Fluid Phase Equilibria 230 (2005) 51–57

Solubility of thiophene in carbon dioxide and carbon dioxide + 1-propanol

mixtures at temperatures from 313 to 363 K
O. Elizalde-Solis, L.A. Galicia-Luna∗
Instituto Politécnico Nacional, ESIQIE, Laboratorio de Termodinámica, Edif. Z, Secc. 6, 1ER piso, UPALM, Col. Lindavista, C.P. 07738, México DF, Mexico

Available online 24 December 2004

Abstract

Solubility measurements of sulfur compounds in supercritical fluids are required in order to determine the feasibility of supercritical
extraction for removing them from gasoline and diesel fuel. In this work, solubility of thiophene in CO2 and in CO2 + 1-propanol mixtures
were measured from 313 to 363 K using an apparatus based on the static–analytical method. Vapor–liquid equilibria (VLE) data of binary
mixtures were fitted to the Peng–Robinson equation of state (EoS) with classical mixing rules. The binary interaction parameters (kij ) obtained
were used to predict the VLE data of ternary systems. The calculated values given by this simple model agree well to the experimental data.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Solubility; Sulfur compounds; Equation of state

1. Introduction gas chromatograph HP 6890 equipment. It is shown that thio-

Phase equilibrium data are of great significance in the
petroleum industry for development and validation of ther-
modynamic models. Separation processes, design, and su-
percritical fluid extraction, in particular, strongly depend on
accurate vapor–liquid and vapor–liquid–liquid equilibrium
data.
Sulfur compounds extraction from oil fractions is very
important in the petroleum refining industry, especially the
extraction of thiophene and benzothiophene from gasoline
and diesel fuel. In Mexico, the Maya oil has about 4% of total
sulfur; therefore an economical process without environmen-
tal impact for sulfur removing is required. The most common
process for sulfur removal from gasoline uses a metal catalyst
in the presence of hydrogen at high temperature (≈600 K),
where the supercritical extraction might be a competitive op-
tion to eliminate these compounds at lower temperature.
An analysis of sulfur compounds from a Mexican com-
mercial premium gasoline is presented in Fig. 1. This was
done using a pulsed flame photometric detector (PFPD) in a
∗ Corresponding author. Tel.: +52 55 5729 6000x55133;
fax: +52 55 5586 2728.
E-mail address: lgalicial@ipn.mx (L.A. Galicia-Luna).
phene and benzothiophene are the major sulfur compounds
in this gasoline. Based on these results, a systematic experi-
mental study of solubility of thiophene and benzothiophene
in supercritical CO2 and CO2 + alcohol is being carried out.
In this work, experimental solubility data of thiophene in car-
bon dioxide and carbon dioxide + 1-propanol mixtures from
313 to 363 K are presented. These systems have not been
reported in literature.
2. Experimental method and apparatus
Measurements were made in an apparatus showed in Fig. 2
and previously described by Elizalde-Solis et al., based on
static–analytic method [1]. It is based on the same principle
described by Galicia-Luna et al. [2]. The equilibrium cell can
be used up to 60 MPa and 673.15 K. This apparatus allows
studying systems in one, two or three phases.
A gas chromatograph (HP 5890 II) with a thermal con-
ductivity detector TCD and a 4-ft by 1/8-in. diameter packed
column packed (Chromosorb 101) was used for analysis. The
carrier gas was helium at flow rate of 30 ml/min. Pressure was
measured using a thermoregulated Druck transducer model
PDCR. This was calibrated against a Desgranges & Huot

0378-3812/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2004.11.018
52 O. Elizalde-Solis, L.A. Galicia-Luna / Fluid Phase Equilibria 230 (2005) 51–57
Fig. 1. GC chromatogram of a commercial Mexican Premium gasoline using a PFPD detector.
dead weight gauge (Model 5304 Class S2, ±0.005% F.S.
precision up to 138 MPa). Temperature was measured using
two platinum probes Pt100 (Specitec, France) immersed in
Fig. 2. Flow diagram of the equilibrium cell: AB, air bath; CT, titanium
cap; CNi, connecting nuts; ECT, titanium equilibrium cell; MCS, movable
capillary sampler; MR, magnetic rod; MSD, magnetic stirring device; OR,
O-ring; PT, pressure transducer; PTPi, platinum temperature probe; TRi,
thermal regulator i, and Vi, shut-off valve i.
thermometric wells at the top and bottom of the cell body
[1]. They were connected to a digital indicator (F250, USA,
accuracy ±0.03 K). Platinum probes were calibrated against
a 25-
reference probe (model 162CE of ±0.005 K certified
accuracy) connected to an Automatic Systems F300S cali-
bration system.
Estimated uncertainties are within ±0.03 K and ±0.04%
for temperature and pressure, respectively. Composition un-
certainties were estimated to be less than 1%, according to

