study was vigorously stirred for
volume of the sample taken, the less the phase equilibrium in the 30 min using a stirring mechanism. The stirring of the mixture of
system is disturbed, but on the other hand, the sample volume propane/n-butane + n-hexadecane (acetophenone) was per-
must be sufficient for accurate weighing. The combined formed by swinging the measuring cell 90 deg around its axis
expanded uncertainty of the concentration measurements was with a frequency of 8 rpm using a special mechanical device
estimated to be 0.03. This uncertainty includes the uncertainty (electric motor and linkage mechanism). The measuring cell
of the temperature and pressure measurements. swing principle is showing in Figure 8.
2.7. Procedure of Measurements. For the experiment, As a rule, the equilibrium condition is defined as the condition
approximately one-third of the optical cell was filled with solute at which all measuring properties remain constant or their
(n-hexadecane or acetophenone) through an open sapphire fluctuations are within the experimental uncertainty. In the
window. In fact, the initial filling factor of the cell does not play present study phase equilibria was identified as the conditions
an important role in this method. The main requirement for the under which pressure and temperature in the optical cell along
present technique of the phase equilibrium study is the presence with the concentration of the extracts remain constant within
and visual observation (monitoring) of the phase boundary their experimental uncertainties. To determine the equilibrium
(meniscus) in the optical cell under experimental conditions. state of the system, a series of experiments were carried out by
The optical cell design allows visual control of the meniscus extracting the samples for analysis and/or pressure changes in
movement and the ability to adjust it by changing the filling the optical cell. After reaching the equilibrium condition in the
factor, which depends on the physical−chemical characteristics optical cell, the sample stirring was stopped. Then the optical cell
of the mixture under study. Section 3.1 provides the details of was mounted in an upright position and held for 40 min. Then
the effect of filling factor on the visual observation of the phase the procedure of sampling and concentration analysis was
and critical states of the mixture under study. Then, the whole started as described above.
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Figure 8. Measuring cell swing principle.
Thus, it is apparent that the present design of the high-
pressure VLE apparatus has some advantages over conventional
methods. The main advantages of using the present method and
new designed optical cell for high-temperature and high-
pressure VLE measurements include the following:
(1) Separation of the extracted sample from coexisting phases
in the sampling tube is avoided and complete separation
of it in the sampler is provided. In the present method
there is the possibility to change the annular gap area,
which makes it possible to use the sampler design for the
study of various types of complex multicomponent
systems (for example, especially mixtures with low and
high volatility components, light and heavy hydrocarbons
mixtures, or solid and SC solvent, etc.).
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(2) The temperature in the phase equilibrium cell is precisely
maintained by using three-zone temperature controls: a
copper shirt; thermal insulation; and thermostatic air. The
accuracy of maintaining the temperature in the system,
along with the accuracy of measuring pressure, is an
important condition for the correctness of the results of
studying the phase equilibrium in thermodynamic
systems.
(3) The high-pressure measuring cell has a large internal
volume of 117 cm3 and sapphire windows. A sufficiently
large volume of the measuring cell allows extraction of a
relatively large sample volume (in our case 4.1 cm3) from
the liquid and vapor phases independently without
disturbing the phase equilibrium conditions during each
sampling procedure. For the gravimetric method of
sample analysis used in this work, the volume of the
extracted sample determines the accuracy of the
concentration measurement. Also, the presence of
sapphire optical windows in a high-pressure cell makes
it possible to visualize the processes, including observing
such an important phenomenon as critical opalescence
and accurately determining the critical parameters using a
visual observation method.
(4) The concentrations of the coexisting phases were
accurately determined without disturbing the phase
equilibrium conditions during the high-pressure sampling
procedure, thereby provide reliable thermodynamically
consistent PTxy data.
(5) Very simple (accessible for any laboratory) and effective
(accurate) enough gravimetric sampling methods can be
used in the present method without chromatographic
analyses. Accessibility is available even though, for
example, most analytical methods of sample analysis use
expensive chromatographic columns. At the same time,
the same chromatographic column is not always suitable
for the analysis of various types of systems under study.
The gravimetric method is suitable for any cases and any
type of mixtures.
