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Liquid-Liquid Equilibria of The Methyl Oleate-Glycerol-Hexane-Methanol System Roza Tizvar, David D. McLean,, Morris Kates, and Marc A. Dube
Liquid-Liquid Equilibria of The Methyl Oleate-Glycerol-Hexane-Methanol System Roza Tizvar, David D. McLean,, Morris Kates, and Marc A. Dube
443
Liquid-liquid equilibria of the quaternary system of methyl oleate, glycerol, hexane, and methanol were
experimentally quantified at room temperature and atmospheric pressure. UNIFAC and Modified UNIFAC
activity coefficient models were used to predict the properties of the coexisting phases at equilibrium. These
models used the previously reported binary group interaction parameters without any regression. Overall, the
predicted tielines showed no significant lack of fit when compared to the experimental tielines for both models;
however, the precision of the experimental data was insufficient to verify achievement of the ASTM standard
for the glycerol content of the methyl oleate-rich phase. Nevertheless, the hexane-methanol solvent system
showed potential to achieve the required separation.
Introduction and Background
Biodiesel (i.e., fatty acid alkyl esters) is one of the best
substitutes for petroleum-based fuels, mainly because of its
renewability and biodegradability.1-3 Biodiesel is usually
produced via the catalytic transesterification of triglycerides with
an alcohol. The main byproduct is glycerol, which impacts
negatively on the properties of the biodiesel fuel.4 Based on
the ASTM standard for biofuels (ASTM Standard D-6751-02),
the maximum allowable quantity of free glycerol in biodiesel
is 0.02 wt %.5 Hence, before its use, biodiesel must be almost
completely separated from the glycerol byproduct, which has
an economic value in the pharmaceutical and other industries.
Consecutive stages of water washing have been commonly used
to purify biodiesel, sometimes together with another extraction
solvent, such as hexane or petroleum ether.6-9 The main
disadvantage of water washing is the formation of emulsions,
which results in a significant reduction in the efficiency of the
purification process. This phenomenon is especially severe when
biodiesel is made via the alkali-catalyzed transesterification of
waste cooking oil, because of the formation of soaps from the
free fatty acids in the waste oils,10 but is greatly reduced when
biodiesel is made via the acid-catalyzed reaction.10-12 In a
benchscale study, Nye et al.13 added hexane to the alkalicatalyzed reaction mixture, which contained biodiesel, glycerol,
residual methanol, and the catalyst, to form a biodiesel-hexane
phase and a glycerol-methanol-catalyst phase. This method
was one of the first approaches for hexane extraction of
biodiesel. At ambient temperature and atmospheric pressure,
extraction with hexane, water, and methanol (with a water:
methanol volume ratio of 1:9) was experimentally determined
to be a suitable technique to separate glycerol and biodiesel.12,14
When hexane and aqueous methanol are added to the reaction
mixture, which mainly contains biodiesel, glycerol, and some
methanol, two liquid phases will form. Because of the relatively
high solubility of biodiesel in hexane and that of glycerol in
the methanol-water system, the hexane phase contains almost
all of the biodiesel and the methanol-water phase contains
* To whom correspondence should be addressed. Tel.: +1-613-5625800, ext. 6110. Fax: +1-613-562-5172. E-mail address: mclean@
genie.uottawa.ca.
almost all of the glycerol. In this way, the biodiesel and glycerol
are well-separated and can be readily isolated by distillation or
flash evaporation of the respective extraction solvents. To our
knowledge, quantitative examination of the phase equilibria of
the five-component liquid system (biodiesel-glycerol-hexanemethanol-water) involved in the purification of biodiesel has
not been reported. Such information is required for detailed
design of biodiesel isolation and purification processes. The
liquid-liquid-phase equilibria of ternary systems of methyl
oleate (biodiesel fuel)-glycerol-methanol,15-17 biodiesel fuelmethanol-water,18 and hexane-water-methanol19 have been
studied previously. Negi et al.15 reported five experimental
liquid-liquid equilibrium data points for the methyl oleateglycerol-methanol system. They compared these experimental results with the predictions of the Universal Quasichemical Functional Group Activity Coefficient (UNIFAC) and
UNIFAC-Dortmund (i.e., Modified UNIFAC) activity coefficient models, and they concluded that both models were
capable of predicting the phase equilibria at 60 C. Working
on approximately the same system, Gutschke et al.16 and Komers
et al.17 studied the liquid-liquid equilibria of the biodiesel fuelmethanol-glycerol ternary system. The ternary phase diagram
of biodiesel fuel-methanol-water in the temperature range of
25-65 C was investigated by Stloukal et al.18 In another study,
Liu et al.19 experimentally investigated the liquid-liquid
equilibria for the methanol-water-hexane ternary system at
temperatures of 25, 35, and 45 C. Although the authors did
not make any predictions of phase equilibria of that system with
the available models, they covered a rather wide range of
experimental compositions. In our work, difficulties were
encountered in the experimental study of the five-component
system, because of the lack of precise analytical procedures for
simultaneous analysis of the five components, particularly for
water. Thus, as a first step, the present study addresses the
experimental study and prediction of liquid-liquid equilibria
of the quaternary system that consists of biodiesel, glycerol,
hexane, and methanol at room temperature and atmospheric
pressure. UNIFAC and Modified UNIFAC activity coefficient
models were used for the liquid-liquid equilibria predictions.
