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Abstract
Temperature dependent vapor pressures of the methyl esters of fourteen fatty acids that are commonly present in biodiesel fuels were
predicted by the Antoine equation and a group contribution method. The predicted boiling points of these esters up to a pressure of
100 mmHg were within G1.0% of reported data for these two methods. Normal boiling points were determined from both the predicted
vapor pressure and a correlation equation and the prediction errors were less than 5 K comparing to available published data. The vapor
pressure and normal boiling points of 19 real-world biodiesel fuels were predicted and compared with reported data where available. The
prediction errors of normal boiling points were less than 1.0%, and the predicted vapor pressures were also observed to closely match the
reported data among the methyl esters of soybean oil, rapeseed oil and tallow. The predicted results showed that, except for coconut and
butterfat, most of the methyl esters of the vegetable oils and animal fats had a normal boiling point in the range of 620630 K. A sensitivity
analysis indicated that the variation of fatty acid composition and the uncertainty of the normal boiling point of C18:2 were the main factors
that affected the predicted normal boiling points of the biodiesel fuels.
q 2005 Elsevier Ltd. All rights reserved.
Keywords: Biodiesel; Methyl ester; Normal boiling point; Vapor pressure
1. Introduction
Animal fat or vegetable oil ester biodiesel fuels have
been shown to be a very promising alternative to crude-oil
derived diesel fuels because they are renewable, they reduce
particulate matter emissions and the net production of CO2
from combustion sources, and they relieve US dependence
on foreign crude oil. Because of these advantages, biodiesel
has gained considerable attention and support in the past
few years, as demonstrated by its commercial availability in
many parts of the US and the provision of state tax
incentives to encourage its use. The provision of standards
and quality control in the manufacture and distribution of
biodiesel is necessary to insure that the quality and
properties of this fuel are reliable and consistent when
* Corresponding author. Tel.: C1 217 333 8595; fax: C1 217 244 0323.
E-mail address: wyuan@uiuc.edu (W. Yuan).
0016-2361/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2005.01.007
944
B
T
logPv Z A K
B
T CC
(1)
(2)
(3)
2. Method
The Antoine equation, Eq. (3), was used to predict the
vapor pressure of saturated FAMEs from C8 to C18 with the
aid of published vapor pressure data as detailed in Section
2.1. The normal boiling points of these esters were also
C8:0
C10:0
C12:0
C14:0
C16:0
C18:0
C18:1
C18:2
C18:3
C20C24
equations:
ln Pi;vp Z
Nk A1k C
"
C Mi
X
k
B1k
K C1k ln T K D1k T
T 1:5
Nk
B2k
A2k C 1:5
K C2k ln T K D2k T
T
#
CQ
(4)
Q Z x1 q C x2
q ZaC
b
K g ln T K dT
T 1:5
945
(5)
(6)
x1 Z f0 C Nc f1
(7)
x2 Z s0 C Ncs s1
(8)
Fig. 1. Correlation of Tnb with carbon number for alkanes and FAMEs.
946
(9)
where Pvi and Pvmix are the vapor pressures of the ith pure
FAME and the mixture respectively, and xi is the molar
fraction of that composition.
The normal boiling point of the mixture of FAMEs was
determined from the mixture vapor pressure by finding the
temperature where the mixture vapor pressure equaled
1 atm. All the calculations above were processed in a
computer program developed for this study.
