Fuel Processing Technology 133 (2015) 152160

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Fuel Processing Technology

journal homepage: www.elsevier.com/locate/fuproc

Biodiesel production from mixtures of waste sh oil, palm oil and waste
frying oil: Optimization of fuel properties
Vanessa F. de Almeida a, Pedro J. Garca-Moreno b,, Antonio Guadix b, Emilia M. Guadix b
a
b

College of Chemical Engineering, State University of Campinas UNICAMP, PO Box 6066, 13081-970 Campinas, Brazil
Department of Chemical Engineering, University of Granada, 18071 Granada, Spain

a r t i c l e

i n f o

Article history:
Received 18 December 2014
Received in revised form 29 January 2015
Accepted 30 January 2015
Available online 13 February 2015
Keywords:
Biodiesel
Fish oil
Palm oil
Frying oil
Optimization
Fuel properties

a b s t r a c t
The present work studies the inuence of waste sh oil, palm oil and waste frying oil as raw material on biodiesel
properties. The experimental planning was executed through acid esterication (6:1 methanol to oil ratio, 1 wt.%
sulfuric acid, at 60 C, 1 h) followed by transesterication (9:1 methanol to oil ratio, 0.5 wt.% sodium hydroxide, at
60 C for 1 h). Biodiesel samples showed yield higher than 82%, reaching 90% for palm oil (33.3 wt.%) and waste
frying oil (66.7 wt.%) biodiesel. FAME content was higher than 92.3% and had a maximum of 98.5% for waste sh
oil (33.3 wt.%) and palm oil (66.7 wt.%) biodiesel. Special cubic models were used to t experimental data, and
were optimized by response surface methodology and multi-objective optimization. Viscosity (4.3 mm2/s) and
COM (2.5 C) were minimized when pure sh oil was used as raw material, whereas IP maximum (22.0 h)
was found for palm oil biodiesel. Multi-objective optimization evidenced that although the use of the pure oils
as feedstock presented more advantages to biodiesel properties, the waste sh oil (42.1 wt.%) and waste frying
oil (57.9 wt.%) mix is benecial, if the aim is IP (20%) and COM (80%) improvement.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Biodiesel is dened as mono-alkyl esters of vegetable oils or animal
fats, obtained by transesterication of an oil or fat with an alcohol [1].
It is a biodegradable and nontoxic biofuel, so is environmental benecial
[2]. That is one of the reasons why biodiesel has received increasing
attention, besides the fact of petroleum reserves are diminishing and
it is necessary to nd other competitive energy sources [3].
Fish oil is recommended in a healthy diet because of its content in
omega-3 polyunsaturated fatty acids such as eicosapentaenoic (EPA)
and docosahexaenoic (DHA) acids. [4]. However, rening of sh oil
extracted from sh wastes would result in low yields because of its
high content of free fatty acids and oxidation products [5]. Moreover,
waste sh oil might have a low amount of EPA and DHA reducing its
application on the pharmaceutical and functional food elds [6]. Thus,
biodiesel using waste sh oil as feedstock has been recently researched
[712]. Nevertheless, biodiesel from sh oil has low oxidative stability,
mostly due to its high content of polyunsaturated fatty acids (PUFA)
containing more allylic methylene positions [13]. Biodiesel oxidation
is undesirable because it can increase viscosity and may lead to formation of insoluble species, which can lead to clog fuel lines and pumps
[14]. In order to improve this property, antioxidants can be added to
biodiesel [15] or sh oil can be mixed with more stable oils and used
as biodiesel feedstock [16].
Corresponding author. Tel.: +34 958241329; fax: +34 958248992.
E-mail address: pjgarcia@ugr.es (P.J. Garca-Moreno).

http://dx.doi.org/10.1016/j.fuproc.2015.01.041
0378-3820/ 2015 Elsevier B.V. All rights reserved.

In this sense, palm oil, which is usually employed as raw material for
biodiesel production, has a high resistance to oxidation due to its significant content of saturated fatty acids (SFA) [17]. Hence, it can be an
appropriated oil to be mixed with sh oil before transesterication.
Furthermore, waste frying oil, which is also more oxidatively stable
than sh oil, is a substantial alternative of feedstock since it is cheap
and diminishes the environmental impacts of inappropriate waste oil
disposals [18]. Most of the scientic works on oil mixtures as feedstock
are devoted to vegetable oils such as rapeseed, soybean and sunower
[19,20]. Some studies are also focused on mixtures of vegetable oils
and animal fats. For instance, Galvan et al. [21] evaluated the oxidative
stability of biodiesel obtained from a ternary mixture of soybean oil
(50%), beef tallow (20 wt.%) and poultry fat (30 wt.%). Nevertheless, except for the work of Costa et al. [16] who carried out a preliminary study
on the production of biodiesel from a mixture of waste sh oil (20 wt.%)
and waste olive oil (80 wt.%), studies evaluating the fuel properties of
biodiesel obtained from mixtures of waste sh oil and vegetable oils
have not been reported in the literature.
Therefore, the aims of this work were: a) to study, by means of
experimental design and analysis of variance (ANOVA), the inuence
of mixtures of waste sh oil, palm oil and waste frying oil as feedstock
on the fuel characteristics of the biodiesel obtained, b) to obtain, by
means of response surface methodology, the feedstock mixture that
optimizes viscosity, oxidative stability and cold ow properties of the
biodiesel produced, and c) to determine, by means of multi-objective
optimization, the feedstock mixture that optimizes simultaneously the
fuel properties of the biodiesel samples.