Nd exp exp
|z − zcali /zi |
% error z = i=1 i × 100 (1)
Nd
where z and Nd are the variables to calculate and total num-
ber of data points, respectively. The purities of the com-
pounds used in this work were 99.7% for thiophene and
1-propanol, both supplied by Aldrich Chemical Co. Inc. Cer-
tified purities of carbon dioxide and helium were 99.995
and 99.998%, respectively. Air Products-Infra supplied both
gases. These compounds were used without any further pu-
rification, except for careful degassing of thiophene and
1-propanol.
A detailed description of the apparatus is found at the Ref.
[1] and is illustrated in Fig. 2. Thiophene was introduced into
the equilibrium cell, and then it was degassed under vacuum
and vigorously stirred with the magnetic rod. After 20 min
of degassing, the system was closed, and then reopened to
introduce CO2 into the measuring cell using an Isco syringe
 O. Elizalde-Solis, L.A. Galicia-Luna / Fluid Phase Equilibria 230 (2005) 51–57 53

Table 1 methodology. CO2 + ethanol system was compared with

Vapor–liquid equilibria for the carbon dioxide (2) + ethanol (1) system at those reported by Galicia-Luna et al. [2] and both data sets
333.15 K
are in good agreement. These results are reported in Table 1
P (MPa) x2 y2 and are plotted in Fig. 3.
3.050 0.1342 0.9768 Solubility data of thiophene in pure CO2 were determined
4.543 0.2118 0.9787 at 314.47, 334.28, 363.53 and 383.03 K and they are reported
5.318 0.2515 0.9799
7.138 0.3542 0.9780
in Table 2. At constant pressure, the solubility of this sulfur
8.515 0.4442 0.9745 compound increased while temperature was increased. More-
9.561 0.5376 0.9641 over, at constant temperature, it increased considerably over
10.406 0.7808 0.9203 the critical point of CO2 with a little pressure increasing.
However, at subcritical solvent conditions, pressure increas-
pump (100DM) until the desired pressure was achieved. A
loading cell is used for charging the CO2 + 1-propanol mix-
Table 2
ture into the equilibrium cell. It was used the same feeding cell Vapor–liquid equilibria for the thiophene (1) + carbon dioxide (2) system at
procedure used by Zúñiga-Moreno and Galicia-Luna [3] to four different temperatures
determine the liquid mole fractions xi , where i are the species P (MPa) x1 y1
of binary mixture. First, the degassed less-volatile component
T = 314.47 K
(1-propanol) is transferred by low-pressure distillation into 2.008 0.0155
the empty weighed loading cell. Then a new weighing of the 3.007 0.0133
loading cell is performed to determine the exact amount of 4.018 0.6674 0.0119
liquid introduced. Afterwards, CO2 is transferred in the same 5.022 0.5545 0.0111
manner into the feed cell. A third weighing yields the mass 6.143 0.3396 0.0118
6.772 0.2200 0.0119
of the second component and therefore the mixture compo- 7.047 0.1715 0.0131
sition. Once the cell has been charged, the solvent mixture is
T = 334.28 K
compressed to the liquid phase and loaded into the equilib-
2.088 0.8679 0.0305
rium cell. 3.079 0.8032 0.0246
A Sartorius comparator balance was used for weighing 3.977 0.7477 0.0222
purposes (model MCA1200, accuracy: ±10−7 kg). Compara- 5.142 0.6670 0.0208
tor balance was calibrated with a mass of 1 kg class E1 (Sar- 6.032 0.6010 0.0205
torius, Germany). Weighing is carried out within 10−7 kg 6.957 0.5221 0.0219
8.021 0.4029 0.0225
(maximum content of the feed cell: 100 cm3 , and mass of the 9.034 0.2585 0.0298
empty cell ∼ =1 kg). 9.601 0.1722 0.0409
T = 363.53 K
2.042 0.0757
3. Experimental results and discussion 3.030 0.0582
4.025 0.8035 0.0497
Experimental VLE data for CO2 + ethanol system at 4.980 0.7560 0.0461
333.15 K were measured in order to test experimental 5.963 0.7087 0.0438
7.066 0.6567 0.0427
7.978 0.5999 0.0420
8.934 0.5548 0.0436
10.046 0.4845 0.0460
11.027 0.4148 0.0517
11.651 0.3603 0.0639
12.194 0.2956 0.0763
12.724 0.2423 0.1001
T = 383.03 K
4.145 0.8261 0.0795
5.107 0.7849 0.0707
5.975 0.7499 0.0673
6.989 0.7099 0.0645
8.061 0.6627 0.0650
9.118 0.6164 0.0668
10.132 0.5741 0.0682
11.023 0.5290 0.0711
12.116 0.4649 0.0817
13.175 0.4014 0.0998
Fig. 3. Vapor–liquid equilibria for carbon dioxide + ethanol: the experimen- 13.933 0.3213 0.1166
tal data reported in this work at (
) 333.15 K and those published by Galicia- 14.421 0.2693 0.1461
Luna et al. [2] at (䊉) 333.82 K and ( ) 333.75 K.
54 O. Elizalde-Solis, L.A. Galicia-Luna / Fluid Phase Equilibria 230 (2005) 51–57

