Fluid Phase Equilibria 384 (2014) 134142

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Isothermal vaporliquid equilibrium for binary mixtures containing

furfural and its derivatives
Wen-Ping Tai, Hao-Yeh Lee, Ming-Jer Lee *
Department of Chemical Engineering, National Taiwan University of Science and Technology, 43 Keelung Rd., Sec. 4, Taipei 106-07, Taiwan

A R T I C L E I N F O A B S T R A C T

Article history: The isothermal vaporliquid equilibrium (VLE) data were measured for the binary systems of
Received 5 August 2014 2-methylfuran + furfuryl alcohol, isopropyl alcohol + furfuryl alcohol, and furan + furfural at 353.2, 373.2,
Received in revised form 23 October 2014 and 408.2 K over entire composition range, including the vapor pressures of ve constituent compounds.
Accepted 25 October 2014
The experimental results of the investigated binary systems show no azeotrope formation and positive
Available online 29 October 2014
deviations from Raoults law. The thermodynamic consistency of these new binary VLE data has been
conrmed by point, area, and innite dilution tests. The WilsonHOC, the NRTL-HOC, and the UNIQUAC-
Keywords:
HOC models were used to correlate the VLE data. Comparable results were obtained from these three
VLE
2-Methylfuran
models.
Furfuryl alcohol 2014 Elsevier B.V. All rights reserved.
Furan
Furfural

1. Introduction 2. Experimental section

As fossil fuels are gradually depleted, biomass will inevitably
become an alternative resource to provide a kind of renewable
energy and raw materials for chemical industries in the future.
Furfural is one of the key intermediates to connect the bio-resource
to bio-fuels or chemical products [1]. In this green manufacturing
route, furfural alcohol can be synthesized via hydrogenation of
furfural using isopropyl alcohol as a solvent. Simultaneously,
several by-products, including 2-methylfuran and furan, may also
be generated from this series of chemical reactions [2]. To provide
reliable VLE data for the related process development, we
measured the isothermal VLE for three binary systems:
2-methylfuran + furfuryl alcohol, isopropyl alcohol + furfuryl alco-
hol, and furan + furfural at 353.2, 373.2, and 408.2 K over entire
composition range, including the vapor pressures of ve constitu-
ent compounds. No VLE data at the comparable conditions are
available in literature for the above mentioned mixtures. All the
new binary VLE data were validated by thermodynamic consis-
tency tests and then correlated with the WilsonHOC [3], the
NRTL-HOC [4], and the UNIQUAC-HOC [5] models. The optimal
values of binary parameters were obtained from the data
correlation.
2.1. Chemicals
2-Methylfuran (purity: 0.99 in mass fraction) was purchased
from ACROS (USA) and furan (purity: 0.99 in mass fraction) from
Alfa Aesar (USA). Furfural (purity: 0.99 in mass fraction), furfural
alcohol (purity: 0.98 in mass fraction), and isopropyl alcohol
(purity: 0.999 in mass fraction) were supplied by SigmaAldrich
(USA). The purity levels of these chemicals were conrmed by
chromatographic analysis. All the chemicals were used without
further purication. The materials description is given in Table 1
for each pure compound. The density of each compound has been
measured with a vibrating-tube densimeter (DMA 4500, Anton
Paar, Austria) to an uncertainty of 0.1% and compared with
literature value in Table 1. The deviations between experimental
and literature values are from 0.01 to 0.19%. It should also be noted
that furfural and furfural alcohol are light-sensitive compounds.
We handled these two substances with care. The degassing process
was operated in dark and the ask was warped with aluminum foil.
The color will become from yellowish, initially, to brownish after
the measurement process, especially at higher temperature
408.2 K. A small impurity peak can be detected from the phase
equilibrium samples by GC, but the amount of the impurity is less
than 0.7% in the worst case.

2.2. Apparatus and procedure

* Corresponding author. Tel.: +886 2 2737 6626; fax: +886 2 2737 6644. A static VLE apparatus was employed in the present study to
E-mail address: mjlee@mail.ntust.edu.tw (M.-J. Lee). measure the VLE data. The equipment is similar to that of Lee and

http://dx.doi.org/10.1016/j.uid.2014.10.037
0378-3812/ 2014 Elsevier B.V. All rights reserved.
 W.-P. Tai et al. / Fluid Phase Equilibria 384 (2014) 134142 135