V.F. de Almeida et al. / Fuel Processing Technology 133 (2015) 152160

2. Materials and methods

2.1. Materials

153

capillary column of fused silica Omegawax (0:25 mm 30 m, 0:25 m

standard lm; Supelco, Bellefonte, PA) and a ame-ionization detector.
Nitrogen was used as the carrier gas, and the total column ow was
44 ml/min. The oven temperature was initially set at 150 C for 3 min,
then increased at a rate of 10 C/min until 240 C, and then kept at
this temperature during 12 min. Matreya (Pleasant GAP, PA) n-3
PUFAs standard (catalogue number 1177) was used for the qualitative
fatty acid determination and methyl heptadecanoate was employed as
analytical standard for the quantitative determination. Firstly, the
FAME of biodiesel samples was identied and then the peak areas
were utilized to quantify the FAME content, according to Eq. (1):

Fish oil was purchased from Industrias Anes, S.L. (Pontevedra,

Spain) and presented the following properties: acid value of 16.4 mg KOH/g
oil, peroxide value of 2.5 meq O2/kg oil and a composition of 32.7 wt.% in
oleic acid, 11.7 wt.% in linoleic acid, 3.6 wt.% in EPA and 5.7 wt.% in DHA.
Palm oil was donated by the company Lpidos Santiga S.A. (Barcelona,
Spain) and presented an acid value of 16.3 mg KOH/g oil, peroxide value of
2.1 meq O2/kg oil and a composition of 44.5 wt.% in palmitic acid and
38.6 wt.% in oleic acid. Waste frying oil was collected from local domestic consumers (Granada, Spain) and had an acid value of 2.4 mg KOH/g oil, peroxide
value of 4.6 meq O2/kg oil and a composition of 55 wt.% in oleic acid and
26.7 wt.% in linoleic acid. Sodium hydroxide ( 99%), potassium
hydroxide in ethanol (0.1 M), n-heptane ( 99%) and methyl
heptadecanoate ( 99%) were purchased from Sigma-Aldrich, while
methanol ( 99.8%) and diethyl ether ( 99%) were acquired from
Scharlau. Ethanol (99%) and anhydrous sodium sulfate (99%) were
provided by Panreac, whereas sulfuric acid (95%) was purchased from
VWR International. Phenolphthalein (1% in ethanol) was provided by
J. T. Barker.

Where C = fatty acid methyl content (%); A = total peak area;

AEI = peak area corresponding to the methyl heptadecanoate; CEI =
concentration of methyl heptadecanoate solution in heptane (mg/ml);
VEI = volume of methyl heptadecanoate solution (ml); m = mass of
biodiesel sample (mg).
The biodiesel yield was calculated following the Eq. (2):

2.2. Production process

Yield

Waste sh oil, palm oil and waste frying oil were used to produce
biodiesel. A simplex centroid design with 16 experiments was carried
out. It comprised 16 different oil contents as biodiesel feedstock,
including pure oils and mixtures of two and three oils in different ratios.
The content in free fatty acids (FFA) of the three oils was higher than
2 mg KOH/g oil, what impairs the biodiesel production, since it reduces
the yield because of soap formation. Therefore, a two-step process
was performed [22]. The rst step consists in an acid-catalyzed pretreatment that converts the FFA content into methyl esters, reducing
acid value below 2 mg KOH/g oil. In summary, 200 g of oil, methanol
(molar ratio methanol to oil of 6:1) and 1 wt.% sulfuric acid as catalyst
were placed into a at-bottomed ask. The samples were stirred at
300 rpm and kept at 60 C for 60 min, using a hot plate controlled by
a thermo regulator. After the reaction ending, the reactor content was
transferred to a separating funnel to settle for 1 h. The bottom phase
containing mainly unconverted oil and methyl esters was collected to
carry out the next step [13].
In the second step the unreacted oil was submitted to an alkaline
transesterication. In brief, the collected phase from the rst step was
introduced into a at-bottomed ask with methanol (molar ratio
methanol to oil of 9:1) and 0.5 wt.% sodium hydroxide. The samples
were also stirred at 300 rpm and kept at 60 C for 60 min, using a hot
plate controlled by a thermo regulator. It should be noted that some
amount of the alkali catalyst may have reacted in the neutralization of
the rst step samples, which had an increased acidity.
After the reaction completion, the content of the reactor was poured
into a separating funnel, where it settled during 1 h. Then, the top phase
containing mainly methyl esters was collected to be puried by washing, three times, with distillated water at 50 C [13]. The aim of this
step is removing impurities, such as unreacted catalyst, soap, glycerol
and unreacted methanol. Finally, samples were vacuum ltered through
anhydrous sodium sulfate and stored under nitrogen in amber bottles at
20 C until analysis.

X 
A AEI
AEI

CEI  VEI
 100:
m

MBiodiesel  C
 100:
MOil

Where MBiodiesel = mass of nal biodiesel (g); MOil = mass of oil

used as raw material (g); C = fatty acid methyl content descripted
above (%).
2.4. Kinematic viscosity
Oils and biodiesel viscosities were evaluated using a rotational
viscometer Haake model VT500 and a NV sensor (Fisher Scientic,
Aalst, Belgium). The samples were kept at 40 C using a water bath
and 10 ml of each sample was introduced between the two coaxial
cylinders, maintaining the specied temperature. Shear stress () was
measured using different shear rates (), from 0 to 3000 s 1. Then,
the dynamic viscosity (, Pa.s) was determined by the slope of the line
obtained when plotting shear stress (, Pa) versus shear rate (, s1)
for all the samples. The density of all the samples was measured at
40 C. Using an electronic pipette, 5 ml of each sample were taken and
then weighted to determine its mass. The dynamic viscosity and density
were used to determine the kinematic viscosity at 40 C, expressed
in mm2/s.
2.5. Oxidative stability
The biodiesel oxidative stability was evaluated using the Rancimat
method, a test of accelerated oxidation. The Metrohm Rancimat model
743 (Methrom Instruments, Herisau, Switzerland) apparatus was used
to carry out the measurements as specied in the European standard
EN 15751 [25]. A stream of ltered, cleaned and dried air in a rate of
10 l/h was bubbled into 7.5 g of biodiesel samples in a glass tube, maintained at 110 C. The efuent air containing volatile organic compounds
was bubbled into a vessel containing 60 ml of distillated water where
the conductivity was continually measured. The induction period (IP)
was automatically calculated by the program. It represents the resistance time (in hours) of the biodiesel to oxidation.

