Fuel 85 (2006) 16661670

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Thermodynamic study on cloud point of biodiesel

with its fatty acid composition*
Hiroaki Imahara, Eiji Minami, Shiro Saka *
Department of Socio-Environmental Energy Science, Graduate School of Energy Science,
Kyoto University, Yoshida-honmachi, Sakyo-ku, Kyoto 606-8501, Japan
Received 6 December 2005; received in revised form 4 March 2006; accepted 7 March 2006
Available online 3 April 2006

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

point lower, and simultaneously, causes high vulnerability to

oxidation.
Since biodiesel fuel takes over these characteristics of
feedstock, biodiesel from vegetable oils such as rapeseed oil
has better fluidity in cold climate than that from animal fats
such as beef tallow. If the composition of unsaturated fatty
acids gets too high, however, its biodiesel tends to be
vulnerable to oxidation. This tendency causes adverse effects
on fuel conservation and combustion. From the point of tradeoff relation between fluidity in cold climate and oxidation
stability, biodiesel fuel is mainly produced from semi-drying
oils such as rapeseed and soybean oils.
For the commercialization of biodiesel, however, not only
rapeseed and soybean oils but also palm oil, whose production
is about 30 Mt/year in the world [1], waste beef tallow and
other various oils/fats should be efficiently utilized. Concurrently, optimized production of biodiesel fuel is necessary to
satisfy fuel specification. Based on these situations, prediction
of fuel characteristics from various feedstocks, especially fuel
cold properties, is one of the important issues.
Cold properties of diesel fuel is evaluated by the following
three temperatures; cloud point (CP) at which crystallization
begins, cold filter plugging point (CFPP) at which fuel starts to
plug a fuel filter, and pour point (PP) at which fuel no longer
pours. If prediction of cold properties can be made feasible,
troublesome measurements can be eliminated and the feedstock can be appropriately selected to produce a biodiesel that

H. Imahara et al. / Fuel 85 (2006) 16661670

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

can meet specification. Since CP is the trigger for negative

effect on fuel injection, its prediction is extremely meaningful.
For the fossil diesel fuel, CP prediction was studied through
thermodynamic approach, based on solidliquid equilibria
[29]. Non-ideality in both liquid and solid phases is described
with activity coefficients that were calculated using modified
UNIFAC model for liquid phase and Wilson, NRTL, and
UNIQUAC models for solid phase [58]. From these studies,
Coutinho et al. reported that UNIQUAC model was the best to
describe solid phase non-ideality.
Even though behavior of biodiesel at lower temperature has
been investigated by some researchers [1012], CP prediction
from fatty acid composition has never been carried out yet. In
this study, therefore, correlations of fuel cold properties of
biodiesel with its fatty acid composition were investigated.

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

Limited, Tokyo), covering a range from K60 8C (213 K) to

51 8C (324 K). This tester is in accordance with JIS K2269.
2.2. Thermodynamic model (solidliquid equilibria)
As mentioned above, the CP is a temperature at which the
solid phase begins to form, thus it can be thermodynamically
described by the solidliquid equilibrium. At the equilibrium,
the fugacity of each component i for liquid and solid phases
(fiL
and fiS
, respectively) is identical as follows
fiL
Z fiS
; thus gLi xi fiL Z gSi zi fiS

(1)

where gLi and gSi are activity coefficients of a component i in

liquid and solid phases, respectively. fi is fugacity of a pure
component i in each phase. The xi and zi are mole fractions of a
component i in liquid and solid phases, respectively. According
to thermodynamic theory, the ratio of fi in both phases can be
described as follows [15]




DHm;i Tm;i
fL
DC Tm;i
ln iS Z
K1 K i
K1
RTm;i
T
R
T
fi
C

DCi Tm;i
ln
R
T

(2)

where DHm,i and Tm,i are enthalpy and temperature of melting,

and DCi is a difference in heat capacity of a pure component i
between liquid and solid forms. Generally, DCi is small enough
to be omitted compared with other terms in Eq. (2). The ratio of
fi can be thus simply rewritten as follows [16]:




T KTm;i
DHm;i
fiS
gLi xi
Z
exp
T
Z
Z
q
(3)
i
RT
Tm;i
fiL
gSi zi

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

H. Imahara et al. / Fuel 85 (2006) 16661670

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).

As is well known for the CP prediction, non-ideality in

liquid phase is negligible when ambient pressure around the
system is low [9]. In this study, therefore, activity coefficient in
the liquid phase gLi was regarded as unity, assuming that liquid
phase is an ideal solution. In the case of biodiesel fuel, methyl
esters of saturated fatty acids such as C16:0 and C18:0 have
relatively high CP and are considered to be a precursor for

crystallization. This means that the solid phase consists mainly

of these saturated methyl esters at the equilibrium point.
Therefore, activity coefficient in solid phase gSi can be also
regarded as unity as well as one in liquid phase. In this study,
furthermore, the value of Tm,i in Eq. (3) was replaced by CP
measured for pure esters, while the values in Table 2 were used
for DHm,i. Although DHm,i values for some esters are not

H. Imahara et al. / Fuel 85 (2006) 16661670

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.