The results obtained using the models were compared with the
experimental data. A three-dimensional plot of the phase
diagram of such a multicomponent systems was simulated using
444
Table 1. Mean Retention Time, Standard Error, Standard Deviation, and Minimum and Maximum Retention Times Observed in Calibration
Experiments of Each Individual Component
component
number of
data points
mean retention
time (min)
standard
error
standard
deviation
minimum retention
time detected (min)
maximum retention
time detected (min)
methyl oleate
glycerol
hexane
methanol
31
76
61
82
29.00
31.05
33.90
35.12
0.040
0.022
0.033
0.013
0.21
0.19
0.26
0.12
28.68
30.80
33.58
34.82
29.75
31.95
34.65
35.53
( )
phase composition ) xj ( 2
s
xN
(1)
0.033
0.042
0.067
0.083
0.085
0.089
0.100
0.113
0.125
0.135
0.146
0.183
0.113
0.134
0.218
0.254
0.279
0.256
0.309
0.324
0.366
0.355
0.392
0.442
1
2
3
4
5
6
7
8
9
10
11
12
1
2
3
4
5
6
7
8
9
10
11
12
0.439
0.452
0.398
0.395
0.359
0.410
0.361
0.376
0.341
0.376
0.346
0.342
0.412
0.457
0.394
0.416
0.352
0.459
0.376
0.422
0.375
0.460
0.415
0.456
glycerol
0.385
0.385
0.311
0.294
0.259
0.308
0.247
0.249
0.213
0.246
0.214
0.194
0.386
0.416
0.329
0.331
0.272
0.369
0.275
0.299
0.250
0.322
0.274
0.277
hexane
0.063
0.029
0.074
0.056
0.103
0.026
0.083
0.051
0.079
0.024
0.048
0.022
0.169
0.085
0.210
0.170
0.291
0.083
0.249
0.166
0.250
0.083
0.165
0.084
methanol
0.223 [(0.022]
0.261
0.422 [(0.046]
0.477 [(0.045]
0.542 [(0.027]
0.469 [(0.004]
0.573 [(0.031]
0.590 [(0.002]
0.650
0.607 [(0.024]
0.667 [(0.010]
0.701
0.076 [(0.009]
0.093
0.172 [(0.026]
0.208 [(0.031]
0.247 [(0.013]
0.204 [(0.003]
0.273 [(0.024]
0.291 [(0.002]
0.343
0.307 [(0.021]
0.363 [(0.008]
0.388
methyl oleate
0.008 [(0.001]
nd
0.003 [(0.001]
0.003 [(0.003]
0.014 [(0.011]
nd
0.006 [(0.002]
0.005 [(0.001]
0.008
0.002 [(0.000]
0.004 [(0.002]
0.014
0.011 [(0.000]
0.005
nd
0.009 [(0.007]
0.005 [(0.001]
nd
nd
nd
0.011
nd
nd
0.008
Mass Fractions
0.758 [(0.022]
0.734
0.575 [(0.042]
0.512 [(0.049]
0.440 [(0.038]
0.531 [(0.004]
0.420 [(0.032]
0.405 [(0.002]
0.331
0.391 [(0.016]
0.329 [(0.009]
0.277
methanol
0.024 [(0.002]
nd
0.013 [(0.005]
0.012 [(0.010]
0.057 [(0.045]
nd
0.028 [(0.007]
0.022 [(0.006]
0.037
0.008 [(0.001]
0.018 [(0.009]
0.070
hexane
Mole Fractions
0.012 [(0.001]
0.888 [(0.008]
0.006
0.901
nd
0.806 [(0.025]
0.012 [(0.010]
0.768 [(0.036]
0.007 [(0.001]
0.689 [(0.058]
nd
0.796 [(0.003]
nd
0.689 [(0.034]
nd
0.687 [(0.005]
0.019
0.601
nd
0.680 [(0.009]
nd
0.617 [(0.012]
0.014
0.528
glycerol
0.026 [(0.049]
0.011
0.024 [(0.028]
0.008 [(0.013]
0.013 [(0.018]
0.007 [(0.002]
0.021 [(0.016]
0.008 [(0.001]
0.009
0.028 [(0.001]
0.019 [(0.012]
0.073
0.007 [(0.014]
0.003
0.006 [(0.007]
0.002 [(0.003]
0.003 [(0.004]
0.002 [(0.000]
0.005 [(0.004]
0.00 [2(0.000]
0.002
0.008 [(0.000]
0.005 [(0.003]
0.022
methyl oleate
0.882 [(0.033]
0.936
0.827 [(0.029]
0.891 [(0.008]
0.824 [(0.022]
0.938 [(0.001]
0.816 [(0.020]
0.888 [(0.003]
0.809
0.919 [(0.003]
0.876 [(0.007]
