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When transesterifying alcohols with fats and oils to produce biodiesel, the phase
behavior and respective distribution of catalyst and alcohol between liquid phases can
signicantly impact both reaction rates and product workup. To better understand this
phase behavior, the distribution of methanol and catalysts, potassium hydroxide and
sulfuric acid, between the biodiesel and alcohol phases was experimentally investigated
and modeled. Experimental vapor-liquid equilibrium data were modeled by using the
Wilson activity coefcient model and two temperature-independent model parameters are
used to obtain good agreement between calculated and experimental data. The distribution coefcients of methanol between biodiesel and glycerin phases were accurately
predicted by the VLE activity coefcients and Wilson model. 2005 American Institute of
Chemical Engineers AIChE J, 51: 1274-1278, 2005
Introduction
Currently, fossil fuels are used in diesel engines and are
essential in industrialized nations. However, petroleum-based
diesel fuels increase environmental pollution. In order to solve
this problem, use of fatty acid methyl esters (FAME) derived
from vegetable oils and animal fats as diesel fuel extenders
(biodiesel) has received considerable attention because of its
many environmental benets. Transesterication is used to
convert triglycerides to FAME. The transesterication of vegetable oils with alcohols using basic or acid homogeneous
catalysts has been studied extensively1-4. Many studies have
identied the most important variables that inuence the transesterication reaction including; the reaction temperature, the
type and amount of catalyst, the reaction time, and so on.5-9
However, partitioning phenomenon in the biodiesel production
(namely, the distribution of methanol and catalysts among the
transesterication products) has not been extensively studied.
The distribution of a solute among coexisting liquid phases
Correspondence concerning this article should be addressed to G. J. Suppes at
suppesg@missouri.edu.
1274
April 2005
AIChE Journal
(1)
xP
i i
Sat
i
(2)
(3)
Experimental procedures
Materials. Methanol HPLC grade, glycerin certied
A.C.S., potassium hydroxide certied A.C.S. pellets and sulfuric acid certied A.C.S. were purchased from Fisher Scientic Co. (Fairlawn, NJ). SOYGOLD Biodiesel Fuel (soybean
oil methyl esters) was purchased from AG Environmental
Products L.L.C. (Omaha, NE). The pure biodiesel, glycerin and
methanol were used to simulate the system of transesterication products. The potassium hydroxide and sulfuric acid were
used to simulate the basic and acid catalyst in the transesterication.
Distribution of Catalysts. The simulation of the distribution of basic and acid catalysts was carried out by loading
varying amounts of methanol, biodiesel, and glycerin at given
temperatures. Three different molar ratios of 0:1:3, 3:1:3 and
6:1:6 methanol/glycerin/biodiesel were used to examine the
distribution of catalysts between the glycerin-rich and biodiesel-rich phases at 25 and 75C.
For the 25C measurement, the biodiesel, glycerin, methanol
and catalyst (1 wt. % potassium hydroxide or 0.5 wt. % sulfuric
acid) were individually added into a 50-mL separatory funnel
and weighed. The funnel was stoppered and shaken to ensure
AIChE Journal
April 2005
1275
Table 1. Distribution of Basic and Acid Catalyst among Glycerin/Biodiesel Mixture Loaded with Different Amounts of
Methanol at 25C and 75C
Solute, wt.%
Temperature
C
Solute
25
1 wt.% KOH
75
1 wt.% KOH
25
75
Solvent*
Glycerin-rich
Phase
Biodiesel-rich
Phase
K**
0:1:3
3:1:3
6:1:3
0:1:3
3:1:3
6:1:3
0:1:3
3:1:3
6:1:3
0:1:3
3:1:3
6:1:3
8.60
5.79
4.29
8.11
5.57
4.13
4.52
2.91
2.27
3.39
1.98
1.60
0.088
0.061
0.056
0.172
0.125
0.119
0.075
0.055
0.049
0.108
0.071
0.066
97.6
94.5
77.1
47.2
44.5
34.7
60.3
52.9
46.3
31.4
27.9
24.2
Methanol, wt.%
Molar Ratio*
Glycerin
Biodiesel
3:1:3
6:1:3
3:1:3
6:1:3
37.3
54.2
35.9
41.7
3.41
6.38
4.79
8.60
10.9
8.5
7.5
4.8
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April 2005
ln 1 lnx1 x2 12 x2
21
12
x1 x2 12 x2 x1 21
(4)
(5)
Mole Fraction
Methanol
100C
120C
0.0430
0.1543
0.2714
0.4374
0.4983
0.6909
0.7930
0.8994
0.9543
0.28
0.86
1.40
2.21
2.52
3.08
3.21
3.27
3.31
0.54
1.79
3.12
4.57
4.93
5.63
5.72
5.96
6.14
AIChE Journal
Mole Fraction
Methanol
100C
120C
0.0554
0.1314
0.2421
0.4182
0.5520
0.7419
0.09
0.22
0.43
0.83
1.21
2.00
0.18
0.46
0.89
1.81
2.45
3.67
ln 2 lnx2 x1 21 x1
ij
21
12
x1 x2 12 x2 x1 21
V jL
ij
L exp
RT
Vi
Figure 2. Experimental and calculated activity coefcients for the methanol-glycerin binary system
at 100 and 120C.