3. Results and discussion

3.1. Binary mixture of fatty acid methyl esters
Fig. 1 shows changes in CP of various binary mixtures of
fatty acid methyl esters. In Fig. 1(a), CP was found to be 259 K
for pure methyl oleate (C18:1) and increased largely with
methyl palmitate (C16:0) added even in its low mole fraction. It
was then increased gradually and monotonously at higher
fraction of C16:0 and finally reached at the intrinsic value of
C16:0 (301 K). Similar behaviors were also observed for binary
mixtures of other saturated and unsaturated esters, as shown in
Fig. 1(b)(d). These results mean that saturated esters, which
have higher CP than unsaturated ones, have a significant effect
on characterizing its cold properties. For the binary mixture of
unsaturated esters, C18:1 and methyl linoleate (C18:2) shown in
Fig. 1(e), a monotonous increase was similarly observed.
In the case of the mixtures consisting of only saturated esters
as in Fig. 1(f)(h), on the other hand, dissimilar behavior was
observed. In Fig. 1(f), CP of pure C18:0 was at 310 K, and it
gradually decreased to the eutectic point (296 K), and then
increased. This tendency in CP change is very similar with
other mixtures of two saturated esters. It indicates that binary
mixture of saturated esters has the lower CP at a eutectic point
than that of either component of esters.
The existence of such eutectic point indicates that the first
crystal formed at the CP consists of only a single pure methyl
ester especially for saturated one having high melting point.
Based on this assumption, one of the mole fraction zi in solid
phase can be assigned to be 1.0, and others are null at the CP.
The CP value of the binary mixture can be, thus, expressed by
the following equation
x1 Z q1 T or

x2 Z q2 T

(4)

1669

and the eutectic point Tep can be calculated by:

q1 Tep C q2 Tep Z 1

(5)

By applying these equations, theoretical curves for CPs

were drawn in Fig. 1 represented by solid lines. Although some
discrepancies exist between experimental result and theoretical
curve, measured values of CP were fitted well with this simple
model.
For binary systems of saturated/unsaturated and unsaturated/unsaturated esters, obvious eutectic point was not found
experimentally since difference in melting point between two
esters was too large. However, these binary systems could be
also described by the same model as well as saturated/saturated
mixtures, in which only one ester is firstly crystallized at CP.
3.2. Multi-component mixture of fatty acid methyl esters
For applying the model to the multi-component mixture,
above four fatty acid methyl esters were mixed at various ratios
and CPs were measured. Obtained results are shown in Table 3
with calculated values from composition of these fatty acid
methyl esters. As one can observe from sample nos. 13, CPs
were almost the same, although the mole fractions of C18:1 and
C18:2 changed in their composition. This behavior was also
observed with regard to sample nos. 4 and 5, where saturated
ester fractions were fixed and only unsaturated ones changed.
On the other hand, as shown in sample nos. 611, a drastic
increase in CP was observed when the total amount of saturated
esters increased. These data suggest that CP can be mainly
determined by the amount of saturated esters, regardless of
composition of unsaturated ones. Among the sample nos.
1215, however, a specific composition of saturated esters
(C16:0 and C18:0) was found to offer the lowest CP, even though
the total amount of them was not changed. This tendency is
similar to the eutectic point as previously noted in Fig. 1.
In addition, CP of the multi-component mixtures could be
successfully estimated by using only the proposed model with
values of DHm,i available in the literature.

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

Mole fraction of methyl esters

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

H. Imahara et al. / Fuel 85 (2006) 16661670

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

Fatty acid methyl esters (wt%)

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

3.3. Biodiesel fuel

Acknowledgements

Table 4 shows measured CP of various biodiesel fuels with

calculated ones from composition of four methyl esters. It
could be noted that CPs for actual biodiesel were also well
predicted by the model. Discrepancies observed were possibly
attributed to assumption of ideal solution and crystal, effect of
other shorter or longer fatty acid methyl esters.
Interestingly, the calculated values were close to the
measured ones even though calculation was carried out without
the effect of methyl linolenate (C18:3), which has extremely low
CP. This is an indication that, as observed in multi-component
mixture (shown in Table 3), CP depends mostly on the
saturated ester content and the effect of unsaturated ester
composition can be negligible.
As mentioned above, high unsaturation of fatty acid methyl
esters causes polymerization and oxidation of the fuel.
Therefore, mono-unsaturated fatty acid methyl esters such as
C18:1 is considered to be better than poly-unsaturated ones such
as methyl linoleate (C18:2) and C18:3 for oxidation stability
without any adverse effect on fuel cold properties.

This work has been done under the Kyoto University 21

COE program Establishment of COE on Sustainable-Energy
System (2002. 4w) supported by the Ministry of Education,
Culture, Sports, Science and Technology, Japan, and the
Highly Efficient Bioenergy Conversion Project (2003.
6w2006. 3) from New Energy and Industrial Technology
Development Organization (NEDO), for which the authors are
highly acknowledged.

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.