2.3. FAME content and yield

2.6. Differential scanning calorimetry
Gas chromatography was used to determine the fatty acid methyl
ester (FAME) content in biodiesel samples, using the European standard
EN 14103 [23]. Samples were analyzed according to the method from
Camacho-Paez et al. [24] in a gas chromatographer Agilent 7890A
(Agilent Technologies, S.A., Santa Clara, California, USA) connected to a

Differential scanning calorimetry (DSC) was employed to evaluate

the cold ow properties of the biodiesel produced. DSC heating curves
were used to determine the completion of melt onset temperature
(COM), minimal high melting peak temperature (P1) and melting

154

V.F. de Almeida et al. / Fuel Processing Technology 133 (2015) 152160

point (MP) of biodiesel samples. The analysis was executed in a DSC

apparatus Metler Todelo DSC 1 (Metler Toledo, Barcelona, Spain). Ten
mg of biodiesel samples was hermetically sealed in an aluminum pan,
and also an empty vessel was used as reference. To determine the
biodiesel transition phases, a ramp of 5 C/min was used under nitrogen
atmosphere (50 ml/min). All the samples were cooled until 80 C,
kept at this temperature during 10 min, and then heated until 100 C.
From each DSC analysis, it obtained a graphic of heat ow (mW) versus
temperature (C), where it is possible to nd the values of COM, P1
and MP.
2.7. Acid value
The acid value shows the FFA content of the sample. It was determined for the oils, the products from the rst step reaction and nal
biodiesel, according to the European standard EN 14104 [26]. The method is based on titration of the sample, diluted in ethanoldiethyl ether
mixed solvent, with potassium hydroxide solution in ethanol
employing phenolphthalein as indicator to detect the end point. Results
were calculated according to Eq. (3) and they were expressed in
milligrams of potassium hydroxide per gram of sample (mg KOH/g).
Acid value

56:1  V  C
m

Where V = volume of potassium hydroxide solution (ml); C = concentration of potassium hydroxide solution (M); m = mass of sample
(g).
2.8. Statistical analysis and optimization
Statgraphics Centurion XVI was used to correlate biodiesel properties (yield, viscosity, induction period, COM, P1, MP) to oil content and
type (waste sh oil, palm oil and waste frying oil) in the raw material.
Special cubic models were developed by means of response surface
methodology and were then used to predict biodiesel properties according to Eq. (4)
Y

X3

bX
i1 i i

X3

b XX
ib j i j i j

X3

b XX X :
ib jbk i jk i j k

Where Y = value of the specic property; X = content of oil in the

raw material (%), bi is related to the linear effect, bij and bijk are related
to the interaction between the respective oils. The analysis of variance
ANOVA was used to evaluate the biodiesel properties with a condence
level of 95% (p b 0.05). The estimated parameters were used to generate
contour plots and to dene the feedstock composition that optimizes
biodiesel properties.
2.9. Multi-objective optimization
Multi-objective optimization is required if an issue with several
objectives is proposed. In this work, the objectives are minimizing
viscosity and COM and maximizing IP, which is a controversial issue.
The Pareto Front is dened as a set of non-inferior solutions, with the
aim of satisfying all the three objectives [27]. The weighted-sum
method was used to generate the Pareto Front [28]. This method
consists of expressing a comprehensive objective function (OBJ) as a
linear combination of the individual objectives (viscosity, IP and
COM), by means of weight factors (wi), which quanties the relative
importance given to the accomplishment of each individual objective,
Eq. (5):
OB J w1 :viscosity w2 :IP w3 :COM:
Where w1 + w2 + w3 = 1 and 0 wi 1.