thermometer (Model-1560, Hart Scientic, USA) with a platinum

Nomenclature
RTD probe to an accuracy of
0.02 K. Two pressure transducers
(Model: PDCR-912, pressure ranges: 0101.325 kPa and 02.0 MPa,
A index of area consistency test
Druck, UK) with digital indicators (Model: DPI-280, Druck, UK)
A1A9 parameters of the extended Antoine equation
displayed the equilibrium pressure to an accuracy of
0.1%. While
Aij interaction variables in Wilson model
the vapor sample was taken with a six-way sampling valve (Model
aij parameters of the activity coefcient model
6T, operable up to 573 K and 2067 kPa, sample size 100 ml, VICI AG
bij parameters of the activity coefcient model (K)
International, Switzerland), the liquid sample was taken with a
C0C2 variables used in consistency tests
four-way sampling valve (Model 6CI4UWT1/2, operable up to
D0D3 variables used in consistency tests
603 K and 2067 kPa, sample size 0.5 ml, VICI AG International,
G molar Gibbs free energy (J mol1)
Switzerland). Compositions of both vapor and liquid samples were
I1 and I2 indices of innite dilution consistency test
analyzed by a gas chromatography (Model: 8700T, China
MW molecular weight (g mol1)
Chromatography, Taiwan) with a thermal conductivity detector
n number of data points
(TCD). A stainless steel column Porapak QS (80/100 mesh,
P pressure (kPa)
1.5 m  1/8  I.D. 2 mm) was used for sample analysis. High purity
q surface area parameter of UNIQUAC model
helium (99.99% purity, Gu-Fong Gas Company, Taiwan) was used as
r volume parameter of UNIQUAC model
carrier gas. Four samples were replicated for individual phase at
R gas constant (kPa cm3 mol1 K1 or J mol1 K1)
each experimental condition. The averaged area fraction of the
Rg radius of gyration ()
replication samples was converted into mole fraction via
T temperature (K)
calibration equations. The uncertainties of the reported mole
Tb normal boiling temperature (K)
fractions for liquid and vapor phases are within 0.005 and 0.005,
V molar volume (cm3 mol1)
respectively.
x mole fraction of liquid phase
y mole fraction of vapor phase
Z compressibility factor
3. Results and discussion

Greek letters
The isothermal VLE data are measured in the present study for
a parameter of NRTL model the binary systems of 2-methylfuran + furfuryl alcohol, isopropyl
g activity coefcient
alcohol + furfuryl alcohol, and furan + furfural at 353.2, 373.2, and
d index of point consistency test 408.2 K over entire composition range. Table 2 lists the coefcients
D deviation
of the extended Antoine equation for each constituent compound
h association parameter of HOC model where the equation is dened as
m dipole moment (Debye) " #  
p objective function Psat kPa A2
r density (g cm3) ln A1 A4 T A5 lnT
100 T K A3
s standard deviation
A6 T A7 forA8
t ij
interaction variables in NRTL and UNIQUAC models  T  A9 (1)
^
f fugacity coefcient of component i
i
v acentric factor

The values of A1A9 are available from the Aspen thermody-

Subscripts
namic databank, except for 2-methylfuran. The vapor pressures of
c critical property
all pure compounds are also determined experimentally in this
cal calculated value
study. As shown in Table 3, the measured vapor pressures of
i component i
furfuryl alcohol, furan, furfural, and isopropyl alcohol agree well
exp experimental value
with the smoothed literature values, which are calculated from the
ij i-j pair
extended Antoine equation using the coefcients listed in Table 2.
P pressure
Eon et al. [12] reported the vapor pressures of 2-methylfuran at
T temperature
temperatures from 333.45 to 373.45 K and the Antoine constants
x1 liquid composition of component 1
determined from these data have been collected in the NIST
y1 vapor composition of component 1
Chemistry WebBook [13]. Kobe et al. [14] measured the vapor
pressures from 336.72 to 527.59 K. In this study, we measured 23
Superscripts
new data points for 2-methylfuran at temperatures from 353 to
cal calculated value
409 K as given in Table 4. The coefcients of the extend Antoine
E excess property
equation for 2-methylfuran are obtained by tting these new data
exp experimental value
to Eq. (1) and listed in Table 2. Table 4 and Fig. 1 compare the
L liquid phase
experimental values with the correlated results from the extended
sat saturation
Antoine equation and those from of the Antoine equation using the
constants taken from NIST Chemistry WebBook [13] and the data
reported by Kobe et al. [14]. The deviations are all within 1.0% over
the entire temperature range.
The isothermal VLE data are listed in Tables 57 for the binary
Hu [10] and several modications have been made by Hwang et al. systems of 2-methylfuran + furfuryl alcohol, isopropyl alcohol +
[11]. A stainless steel made equilibrium cell was placed in a furfuryl alcohol, and furan + furfural, respectively. The tabulated
thermostatic bath (Model: B503S, stability =
0.03 K, Firstek, activity coefcients (gi) were calculated from the criteria of phase
Taiwan). The bath temperature was measured by a precision equilibria, i.e.,
136 W.-P. Tai et al. / Fluid Phase Equilibria 384 (2014) 134142

Table 1
Description of the materials useda .

