Article

pubs.acs.org/jced

Phase Equilibria in Systems with Levulinic Acid and Ethyl Levulinate

Alexander J. Resk, Lars Peereboom, Aspi K. Kolah, Dennis J. Miller, and Carl T. Lira*
Michigan State University, East Lansing, Michigan 48824-1226, United States

ABSTRACT: P−x data for the vapor−liquid equilibrium (VLE) of four

binary systems water + levulinic acid, water + ethyl levulinate, ethanol +
levulinic acid, and ethanol + ethyl levulinate were collected at 60 °C.
Liquid−liquid equilibrium (LLE) data for ethyl levulinate + water +
levulinic acid and ethyl levulinate + water + ethanol were measured at 30
°C. The consistency of the LLE data was confirmed using the Othmer−
Tobias method. Data were regressed using ASPEN PLUS software to
generate binary interaction parameters for the NRTL-HOC property
method. The resulting parameters were able to successfully reproduce
experimental VLE data, and were semiquantitative for reproducing
experimental LLE data.

■ INTRODUCTION
Biobased chemical manufacturing using environmentally friendly
methods is of increasing interest for many chemical producers.
Levulinic acid and its derivatives are of significant potential as
platform chemicals for biobased materials.1 Levulinic acid is
obtained easily by treating six-carbon sugars with acid, or it can be
obtained from five-carbon sugars by adding a reduction step
before the acid treatment.2 Ethyl levulinate is used primarily as a
fuel additive for the oil and gas industry, a fragrance additive in
cosmetics, and a flavor additive in some foods. The phase
equilibria reported here supports the development of ester-
ification of levulinic acid with ethanol to produce ethyl levulinate
with water as a byproduct.
Ethyl levulinate can be produced by reactive distillation (RD).
RD has significant potential for biobased chemical manufacturing
of esters.3 RD has the capability to be more economical than
traditional reactor + separator systems because the products can
be separated in the column, overcoming equilibrium conversion
limitations present in batch or flow reactors. Both LLE and VLE
are important because ethyl levulinate has a heteroazeotrope
with water.
In this study, experimental VLE data for four binary systems
were obtained, including the water + levulinic acid system, the
water + ethyl levulinate system, the ethanol+ levulinic acid
system, and the ethanol + ethyl levulinate system. LLE data for
two ternary systems were collected, including the ethyl levulinate
+ water + levulinic acid system and the ethyl levulinate + water +
ethanol system. These data were correlated with the nonrandom
two liquid (NRTL) + Hayden-O’Connell method (NRTL-
HOC). The NRTL model is a local composition theory inspired
by the Wilson model.4 The NRTL model is used here because of
its ability to model LLE. The Hayden-O’Connell method is used
because of the presence of organic acids, alcohols and water.
Ethanol (i) + Water (j) System. This work includes
modeling incorporating the ethanol + water system for which
parameters from the Aspen Plus version 7.3.2 NRTL-HOC
database are used; τij = −0.9852 + 302.237/T(K), τji = 3.7555 −
676.031/T(K). The HOC parameters are ηii = 1.4, ηij = ηji = 1.55,
ηjj = 1.7.
■ EXPERIMENTAL DETAILS
Chemicals. Reagents and purities are summarized in Table 1.
Levulinic acid obtained from Penta Manufacturing was purified
by vacuum distillation. The initial overhead fraction (10% of
initial volume) and the final reboiler residue (10%) were
discarded, while the middle fraction (80%) was collected for use.
The vacuum distilled levulinic acid was > 98 % pure, with water as
the primary contaminant, as determined by gas chromatography
(GC) and Karl Fischer titration (Aqua Counter AQ-2100). The
levulinic acid was checked for purity before each use and stored in
an airtight container between uses to minimize water absorption
from air.
P−x Apparatus. A custom P−x apparatus was created for
VLE measurements of binary mixtures at temperatures between
303 K and 353 K as shown in Figure 1. The apparatus is a
modification of the system described by Vu, et al.5 The main
equilibrium chamber has been modified to use a liquid jacket for
temperature control, and the liquid pumps and external
degassing were eliminated. Valves on the top permit sampling
and evacuation. A side valve for the system for liquid sampling is
also present, but not used in this study. The main chamber (∼500
mL) usually holds 50 to 100 mL of liquid. A glass stem is attached
at the top of the apparatus to allow the connection of the MKS
Baratron model PDR 2000 dual capacitance diaphragm absolute
pressure gauge. The pressure gauge provides reliable measure-
ments of pressure between 0.013 and 133 kPa with an error of
Special Issue: In Honor of Grant Wilson
Received: September 10, 2013
Accepted: February 12, 2014
Published: March 3, 2014