It should be noted that the IP contribution is negative in order to set

the problem as a minimization of the objective function. The Solver Tool
in MS Excel software was used to execute all the calculations for the
multi-objective optimization.
3. Results and discussion
3.1. Characterization of biodiesel samples
Table 1 shows the experimental values of FAME, SFA, MUFA and
PUFA content, yield, kinematic viscosity, IP, COM, P1 and MP of the
biodiesel samples.
3.1.1. FAME content and yield
High FAME content was found in all biodiesel samples, since the
minimum FAME content was 92.3% for the experiments 5 (50 wt.%
palm oil and 50 wt.% frying oil) and 16 (33.3 wt.% sh oil and
66.7 wt.% frying oil). The highest FAME content was 98.5%, found for
the experiment 12 (33.3 wt.% sh oil and 66.7 wt.% palm oil). However,
just the experiments 12 (33.3 wt.% sh oil and 66.7 wt.% palm oil), 14
(33.3 wt.% palm oil and 66.7 wt.% frying oil) and 15 (66.7 wt.% sh oil,
33.3 wt.% frying oil) were within the required value by the European
standard EN 14214 (96.5%) [29].
The fatty acids methyl esters of the waste sh oil biodiesel were
composed of 15.0 wt.% saturated fatty acids (SFA), 42.2 wt.% monounsaturated fatty acids (MUFA) and 26.1 wt.% PUFA. The palm oil biodiesel
had a considerably higher content of methyl esters of SFA (44.3 wt.%),
similar content of methyl esters of MUFA (35.8 wt.%) and lower content
of methyl esters of PUFA (10.0 wt.%). Last, the composition of waste
frying oil biodiesel was of 13.7 wt.% methyl esters of SFA, methyl esters
of 51.4 wt.% MUFA and 24.3 wt.% methyl esters of PUFA (Table 1). The
sum of methyl esters of SFA, MUFA and PUFA content in each biodiesel
sample were not 100 wt.%, because some unrecognized peaks, found at
the biodiesel chromatograms, which prevented all the fatty acids to be
identied. As expected, biodiesel from oil mixtures showed methyl
esters content of SFA, MUFA and PUFA proportional to the content of
these fatty acid types in the oils and to the amount of oil employed in
the mixture.
Yield was also high in all experiments, and varied between 82% for
the experiment 16 (33.3 wt.% sh oil and 66.7 wt.% frying oil) and 90%
for the experiment 14 (33.3 wt.% palm oil and 66.7 wt.% frying oil)
(Table 1). For biodiesel obtained from sh oil a yield of 85% was found
(Table 1). Garca-Moreno et al. [13] obtained a lower yield (79.9%) for
biodiesel from waste sh oil having similar fatty acid composition
(17.7 wt.% SFA, 42.8 wt.% MUFA and 33.2 wt.% PUFA) and using the
same operating conditions, except the catalyst content (1 wt.% of
NaOH). Another work also demonstrated that using 0.5 wt.% of NaOH
increases the biodiesel yield, comparing to 1 wt.% of NaOH [30]. Thus,
the difference in yield may be related to the catalyst content, which in
excess, contributes to soap formation. The yield found for biodiesel
obtained from palm oil (87.1%) was in the line of previous works.
Hayyan et al. [31] studied the production of biodiesel from sludge
palm oil using an acid esterication process (0.75 wt.% of sulfuric acid,
molar ratio of methanol to oil of 8:1, 60 min reaction time at 60 C)
previous to the transesterication. Despite these authors employed
different transesterication operating conditions (1 wt.% KOH, molar
ratio of methanol to oil of 10:1, 60 min of reaction at 60 C), they obtained a similar biodiesel yield (83.7%). It should be noted that the fatty acid
composition of the sludge palm oil employed (47.2 wt.% SFA and
52.8 wt.% unsaturated fatty acids) is similar to the palm oil used in
this study (50.3 wt.% SFA and 49.7 wt.% unsaturated fatty acids). Uzun
et al. [32] obtained the highest yield (96.0%) for biodiesel obtained
from waste frying oil by one-step transesterication process (0.5 wt.%
of NaOH, methanol to oil molar ratio of 7.5:1, 30 min of reaction at
50 C). This value is considerably higher than the yield (87.6%) obtained
in this work for experiment 2 (100% waste frying oil). Besides the

V.F. de Almeida et al. / Fuel Processing Technology 133 (2015) 152160

155

Table 1
Experimental design and measured values for the response variables.
Exp#

Fish oil
(%)

Palm oil
(%)

Frying oil
(%)

FAME
(%)

SFA
(%)

MUFA
(%)

PUFA
(%)

Yield
(%)

Viscosity
(mm2/s)

IP
(h)

COM
(C)

P1
(C)

MP
(C)