Compound Supplier Purity in mass fraction Purication method rexp (g/cm3) rlit(g/cm3) Data source
2-Methylfuran Acros, USA 0.99 Degas 0.9132 0.91500 [6]
Furan Alfa Aesar, USA 0.99 Degas 0.9331 0.9340 [7]
Furfural SigmaAldrich, USA 0.99 Degas 1.1546 1.15525 [8]
Furfural alcohol SigmaAldrich, USA 0.98 Degas 1.1320 1.13028 [8]
Isopropyl alcohol SigmaAldrich, USA 0.999 Degas 0.7809 0.78082 [9]
a
u(r) = 0.1%.

Table 2
Parameters of the extended Antoine equationa .

Compound A1 A2 A3 A4 A5 A6 A7 A8 (K) A9 (K)

2-Methylfuranb 17.4859 225.3 248.3232 0.0306 6.8370 14.7121 0.0033 353.0 409.2
Furanc 63.2251 5417.0 0 0 8.0636 7.5E-06 2 187.0 490.2
Furfuralc 83.0571 8372.1 0 0 11.1300 8.8E-03 1 236.0 670.2
Furfural alcoholc 63.5521 8846.6 0 0 7.2425 2.8E-06 2 258.0 632.2
Isopropyl alcoholc 99.2071 9040.0 0 0 12.6760 5.5E-06 2 185.2 508.3
 
a
Extended Antoine equation: lnPsat kPa=100 A1 A2 = TK A3  A4 T A5 lnT A6 T A7 forA8  T  A9 .
b
Determined from the vapor pressure data measured in this work.
c
Taken from thermodynamic databank of Aspen Plus process simulation package.

^ yP
f
gi i i
(2) estimated from the Hayden and OConnell model [16]. The molar
xi f
sat sat
i P i exp
V Li P  Psat
i =RT
excess Gibbs free energies, GE, listed in Tables 57 were calculated
from the following denition:
where xi, yi, and Psat
i are liquid mole fraction, vapor mole fraction, X
2
and vapor pressure for component i, respectively. The liquid molar G E RT xi lng i (3)
volume, V Li , was estimated from the modied Rackett model [15]. i1
sat
The variables fi and f ^ are the fugacity coefcients of pure i at
i
saturation condition and the fugacity coefcient of component i in Figs. 24 are the phase diagrams of 2-methylfuran + furfuryl
the vapor phase. These two fugacity coefcients were calculated alcohol, isopropyl alcohol + furfuryl alcohol, and furan + furfural,
from two-term virial equation with the second virial coefcient respectively. All these investigated systems exhibit positive

Table 3
Vapor pressures of furan, furfural, furfuryl alcohol, and isopropyl alcohola .
Psat
exp (kPa) Dev Pc (%)
T (K) Psat b
cal (kPa)

Furan
353.4 455.1 455.7 0.13
373.1 735.6 735.1 0.07
407.9 1513.3 1513.6 0.02

Furfural
353.2 5.9 5.9 0.00
373.4 13.6 13.7 0.74
408.0 46.3 46.3 0.00

Furfuryl alcohol
353.3 2.6 2.6 0.00
373.0 7.0 7.0 0.00
407.9 30.1 30.2 0.33

Isopropyl alcohol
353.3 93.8 94.0 0.21
373.5 200.1 200.9 0.40
408.3 593.8 594.3 0.08
a
u(T) = 0.1 K; u(P) = 0.1%.
b
Calculated from theextended Antoine  equation.
c
DevP% 100%  Psat sat sat
cal  P exp =P exp .
 W.-P. Tai et al. / Fluid Phase Equilibria 384 (2014) 134142 137

Table 4
Vapor pressures of 2-methylfurana .

T (K) Psat b
exp (kPa) Psat c
cal (kPa)
Dev Pd (%) Psat
lit
e
(kPa) Dev Pf (%)