Table 3
Vapor–liquid equilibria for the thiophene (1) + carbon dioxide (2) + 1-propanol (3) systems at different temperaturesa
P (MPa) x1 x2 x3 y1 y2 y3
T = 314.17 K
2.027 0.7592 0.1850 0.0558
2.025 0.7588 0.1854 0.0558 0.0117 0.9869 0.0014
2.982 0.6834 0.2668 0.0498 0.0084 0.9906 0.0010
5.076 0.4737 0.4911 0.0352 0.0089 0.9901 0.0010
5.541 0.4173 0.5510 0.0317 0.0092 0.9898 0.0010
T = 333.89 K
1.827 0.7942 0.1455 0.0603 0.0240 0.9727 0.0033
2.625 0.7577 0.1868 0.0555 0.0190 0.9784 0.0026
4.866 0.5852 0.3782 0.0366 0.0169 0.9813 0.0018
6.015 0.5120 0.4572 0.0308 0.0163 0.9820 0.0017
6.962 0.4426 0.5349 0.0225 0.0178 0.9805 0.0017
7.989 0.3355 0.6505 0.0140 0.0191 0.9795 0.0014
8.397 0.2679 0.7174 0.0147 0.0209 0.9773 0.0018
T = 363.35 K
2.173 0.8840 0.1121 0.0039 0.0619 0.9374 0.0007
3.387 0.0454 0.9538 0.0008
4.241 0.7519 0.2402 0.0079 0.0413 0.9578 0.0009
6.000 0.0361 0.9628 0.0011
7.341 0.5982 0.3891 0.0127 0.0351 0.9634 0.0015
9.322 0.4751 0.5118 0.0131 0.0413 0.9566 0.0021
10.102 0.0460 0.9514 0.0026
10.782 0.3756 0.6106 0.0138 0.0503 0.9467 0.0030
11.304 0.3294 0.6569 0.0137
a Carbon dioxide (0.9769) + 1-propanol (0.0231).

Table 4
Vapor–liquid equilibria for the thiophene (1) + carbon dioxide (2) + 1-propanol (3) systems at different temperaturesa
P (MPa) x1 x2 x3 y1 y2 y3
T = 314.32 K
2.361 0.7874 0.1876 0.0250 0.0149 0.9841 0.0010
3.355 0.6710 0.2951 0.0339 0.0110 0.9870 0.0020
4.385 0.5456 0.4113 0.0431 0.0099 0.9883 0.0018
4.910 0.0097 0.9884 0.0019
5.921 0.3123 0.6394 0.0483 0.0108 0.9870 0.0022
6.423 0.2140 0.7376 0.0484 0.0114 0.9864 0.0022
6.674 0.1674 0.7862 0.0464 0.0115 0.9860 0.0025
T = 334.14 K
1.917 0.0256 0.9684 0.0060
2.778 0.0209 0.9741 0.0050
3.805 0.5633 0.2480 0.1887 0.0189 0.9765 0.0046
4.778 0.4862 0.3519 0.1619 0.0180 0.9776 0.0044
5.784 0.4250 0.4336 0.1414 0.0177 0.9779 0.0044
6.815 0.3540 0.5285 0.1175 0.0183 0.9770 0.0047
7.814 0.2727 0.6379 0.0894 0.0206 0.9739 0.0055
8.798 0.1997 0.7330 0.0673 0.0243 0.9689 0.0068
9.289 0.1470 0.8052 0.0478 0.0274 0.9647 0.0079
T = 363.67 K
3.432 0.0626 0.9337 0.0037
4.458 0.0464 0.9496 0.0040
5.448 0.0430 0.9525 0.0045
6.433 0.0417 0.9531 0.0052
7.423 0.5537 0.3886 0.0577 0.0413 0.9528 0.0059
8.587 0.4853 0.4515 0.0632 0.0419 0.9512 0.0069
9.834 0.4033 0.5294 0.0673 0.0443 0.9474 0.0083
10.736 0.3277 0.6070 0.0653 0.0500 0.9395 0.0105
11.667 0.2589 0.6822 0.0589 0.0599 0.9257 0.0144
12.533 0.1697 0.7844 0.0459 0.0851 0.8913 0.0236
a Carbon dioxide (0.9350) + 1-propanol (0.0650).
 O. Elizalde-Solis, L.A. Galicia-Luna / Fluid Phase Equilibria 230 (2005) 51–57 55