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

0.0
0.0
100.0
50.0
0.0
50.0
16.7
16.7
66.7
33.3
66.7
33.3
0.0
0.0
66.7
33.3

100.0
0.0
0.0
0.0
50.0
50.0
66.7
16.7
16.7
33.3
33.3
66.7
66.7
33.3
0.0
0.0

0.0
100.0
0.0
50.0
50.0
0.0
16.7
66.7
16.7
33.3
0.0
0.0
33.3
66.7
33.3
66.7

94.8
96.4
95.1
94.5
92.3
93.4
94.4
93.0
94.9
94.7
96.0
98.5
95.2
97.0
98.1
92.3

44.3
13.7
15.0
14.5
29.5
30.1
35.0
19.4
19.8
24.7
25.1
35.2
34.7
24.4
14.5
14.2

35.8
51.4
42.2
47.4
43.5
39.5
39.8
47.7
43.1
43.4
40.7
38.4
40.8
46.2
45.9
48.8

10.0
24.3
26.1
25.3
17.0
18.1
15.1
22.3
23.1
20.1
20.7
15.3
14.6
19.4
25.6
25.0

87.1
87.6
85.0
84.3
85.4
82.6
84.6
84.0
84.8
82.2
88.2
87.3
88.0
90.0
84.7
82.0

5.6
5.3
4.2
5.5
5.5
5.4
5.4
5.5
5.3
5.4
5.2
5.5
5.6
5.7
5.5
5.5

22.9
6.1
1.6
3.9
14.7
7.0
15.3
9.3
5.3
9.1
5.6
10.8
12.9
12.1
3.0
5.1

21.0
3.7
2.8
3.2
14.1
14.6
17.1
7.5
7.3
11.0
8.5
17.0
16.8
11.2
2.6
2.9

19.0
35.1
37.4
37.4
34.2
37.1
35.0
35.3
38.7
37.0
38.6
37.5
34.1
34.7
38.7
36.4

54.2
56.4
67.5
64.4
56.6
65.8
60.7
60.8
66.9
62.6
67.6
63.6
56.2
56.8
67.0
62.7

operating conditions, the yield differences are probably associated to

the differences in the MUFA and PUFA content of the frying oil used
by these authors (36.7 wt.% MUFA and 52.2 wt.% PUFA) when compared
to the waste frying oil employed in this study (56.6 wt.% MUFA and
26.6 wt.% PUFA). Furthermore, while these authors allowed the reaction
mixture to separate overnight, in this work the period of phase's separation lasted 1 h.
3.1.2. Viscosity
Viscosity is a key property for biodiesel, since high viscosity can
cause operational problems such as engine deposits [33]. Waste sh
oil, palm oil and waste frying oil had viscosity at 40 C of 33.7 mm2/s,
56.1 mm2/s and 45.2 mm2/s, respectively. After transesterication,
waste sh oil, palm oil and waste frying oil biodiesels had viscosity of
4.2 mm2/s, 5.6 mm2/s and 5.3 mm2/s, respectively (Table 1). Viscosity
reduction demonstrates that the transesterication process was
effective.
Table 1 shows that kinematic viscosity of the biodiesels obtained
ranged from 4.2 mm2/s for experiment 3 (100% sh oil) to 5.7 mm2/s
for experiment 14 (33.3 wt.% palm oil, 66.7 wt.% frying oil). The viscosity
value found for experiment 14 was not expected, since it was higher
than palm oil and waste frying oil biodiesel viscosity. It should be
noticed that, although the biodiesels obtained were close to meet the
European standard EN 14214 (3.55 mm2/s at 40 C) [24], only the
viscosity of the biodiesel produced using 100% sh oil as feedstock
(4.2 mm2/s) was in the range required.
Viscosity increases with chain length and decreases with the
number of double bonds in the chain [33]. Therefore, the lower viscosity
found for sh oil biodiesel (4.2 mm2/s) can be explained by its high
content in PUFA (26.1 wt.%), comparing to the biodiesel from palm oil
(10.0 wt.% PUFA) and waste frying oil (24.3 wt.% PUFA) (Table 1).
Moreover, cis double bonds present lower viscosity than trans double
bonds, which shows similar viscosity to a correspondent saturated
compound [33]. Waste frying oil is usually partially hydrogenated and
contains higher amounts of trans fatty acid chains [33]. This explains
the fact that frying oil biodiesel, with contents in SFA, MUFA and PUFA
similar to sh oil biodiesel, had a higher viscosity (5.3 mm2/s)
(Table 1). The higher viscosity for palm oil biodiesel (5.6 mm2/s) is associated to its high content in SFA (44.3%) (Table 1).
The viscosity values obtained in this work are in the line of previous
reported studies. For instance, Garca-Moreno et al. [13] found for sh
oil biodiesel (17.7 wt.% SFA and 33.2 wt.% PUFA), produced under the
same process conditions (except 1 wt.% NaOH), viscosities that varied
from 6.05 mm2/s to 6.66 mm2/s at 30 C. These values are higher than
found in this work (4.2 mm2/s) for waste sh oil biodiesel (15.0 wt.%
SFA and 26.1 wt.% PUFA) at 40 C. Taking into account that viscosity
decreases with temperature increase and that sh oil composition is

similar, the difference in viscosity may be reduced if both sh oil biodiesel viscosities were compared at 40 C. Sarin et al. [34] found for palm oil
biodiesel a viscosity at 40 C of 4.5 mm2/s, very similar to the value
found in this work (4.4 mm2/s) for the same biodiesel. Although they
did not show the fatty acid composition of biodiesel, the palm oil used
as feedstock has high content of saturated fatty acids (43.4 wt.% SFA),
as palm oil used in this study (50.3 wt.% SFA), which may explain the
close viscosities achieved. For waste cooking oil biodiesel (10.1 wt.%
SFA and 55.7 wt.% PUFA), Uzun et al. [32] found a viscosity value of
4.4 mm2/s at 40 C, lower than the viscosity value found in this work
(5.3 mm2/s) for the biodiesel obtained from waste frying oil
(13.7 wt.% SFA and 24.3 wt.% PUFA). This is explained by the difference
in the PUFA content between both oils [33].
3.1.3. Oxidative stability
Oxidative stability of biodiesel determines its fuel quality, especially
when storing biodiesel for a long period of time. The fatty acid composition of biodiesel is the main factor affecting its oxidative stability
[14]. Rancimat induction period (IP) was assayed as a measure of biodiesel resistance to oxidation. The lowest value of IP (1.6 h) was found
for sh oil biodiesel, while the highest value of IP (22.9 h) was obtained
for palm oil biodiesel (Table 1).
Similar values of IP for sh oil biodiesel were obtained by GarcaMoreno et al. [13]. These authors obtained IP values ranging from
1.05 h to 2.22 h. In the case of palm oil biodiesel, Sarin et al. [34]
found an IP value of 13.4 h, lower when comparing to the IP achieved
in this work for the same biodiesel (22.9 h), but much greater than
the required for the standard EN 14214 [29]. This is attributed to the
different fatty acid compositions of the palm oil employed as feedstock.
These researchers used palm oil with 40.3 wt.% palmitic acid and
43.4 wt.% oleic acid, whereas palm oil used in this study had 44.5 wt.%
in palmitic acid and 38.6 wt.% in oleic acid. In general terms, it was
observed that while IP decreases with the content of sh oil in the feedstock, IP increases with the content of palm oil. This is explained due to
adding palm oil (50.3 wt.% SFA, 38.6 wt.% MUFA and 11.1 wt.% PUFA)
increased the SFA content in the mixture, improving is resistance to
oxidation [33].
For biodiesel produced from waste frying oil, an IP of 6.1 h was
obtained. This value is considerably higher than the IP (0.9 h) found
by Uzun et al. [32], who produced waste frying oil biodiesel with a
higher unsaturated fatty acid content (89.8 wt.%) in comparison to the
produced in this study (75.7 wt.%). The mixtures of waste frying oil
(16.8 wt.% SFA, 56.6 wt.% MUFA and 26.7 wt.% PUFA) and waste sh
oil (16.2 wt.% SFA, 46.6 wt.% MUFA and 37.2 wt.% PUFA) produced a
fuel that showed IP values higher than pure waste sh oil biodiesel.
Both oils have similar content of unsaturated fatty acids (about
83.6 wt.%). However, waste sh oil had more polyunsaturated fatty

156

V.F. de Almeida et al. / Fuel Processing Technology 133 (2015) 152160

acids, which are more unstable, because of the bis-allylic positions. This
fact explains why sh oil biodiesel is more susceptible to oxidation and
the mix of waste sh oil and waste frying oil as biodiesel feedstock
increases the biodiesel oxidation resistance.
It should be noticed that most IP values are up the European
standard EN 14214 specications (minimum IP of 8 h) (Table 1) [29].
Thus, antioxidant addition is not necessary.