Table 2
Reported and predicted boiling points of selected FAMEs at various pressures
Esters
0.53 (4)
0.8(6)
1.07(8)
1.33(10)
2.67(20)
5.33(40)
8.0(60)
10.67(80)
13.33(100)
342.1
339.5
340.7
371.3
370.0
370.4
397.6
397.1
396.9
423.5
421.9
421.5
445.8
445.4
444.7
466.8
467.2
467.2
347.0
344.8
345.9
376.5
375.7
375.8
403.6
403.0
402.6
429.8
428.1
427.6
452.4
451.8
451.3
472.0
473.8
474.2
351.0
348.9
350.0
381.2
380.2
380.1
408.2
407.7
407.2
435.0
433.0
432.5
458.0
456.9
456.5
479.8
479.1
479.9
364.1
362.8
363.7
395.5
395.0
394.5
424.2
423.2
422.6
451.8
449.4
448.9
475.4
473.9
474.3
***
496.8
***
378.4
378.1
378.7
411.0
411.2
410.5
441.0
440.5
439.7
470.0
467.5
467.6
***
492.6
***
***
516.2
***
387.3
387.9
388.2
420.4
421.4
420.7
452.0
451.4
450.9
481.4
478.9
479.8
***
504.4
***
***
528.6
***
392.3
395.2
395.4
428.0
429.0
428.5
459.6
459.6
459.4
***
487.5
***
***
513.3
***
***
537.9
***
398.8
401.1
401.2
433.8
435.2
434.8
465.2
466.2
466.3
***
494.4
***
***
520.4
***
***
545.4
***
Temperature (K)
C8:0
C10:0
C12:0
C14:0
C16:0
C18:0
Reporteda
Predictedb
Predictedc
Reporteda
Predictedb
Predictedc
Reporteda
Predictedb
Predictedc
Reporteda
Predictedb
Predictedc
Reporteda
Predictedb
Predictedc
Reporteda
Predictedb
Predictedc
324.7
321.3
322.4
351.9
350.3
351.4
376.0
376.7
377.0
400.3
400.3
400.3
421.7
423.1
422.2
442.6
444.2
443.2
335.7
332.5
333.7
364.0
362.5
363.1
389.2
389.2
389.2
414.5
413.6
413.3
436.4
436.8
436.0
457.8
458.3
457.9
947
Table 3
Tnb and Antoine equation constants of pure FAMEs
C8:0
C10:0
C12:0
C14:0
C16:0
C18:0
C18:1
C18:2
C18:3
C20:0
C20:1
C22:0
C22:1
C24:0
Tnba
Tnbb
Tnbc
Tnbd
466.2
497.2
535.2
568.2
611.2
625.2
622.2
639.2
***
***
***
***
***
***
457.9
504.0
541.6
573.4
601.0
625.3
622.2
639.2
639.2
647.0
644.0
666.7
663.7
684.6
466.2
501.6
539.8
570.5
599.4
628.9
***
***
***
***
***
***
***
***
***
496.2
536.0
569.7
598.8
624.6
622.2
639.2
639.2
647.6
644.6
668.4
665.4
687.4
9.4660
10.0582
9.4297
9.6258
9.5714
9.3746
9.9155
8.2175
8.1397
10.3112
10.3525
10.6867
10.7518
11.0539
1765.00
2261.99
1958.77
2194.36
2229.94
2174.39
2583.52
1450.62
1387.93
2987.15
3009.62
3380.86
3423.99
3776.89
K70.61
K53.91
K96.99
K95.50
K111.01
K131.23
K96.15
K188.03
K196.16
K84.56
K81.66
K73.20
K69.43
K62.90
(11)
C18:1
C18:3
C20:0
C24:0
Pressure
(Pa)
Predicted Tb
(K)
Reported Tb
(K)
Ref.
2000
400
300
500
486.7
446.8
465.9
514.9
487
455
461
505
[5]
[5]
[5]
[16]
948
Table 5
Fatty acid compositions of nineteen fats and oils provided by Allen et al. [17] and Goering et al. [18]
Oil or fat type
C8:0
C10:0
C12:0
C14:0
C16:0
C18:0
C20:0
C22:0
C24:0
C18:1
C22:1
C18:2
C18:3
Soybean
Rapeseed
Beef tallow
Peanut
Canola
Olive
Coconut
Corn
Palm
Safflower
Sunflower
Sunola
Butterfat
Lard
Cottonseed
Crambe
Linseed
H.O. safflower
Sesame
0
0
0
0
0
0
8.3
0
0.1
0
0
0
5.5
0
0
0
0
0
0
0
0
0.1
0
0
0
6
0
0.1
0
0
0
3
0.1
0
0
0
0
0
0
0
0.1
0
0
0
46.7
0
0.9
0
0
0
3.6
0.1
0
0
0
0
0
0.1
0
3.3
0
0.1
0
18.3
0
1.3
0.1
0.1
0
11.6
1.4
0.8
0
0
0.34
0
10.3
2.7
25.2
10.4
3.9
11
9.2
9.9
43.9
6.6
6
3
33.4
25.5
22.9
2.07
4.92
5.46
13.1
4.7
2.8
19.2
8.9
3.1
3.6
2.9
3.1
4.9
3.3
5.9
4.4
11.4
15.8
3.1
0.7
2.41
1.75
3.92
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2.09
0
0.23
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.8
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1.12
0
0
0
22.5
21.9
48.9
47.1
60.2
75.3
6.9
29.1
39
14.4
16
88.2
27.8
47.1
18.5
18.86
19.7
79.36
52.84
0
50.9
0
0.2
0.5
0
0
0
0
0
0
0
0
0
0
58.51
0
0
0
54.1
13.1
2.7
32.9
21.1
9.5
1.7
56.8
9.5
75.5
71.4
4.3
3.1
8.9
54.2
9
18.03
12.86
30.14
8.3
8.6
0.5
0.5
11.1
0.6
0
1.1
0.3
0.1
0.6
0.1
0.6
1.1
0.5
6.85
54.94
0
0
Fig. 2. Predicted and measured vapor pressure of RME, SME and TME.