(6)
The solid line and dashed line represent the Wilson model
with regressed parameters of ij -868.41 and ji 1106.17.
(7)
Equation 8 allows experimentally measured values of the distribution coefcient to be independently conrmed by VLE
data from a solution model.
Using the Wilson activity coefcient model parameters of
ij 1326.57 and ji 797.20 for methanol-biodiesel
system, and ij -868.41 and ji 1106.17 for methanolglycerin system the distribution coefcients for these systems were calculated. Table 5 compares experimental and
predicted values of the distribution coefcients of methanol.
Good agreement between experimental and predicted data
was obtained.
Here VLi and VLj are the molar volumes of each component.
These ij and ji are the Wilson paired energy parameters
which are considered temperature-independent and regressed
to experimental data by ChemCAD Process Flowsheet Simulator 5.317. The parameters ij and ji were determined at 100
and 120C and found to give a good t to data at both
temperatures (Figure 1 and 2). The dashed line denotes the
regressed line for the 120C experimental data, and the solid
line denotes the regressed line for 100C experimental data.
The distribution coefcient can be related to the activity
coefcients of the distributing components through the LLE
condition of Eq. 1. The distribution coefcient for solute mole
fractions is equal to the reciprocal of the ratio of the solute
activity coefcients in the two phases. In terms of the equilibrium relation, the ratio of concentrations of a solute in twoliquid phases becomes
iBDT, P, x iBD
x iAl
BD K
xi
iAlT, P, x iAl
(8)
Conclusions
In a molar ratio of 3:1 blend of biodiesel and glycerin
system, the distribution coefcients of methanol and catalysts
(potassium hydroxide and sulfuric acid) were measured. The
distribution of methanol was observed to be in good agreement
with values predicted by the Wilson equation and independent
VLE data. Methanol, potassium hydroxide and sulfuric acid,
each, selectively distributed into the glycerin phase. On a mass
basis, the measured distribution coefcients varied from a high
of 97 for potassium hydroxide at 25C to a low of 4.8 for
methanol at 75C.
The presence of methanol in the biodiesel-glycerin system
tends to increase the distribution of catalyst in the biodiesel
phase. However, if the mass of all other components are held
Table 5. Comparison between Experimental (Ke) and
Predicted (Kp) Distribution Coefcients, Obtained Using the
Experimental Equilibrium Data and the ChemCAD Process
Flowsheet Simulator 5.3
Temperature Molar
C
Ratio*
25
Figure 1. Experimental and calculated activity coefcients for the methanol-biodiesel binary system at 100 and 120C.
The solid line and dashed line represent the Wilson model
with regressed parameters of ij 1326.57 and ji 797.20.
AIChE Journal
April 2005
75
3:1:3
6:1:3
3:1:3
6:1:3
Experimental
Value
Predicted Value
Ke**
Biodiesel
Glycerin
Methanol
*** Methanol
*** Kp**
2.5208
2.0418
1.9881
1.4379
1.643
1.371
1.510
1.316
0.717
0.838
0.794
0.891
2.29
1.64
1.90
1.48
1277
Acknowledgment
This work has support by the University of Missouri Program for
Research Infrastructure, College of Engineering, Dept. of Chemical Engineering, the NSF STTR program, the USDA-NRI program grant number
2001-35504-11208, and Renewable Alternatives LLC. We are grateful to
Dr. William Sutterlin for helpful suggestions and discussions; Mohanprasad Dasari for GC analysis.
6.
7.
8.
9.
10.
11.
12.
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April 2005
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AIChE Journal