© 2014 American Chemical Society 1062 dx.doi.org/10.1021/je400814n | J. Chem. Eng. Data 2014, 59, 1062−1068
Journal of Chemical & Engineering Data
Table 1. Reagents and Purities for Compounds Used
compound CAS No. source initial mole fraction purity
dimethyl sulfoxide Sigma-Aldrich 99+ %
ethyl levulinate 539-88-8 Sigma-Aldrich 99 %
ethyl alcohol 64-17-5 Sigma-Aldrich 99+ %
water, HPLC grade 7732-18-5 J.T. Baker
levulinic acid 123-76-2 Penta Mfg.
nitrogen (inert gas) AGA 99.998 %
Figure 1. Schematic of custom P−x apparatus.
0.25 % from the reported value. On the upper side of the
apparatus, two valves are used to attach rubber hoses, one
connected to a vacuum pump, and the other connected to an
ultrahigh purity nitrogen tank. The vacuum line uses a dry ice +
acetone trap to protect the vacuum pump. A straight connecting
glass stopcock is used as a the upper liquid sampling valve. The
valve outlet is capped with a septum. When the sample valve is
opened, a 25 cm long, 16 gauge syringe needle is passed through
the septum and valve orifice to collect liquid samples. A
thermowell extending to the bottom of the equilibrium chamber
is filled with mineral oil to allow temperature measurement
within the apparatus. An Omega DP 460 thermistor readout is
used to monitor the temperature within the apparatus using a
thermistor calibrated against a certified mercury thermometer
with accuracy better than ± 0.01 °C. The equilibrium chamber is
surrounded by a water jacket connected to a Thermo Scientific
DC10 circulator. Besides a brief, small drop in temperature each
time the chamber pressure was lowered with vacuum, the
apparatus maintains the target temperature during all experi-
ments with a precision of ± 0.1 °C. A magnetic stir bar placed in
the apparatus improves thermal equilibrium and degassing.
Electric heating tape and fiberglass insulation are used around the
pressure gauge stem attachment to ensure that the stem was
always above the equilibrium chamber pressure, preventing
condensation.
Prior to each use, the P−x apparatus was cleaned, sealed, and
checked for leaks. The apparatus was cleaned with acetone, joints
were sealed, and valves were heated, coated lightly with vacuum
grease, and assembled. After assembly, the pressure was lowered
to 0.013 kPa by connecting to a vacuum pump for 10 min. All
valves were then closed, and the apparatus was left for 20 min and
checked to make sure the pressure had not increased due to leaks.
Procedure for VLE Experiments. A temperature of 60.0 °C
was selected for VLE experiments that provided for reasonable
vapor pressures for water. After testing for leaks, the equilibrium
chamber was filled with approximately 50 mL of the less volatile
1063
Article
purification method final mole fraction purity analysis method
99+ %
99 % GC Karl Fischer
99+ %
99+ %
vacuum distillation 98+% GC Karl Fischer
99.998 %
liquid for the binary pair. This liquid was loaded using a 70 mL
syringe with a needle inserted through the open sampling valve
and septum. All valves were then closed, and the vacuum pump
was started. After 5 s, the vacuum valve was opened, allowing the
pressure to drop below the pure liquid’s vapor pressure. After
allowing the liquid to boil for 20 s, the vacuum valve was closed,
and the vacuum was turned off. The pressure in the equilibrium
chamber was recorded after it remained steady, and the
temperature remained constant for 30 s. The vacuum pump
was turned on once again, and the vacuum valve opened for 5 s
then closed. The pressure was recorded once again after
steadying. This process was repeated until the successive
pressure readings indicated complete degassing. For binary
experiments, the short evacuation of vapor from the apparatus
lowered the content of the more volatile component and the
pressure readings would trend slightly toward the vapor pressure
of the less volatile component. For this reason, when three
successive pressure readings exhibited a small constant decline,
the degassing was considered complete, and the final pressure
would be recorded and liquid sampling would begin.
Sampling of the liquid within the equilibrium chamber was
done by taking 3 mL of liquid from the bottom of the apparatus.
A 10 mL syringe with a long needle was used to gather the
samples. The syringe would only allow liquid to travel through
the needle when the equilibrium chamber was at a pressure
greater than about 20 kPa. So, if the pressure inside the apparatus
was below this level, the nitrogen valve was opened to allow
nitrogen gas to raise the pressure above 20 kPa. The syringe
needle was then inserted through the sampling valve and septum,
and the 3 mL sample was gathered. The sample was placed in an
airtight vial, and the composition was determined by GC analysis.
After the liquid sample with only the less volatile pure
component present was taken, a volume of the more volatile
liquid was added to allow the liquid composition within the
apparatus to reach a composition 5 mol % to 10 mol % richer in
the more the volatile component. The steps described previously
for determining the vapor pressure and gathering a liquid sample
were executed once again. This process was repeated until the
liquid in the apparatus contained 90 % to 95 % of the more
volatile component. Then, the apparatus was disassembled,
cleaned, and prepared once again. The same process was
repeated, but this time initiated with the more volatile pure
component while the less volatile component was added.
Approximately 7 to 12 vapor pressure and liquid composition
pairs were recorded for both runs from purities to 90 % to 95 %.
This provided 14 to 24 data points on each P−x diagram for a
binary pair.
Procedure for LLE Experiments. LLE data for ternary
mixtures were determined at a constant temperature of 30 °C,
selected to provide temperature control with limited concern of
volatilization. An isothermal bath was assembled and equipped
with a Fischer Scientific Isotemp Immersion Circulator model
730. The temperature of the bath was monitored with an ASTM
dx.doi.org/10.1021/je400814n | J. Chem. Eng. Data 2014, 59, 1062−1068
Journal of Chemical & Engineering Data Article