353.8 161.8 162.3 0.31 163.3 0.93

353.8 162.6 162.5 0.06 163.6 0.62
357.5 181.5 181.7 0.11 181.9 0.22
357.5 181.7 181.9 0.11 182.1 0.22
358.3 186.5 186.4 0.05 186.4 0.05
362.4 210.5 210.6 0.05 209.9 0.29
362.5 211.1 210.7 0.19 209.9 0.57
363.1 214.9 214.5 0.19 213.6 0.60
367.2 242.1 241.3 0.33 240.0 -0.87
367.4 242.7 242.2 0.21 240.9 0.74
367.9 246.0 245.5 0.20 244.1 0.77
373.4 285.3 285.3 0.00 283.7 0.56
373.6 286.4 286.4 0.00
373.9 288.4 289.3 0.31
398.2 527.6 527.1 0.09
398.4 530.3 530.1 0.04
398.8 533.8 534.6 0.15
403.0 587.6 589.1 0.26
403.2 591.7 592.0 0.05
403.3 592.3 593.5 0.20
408.4 667.2 666.4 0.12
408.6 670.2 669.4 0.12
409.0 676.7 675.5 0.18
AARDg (%) = 0.14 AARDg (%) = 0.53
a
u(T) = 0.1 K; u(P) = 0.1 %.
b
Experimental data obtained from this work.
c
Correlated results from the extended  Antoine equation.
d
DevP% 100%  Psat sat sat
cal  P exp =Pexp .
e
Calculated from the Antoine equation  by using parameters reported in NIST Chemistry WebBook [13] (original data source: Eon et al. [12]).
f
DevP% 100%  Psat sat sat
lit P exp =Pexp . 
n
g
AARD% 100%=nSi1 jPX  Pexp j=Psat
sat sat
exp , where subscript X represents cal or lit, and n is the number of data points.
i

deviations from Raoults law. In each binary system, no azeotrope

is formed and the light component is dominant in the vapor phase.
[(Fig._1)TD$IG] According to the experimental results, the compounds in the
1000 related mixtures can be separated efciently by using distillation
technique.
Thermodynamic consistency tests were made for all the new
VLE data. The testing method has been detailed in Kojima et al. [17]
and Lee and Hu [10]. Table 8 gives the results of the
thermodynamic consistency test. All the binary VLE data passed
the thermodynamic consistency evaluation, including the point,
the area, and the innite dilution tests.
P/kPa

4. Vaporliquid equilibrium data correlation

The gw method was employed to correlate the new binary VLE

data. Three activity coefcient models, including the Wilson, the
NRTL, and the UNIQUAC, were selected to represent the non-
ideality of liquid mixtures, while the fugacity coefcient in the
vapor phase were estimated from the two-term virial equation
accompanying with the HaydenOConnell (HOC) model for
calculating the second virial coefcient. The optimal values of
the binary parameters were determined by the minimization of the
100 following objective function p:
340 360 380 400 420 8" # " cal #2 " cal #2 " cal #2 9
n <
X exp 2
x1;k  xexp y1;k  yexp =
T/K Pcal
k P T k  T exp 1;k 1;k
p k
k

k1
: sp sT s x1 sy1 ;
Fig. 1. Comparison of experimental vapor pressures with literature values for 2-
methylfuran (open circle: experimental point; open square: literature value [13]; (4)
open triangle: literature value [14]; solid line: correlation with extended Antoine
equation).
138 W.-P. Tai et al. / Fluid Phase Equilibria 384 (2014) 134142

Table 5
VLE data of 2-methylfuran (1) + furfural alcohol (2)a .

T(K) P(kPa) x1 y1 g1 g2 ln(g 1/g 2) (GE/RT)/x1x2

353.2 2.6b 0.0 0.0
19.3a 0.058 0.869 1.832 1.015 0.590 0.903
32.0a 0.112 0.925 1.673 1.021 0.494 0.767
53.8a 0.207 0.959 1.576 1.049 0.407 0.805
62.2a 0.259 0.966 1.466 1.076 0.310 0.798
83.8a 0.397 0.978 1.303 1.150 0.125 0.792
97.3a 0.482 0.983 1.252 1.200 0.042 0.812
111.1a 0.572 0.987 1.208 1.267 0.047 0.855
127.8a 0.712 0.991 1.120 1.497 0.290 0.960
146.4a 0.865 0.995 1.059 2.029 0.650 1.245
150.0a 0.929 0.996 1.011 3.162 1.140 1.399
159.1b 1.0 1.0
373.2 7.1b 0.0 0.0
25.7a 0.032 0.729 2.218 1.007 0.790 1.042
54.2a 0.111 0.878 1.611 1.023 0.454 0.746
86.4a 0.208 0.929 1.437 1.046 0.318 0.673
112.5a 0.290 0.949 1.362 1.074 0.237 0.681
159.0a 0.399 0.968 1.409 1.095 0.252 0.797
179.2a 0.475 0.974 1.334 1.134 0.163 0.814
198.1a 0.571 0.979 1.227 1.225 0.001 0.833
224.9a 0.709 0.985 1.121 1.442 0.252 0.907
254.7a 0.854 0.991 1.051 1.919 0.602 1.106
270.6a 0.929 0.995 1.026 2.308 0.810 1.268
283.3b 1.0 1.0
408.2 30.4b 0.0 0.0
62.5a 0.028 0.522 1.994 0.996 0.694 0.572
148.9a 0.112 0.809 1.807 1.002 0.589 0.685
241.6a 0.210 0.891 1.689 1.005 0.519 0.688
297.9a 0.300 0.916 1.481 1.054 0.340 0.737
380.5a 0.402 0.942 1.427 1.053 0.304 0.724
424.7a 0.468 0.951 1.369 1.097 0.221 0.788
467.1a 0.571 0.960 1.235 1.201 0.027 0.812
515.2a 0.704 0.969 1.104 1.460 0.28 0.872
581.2a 0.841 0.980 1.040 1.929 0.618 1.027
626.6a 0.925 0.989 1.019 2.383 0.849 1.190
662.3b 1.0 1.0
a
u(T) = 0.1 K; u(P) = 0.1%; u(x1) = 0.005; u(y1) = 0.005.
b
Calculated from the extended Antoine equation.