3.1.4. Cold ow properties

Biodiesel often presents poor cold ow properties, due to the high
melting point of methyl esters of SFA found in biodiesel [35]. DSC curves
were analyzed to determine COM, P1 and MP for the 16 biodiesel
samples (Table 1).
From 3 to 5 distinct peaks were found at the DSC curves (Fig. 1). The
rst peak varied from 60.54 C for the experiment 11 (66. 7 wt.% sh
oil and 33.3 wt.% palm oil) to 50.98 C for the experiment 1 (100%
palm oil) and it may be associated to the methyl esters of PUFA. The
last peak varied from 4.88 C for the experiment 8 (16.7 wt.% waste
sh oil, 16.7 wt.% palm oil and 66.6 wt.% frying oil) to 18.99 C for the
experiment 1 (100% palm oil) and it is associated to the methyl esters
of SFA.
The number of peaks between the rst and the last peaks varied
from 13 (intermediated peaks) (Fig. 1). They are associated to the
content of methyl esters of unsaturated fatty acids. There may be
more than one intermediated peak when the methyl esters of unsaturated fatty acids have considerably different melting point temperatures. Otherwise, there would be just one larger peak. The
intermediated peaks ranged between 50.05 C for experiment 15
(66.7 wt.% sh oil and 33.3 wt.% frying oil) to 23.58 C for experiment
1 (100% palm oil). For the experiments 1, 2, 5, 7, 13 and 14, three
intermediated peaks were found, being one of them an exothermic
peak (Fig. 1a). According to Foon et al. [36], the exothermic peak occurs
due to a simultaneous melting and crystallization of the palm oil methyl
esters in the samples. The fatty acid methyl esters that are already
melted start to re-crystallize in the crystals that have higher MP, and
then at a superior temperature they all melt together. Therefore, the
re-crystallization may cause the exothermic peaks found in some DSC
heating curves.
COM is dened as the temperature at which the melting phenomenon ends, varied from 2.6 C for the experiment 15 (66.7 wt.% sh oil
and 33.3 wt.% frying oil) to 21 C for the experiment 1 (100% palm
oil). For biodiesels obtained from pure oils (experiments 13), COM
value decreases (21.0, 3.7 and 2.8 C) with the polyunsaturated
compounds content (10.0, 24.3 and 26.1 wt.%, respectively) (Table 1).
Garca-Moreno et al. [13] found for waste sh oil biodiesel COM values
that varied from 3.31 C to 3.83 C, which are in the range of the value
found in this work for waste sh oil biodiesel (2.8 C). The similar
content in SFA explains the result accordance. Foon et al. [36] found
for palm oil biodiesel (49.41 wt.% SFA) a DSC heating curve with the
same prole to the achieved here, with four endothermic peaks and
one exothermic peak. The COM value was 24.7 C, very close to the
COM value for palm oil biodiesel (44.3 wt.% SFA) determined in this
work (21.0 C). The superior COM value found for these authors is
probably related to the slight higher SFA content in palm oil biodiesel.
P1 values were around 36.5 C, in exception of P1 value for the
biodiesel obtained from only palm oil (19 C) (Table 1). Foon et al.
[36] found for palm oil biodiesel P1 value of 24.32 C. The P1 value
difference may be due to the content of SFA methyl esters that melt in
higher temperature, which seems to be greater in the palm oil biodiesel
used in this work, and so is expressed for a higher peak at the DSC
heating curve. MP values ranged from 67.6 C for experiment 11
(66.7 wt.% sh oil and 33.3 wt.% palm oil) to 54.1 C for the experiment 1 (100% palm oil) (Table 1). Foon et al. [36] found MP value for
palm oil biodiesel (49.41 wt.% SFA) of 61.55 C, similar to that found
in this study (54.1 C) for the palm oil biodiesel (44.3 wt.% SFA).

Fig. 1. DSC heating curve of biodiesel: (a) Exp. 1, (b) Exp. 9 and (c) Exp. 10.

V.F. de Almeida et al. / Fuel Processing Technology 133 (2015) 152160

3.1.5. Acid value

The acid value is a measure of the content of free fatty acids in the
biodiesel and it determines its corrosiveness and long-term stability.
All the biodiesel samples are in accordance to the European standard
EN 14214 (b0.5 mg KOH/g) [29], having acid values lower than
0.39 mg KOH/g of biodiesel.

3.2. Statistical modeling and optimization of biodiesel properties

Special cubic models were selected to relate the content of sh oil,
palm oil and frying oil in the raw material to yield, viscosity, IP, COM,
P1 and MP values. Table 2 shows the polynomial coefcients, calculated
by multiple regressions for each response variable, as well as the associated p-values and R2 for each model obtained. All the models were
statistically signicant (p b 0.05), except the model found for yield
(p = 0.2325). Furthermore, it should be noted that, apart for yield, all
the models explain the experimental data to a large extent with coefcients of determination (R2) higher than 0.8616, reaching 0.9935 for
COM.
Viscosity, IP and COM were chosen as most important output variables indicating the fuel properties of the biodiesels. Thus, they were
optimized using response surface methodology. Firstly, the goodness
of the t of the models obtained for these variables was also proved
by plotting measured values against the predicted ones, for viscosity
(Fig. 2a), IP (Fig. 2b) and COM (Fig. 2c). A regression line correlated
the data, whose equation and coefcient of determination were
inserted in each gure. A high coincidence was observed between this
regression line and the diagonal. Furthermore, almost all points were
inside the region delimited by the dotted lines, which show a deviation
of 10% between predicted and measured values (Fig. 2). Both facts
indicate a high correlation.
Afterwards, through the polynomial equations obtained and using
response surface methodology, contour maps were generated where
viscosity, IP and COM values were determined by the raw material
composition in waste sh oil, palm oil and waste frying oil (Fig. 3ac).
For biodiesel properties of improvement, viscosity and COM were set
to minimize, whereas IP was set to be maximum. Viscosity inuences
the atomization of a fuel and upon injection into the combustion
chamber and thus the formation of engine deposits. The higher the
viscosity, the greater is the appearance of such problems [37]. COM is
the temperature in which the fatty acid methyl esters start to crystallize.
The crystals rapidly grow and agglomerate, clogging fuel lines and lters
[37]. Therefore, COM was set to be minimum, so biodiesel can be used at
low temperatures without causing operational problems. The biodiesel
oxidative stability is also an important issue, mainly when biodiesel is
stored during an extended period of time [37]. As IP is a measure of