certified glass thermometer. A vial holding rack with room for 10
5-cm3 vials was assembled in the center of the bath. Each vial was
filled with a ternary mixture of known overall composition within
the two phase region. The mixtures were stirred with a magnetic
stir bar for two minutes. The vials were then place in the
isothermal bath overnight (for at least 16 h) to equilibrate. After,
each vial was taken from the bath and a needle syringe was used
to collect a 1 cm3 sample from each phase. The samples were
placed in 5-cm3 vials for analysis.
Analytical Methods. The liquid compositions of samples
from VLE and LLE experiments were determined by GC
analysis. Samples were prepared with 15 % to 25 % by weight
DMSO, used as an internal standard. A 10 μL syringe was used to
collect 1 μL of liquid from the sample containing DMSO. This
liquid was surrounded by 4 μL of air on each side in the syringe.
The sample was then injected by hand. The Varian 3400 gas
chromatograph (GC) operated with an initial oven temperature
of 200 °C, thermal conductivity detector temperature of 250 °C,
and injector temperature of 270 °C. The oven temperature
increased at a rate of 20 (°C/min) for 2.5 min and was held for 3
min. The GC was equipped with a 2 m x 2 mm i.d. Chromosorb
101 80/100 column.
Standard Uncertainty in Experimental Data and
Regression Methods. The GC was calibrated before each set
of samples were tested. Two samples of known composition were
used to obtain the relationship between the ratio of peak area and
the mixture compositions. The standard uncertainty in
compositions based on comparisons of repeated injections of
standards is u(x) = ± 0.002. Temperature uncertainty is u(T) = ±
0.05 K. Pressure uncertainty is dominated by the degree of
outgassing rather than the precision of the Baratron and is
estimated as u(p) = ± 0.25 kPa. All data were regressed using the
Maximum Likelihood objective function using the Britt-Luecke
Algoririthm within ASPEN 7.3.2
collected from experiments starting at each side of the
composition range. The P−x line is only moderately nonideal
in the liquid with some curvature in the bubble pressure line at
high water concentration. For the HOC method, η values of 2.5
for levulinic acid + water and 4.5 for levulinic acid and itself were
assumed as summarized in Table 4. These values were based on
the assumption that levulinic acid would behave similarly to
acetic acid in water and that levulinic acid would have self-
interactions similar to acetic acid. The model compares well with
the isobaric T−x−y data reported by Shil’nikova and Ekimova6 as
shown in Figure 3.
Ethyl Levulinate + Water VLLE System. Isothermal VLLE
data for the ethyl levulinate + water system at 60.0 °C are
summarized in Table 5. The binary parameters are summarized
in Tables 3 and 4, giving γEtLv∞ = 25.2, γwat∞ = 4.35 at 60.0 °C.
Figure 4 compares the experimental data and the NRTL-HOC
model. The NRTL-HOC bubble line fits the data well at water
concentrations less than 45 mol %. At water concentration
between 45 mol % and 95 mol %, the three-phase VLLE is at a
slightly lower pressure than the data suggests indicated with the
asterisk (∗) in Table 5. No effort was taken to identify the
experimental L+L phase boundaries with certainty. The value of
α = 0.285 is recommended in the ASPEN for systems exhibiting
liquid−liquid immiscibility. The η values for the HOC method
were 1.3 for ethyl levulinate + water and 0.53 for ethyl levuilnate
and itself. These values are based on the assumption that ethyl
levulinate would behave similarly to ethyl acetate for the
purposes considered.
Ethanol + Levulinic Acid VLE System. Isothermal VLE
data for the ethanol + levulinic acid system were collected at 60
°C. Owing to the hygroscopic nature of levulinic acid, between 2
mol % and 5 mol % water was detected in each sample, as shown
in Table 6. The system was treated as a ternary system for
regression of the ethanol + levulinic acid constants. The binary