Table 6
VLE data of isopropyl alcohol (1) + furfuryl alcohol (2)a .

T(K) P(kPa) x1 y1 g1 g2 ln (g 1/g 2) (GE/RT)/x1x2

353.2 2.6b 0.0 0.0
9.5a 0.062 0.737 1.247 1.004 0.217 0.293
18.6a 0.148 0.877 1.213 1.005 0.188 0.260
23.6a 0.196 0.908 1.201 1.007 0.176 0.263
33.9a 0.296 0.943 1.182 1.016 0.152 0.291
45.0a 0.412 0.963 1.147 1.039 0.098 0.327
52.5a 0.499 0.972 1.112 1.071 0.037 0.350
58.0a 0.561 0.977 1.096 1.105 0.008 0.387
67.1a 0.658 0.984 1.085 1.134 0.044 0.431
73.5a 0.755 0.989 1.039 1.187 0.133 0.383
84.5a 0.901 0.996 1.004 1.218 0.193 0.260
93.3b 1.0 1.0
373.2 7.1b 0.0 0.0
27.0a 0.084 0.756 1.287 1.007 0.245 0.354
35.2a 0.123 0.820 1.240 1.006 0.208 0.297
46.5a 0.181 0.871 1.178 1.014 0.150 0.276
60.1a 0.250 0.907 1.144 1.024 0.111 0.272
87.9a 0.392 0.947 1.105 1.036 0.064 0.254
100.4a 0.460 0.958 1.084 1.048 0.033 0.252
116.6a 0.541 0.968 1.077 1.081 0.004 0.305
140.8a 0.669 0.980 1.057 1.116 0.055 0.332
153.3a 0.740 0.985 1.042 1.152 0.101 0.350
179.8a 0.904 0.995 1.003 1.202 0.181 0.234
198.4b 1.0 1.0
408.2 30.4b 0.0 0.0
92.0a 0.099 0.693 1.206 1.005 0.182 0.259
108.3a 0.125 0.745 1.205 1.005 0.181 0.257
157.1a 0.206 0.837 1.179 1.008 0.157 0.247
242.4a 0.350 0.909 1.143 1.027 0.108 0.280
262.1a 0.387 0.920 1.127 1.027 0.093 0.263
304.8a 0.461 0.938 1.112 1.035 0.071 0.272
 W.-P. Tai et al. / Fluid Phase Equilibria 384 (2014) 134142 139

Table 6 (Continued)
T(K) P(kPa) x1 y1 g1 g2 ln (g 1/g 2) (GE/RT)/x1x2
346.1a 0.536 0.951 1.092 1.062 0.027 0.302
402.4a 0.651 0.967 1.050 1.083 0.030 0.263
433.5a 0.715 0.974 1.031 1.112 0.075 0.256
512.3a 0.857 0.987 1.014 1.271 0.226 0.375
591.4b 1.0 1.0
a
u(T) = 0.1 K; u(P) = 0.1%; u(x1) = 0.005; u(y1) = 0.005.
b
Calculated from the extended Antoine equation.

Table 7
VLE data of furan (1) + furfural (2)a .