157

biodiesel oxidative stability and biodiesel requires high resistance to

oxidation in order to avoid the formation of high-molecular-weight
products from polymerization reactions, IP was set to maximize.
The small circles at the diagrams (Fig. 3ac) are indicating the
composition that optimizes biodiesel properties. The circle allocated at
the diagram tip (Fig. 3a), which represents 100% sh oil, indicates that
biodiesel viscosity is minimized (4.3 mm2/s) when pure sh oil is
used as feedstock. The bold contour line in Fig. 3a shows the maximum
viscosity value at 40 C specied in EN 14124 (5.0 mm2/s). Fig. 3b indicates that biodiesel IP is maximum (22.0 h) when just palm oil is
employed as raw material. A bold contour line was also added to
Fig. 3b showing in this case the minimum IP value according to EN
14124 (8.0 h). At Fig. 3c, the indication is evidencing that pure sh oil
as raw material minimizes COM (2.5 C). The bold contour line in this
gure shows the minimum COM value required for grade D biodiesel
in the European standard EN 14214. According to this standard, grade
D biodiesel should have a maximum cloud point of 5 C, which denotes
a COM value lower than 10.2 C when calculated by Eq. (6) [38]:
COM 7:06 0:6377  CP:

Where COM: completion of melt onset temperature, C; and CP:

cloud point, C.
The optimum values found t well with the minimum experimental
values obtained for viscosity (4.2 mm2/s) and COM (2.6 C) and the
maximum for IP (22.9 h). According to Knothe et al. [37], fuel properties
are strongly inuenced by the properties of individual fatty esters in
biodiesel. SFA methyl ester content increases IP [39], while unsaturated
methyl ester content decreases viscosity and COM [33,35]. The highest
content of methyl esters of SFA was found in palm oil, whereas highest
content of polyunsaturated methyl esters in sh oil biodiesel, explaining
the fact that contour maps indicate minimum viscosity and COM for sh
oil biodiesel and maximum IP for palm oil biodiesel.
3.3. Multi-objective optimization
The aim of determining a feedstock composition that optimizes
biodiesel properties (viscosity, IP and COM) simultaneously prompts
the use of multi-objective optimization. Table 3 displays the Pareto
Front and the decision space. The Pareto Front was generated by the
weight-sum method and then transferred to the decision space, by the
determination of input variables (waste sh oil, palm oil and waste
frying oil contents) for each selection of weight factors (w1, w2, w3).
Viscosity, IP and COM weight factors were w1, w2 and w3,
respectively. In rows 13 two weight factors had a value of zero,
which is equivalent to a single objective optimization. In rows 430,
just one weight factor had a value of zero, so a bi-objective optimization

Table 2
Polynomial coefcients, p-values and R2 for the models of the response variables.
Yield
(%)

A: Fish oil,
%
B: Palm oil,
%
C: Frying
oil, %
AB
AC
BC
ABC
p-Value
R2

IP
(h)

Viscosity
(mm2/s)

COM
(C)

P1
(C)

MP
(C)

Coefcient

Standard
error

Coefcient

Standard
error

Coefcient

Standard
error

Coefcient

Standard
error

Coefcient

Standard
error

8.62E-01

1.9138

4.32E-02

0.1232

1.83E-02

1.2824

2.45E-02

0.6935

3.45E-01 6.1881

6.75E-01 0.4405

8.68E-01

1.9138

5.49E-02

0.1232

2.20E-01

1.2824

2.13E-01

0.6935

1.13E-01

6.1881

5.44E-01 0.4405

8.73E-01

1.9138

5.30E-02

0.1232

6.92E-02

1.2824

3.67E-02

0.6935

3.14E-01 6.1881

5.65E-01 0.4405

2.35E-04
1.29E-03
2.25E-04
7.79E-05
0.2325
0.5282

8.0178
8.0178
8.0178
54.1942

1.97E-04
3.07E-04
7.10E-05
6.35E-06
0.0004
0.9057

0.5163
0.5163
0.5163
3.4895

1.76E-03
1.35E-04
4.55E-04
6.18E-05
0.0000
0.9625

5.3728
5.3728
5.3728
36.3162

6.90E-04
6.66E-05
6.81E-04
1.66E-05
0.0000
0.9910

2.9056
2.9056
2.9056
19.6397

1.15E-02
1.59E-03
1.07E-02
1.58E-04
0.0019
0.8616

2.03E-03
1.18E-03
5.24E-04
1.07E-05
0.0000
0.9935

25.9255
25.9255
25.9255
175.2360

Coefcient

Standard
error

1.8456
1.8456
1.8456
12.4747

158

V.F. de Almeida et al. / Fuel Processing Technology 133 (2015) 152160

a)

a)

Predicted Viscosity (mm2/s)

6.0

4.5

5.5

5.0

5.0

4.5

4.0

5.5

y = 0.9057x + 0.5074
R = 0.9057
4.0

4.5

5.0

5.5

5.5

6.0

Measured Viscosity (mm 2 /s)

b)

b)

25
4.0

Predicted IP (h)

20
15

8.0

10

12.0

5
0

20.0

y = 0.9625x + 0.3391
R = 0.9625
0

10

15

20

25

c)

Measured IP (h)

c)

16.0

25
5.5

Predicted COM ( C)

20
15

10.2
14.9

10
19.6

5
0

y = 0.9910x + 0.0903
R = 0.9910
0

10
15
Measured COM ( C)

20

Fig. 3. Contour plots for (a) Viscosity, mm2/s; (b) IP, h; and (c) COM, C.