■
interaction parameters were regressed after the levulinic acid +
RESULTS AND DISCUSSION water regression already established the parameters for that
binary pair. Final binary NRTL parameters are shown in Table 3,
Levulinic Acid + Water VLE System. Isothermal VLE data giving γEtOH∞ = 0.912, γLvA∞ = 1.19 at 60.0 °C. Experimental P−x
for the levulinic acid + water system at 60.0 °C are summarized in data are compared to the regressed data using the dash−dot lines
Table 2. The binary NRTL parameters obtained are shown in in Figure 5. Also included in the plot is the binary prediction of
Table 3, giving γLvA∞ = 3.47, γwat∞ = 1.18 at 60.0 °C. The the ethanol + levulinic acid system. The NRTL parameter α = 0.3
experimental P−x data are compared with the NRTL Hayden was used. The HOC parameters for levulinic acid + ethanol and
O’Connell (HOC) P−x plot generated by the final binary levulinic acid with itself were 2.5 and 4.5, respectively, as
parameters from the regression in Figure 2. The plot shows data tabulated in Table 4. This assumes that levulinic acid behaves
similarly to acetic acid under the conditions considered.
Table 2. Isothermal P−x Data for Levulinic Acid + Water at Ethanol + Ethyl Levulinate VLE System. Isothermal VLE
60.0 °Ca data for the ethanol + ethyl levulinate system was collected at
p/kPa xwater p/kPa xwater 60.0 °C, and recorded in Table 7. In each sample, there was less
0.49 0.038 16.15 0.709 than (0.1 mol %) levulinic acid present, which was ignored in
1.59 0.070 17.55 0.819 regression, and between 0.5 and 2 mol % water present. The
3.07 0.116 18.51 0.927 NRTL parameters for this system were regressed using two
4.77 0.192 18.83 0.952 methods. One regression was conducted as a ternary system by
5.64 0.233 18.48 0.908 including water, adjusting only the binary NRTL parameters for
7.29 0.295 17.55 0.804 ethanol + ethyl levulinate. Parameters for ethyl levulinate + water
8.37 0.334 16.00 0.683 were fixed to values tabulated in Tables 3 and 4. Another
9.65 0.379 14.13 0.590 regression was performed using water-free mole fractions for
11.11 0.442 12.08 0.473 ethanol and ethyl levulinate and ignoring the water. Both
12.15 0.494 8.92 0.334 parameter sets are presented in Table 3. The HOC η parameters
13.47 0.552 6.92 0.264 for ethyl levulinate + ethanol and ethyl levulinate with itself were
14.80 0.627 4.28 0.171 set as 1.3 and 0.53, respectively. Bubble calculations were
conducted in ASPEN using binary parameters from both
a
Data are listed in the order they were collected. Compositions are in regressions as plotted in Figure 6. There is clearly a better fit
mole fraction. u(x) = ± 0.002, u(p) = ± 0.25 kPa, u(T) = ± 0.05 K. to the data when the regression is performed ignoring the
1064 dx.doi.org/10.1021/je400814n | J. Chem. Eng. Data 2014, 59, 1062−1068
Journal of Chemical & Engineering Data Article