Fig. 4. Solubility of thiophene at ≈314 K in CO2 and CO2 + 1-propanol Fig. 6. Experimental and calculated K1 values for thiophene in carbon diox-
mixtures at different CO2 concentrations: (
) 0.9769, ( ) 0.9350 and (䊉), ide (0.9769) + 1-propanol (0.0231) at (
) 314.17 K, ( ) 333.89 K, (䊉)
pure CO2 . 363.35 K and (—) Peng–Robinson EoS.

ing did not benefit solubility of thiophene. In general, almost

every VLE systems have this distinctive behavior at dew point with both pressure (P) and temperature (T) changes at high
[4]. pressures, and at subcritical solvent conditions K1 had similar
Then, solubility data for thiophene (1) in CO2 (2) + 1- effect as in y1 solubility data with P and T changes. In those
propanol (3) (solvent) mixtures were obtained at 314, 334 figures, K1 values for thiophene are a little higher for the
and 363 K. These are reported in Tables 3 and 4. Mixtures system 1 than for the system 2 at equal P and T conditions,
containing 2.3 mol% in system 1, and 6.5 mol% in system so adding 1-propanol benefits the solubility of this sulfur
2 of 1-propanol as co-solvent were selected to determine if compound in CO2 .
the solubility of thiophene could be improved by adding 1-
propanol, as illustrated in Figs. 4 and 5. These mixtures were
prepared into a loading cell to charge them into the equi-
librium cell as described at previous section. The loading
cell was restrained to its volume capacity. Therefore, only
few data points were determined at high pressures for the
2.3 mol% of 1-propanol mixture.
Experimental equilibrium ratios (K1 = y1 /x1 ) for thiophene
in ternary mixtures plotted in Figs. 6 and 7 were proportional

Fig. 7. Experimental and calculated K1 values for thiophene in carbon diox-

ide (0.9350) + 1-propanol (0.0650) at (
) 314.32 K, ( ) 334.14 K, (䊉)
363.67 K and (—) Peng–Robinson EoS.

Table 5
Binary interaction parameters used to predict thiophene + carbon diox-
ide + 1-propanol systems
Mixtures kij
Thiophene + 1-propanol 0.08114
Fig. 5. Solubility of thiophene at ≈363 K in CO2 and CO2 + 1-propanol Carbon dioxide + 1-propanol 0.11104
mixtures at different CO2 concentrations: (
) 0.9769, ( ) 0.9350 and (䊉) Carbon dioxide + thiophene 0.07508
pure CO2 .
56 O. Elizalde-Solis, L.A. Galicia-Luna / Fluid Phase Equilibria 230 (2005) 51–57

