Professional Documents
Culture Documents
www.fuelfirst.com
Abstract
A thermodynamic study was made for binary mixture of various fatty acid methyl esters to establish a prediction model for the cloud point of
actual biodiesel fuel from various feedstocks. When considering a eutectic system for ester mixture, measured values of cloud point were fitted
well with a theoretical curve according to solidliquid equilibria, even though an ideal solution was assumed. A simple model to agree with
experimental results was, thus, proposed for predicting the cloud point of actual biodiesel. Through this study, it was found that cloud point of
biodiesel could be determined only by the amount of saturated fatty acid methyl esters regardless of composition of unsaturated esters.
q 2006 Elsevier Ltd. All rights reserved.
Keywords: Biodiesel; Cloud point; Fatty acid composition
1. Introduction
Biodiesel is an alternative for petroleum fuel that can be
commercially produced through transesterification of vegetable oils and animal fats with alcohol and alkaline catalyst.
Utilization of biodiesel fuel will greatly contribute to
mitigation of our environmental issues such as global warming
and air pollution since its feedstock of biomass is carbonneutral and low in sulfur content.
These oils/fats are characterized according to their oxidation
stabilities and cold properties, which are attributed to their fatty
acid composition. In general, unsaturated fatty acids are low in
melting point, while saturated ones high. Thus, oils, which
contain a large amount of unsaturated fatty acids are liquid,
whereas, fats, which are rich in saturated ones are solid at an
ambient temperature. These oils/fats are classified into
vegetable-derived and animal-derived groups. The former
group is further classified into three sub-groups, drying oil,
semi-drying oil, and non-drying oil in order of the degree of
unsaturation. The high degree of unsaturation makes a melting
*
This paper is based on the article in the proceedings of Science in Thermal
and Chemical Biomass Conversion held in Victoria (2004) and refined.
* Corresponding author. Tel./fax: C81 75 753 4738.
E-mail address: saka@energy.kyoto-u.ac.jp (S. Saka).
0016-2361/$ - see front matter q 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2006.03.003
1667
Table 1
Typical fatty acid composition of various oils/fats feedstocks (values in wt%) [14]
Oils/fats
Lauric
C12:0
Myristic
C14:0
Palmitic
C16:0
Stearic
C18:0
Oleic
C18:1
Linoleic
C18:2
Linolenic
C18:3
Others
Sunflower
Rapeseed
Soybean
Olive
Peanut
Palm
Coconut
Beef tallow
0.0
0.3
48.2
0.1
0.0
1.1
18.4
2.3
6.1
4.2
10.5
12.2
11.2
42.7
9.2
23.1
4.1
2.0
3.9
2.5
3.2
4.3
2.9
15.4
18.6
60.8
23.3
71.9
45.5
40.9
6.7
45.8
69.0
20.6
53.0
10.5
31.7
9.2
1.6
3.5
0.3
9.2
7.6
0.6
0.4
0.2
0.6
1.9
3.2
1.7
2.3
8.0
1.3
13.0
9.2
2. Experimental method
2.1. Materials
Table 1 shows fatty acid composition of typical oils/fats. It
is clear that most of the feedstocks, except for coconut oil,
consist mainly of palmitic (C16:0), stearic (C18:0), oleic (C18:1)
and linoleic (C18:2) acids, in which the first number in the
subscript is total number of carbon atoms in the fatty acid unit
of the molecule, while the second is that of double bonds. In
this study, therefore, methyl esters of above four fatty acids,
purchased from Nacalai Tesque, Inc., Kyoto, were chosen for
the CP measurement. These methyl esters were mixed at
various molar ratios to make binary or multi-component
mixture as a model of actual biodiesel fuel.
To prepare actual biodiesel fuels, refined oils such as linseed
oil, safflower oil, sunflower oil, rapeseed oil, soybean oil, olive
oil, palm oil and beef tallow were converted to their methyl
esters with alkali-catalyzed method reported by Freedman et al.
[13]. Yield of methyl esters and their composition for each
biodiesel fuel were analyzed by high performance liquid
chromatography (HPLC) carried out with a Shimadzu LC-10A
system under the following conditions: column, STR ODS-II;
flow rate, 1.0 mL/min; eluent, methanol; detector, refractive
index detector; temperature, 40 8C. The CP of fatty acid methyl
ester mixtures and actual biodiesel fuels was measured by a
Mini Pour/Cloud Point Tester MPC-102 (TANAKA Scientific
(1)
DCi Tm;i
ln
R
T
(2)
Table 2
Molar enthalpy of melting for each fatty acid and its methyl ester [17,18]
Fatty acid species
Lauric C12:0
Myristic C14:0
Palmitic C16:0
Stearic C18:0
Oleic C18:1
Linoleic C18:2
DHm,i (J/mol)
Fatty acid
Methyl ester
36,610
45,020
53,970
62,340
39,600
33,600
44,480
55,350
64,430
1668
Fig. 1. CP changes of various binary mixtures as a function of mole fraction (C12:0, methyl laurate; C14:0, methyl myristate; C16:0, methyl palmitate; C18:0, methyl
stearate; C18:1, methyl oleate; C18:2, methyl linoleate; circle, CP; solid line, theoretical curve).