3. RESULTS AND DISCUSSION
3.1. Test Measurements. The reliability and accuracy of
the present new VLE apparatus (new design of the high-pressure
optical cell) and the experimental methods of equilibrium phase
concentration determination at given P and T conditions were
verified by measuring the VLE properties of well-studied pure
binary and ternary mixtures such as pure propane, binary
(propane + n-butane), (propane + n-hexadecane), (propane +
naphthalene), and ternary (propane/n-butane + n-hexadecane)
mixtures (see also refs 24 and 25). The measured VLE property
data for these mixtures were compared with the reference,35 and
the reported data are available in the NIST/TRC database.33
Propane has been recommended34 as a reference fluid for
calibration of the experimental apparatus. NIST recommen-
ded35 values of the critical parameters for propane are TC =
369.89 K, PC = 4.2512 MPa, and ρC = 220.48 kg·m−3. The
present design of the high-pressure optical cell allows an
accurate measurement of the critical parameters of pure fluids
and fluid mixtures by visually observing the critical opalescence
and the simultaneous disappearance and reappearance of the
meniscus, that is, of the liquid−vapor interface from the middle
of the view cell. Heating of the two-phase (L−G) propane at
constant volume can lead to various different sequences of phase
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transitions, depending on the fill coefficient (ratio of the volume
of the sample to the volume of the measuring cell at ambient
temperature) or the average fill density (ratio of the mass of
sample to the volume of the measuring cell at ambient
temperature):
1. At highest average densities (ρ > ρC), the liquid part of the
initial two-phase (L−V) system expands on heating at
constant volume and fills the entire vessel at saturated
temperature (TS), while the vapor phase disappears, that
is, the disappearance of the meniscus (L−V interface) on
the top of the cell is observed (see Figure 9). A transition
Figure 9. P−ρ phase diagram of pure propane24 calculated from
REFPROP.35 Observation of the liquid−vapor interface (meniscus)
location and the critical opalescence at various temperatures for
different filling densities of propane.
from two phases (L−V) to one phase (L), (L−V ⇒L)
occurs. The temperature (TS) at which the vapor−liquid
interface disappears at the initial filled density (ρ) is the
phase transition temperature (TS) at the liquid−gas
coexistence curve (saturated liquid density, ρ = ρS′ , see
Figure 9, right inset photo).
2. At the lowest average densities (ρ < ρC), heating increases
the vapor density resulting in disappearance of the liquid
phase (the vapor part of the two-phase L−V system
expands and fills the entire vessel), that is, the
disappearance of the meniscus (vapor−liquid interface)
on the bottom of the cell is observed. A transition takes
place from two-phase (L-V) to one-phase (V), (L-V⇒V)
occurs. The temperature (TS) at which the vapor−liquid
interface disappears at the initial filled density (ρ) is the
phase transition temperature at the liquid−gas coex-
istence curve (saturated vapor density, ρ = ρS″, see Figure
9, left inset photo).
3. At some intermediate average density (ρ ≈ ρC), ρ′S = ρ″S =
ρC. In this case the vapor−liquid interface became cloudy,
thick, and then occupied the entire cell when the
temperature of the system approached the critical value
where both saturated liquid and vapor densities became
identical, ρS′ = ρS″ = ρC. The cell became orange (see
Figure 9, middle inset photo), which is a characteristic of
the critical opalescence. After reaching the supercritical
phase, the temperature of the cell was gradually decreased
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(cooling run). At a little above the critical temperature
and pressure, the fluid color changed from colorless to
yellow, then from yellow to yellow−red, and finally
became dark orange. Then the vapor−liquid interface
reappeared in the middle of the view cell. This clearly
illustrates that the systemis in the supercritical condition.
The critical temperature and pressure were recorded at
the point where complete darkness was observed in the
cell. For each measurement, the heating and cooling
processes were repeated a few times, and the average of
the recorded temperatures and pressures were taken as
the critical values of the propane. The same phenomena
were observed for different near-critical isochores. All
these cases (see earlier) have been found in the present
experiments (see Figure 9). The third case was
encountered in our experiment for the critical state
observation. The present values of the critical temper-
ature, pressure, and density for propane derived using the
described method are TC = 371.15 ± 1.0 K, PC = 4.25 ±
0.02 MPa, and ρC = 227.27 ± 5 kg·m−3, respectively.
These values of the critical temperature, pressure, and
density agree with the reference data35 within 1.26 K,
0.0003, and 0.03, respectively. The relatively large
discrepancy in the critical temperature value is the result
of a purity effect.
The P−ρ diagram of pure propane calculated from reference
equation of state (NIST/REFPROP35) is depicted in Figure 9
for various sub-, near-, and supercritical isotherms including
one- (liquid and vapor) and two-phase (liquid + vapor) regions.
This figure demonstrates a comparison of the liquid + vapor
interface (meniscus) disappearing and the intensity of the
critical opalescence using photos of the observed meniscus at the
temperature at which the meniscus disappears for various
densities. For three different densities of (250.00, 227.27, and
200.00) kg·m−3 the location of the meniscus at different
temperatures is shown in Figure 9.