Table 6
Comparison of predicted and measured normal boiling point [9] of RME,
SME and TME
RME
SME
TME
Predicted
Tnb (K)
Measured
Tnb (K)
Absolute
error (K)
Relative
error (%)
642.5
627.0
612.4
642.1
620.8
611.3
0.4
6.2
1.1
0.06
1.0
0.18
949
Table 7
The range of the weight percent of fatty acid compositions for soybean, rapeseed, and beef tallow methyl esters reported by Graboski and McCormick [3]
Fuel
C14:0
C16:0
C18:0
C18:1
C18:2
C18:3
C22:1
Soybean
Rapeseed
Beef tallowa
0.1
0
3.3
711
25
2530
36
13 (2)
19.2 (21)26
2234
1022.5 (15)
3948.9 (42)
5060
1020
2.7
210
510
0.5
0
5060
0
include the compositions listed in Table 5. A computational step of 0.5% of weight percent for each fatty acid
was applied.
The computed maximum and minimum normal boiling
points of SME, RME and TME due to variations in
composition are shown in Table 8. The difference
between minimum and maximum values is the expected
variance of normal boiling point due to changes in
composition. Considering that the reported Tnb could
fall into the lower or upper end of the Tnb range, the
expected range of the Tnb was calculated from the
reported value G (MaxMin), which represents the full
range of possible predicted normal boiling points for the
variations of compositions in Table 7. The predicted value
of SME (627.0 K) is a little beyond its expected range.
This suggested that there could be other factors, besides
the variance of fatty acid compositions in the source
materials, that affected the predicted normal boiling point
of the biodiesel fuels.
3.3.2. Normal boiling points of C18:2 and C18:3 methyl
esters
As described in Section 2.2, the published data for the
normal boiling point of highly-unsaturated FAMEs, such as
C18:2 and C18:3 are limited. For the fatty acid chains with
more than one double bond, the normal boiling point
depends on both the number and the position of these double
bonds, similar to the unbranched alkenes. In order to study
the effect of the uncertainty of the normal boiling point of
C18:2 and C18:3 on the predicted normal boiling point of
biodiesel fuels, combinations of normal boiling point for
C18:2 and C18:3 were applied within the range of 620
650 K at a computational step of 2 K. The boiling point of
other pure FAMEs were fixed in accordance with the values
in Table 1. The lowest and highest predicted fuel normal
boiling points versus the normal boiling point of C18:2 of
SME, RME and TME are shown in Fig. 4.
Table 8
Minimum and maximum limits and expected range of Tnb caused by
composition variation in fatty acid composition
RME
SME
TME
Min (K)
Max (K)
Expected range
(K)
640.5
625.8
611.1
650.0
630.3
612.7
637.6646.6
616.3625.3
609.7612.9
950
Acknowledgements
Fig. 4. The effect of Tnb of C18:2 and C18:3 on predicted Tnb of the fuels.
4. Conclusions
1. The Antoine equation and a group contribution method
were used to predict the temperature dependent vapor
pressures of fourteen pure fatty acid methyl esters that
are commonly present in biodiesel fuels. Antoine
equation constants were calculated for each of these
esters. The predicted boiling points of these esters up to
100 mmHg were within G1.0% of reported data for
these two methods with the exception of C18:3 and
C24:0 which had a prediction error of about 1.9%.
2. A correlation equation was provided to estimate the
normal boiling points of fourteen pure fatty acid methyl
esters within a 1.5 K prediction error. The normal
boiling points were also determined by the predicted
vapor pressure from the Antoine equation and the
prediction errors were less than 5 K compared to
published data.
3. The vapor pressures of nineteen biodiesel fuels were
predicted by weighting the vapor pressure of each
component in the mixture with the percent composition
of each component in the ester blends. The predicted
temperature dependent vapor pressures were found to
closely match the reported data.
4. The normal boiling points of the nineteen biodiesel fuels
were calculated from the predicted vapor pressure. The
maximum prediction error was 1.0%. Except for coconut
and butterfat, most of the methyl esters of the vegetable
oils and animal fats had a normal boiling point in the
range of 620630 K.
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