available in the literature, they are very close to those for their
fatty acids as shown in Table 2. For such methyl esters, DHm,i
values of fatty acids was alternatively used.
x2 Z q2 T
(4)
1669
(5)
Table 3
Measured and calculated CPs of the multi-component mixture of fatty acid methyl esters
Sample no.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
CP (K)
C16:0
C18:0
C18:1
C18:2
Measured
Calculated
0.11
0.11
0.11
0.10
0.10
0.21
0.31
0.36
0.54
0.73
0.81
0.21
0.16
0.05
0.10
0.10
0.05
0.06
0.08
0.09
0.05
0.16
0.21
0.79
0.69
0.59
0.80
0.69
0.59
0.59
0.40
0.19
0.10
0.79
0.79
0.79
0.79
0.10
0.20
0.30
0.80
0.10
0.10
270
270
271
280
280
279
285
284
290
293
294
279
276
284
290
273
273
273
283
283
281
285
287
292
296
298
281
277
288
291
1670
Table 4
Measured and calculated CPs of biodiesel fuel from various oils/fats feedstocks with their fatty acid composition
Oils/fats
Linseed
Safflower
Sunflower
Rapeseed
Soybean
Olive
Palm
Beef tallow
CP (K)
C16:0
C18:0
C18:1
C18:2
C18:3
Others
Measured
Calculated
6.7
6.4
6.1
4.3
10.7
10.7
39.5
23.9
3.7
2.2
4.2
1.9
3.2
2.6
4.1
17.5
21.7
13.9
24.0
61.5
25.0
78.7
43.2
43.9
15.8
76.0
63.5
20.6
53.3
5.8
10.6
2.3
52.1
0.2
0.4
8.3
5.4
0.7
0.2
0.1
1.3
1.8
3.1
2.5
1.5
2.4
12.3
268
267
274
267
272
268
283
286
273
269
275
267
273
273
288
289
Acknowledgements
4. Conclusion
Correlations between CP and fatty acid composition were
investigated to establish a CP prediction model for biodiesel.
As a result, CPs of methyl ester mixtures including actual
biodiesel fuel could be well described with solidliquid
equilibria, assuming that only one ester component is crystallized at CP. The CP is, thus, determined mainly by the amount
of saturated esters and does not depend on the composition of
unsaturated ones.
From these results, it is possible to estimate cold properties
of biodiesel fuel made from various oils/fats feedstocks, thus
providing a useful tool to determine optimized fatty acid
methyl ester composition.
References
[1] Food and Agriculture Organization of the United Nations (FAO).
FAOSTAT statistical databasecommodity balances (Updated on
August 27, 2004); 2005.
[2] Mirante FIC, Coutinho JAP. Fluid Phase Equilib 2001;180:24755.
[3] Coutinho JAP, Dauphin C, Daridon JL. Fuel 2000;79:60716.
[4] Coutinho JAP. Energy Fuels 2000;14:62531.
[5] Coutinho JAP, Andersen SI, Stenby EH. Fluid Phase Equilib 1995;103:
239.
[6] Coutinho JAP. Fluid Phase Equilib 1999;158-160:44757.
[7] Coutinho JAP. Ind Eng Chem Res 1998;37:48705.
[8] Larsen BL, Rasmussen P, Fredenslund A. Ind Eng Chem Res 1987;26:
227486.
[9] Coutinho JAP, Daridon JL. Energy Fuels 2001;15:145460.
[10] Dunn RO, Bagby MO. JAOCS 1995;72:895904.
[11] Dunn RO, Shockley MW, Bagby MO. JAOCS 1996;73:171928.
[12] Kinast JA. National renewable energy laboratory NREL/SR-510-31460;
2003.
[13] Freedman B, Pryde EH, Mounts TH. JAOCS 1984;63:137580.
[14] Ministry of Agriculture, Forestry and Fisheries, Japan. Wagakuni no
Yushi-jijo (Present Status of Oils/fats in Japan); 2000 (in Japanese).
[15] Prausnitz JM, Lichtenthaler RN, Azevedo EG. Molecular thermodynamics of fluid phase equilibria. 3rd ed. Upper Saddle River, NJ: PrenticeHall; 1999.
[16] Suppes GJ, Goff MJ, Lopes S. Chem Eng Sci 2003;58:175163.
[17] Kigawa H. Thermodynamic properties. Japan oil chemists society, the
handbook of oil chemistry 4th ed. Tokyo: Maruzen; 2001, p. 27389 (in
Japanese).
[18] Ueno S, Miyazaki A, Yano J, Furukawa Y, Suzuki M, Sato K. Chem Phys
Lipids 2000;107:16978.