At a density of 250.00 kg·m−3, which is higher than the
reference critical density of 220.48 kg·m−3 (see ref 35) by 0.136,
the meniscus disappearance was observed in the top of the cell at
a temperature of TS = 369.81 K (reference value is TS = 369.70
K35). Therefore, we considered this value of density as a
saturated liquid density ρ′S (right side of the L + V coexistence
curve, see Figure 9). At a density of 200.00 kg·m−3, which is
lower than the reference critical density35 by about 0.102, the
meniscus disappearance was observed in the bottom of the cell
at a temperature of TS = 369.89 K (reference value is TS = 369.81
K35), therefore, we considered this value of density as a saturated
vapor density ρS″ (left side of the L + V coexistence curve, see
Figure 9). In the case of 227.27 kg·m−3, we observed
disappearance of the meniscus at the center of the cell. In this
case we found the critical opalescence with high intensity. Thus,
we considered the density of 227.27 kg·m−3 as a near-critical
density of propane. To accurately determine the critical
parameters in this method, various near-critical isochores should
be studied. The critical value of density should be determined
based on the measurements for series near-critical isochores.
The difference between the present and reference critical
density35 is within 0.0308 (typical uncertainty in the critical
density measurements is within 0.05, including singular
diameter behavior). This is an acceptable agreement because
the critical density of the fluids is difficult to accurately measure
due to high compressibility (KT = ρ−1(∂ρ/∂P)T → ∞ at T →
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TC) of the system near the critical point. The small changes in
the temperature (even within experimental uncertainty) and
pressure near the critical point cause large changes in the density.
The same procedure was used to measure of the critical
parameters and phase equilibrium (VLE) properties of propane
+ the n-butane mixture. The measured values of the critical
parameters for the selected mixture of (0.609 propane + 0.391n-
butane) are TC = 394.25 K and PC = 4.3 MPa (see Figure 10).
Figure 10. P−T phase diagram of binary propane + n-butane mixture25
for various concentrations. Dashed−dotted curve is the critical line
calculated from the correlations by Soo et al.52 Solid curves are
predicted from the GERG model by Kunz et al.53 Dashed lines are
vapor-pressure curves of pure components calculated from RE-
FPROP.35
The present critical properties data for the (0.609 propane +
0.391n-butane) mixture is in good agreement with reported data
(NIST/TRC data33, see also refs 36−39). Discrepancies are
within 1.7 K and 0.0068 for the critical temperature and
pressure, respectively. Figure 10 illustrates the critical
opalescence with high intensity for the binary (0.609 propane
+ 0.391n-butane) mixture. The same behavior of the critical
state was visually observed for a ternary mixture of (0.527
propane + 0.473 n-butane) + acetophenone (see Figure 11). As
can be noted, the critical opalescence behavior of the mixture is
Figure 11. Concentrations (x and y) of acetophenone in the coexisting
liquid and gas phases as a function of pressure P for the mixture of SC
(0.527 propane + 0.473 n-butane) + acetophenone at two selected
constant temperatures of (403 and 423) K: (● and ▲) liquid-phase
(x); (○ and △) gas-phase (y); (∗) critical point.
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visually observed above the critical point of the mixture. This
method and new design of the VLE cell has been also
successfully used to measure phase equilibrium properties of a
complex multicomponent system such as supercritical solvent
(propane + n-butane) + oil sludge, oil-bearing sands, and oil
emulsions, etc. (see our previous publications refs 21, 22, and
26−28).
3.2. New Experimental VLE Data for SC (Propane + n-
Butane) + Acetophenone Mixture. The described high-
temperature and high-pressure VLE apparatus has been used to
measure the phase-equilibrium (VLE) properties of acetophe-
none in a supercritical binary mixture of (propane + n-butane)
with a predetermined composition of 0.527 mole fraction of
propane and 0.473 mole fraction of n-butane. A ready to use
mixed propane + n-butane solvent with fixed composition of x =
0.527 of propane and x = 0.473 of n-butane was selected as a SC
binary mixture solvent due to its commercial availability (see
section 2.1). The measured values of the VLE properties (PTxy)
for SC (propane + n-butane) + acetophenone mixture are given
in Table 2 and depicted in Figure 11 (in P−x and P−y
projections). The measurements were made at pressures up to
5.14 MPa along the two selected isotherms of (403 and 423) K.
The literature search based on the TRC/NIST archive33
(TDE search) and our own search results revealed that there
were no reported experimental VLE data available in the
literature for a ternary mixture of propane/n-butane +
acetophenone mixture. However, previously VLE properties of
acetophenone in pure supercritical CO2 and for other
acetophenone containing binary systems were studied by several
authors.36−43 However, the good agreement (see above section
3.1) between the present and reference35 and reported data from
the NIST/TRC database33 confirms the reliability and accuracy
of the method and measured data for the ternary mixture of
propane/n-butane + acetophenone, that is, it gives us assurance
that the new design of the high-pressure and high-temperature
VLE optical cell is operating correctly.