Table 3. Summary of Regressed NRTL Parameters, τij = bij/T(K)

i water levulinic acid (ternary fit) ethanol (binary fit) ethanol ethanol ethyl levulinate
j ethyl levulinate water ethyl levulinate ethyl levulinate levulinic acid levulinic acid
bij 1014.969 −342.585 −159.872 398.2682 585.396 −285.428
bji 64.60453 880.5534 468.892 −74.662 −376.308 336.234
α 0.285 0.3 0.3 0.3 0.3 0.3

Table 5. Isothermal P−x Data for Ethyl Levulinate + Water at

60.0 °Ca
p/kPa xwater p/kPa xwater
1.41 0.022 19.47 0.471
2.89 0.034 19.77 0.993
4.11 0.047 19.80 0.981*
5.43 0.068 19.77 0.961*
6.75 0.080 19.80 0.919*
8.25 0.102 19.79 0.844*
9.40 0.129 19.79 0.712*
10.68 0.142 18.83 0.404
12.65 0.188 16.68 0.309
14.04 0.220 12.00 0.175
15.60 0.256 6.09 0.073
18.01 0.345 19.71 0.689
Figure 2. P−x diagram for levulinic acid (LvA) + water at 60.0 °C a
compared with the NRTL-HOC model. Data are shown as collected Data are listed in the order they were collected. Compositions are in
starting from each side of the composition range. mole fraction. The approximate three-phase region is denoted by the
asterisk (∗) where overall liquid compositions are tabulated, not
composition of a single liquid phase. u(x) = ± 0.002, u(p) = ± 0.25
Table 4. Hayden-O’Connell η Parameters Used in Data
kPa, u(T) = ± 0.05 K.
Regressiona
ethanol water levulinic acid ethyl levulinate
ethanol 1.4 1.55 2.5 1.3
water 1.55 1.7 2.5 1.3
levulinic acid 2.5 2.5 4.5 2
ethyl levulinate 1.3 1.3 2 0.53
a
All parameters are from the Aspen database except ethyl levulinate
and levulinic acid that were assumed to have the same parameters as
ethyl acetate and acetic acid, respectively.

Figure 4. P−x diagram for ethyl levulinate + water at 60.0 °C compared

with the NRTL-HOC model. Data are shown as collected starting from
each side of the composition range.

Figure 3. Comparison of levulinic acid + water T−x−y data of
Shil’nikova and Ekimova with the model obtained by fitting the P−x
data.
presence of the small amount of water in the samples. From
Figure 6, it is apparent that the bubble pressure from the ternary
fit overestimates bubble pressure at high ethyl levulinate mole
fractions. The results suggest that the small mole fractions of
1065
water in the analysis were not present during the experiment. The
fit of the binary system gives γEtOH∞ = 1.84, γEtLv∞ = 2.60 at 60.0
°C.
During the course of experiments, we noted that ethyl
levulinate purified to less than 200 ppm of water absorbed water
from the air quickly enough to contain up to 1.5 % by weight
water in less than a few hours. We speculate that samples from
this series may have absorbed water from the ambient air while
they were being processed outside of the P−x apparatus such as
when adding DMSO or taking smaller samples for gas
chromatography analysis. This would mean that the recorded
vapor pressure values were actually recorded when less water was
present than that calculated by GC analysis. Despite the
uncertainty in this system, we consider the data will be useful
dx.doi.org/10.1021/je400814n | J. Chem. Eng. Data 2014, 59, 1062−1068
Journal of Chemical & Engineering Data Article