T(K) P(kPa) x1 y1 g1 g2 ln(g 1/g 2) (GE/RT)/x1x2

b
353.2 5.9 0.0 0.0
44.7a 0.08 0.875 1.180 1.012 0.153 0.327
85.4a 0.164 0.939 1.169 1.016 0.141 0.282
135.4a 0.271 0.965 1.141 1.031 0.101 0.295
194.8a 0.401 0.979 1.111 1.049 0.057 0.296
214.4a 0.459 0.982 1.067 1.085 0.016 0.297
248.0a 0.541 0.986 1.044 1.130 0.079 0.319
291.3a 0.642 0.990 1.028 1.187 0.144 0.344
315.7a 0.703 0.992 1.014 1.225 0.189 0.335
360.0a 0.802 0.995 1.007 1.279 0.239 0.342
410.4a 0.918 0.998 0.995 1.371 0.320 0.285
452.4b 1.0 1.0
373.2 13.5b 0.0 0.0
84.7a 0.073 0.845 1.501 1.014 0.392 0.631
148.9a 0.155 0.915 1.330 1.043 0.243 0.608
212.2a 0.248 0.944 1.208 1.070 0.121 0.525
319.2a 0.405 0.968 1.119 1.110 0.008 0.447
348.7a 0.459 0.972 1.077 1.152 0.068 0.446
408.5a 0.548 0.979 1.053 1.181 -0.115 0.418
471.1a 0.656 0.985 1.009 1.244 0.210 0.359
514.1a 0.721 0.988 0.997 1.315 0.277 0.369
591.3a 0.820 0.993 0.999 1.323 0.281 0.337
668.1a 0.920 0.997 0.996 1.395 0.337 0.314
735.8b 1.0 1.0
408.2 46.4b 0.0 0.0
185.8a 0.080 0.754 1.392 1.020 0.311 0.605
273.7a 0.140 0.835 1.281 1.048 0.201 0.624
432.5a 0.257 0.900 1.162 1.105 0.050 0.590
648.6a 0.411 0.942 1.106 1.133 0.025 0.475
709.4a 0.457 0.950 1.087 1.138 0.045 0.437
823.3a 0.547 0.961 1.050 1.192 0.127 0.427
963.1a 0.653 0.972 1.020 1.251 0.204 0.400
1058.6a 0.719 0.978 1.011 1.296 0.248 0.398
1220.8a 0.821 0.987 1.007 1.319 0.270 0.374
1402.8a 0.931 0.995 1.002 1.430 0.355 0.417
1521.0b 1.0 1.0
a
u(T) = 0.1 K; u(P) = 0.1%; u(x1) = 0.005; u(y1) = 0.005.
b
Calculated from the extended Antoine equation.

Table 8
Results of thermodynamics consistency tests.

Consistency test indexa GE/RT coefcientb ln(g 1/g 2) coefcientc

T (K) d A I1 I2 C0 C1 C2 D0 D1 D2 D3
2-Methylfuran (1) + furfuryl alcohol (2)
353.2 4.92 (+) 0.55 (+) 5.8 (+) 7.4 (+) 0.710 0.336 0.394 0.005 0.791 0.269 0.287
373.2 4.08 (+) 0.73 (+) 17.1 (+) 18.5 (+) 0.759 0.227 0.423 0.007 0.727 0.180 0.275
408.2 4.22 (+) 2.10 (+) 11.2 (+) 7.7 (+) 0.787 0.293 0.137 0.021 0.853 0.231 0.068

Isopropyl alcohol (1) + furfuryl alcohol (2)

353.2 4.90 (+) 2.61 (+) 8.9 (+) 16.0 (+) 0.358 0.037 0.127 0.026 0.259 0.035 0.037
373.2 2.24 (+) 2.34 (+) 7.5 (+) 11.8 (+) 0.280 0.007 0.011 0.023 0.237 0.010 0.052
408.2 2.20 (+) 1.37 (+) 9.5 (+) 8.5 (+) 0.257 0.059 0.060 0.014 0.271 0.102 0.053

Furan (1) + furfural (2)

353.2 1.92 (+) 1.24 (+) 18.2 (+) 11.3 (+) 0.226 0.028 0.027 0.012 0.264 0.044 0.063
373.2 2.47 (+) 0.40 (+) 3.2 (+) 25.3 (+) 0.327 0.152 0.033 0.004 0.369 0.105 0.019
408.2 1.52 (+) 1.35 (+) 21.2 (+) 5.4 (+) 0.338 0.109 0.066 0.013 0.316 0.070 0.051

(+): passes the consistency test.

a
Criteria for passing
h the thermodynamic consistency i tests: d < 5, A < 3, I1 < 30, I2 < 30.
b
GE/RT = .x1 x2 C 0 C 1 x1  x2 C 2 x1  x2 2
c
ln g 1 =g 2 D0 D1 x2  x1 D2 6x1 x2  1 D3 x2  x1 1  8x1 x1 .
 140 W.-P. Tai et al. / Fluid Phase Equilibria 384 (2014) 134142
[(Fig._2)TD$IG]
800
353.15 K
373.15 K
408.15 K
NRTL-HOC
600 Wilson-HOC
UNIQUAC-HOC

P/kPa
400

200

0
0 0.2 0.4 0.6 0.8 1
x1 , y1
Fig. 2. VLE of 2-methylfuran (1) + furfural alcohol (2) at 353.2, 373.2, and 408.2 K (solid symbols: experimental liquid phase; open symbols: experimental vapor phase; circle:
353.2 K; square: 373.2 K; triangle: 408.2 K; long dashed line: NRTL-HOC; short dashed line: WilsonHOC; solid line: UNIQUAC-HOC).