0.878
0.774 [(0.005]
0.860
0.666 [(0.014]
0.755 [(0.004]
0.635 [(0.013]
0.858 [(0.001]
0.636 [(0.010]
0.749 [(0.002]
0.607
0.854 [(0.002]
0.744 [(0.004]
0.850
glycerol
0.009 [(0.007]
0.002
0.012 [(0.011]
0.002 [(0.000]
nd
0.002 [(0.002]
0.005 [(0.004]
0.002 [(0.001]
0.001
nd
0.002 [(0.002]
0.005
0.008 [(0.006]
0.002
0.010 [(0.009]
0.002 [(0.000]
nd
0.002 [(0.002]
0.004 [(0.003]
0.002 [(0.001]
0.001
nd
0.002 [(0.002]
0.005
hexane
0.084 [(0.009]
0.051
0.137 [(0.010]
0.099 [(0.004]
0.163 [(0.002]
0.053 [(0.001]
0.158 [(0.004]
0.102 [(0.001]
0.181
0.051 [(0.001]
0.102 [(0.004]
0.044
0.211 [(0.013]
0.135
0.318 [(0.019]
0.241 [(0.007]
0.362 [(0.007]
0.138 [(0.002]
0.355 [(0.007]
0.247 [(0.002]
0.390
0.135 [(0.002]
0.250 [(0.006]
0.123
methanol
a Values given in square brackets represent (2s/xN (see eq 1); the absence of a value in square brackets indicates a single observation. The abbreviation nd denotes a value that was not detectable (a peak area
corresponding to an injected mass of less than 0.003 mg of glycerol, 0.001 mg of hexane, or 0.0005 mg of methanol could not be detected).
methyl oleate
tieline
Table 2. Overall Compositions and Average Liquid-Liquid Equilibria Compositions for the Quaternary System of Methyl Oleate, Glycerol, Hexane, and Methanol at 20 C and 1 bar
446
MSD )
nk
cal 2
(xexp
ilku - xilku)
i)1 l)1 k)1 u)1
(2)
IL
nk
k)1
I
MAD )
nk
cal
|xexp
ilku - xilku|
i)1 l)1 k)1 u)1
(3)
IL
nk
k)1
cal
where xexp
ilku and xilku respectively denote the experimental and
calculated compositions of component i in phase l that belongs
to tieline k and the replicate data point of u. I represents the
number of components, L the number of phases, K the number
of experimental tielines, and nk the total number of replicated
data points for the kth tieline. In the current study, I ) 4, L )
2, and K ) 12. The value of nk varies for each tieline from one
to four replicates, and the total number of individual tieline
K
measurements, k)1
nk, is 30. The MSD and MAD values of
the calculated tielines, relative to the experimental tielines, show
that both models are very capable of predicting the phase
behavior of this system (see Table 5). The 95% confidence
intervals for the expected true values of the mean squared
deviation and the mean absolute deviation (E[MSD] and
E[MAD], respectively) were also calculated over 240 single data
points and are reported in Table 5. No significant difference
was observed between the E[MAD] values obtained using the
UNIFAC and Modified UNIFAC activity coefficient models.
Similarly, no significant difference was observed between the
E[MSD] values obtained using the UNIFAC and Modified
UNIFAC activity coefficient models. To illustrate the closeness
of the model predictions to the experimental tielines graphically,
the experimental compositions were plotted versus the corresponding predicted compositions in Figure 3. The predicted
compositions for both phases show good agreement with the
observed data.