Using analytical and graphical interpolation technique we
have estimated the values of the critical parameters for the
(0.527 propane + 0.473 n-butane) + acetophenone mixture. It is
well-known that the maximum pressure of the VLE data in the
P−x projection (at fixed isotherm) is the critical point; that is,
the pressure where both liquid (full symbols, see Figure 11) and
gas branches of the VLE (P−x curve) intersect (where both
liquid and gas phases become identical) is the critical pressure.
Above the critical pressure for each isotherm we have the SC
state. Figure 11 shows the photos of the visual observation of the
critical opalescence. The derived values are (TC = 403 K, PC =
4.12 ± 0.01 MPa, x = 0.068 ± 0.005 of acetophenone) and (TC =
423 K, PC = 5.26 ± 0.01 MPa, x = 0.08 ± 0.005 of
acetophenone). Figure 12 shows the vapor phase concentration
(y) as a function of pressure at two constant temperatures of
(403 and 423) K. As one can see, different to the liquid phase
concentration, the vapor phase in P−y projection shows a
concentration minimum at pressures (3 and 3.5) MPa for
temperatures of (403 and 423) K, respectively. Such behavior of
the vapor branch of the phase equilibrium curve P−y is typical
for many mixtures (see, for example, ref 44).
4. CONCLUSIONS
A new modified high-pressure (up to 50 MPa) and high-
temperature (from room temperature to 450.15 K) optical cell
has been designed for precise VLE measurements based on the
principle of composition analyses of coexisting phases. The
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Figure 12. Vapor phase concentrations (y) of acetophenone as a
function of pressure P for the mixture of SC (0.527propane + 0.473n-
butane) + acetophenone at two selected constant temperatures of (403
and 423) K.
gravimetric method of equilibrium phase concentration
determination is used in this method without chromatography
analyses. The developed new design of the high-pressure VLE
optical cell avoids separation of the extracted sample from
coexisting phases in the sampling tube and provides complete
separation in the sampler. A sufficiently large volume (117 cm3)
of the measuring cell allows extraction of a relatively large sample
volume (4.1 cm3), which considerably increases the accuracy of
the concentration determination, especially for vapor phase
concentrations (y). The new sampling method also allows
avoidance of the effect of phase equilibrium disturbances during
each sampling procedure from the liquid and vapor phase,
thereby, provideing accurate and thermodynamically consistent
PTxy data. The results of the present work (test measurements)
validate good performance of the new design of the high-
pressure VLE cell and its ability to measure the phase-
equilibrium properties of various types of complex multi-
component mixtures, especially mixtures with low and high
volatile components (complex molecule mixtures), such as light
and heavy hydrocarbon mixtures, or solid and SC solvent, etc.
The developed new high-pressure VLE optical cell was applied
to accurately measure the solubility of acetophenone in the
supercritical binary solvent of (0.527 propane + 0.473 n-
butane). The values of the critical parameters (TC = 403 K, PC =
4.12 ± 0.01 MPa, x = 0.068 ± 0.005 of acetophenone) and (TC =
423 K, PC = 5.26 ± 0.01 MPa, x = 0.08 ± 0.005 of acetophenone
for the ternary mixture of propane/n-butane + acetophenone
have been estimated from the experimental VLE data near the
critical point.
■
AUTHOR INFORMATION
Corresponding Author
Ilmutdin M. Abdulagatov − Department of Physical and Organic
Chemistry, Dagestan State University, Makhachkala 367008,
Russian Federation; Department of Thermophysics, Geothermal
and Renewal Energy Institute of the High-Temperature Joint
Institute of the Russian Academy of Sciences, Makhachkala
367030, Russian Federation; orcid.org/0000-0002-6299-
5280; Phone: +1 (967) 401 00 39; Email: ilmutdina@
gmail.com
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Authors
Vener F. Khairutdinov − Department of Thermal Engineering,
Kazan National Research Technological University, Kazan
420015, Russian Federation
Farid M. Gumerov − Department of Thermal Engineering,
Kazan National Research Technological University, Kazan
420015, Russian Federation
Farizan R. Gabitov − Department of Thermal Engineering,
Kazan National Research Technological University, Kazan
420015, Russian Federation
Zufar I. Zaripov − Department of Thermal Engineering, Kazan
National Research Technological University, Kazan 420015,
Russian Federation
Ilnar Sh. Khabriev − Department of Thermal Engineering, Kazan
National Research Technological University, Kazan 420015,
Russian Federation
Talgat R. Akhmetzyanov − Department of Thermal Engineering,
Kazan National Research Technological University, Kazan
420015, Russian Federation
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jced.0c00104
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the Russian Scientific Foundation,
Project No. 19-73-10029.
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