Table 6. P−x Data and Model for Ethanol + Levulinic Acid + Table 7. P−x Data for the System Ethanol + Ethyl Levulinate
Water at 60.0 °C Used to Regress Interaction Parameters for at 60.0 °Ca
Ethanol + Levulinic Acida
ternary binary
p/kPa p/kPa (model) xwater xEtOH xLvA p/kPa xEtOH xEtLv xwater xEtOH xEtLv
4.80 5.36 0.041 0.096 0.862 2.68 0.031 0.956 0.012 0.032 0.968
9.20 9.11 0.046 0.171 0.784 9.51 0.114 0.871 0.015 0.116 0.884
13.91 13.51 0.043 0.261 0.696 12.05 0.155 0.828 0.017 0.158 0.842
18.75 18.35 0.040 0.358 0.602 14.95 0.193 0.786 0.021 0.197 0.803
23.12 22.50 0.037 0.441 0.521 17.36 0.242 0.743 0.015 0.246 0.754
27.61 27.43 0.037 0.539 0.424 19.96 0.286 0.699 0.014 0.290 0.710
32.18 31.95 0.035 0.633 0.332 22.49 0.336 0.652 0.012 0.340 0.660
36.50 36.22 0.027 0.732 0.241 25.08 0.382 0.603 0.014 0.388 0.612
41.28 42.01 0.020 0.869 0.111 28.09 0.457 0.532 0.012 0.462 0.538
44.24 44.76 0.013 0.938 0.049 31.44 0.544 0.444 0.013 0.551 0.449
41.72 42.69 0.024 0.880 0.096 33.58 0.610 0.380 0.010 0.616 0.384
37.14 37.45 0.032 0.754 0.214 36.12 0.671 0.318 0.012 0.679 0.321
30.62 29.80 0.039 0.585 0.376 38.81 0.769 0.222 0.009 0.776 0.224
25.72 24.99 0.038 0.489 0.472 41.93 0.868 0.126 0.007 0.873 0.127
19.00 17.69 0.035 0.349 0.616 44.24 0.941 0.051 0.008 0.949 0.051
12.51 11.65 0.029 0.234 0.737 45.58 0.955 0.038 0.006 0.961 0.039
6.57 6.52 0.028 0.129 0.843 1.16 0.009 0.979 0.012 0.009 0.991
a
The second column provides the bubble pressure from the regressed 5.04 0.055 0.929 0.017 0.056 0.944
model at the listed composition. Data are listed in the order collected. 6.95 0.081 0.906 0.013 0.082 0.918
Compositions are in mole fraction. u(x) = ± 0.002, u(p) = ± 0.25 kPa, a
Water absorption in the samples is suspected and a second regression
u(T) = ± 0.05 K.
is performed on a water-free basis as a binary as discussed in the text.
Compositions are in mole fractions. u(x) = ± 0.002, u(p) = ± 0.25
kPa, u(T) = ± 0.05 K.