Table 6
Comparison between experimental and calculated values in pressure and solubility of thiophene in carbon dioxide + 1-propanol mixtures at different temperatures
T (K) P (MPa) % error (P) y1 % error (y1 )
Exp. P–R EoS Exp. P–R EoS
314.17a 2.025 2.120 4.7 0.0117 0.0133 14.4
2.982 3.016 1.1 0.0084 0.0108 29.0
5.076 5.250 3.4 0.0089 0.0093 5.0
5.541 5.751 3.7 0.0092 0.0095 3.2
333.89a 1.827 2.167 18.6 0.0240 0.0268 11.9
2.625 2.772 5.6 0.0190 0.0228 20.4
4.866 5.522 13.4 0.0169 0.0178 5.5
6.015 6.597 9.6 0.0163 0.0183 12.2
6.962 7.576 8.8 0.0178 0.0198 11.5
7.989 8.849 10.7 0.0191 0.0241 26.4
8.397 9.472 12.8 0.0209 0.0278 33.1
363.35a 2.173 2.277 4.8 0.0619 0.0680 9.9
4.241 4.821 13.6 0.0413 0.0434 5.2
7.341 7.825 6.6 0.0351 0.0404 15.1
9.322 10.238 9.8 0.0413 0.0464 12.4
10.782 12.040 11.6 0.0503 0.0580 15.4
314.32b 2.361 2.128 −9.9 0.0149 0.0139 −6.2
3.355 3.310 −1.3 0.0110 0.0106 −3.3
4.385 4.526 3.2 0.0099 0.0094 −5.1
5.921 6.474 9.3 0.0108 0.0094 −12.7
6.423 7.052 9.8 0.0114 0.0095 −16.0
6.674 7.276 9.0 0.0115 0.0095 −17.3
334.14b 3.805 3.849 1.2 0.0189 0.0157 −16.7
4.778 5.415 13.3 0.0180 0.0144 −19.9
5.784 6.595 14.0 0.0177 0.0147 −16.9
6.815 7.866 15.4 0.0183 0.0162 −11.2
7.814 9.113 16.6 0.0206 0.0199 −3.1
8.798 9.945 13.0 0.0243 0.0254 4.9
9.289 10.363 11.6 0.0274 0.0322 17.9
363.67b 7.423 7.933 6.9 0.0413 0.0377 −8.7
8.587 9.231 7.5 0.0419 0.0391 −6.7
9.834 10.802 9.8 0.0443 0.0433 −2.1
10.736 12.263 14.2 0.0500 0.0516 3.3
11.667 13.504 15.7 0.0599 0.0656 9.7
12.533 14.697 17.3 0.0851 0.1020 19.9
a Carbon dioxide (0.9769) + 1-propanol (0.0231).
b Carbon dioxide (0.9350) + 1-propanol (0.0650).

4. Modeling

The isothermal VLE data were correlated using the

Peng–Robinson (P–R) EoS [5] combined with classical mix-
ing rules. This kind of EoS is not suitable to predict VLE at
critical point region. Binary interaction parameters (kij ) were
fitted to VLE experimental data reported in literature [4,6]
and in this work using data points at lower temperatures.
VLE data at the highest temperature was well predicted. kij
values for binary systems are reported in Table 5. Critical
properties were taken from literature [7,8].
In the ternary mixtures: thiophene (1) + [CO2 (2) + 1-
propanol (3)] containing 2.3 and 6.5 mol% of 1-propanol
as co-solvent, solubility values of thiophene were pre-
dicted from kij presented in Table 5. Experimental and pre-
dicted y1 values are plotted in Fig. 8. Vapor mole frac- Fig. 8. Comparison between experimental and calculated solubility of thio-
tion (y1 ) and pressure (P) deviations calculated by Eq. phene in carbon dioxide (0.9350) + 1-propanol (0.0650) at (
) 314.32 K,
(1) are reported in Table 6. Calculated K1 values have ( ) 334.14 K, (䊉) 363.67 K and (—) Peng–Robinson EoS.
 O. Elizalde-Solis, L.A. Galicia-Luna / Fluid Phase Equilibria 230 (2005) 51–57
similar behavior as experimental data, these are compared in
Figs. 6 and 7.
5. Conclusions
In this work, new experimental solubility data are reported
for thiophene in CO2 and CO2 + 1-propanol mixtures at tem-
peratures from 313 to 363 K. These mixtures contained 2.3
and 6.5 mol% of 1-propanol as co-solvent. The addition of
small amounts (up to 6.5 mol% fraction) of 1-propanol as co-
solvent did not improve the solubility of thiophene against
pure CO2 , this implies that 1-propanol is not a good co-
solvent for extraction. On the other hand, the solubility of
thiophene was improved as more 1-propanol was added, sug-
gesting that higher concentrations of 1-propanol could pro-
vide a favor for the separation of thiophene. However, it
is not desirable to add large amounts of co-solvent for su-
percritical fluids applications, so this alcohol may not be
useful.
At subcritical and supercritical solvent (pure CO2 or
CO2 + 1-propanol mixtures) pressures has similar solubility
values. This can be seen in Table 2 at 363.53 K with 4.98
and 10.046 MPa. However, supercritical solvent conditions
are suitable for further applications. It means that with a
little change in pressure, solute (liquid) would be separated
from solvent (vapor). It does not occur at subcritical solvent
conditions, where both solvent and solute are in liquid–vapor
mixture.
57
The Peng–Robinson EoS with classical mixing rules was
used to model the binary VLE data and the kij obtained were
used to predict ternary mixtures. The predicted y1 values
given by this simple model and the calculated K1 values are in
agreement to the experimental data over all range of pressure
and temperature studied in this work.
Acknowledgments
The authors are grateful to reviewers for their useful com-
ments and thank CONACYT and IPN for their financial sup-
port.
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