Table 3. Predicted Mole Fractions at Equilibrium of the Quaternary System of Methyl Oleate, Glycerol, Hexane, and Methanol, Using the
UNIFAC Activity Model at 20 C and 1 bar
Methyl Oleate-Rich Phase (Upper Phase)
tieline
methyl oleate
glycerol
hexane
methanol
methyl oleate
glycerol
hexane
methanol
1
2
3
4
5
6
7
8
9
10
11
12
0.078
0.091
0.165
0.197
0.229
0.194
0.258
0.269
0.319
0.294
0.339
0.394
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.001
0.000
0.001
0.001
0.892
0.894
0.791
0.767
0.703
0.789
0.683
0.692
0.618
0.687
0.619
0.584
0.030
0.015
0.043
0.036
0.068
0.017
0.059
0.038
0.063
0.019
0.041
0.021
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.713
0.841
0.661
0.718
0.560
0.847
0.615
0.728
0.617
0.850
0.730
0.852
0.017
0.015
0.016
0.015
0.016
0.014
0.015
0.013
0.013
0.012
0.011
0.010
0.271
0.144
0.323
0.267
0.424
0.140
0.371
0.259
0.370
0.138
0.259
0.138
tieline
methyl oleate
glycerol
hexane
methanol
methyl oleate
glycerol
hexane
methanol
1
2
3
4
5
6
7
8
9
10
11
12
0.078
0.091
0.166
0.198
0.232
0.193
0.261
0.271
0.324
0.294
0.342
0.395
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.915
0.906
0.819
0.789
0.738
0.801
0.713
0.713
0.645
0.699
0.639
0.595
0.007
0.003
0.015
0.013
0.030
0.006
0.026
0.016
0.031
0.008
0.019
0.010
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.712
0.845
0.658
0.716
0.556
0.850
0.611
0.726
0.611
0.851
0.725
0.851
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.287
0.154
0.341
0.283
0.443
0.149
0.388
0.273
0.388
0.148
0.274
0.148
UNIFAC
Modified UNIFAC
0.00046 ( 0.00013
0.00061 ( 0.00019
0.0151 ( 0.0020
0.0157 ( 0.0025
Simulation of the Quaternary Phase Diagram. The liquidliquid phase diagram of quaternary systems can be displayed
graphically by plotting the data in a pyramid, where each of
the corners represent one of the four components. Figure 4
represents the estimated three-dimensional surface of the twophase region shown by the shaded area, for the methyl oleateglycerol-hexane-methanol system at room temperature and
atmospheric pressure obtained using the UNIFAC activity
coefficient model. Every point inside the two-phase region,
which is surrounded by the surface shown, represents a mixture
of the four components and will be separated into two liquid
phases at physical equilibria. One end of each experimental
tieline shown in Figure 4 is approximately on the methanol-
Figure 3. Experimental mole fractions versus predicted mole fractions for (4) methyl oleate, (2) glycerol, (b) hexane, and (O) methanol.
448
ri )
t t Rt
qi )
t t Qt
and ln Ri is given as
ln Ri )
with
t t (ln t - ln (i)t )
i
ln t ) Qt 1 - ln(
Acknowledgment
The financial support of Natural Sciences and Research
Council of Canada (NSERC) is acknowledged. The authors also
wish to thank Dr. Benjamin C. Y. Lu for his assistance with
some thermodynamic concepts.
b )
ln
Ci
()
() [ ( )
( )
T
Q bX b
d QdXd
b xj
j)1
j
Xb )
d xj
j)1 d
j
ln i ) ln Ci + ln Ri
[()
ln Ci ) ln Vi + 1 - Vi - 5qi ln
with
ri3/4
Vi )
i
i
i
i
1
) ln
+1- zqi ln
+1xi
xi
2
i
i
with
xjrj3/4
j)1
and
i )
xiri
Vi )
xjrj
j)1
i )
xiqi
ri
n
xjrj
j)1
where
xjqj
j)1
d dd
ln i ) ln Ci + ln Ri
( )]
btb
-adb
where ln Ci is given as
where ln Ci is given as
db ) exp
b bb ) - b
ri )
t t Rt
i
Vi
Vi
+1Fi
Fi
and
MSD - 1.96
qi
Fi )
xjqj
j)1
Var(SD)
K
IL
e E[MSD] e
nk
k)1
MSD + 1.96
where
qi )
t t Qt
ln
with
t t (ln t - ln
i
ln t ) Qt 1 - ln(
( )]
d dd
QbXb
d QdXd
bjxj
j)1
n
d xj
j)1 d
Var(SD) )
IL
nk - 1
nk
(AD - MAD)2
Var(AD)
K
IL
e E[MAD] e
nk
k)1
MAD + 1.96
nk - 1
k)1
db ) exp -
IL
MAD - 1.96
Var(AD) )
btb
Xb )
nk
k)1
cal
AD ) |xexp
ilku - xilku|
(i)
t )
b bb ) - b
b )
IL
and ln Ri is given as
Ri
Var(SD)
nk
(SD - MSD)2
k)1
Nomenclature
Var(AD)
K
IL
nk
k)1
450