where n is the number of data points and si is the standard from the WilsonHOC, the NRTL-HOC, and the UNIQUAC-HOC
deviation of the measured variable i. In the correlations, the models, respectively. The smoothed curves in Figs. 24
values of s were set to s P = 0.1%, s T = 0.1 K, s x1 = 0.1%, and represent the calculated results. As can been seen from the
s y1 = 1%. The optimization has been made with the aid of tabulated values and the graphs, the data correlations are
Aspen Properties software. Table 9 lists the physical properties satisfactory and the average absolute relative deviations
of each constituent compound which are needed in the (AARD) obtained from these three thermodynamic models
data correlation. Tables 1012 report the correlated results are comparable.

[(Fig._3)TD$IG] [(Fig._4)TD$IG]
600
1600
353.15 K
353.15 K
373.15 K
373.15 K
408.15 K
408.15 K
NRTL-HOC
NRTL-HOC
Wilson-HOC
1200 Wilson-HOC
UNIQUAC-HOC
UNIQUAC-HOC
400
P/kPa
P/kPa

800

200

400

0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
x1 , y1 x1 , y1
Fig. 3. VLE of isopropyl alcohol (1) + furfuryl alcohol (2) at 353.2, 373.2, and 408.2 K Fig. 4. VLE of furan (1) + furfural (2) at 353.2, 373.2, and 408.2 K (solid symbols:
(solid symbols: experimental liquid phase; open symbols: experimental vapor experimental liquid phase; open symbols: experimental vapor phase; circle:
phase; circle: 353.2 K; square: 373.2 K; triangle: 408.2 K; long dashed line: NRTL- 353.2 K; square: 373.2 K; triangle: 408.2 K; long dashed line: NRTL-HOC; short
HOC; short dashed line: WilsonHOC; solid line: UNIQUAC-HOC). dashed line: WilsonHOC; solid line: UNIQUAC-HOC).
 W.-P. Tai et al. / Fluid Phase Equilibria 384 (2014) 134142 141

Table 9
Properties of the constituent compounds.

Compound MWa (g mol1) Tbb (K) Tcb (K) 102 Pcb (kPa) Vc b
(m3 mol1) Zcc hd Rgd () qd rd vd md (Debye)
2-Methylfuran 82.10 337.0 528.0 47.20 247 0.266 0.00e 2.983e 2.6280e 3.1338e 0.249e 0.650f
Furan 68.07 304.5 490.2 55.00 218 0.294 0.00 2.559 1.7400 2.4021 0.202 0.660
Furfural 96.08 434.9 670.2 56.60 252 0.256 0.58 3.350 2.5000 3.1721 0.368 3.598
Furfuryl alcohol 98.10 443.2 632.0 53.50 263 0.268 0.00 3.422 2.6760 3.3784 0.734 1.919
Isopropyl alcohol 60.10 355.3 508.3 47.65 222 0.250 1.32 2.760 2.5276 2.9137 0.663 1.661
a
Taken from National Institute of Standards and Technology (NIST) Chemistry WebBook [13].
b
Taken from thermodynamic databank of Aspen Plus process simulation package.
c
Estimated from Zc = (PcVc)/(RTc).
d
Taken from thermodynamic databank of Aspen Plus process simulation package, except for 2-methylfuran.
e
Obtained from Aspen Plus property estimation by entering MW, Tb,Tc, Pc, Vc and molecular structure.
f
Taken from McClellan [18].

Table 10
Correlated results from the WilsonHOC model.

Mixture (1) + (2) T (K) a12a a21a b12a (K) b21a (K) DP/P AARDb (%) DT/T AARDb (%) Dx1/x1 AARDb (%) Dy1/y1 AARDb (%)
2-Methylfuran + furfuryl alcohol 353.2 0.5190 1.2203 205.5 34.3 0.21 0.17 0.15 0.20
373.2 0.52 0.38 0.40 1.03
408.2 0.20 0.11 0.12 0.29
Isopropyl alcohol + furfuryl alcohol 353.2 0.2879 0.6752 27.4 19.5 0.07 0.08 0.04 0.09
373.2 0.11 0.10 0.11 0.27
408.2 0.07 0.05 0.04 0.37
Furan + furfural 353.2 7.2661 4.2939 2537.5 1582.1 0.20 0.10 0.18 0.22
373.2 0.34 0.15 0.26 0.32
408.2 0.30 0.15 0.23 0.71
a
Binary parameters in the Wilson model: lnAij = aij + bij/T.    
P n
b
AARD: average absolute relative deviation, dened as DP =P AARD% 100% =n nk1 jPcal  Pexp j =Pexp , DT=T AARD% 100%=n Sk1 jT cal  T exp j=T exp ,
 k k
n   n jx1 cal x1 exp j
Dy1 =y1 AARD% 100%=n Sk1 jy1 cal  y1 exp j=y1 exp k , Dx1 =x1 AARD% 100%
n Sk1 xexp
, where n is the number of data points.
1
k

Table 11
Correlated results from the NRTL-HOC model.