Figure 5. Comparison of experimental and modeled bubble pressures at

60.0 °C for ethanol + levulinic acid + water as tabulated in Table 6. The
fit of the ternary data is shown by the dash−dot line. The solid curves
represent the predicted binary behavior of ethanol + levulinic acid after
regression.
for subsequent researchers, and thus provide the full set of data
and parameters.
LLE for Ethyl Levulinate + Levulinic Acid + Water.
Isothermal LLE data were collected at 30.0 °C for the ternary
system ethyl levulinate + levulinic acid + water. Data are
summarized in Table 8 and plotted in Figure 7. The liquid−liquid
immiscibility region is at small levulinic acid concentrations, less
than six mole percent. The levulinic acid peak is somewhat broad
on the GC, so uncertainty in mole fractions are estimated to be ±
0.002 for this system, which is consistent with the scatter in the
figure in the expanded region shown. The consistency of the data
is evaluated with the Othmer−Tobias method7 in Figure 8.
While the Othmer−Tobias correlation may not always be linear,8
clustering about a common curve is expected for good data.
While the experimental data exhibit some scatter, and some
1066
Figure 6. Comparison of experimental data and models for ethanol +
ethyl levulinate at 60.0 °C. For plotting the ternary calculations and
experimental data, the abscissa uses the compositions in column five of
Table 7 for the corresponding row.
experimental tie lines exhibit minor crossing, the experiments are
very challenging and four additional experiments were rejected
due to scatter from the plot.
The NRTL parameters for ethyl levulinate + levulinic acid
were regressed to fit the data in Figure 7 and tabulated in Table 3,
giving γEtLv∞ = 0.870, γLvA∞ = 0.864 at 30.0 °C. Parameters for the
other constituent binaries are fixed during regression. Despite
using these data for the fitting, the LLE region is overpredicted,
though the slopes of the tie lines are approximately correct. The
LLE region for the ethyl levulinate + water system is slightly too
large, which has some effect on the ternary. No further attempts
at fitting LLE and VLE simultaneously were pursued since our
application of the model operates in the single liquid-phase
dx.doi.org/10.1021/je400814n | J. Chem. Eng. Data 2014, 59, 1062−1068
Journal of Chemical & Engineering Data Article

Table 8. Liquid−liquid Data for Ethyl Levulinate + Levulinic

Acid + Water at 30.0 °Ca
water-rich, β organic-rich, α
xLvA xEtLv xLvA xEtLv
0.012 0.034 0.050 0.313
0.014 0.034 0.051 0.297
0.026 0.054 0.057 0.197
0.023 0.040 0.054 0.252
0.004 0.022 0.029 0.461
0.002 0.021 0.006 0.517
0.008 0.027 0.033 0.411
0.000 0.020 0.000 0.558
0.010 0.028 0.045 0.395
0.003 0.022 0.017 0.477
0.007 0.028 0.038 0.366
0.016 0.032 0.055 0.322 Figure 8. Othmer−Tobias plot for ethyl levulinate + levulinic acid +
0.019 0.037 0.055 0.304 water at 30.0 °C. α is the organic-rich phase, and β is the water-rich
0.017 0.033 0.052 0.318 phase. The correlation uses weight fractions, w, and the abscissa uses
weight fractions of water.
0.025 0.047 0.055 0.208
0.008 0.025 0.034 0.430
0.009 0.026 0.037 0.435
Table 9. Liquid−Liquid Data for Ethanol + Ethyl Levulinate +
Water at 30.0 °Ca
a
Each row is a tie line. Compositions are in mole fractions. u(x) = ±
0.002, u(p) = ± 0.25 kPa, u(T) = ± 0.05 K. water-rich, β organic-rich, α
xEtOH xEtLv xEtOH xEtLv
0.000 0.021 0.000 0.569
0.030 0.029 0.049 0.414
0.056 0.063 0.078 0.189
0.052 0.052 0.078 0.222
0.018 0.025 0.037 0.485
0.022 0.026 0.041 0.470
0.044 0.040 0.076 0.308
0.036 0.031 0.068 0.351
0.041 0.034 0.069 0.343
0.034 0.029 0.062 0.386
a
Each row is a tie line. Compositions are in mole fractions. u(x) = ±
0.002, u(p) = ± 0.25 kPa, u(T) = ± 0.05 K.

Figure 7. Liquid−liquid equilibria behavior of ethyl levulinate + levulinic

acid + water at 30.0 °C. Solid lines are from experiments. Dotted lines
are calculated with parameters in Table 3 as described in the text.

region and representation of vapor + liquid data is more

important.
LLE for Ethanol + Ethyl Levulinate + Water. Isothermal
LLE data were collected at 30.0 °C for the ternary system ethanol
+ ethyl levulinate + water. Data are summarized in Table 9 and
plotted in Figure 9, and consistency is evaluated with the
Othmer−Tobias correlation in Figure 10. The scatter on the
Othmer−Tobias plot for this system is minor. The predicted
curves in Figure 9 were generated with parameters obtained by
fitting the VLE systems discussed above. As with the levulinic Figure 9. Liquid−liquid equilibria for the system ethanol + ethyl
acid system in Figure 7, the liquid−liquid region is modeled to be levulinate + water at 30.0 °C. Solid lines are from experiments. Dotted
lines are calculated from parameters in Table 3
too large.