Mixture (1) + (2) T (K) a12a a21a b12a (K) b21a (K) DP/P AARDb (%) DT/T AARDb (%) Dx1/x1 AARDb (%) Dy1/y1 AARDb (%)
2-Methylfuran + furfuryl alcohol 353.2 1.6859 0.1097 154.3 126.8 0.23 0.18 0.15 0.20
373.2 0.55 0.40 0.42 1.05
408.2 0.19 0.11 0.12 0.32
Isopropyl alcohol + furfuryl alcohol 353.2 0.9864 0.5469 63.0 57.4 0.07 0.09 0.04 0.09
373.2 0.11 0.10 0.11 0.27
408.2 0.06 0.05 0.04 0.36
Furan + furfural 353.2 6.1195 8.9728 2243.6 3158.3 0.20 0.10 0.18 0.22
373.2 0.37 0.18 0.28 0.34
408.2 0.28 0.14 0.22 0.70
a
Binary parameters in the NRTL model: t ij = aij + bij/T and a = 0.3 for all binary systems.    
n P
b
AARD: average absolute relative deviation, dened as DP=P AARD% 100%=n Sk1 jPcal  Pexp j=Pexp , DT=T AARD% 100%=n nk1 jT cal  T exp j=T exp ,
 k k
n  exp  n jxcal xexp j
Dy1 =y1 AARD% 100%=n Sk1 jycal exp
1  y1 j=y1 k
, Dx1 =x1 AARD% 100%n Sk1
1
xexp
1
k, where n is the number of data points.
1

Table 12
Correlated results from the UNIQUAC-HOC model.

Mixture (1) + (2) T (K) a12a a21a b12a (K) b21a (K) DP/P AARDb (%) DT/T AARDb (%) Dx1/x1 AARDb (%) Dy1/y1 AARDb (%)
2-Methylfuran + furfuryl alcohol 353.2 0.6592 0.0385 8.5 82.0 0.22 0.18 0.15 0.21
373.2 0.53 0.39 0.41 1.05
408.2 0.19 0.11 0.12 0.31
Isopropyl alcohol + furfuryl alcohol 353.2 0.4936 0.3252 18.6 18.4 0.07 0.08 0.04 0.09
373.2 0.11 0.10 0.11 0.27
408.2 0.07 0.05 0.04 0.37
Furan + furfural 353.2 2.7895 5.2360 912.8 1717.0 0.21 0.11 0.19 0.23
373.2 0.37 0.17 0.28 0.35
408.2 0.31 0.16 0.24 0.74
a
Binary parameters in the UNIQUAC model: t ij = exp (aij + bij/T).  cal exp   
n jP P j n jT cal T exp j
b
AAD: average absolute relative deviation, dened as DP=P AARD% 100%n Sk1 k, DT=T AARD% 100%
n Sk1 k,
 exp
 exp
Pexp T exp
n jy1 y1 j
cal n jx1 x1 j
cal
Dy1 =y1 AARD% 100%
n S k1 yexp
k, D x 1 =x 1 AARD% 100%
n S k1 xexp
k, where n is the number of data points.
1 1
142 W.-P. Tai et al. / Fluid Phase Equilibria 384 (2014) 134142
5. Conclusion
Twenty three new vapor pressure data of 2-methylfuran are
measured in at temperatures ranging from 353 to 409 K and
correlated with the extended Antoine equation. Isothermal VLE
data are also determined experimentally with a static apparatus
for the binary systems of 2-methylfuran + furfuryl alcohol, isopro-
pyl alcohol + furfuryl alcohol, and furan + furfural at temperatures
at 353.2, 373.2, and 408.2 K. No azeotropes are found in these three
investigated systems. The experimental results revealed that all
these three systems are positive deviation from Raoults law. The
WilsonHOC, the NRTL-HOC, and the UNIQUAC-HOC models can
accurately correlate the new VLE data obtained from this study.
The parameters determined from this study are useful for the
process simulation and design for the systems containing furfural
and its derivatives.
Acknowledgements
The authors gratefully acknowledge the nancial support from
the National Science Council, Taiwan, through Grant No. NSC102-
2622-E011-006-CC1. The authors thank to Prof. J. Ward, Prof. I.L.
Chien, and Prof. C.L. Chen for valuable discussions and also thank to
Dr. B.S. Gupta for density measurement.
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