■ SUMMARY AND CONCLUSIONS

Isothermal P−x data were collected at 60 °C for the water +
levulinic acid system, the water + ethyl levulinate system, the
ethanol + levulinic acid system, and the ethanol + ethyl levulinate
system. LLE data were collected isothermally at 30 °C for the
1067
ethyl levulinate + water + levulinic acid system and the ethyl
levulinate + water + ethanol system. The VLE data were
successfully modeled using the NRTL-HOC method. The
parameters represent VLE conditions with good accuracy. The
NRTL model fitted to levulinic acid + water P−x measurements
dx.doi.org/10.1021/je400814n | J. Chem. Eng. Data 2014, 59, 1062−1068
Journal of Chemical & Engineering Data Article

(5) Vu, D. T.; Lira, C. T.; Asthana, N.; Miller, D. J. Vapor−liquid

Equilibria in the Systems Ethyl Lactate + Ethanol and Ethyl Lactate +
Water. J. Chem. Eng. Data 2006, 51, 1220−1225.
(6) Shil’nikova, L. L.; Ekimova, N. V. Liquid−Vapor Equilibrium in the
System Water + Levulinic Acid. Gidroliz. Lesokhim. Prom-st. 1968, 21
(5), 15−16.
(7) Othmer, D. F.; Tobias, P. E. Tie-Line Correlation. Ind. Eng. Chem.
1942, 34, 693−696.
(8) Carniti, P.; Cori, L.; Ragani, V. A Critical Analysis of the Hand and
Othmer-Tobias Correlations. Fluid Phase Equilib. 1978, 2, 39−47.

Figure 10. Othmer−Tobias plot for ethanol + ethyl levulinate + water at

30.0 °C. α is the organic-rich phase and β is the water-rich phase. The
correlation uses weight fractions, w.

reproduces previously published T−x−y data. The ethanol +

levulinic acid system and the ethyl levulinate + levulinic acid are
nearly ideal in the liquid phase. The systems levulinic acid + water
and ethanol + ethyl levulinate have moderate positive deviations.
The system water + ethyl levulinate has large positive deviations
and exhibits a heteroazeotrope. The LLE data were evaluated for
consistency using the Othmer−Tobias method. The LLE regions
for both ternary systems are small, and the systems thus have
limited use for any extraction process. The NRTL-HOC
parameters in this work are useful for only semiquantitate
modeling of the LLE regions, especially near the Plait point. The
size of the LLE region was overpredicted by the NRTL model.
Because the VLE and LLE data are evaluated at only one
temperature for each case, the accuracies of the temperature-
dependences of the NRTL fits are not evaluated except for
levulinic acid + water, and thus should be used at temperatures
near the experimental conditions.

■ AUTHOR INFORMATION
Corresponding Author
*E-mail: lira@egr.msu.edu.
Notes
The authors declare no competing financial interest.

■ ACKNOWLEDGMENTS
The financial support of Trenton Fuel Works, LLC is gratefully
acknowledged.

■ REFERENCES
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Pacific Northwest National Laboratory (PNNL) and the National
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(2) Curran, M. A., Biobased Materials. In Kirk-Othmer Encyclopedia of
Chemical Technology; John Wiley & Sons: New York, 2010; pp 1−19.
(3) Miller, D. J.; Kolah, A. K.; Lira, C. T., Reactive Distillation for the
Biorefinery. In Separation and Purification Technologies in Biorefineries;
Huang, H. J.; Ramaswamy, S., Eds.; J.W. Wiley and Sons: New York, NY,
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(4) Wilson, G. M. Vapor-Liquid Equilibrium. XI. A New Expression for
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1068 dx.doi.org/10.1021/je400814n | J. Chem. Eng. Data 2014, 59, 1062−1068