25

Fig. 2. Correlation between predicted and measured values of (a) Viscosity, (b) IP and
(c) COM.

was carried out. Finally, in rows 3134, all the weight factors had values
higher than zero. The weight factors sum is always one for each row.
Thus, the following cases are possible:
i) Single-objective optimization: in rows 13 viscosity, IP and COM
were the objective, respectively. In row 1, 100% sh oil was the
feedstock obtained to optimize biodiesel viscosity with a value
of 4.3 mm2/s, while IP and COM were 1.8 h and 2.5 C, respectively. In row 2, 100% palm oil was determined as the feedstock that
maximizes biodiesel IP, which valued 22.0 h, while viscosity and

COM valued 5.5 mm2/s and 21.3 C, respectively. Last, in row 3,

in order to optimize biodiesel COM, 100% sh oil was the feedstock dened, and variables took the same values as obtained
for row 1. The single objective results are in accordance to the
optimization by response surface methodology showed before
for viscosity (100% sh oil), IP (100% palm oil) and COM (100%
sh oil).
ii) Bi-objective optimization for viscosity and IP: in rows 412, w3 was
zero. For all the weight factors combination, 100% palm oil
was dened as the feedstock that optimizes both viscosity and
IP. It is known by the single-objective optimization that when
viscosity weight factor is one, sh oil is the raw material that
optimizes this property. However, even though when the weight
factors for viscosity and IP are 90% and 10%, respectively, palm oil

V.F. de Almeida et al. / Fuel Processing Technology 133 (2015) 152160

Table 3
Set of optimal solutions (Pareto Front) and decision space for the multi-objective
optimization problem.
Row

w1

w2

w3

Viscosity
(mm2/s)

IP
(h)

COM
(C)

Fish oil
(%)

Palm oil
(%)

Frying oil
(%)

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34

1.00
0.00
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.50
0.25
0.25
0.33

0.00
1.00
0.00
0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
0.25
0.25
0.50
0.33

0.00
0.00
1.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.25
0.50
0.25
0.33

4.3
5.5
4.3
5.5
5.5
5.5
5.5
5.5
5.5
5.5
5.5
5.5
4.3
4.3
4.3
4.3
4.3
4.3
4.3
4.3
4.3
4.3
5.6
5.3
5.3
5.3
5.5
5.5
5.5
5.5
5.3
5.3
5.5
5.3

1.8
22.0
1.8
22.0
22.0
22.0
22.0
22.0
22.0
22.0
22.0
22.0
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
4.5
6.9
6.9
6.9
22.0
22.0
22.0
22.0
6.9
6.9
22.0
6.9

2.5
21.3
2.5
21.3
21.3
21.3
21.3
21.3
21.3
21.3
21.3
21.3
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
3.0
3.7
3.7
3.7
21.3
21.3
21.3
21.3
3.7
3.7
21.3
3.7

100.0
0.0
100.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
42.1
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0

0.0
100.0
0.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
100.0
100.0
100.0
100.0
0.0
0.0
100.0
0.0

0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
57.9
100.0
100.0
100.0
0.0
0.0
0.0
0.0
100.0
100.0
0.0
100.0

was the optimum feedstock. For all the combinations, viscosity,

IP and COM values were the same as those of row 2: 5.5 mm2/s,
22.0 h and 21.3 C, respectively.
iii) Bi-objective optimization for viscosity and COM: in rows 1321, w2
was zero. As result, it was obtained that 100% sh oil as feedstock
optimizes both viscosity and COM for all weight factors values.
It was previously expected, since sh oil used as feedstock had
optimized both viscosity and COM, separately. Viscosity, IP and
COM were respectively maintained as 4.3 mm2/s, 1.8 h and
2.5 C, equal to the values obtained in rows 1 and 3.
iv) Bi-objective optimization for IP and COM: in rows 2230, w1 was
set as zero. In row 22, the dened feedstock composition was
100% sh oil, in order to optimize both IP (w2 = 0.10) and
COM (w3 = 0.90), and it was obtained the same results from
rows 1, 3 and 1321. For the row 23 the feedstock that optimizes
IP (w2 = 0.20) and COM (w3 = 0.80) is composed by 42.1 wt.% of
waste sh oil and 57.9 wt.% of waste frying oil. Viscosity, IP and
COM showed the respective values: 5.6 mm2/s, 4.5 h and 3 C.
This oil mixture as feedstock for optimization of biodiesel properties is a singular result, and it shows that waste frying may be an
appropriated oil to be mixed with sh oil in the proper ratios. For
rows 2426, waste frying oil was dened as the feedstock that
optimizes IP (w2 from 0.30 to 0.50) and COM (w3 from 0.50 to
0.70), showing values for viscosity, IP and COM of 5.3 mm2/s,
6.9 h and 3.7 C, respectively. Last, in rows 2730, the feedstock
established to optimize both IP (w2 from 0.60 to 0.90) and COM
(w3 from 0.10 to 0.40) was 100% palm oil, and variables showed
the same optimum values found in rows 2, 412.
From these results, it is deduced that when IP has much less
weight (10%) than COM, sh oil is the best raw material. Then,
when IP weight increases (20%), a mix of sh oil and waste frying

159

oil is the best option as raw material. If IP weight grows from 30

to 50%, waste frying oil is the recommended feedstock. However,
if IP weight is in the range of 60 to 90%, palm oil is the best choice
to be used as raw material.
v) Tri-objective optimization: for the rows 3134, the weight factors
value varied from 33% to 50% (Table 3). In row 33 (w1 = 0.25,
w2 = 0.50 and w3 = 0.25) the determined feedstock to optimize
biodiesel properties was 100% palm oil, and the variables showed
the same optimum values as those of rows 2, 412, 29 and 30,
viscosity value of 5.5 mm2/s, IP value of 22.0 h and COM value
of 21.3 C. Finally, in rows 31, 32 and 34, 100% waste frying oil
was obtained, and the biodiesel properties maintained the values
from rows 2426, with the respective values for viscosity, IP and
COM: 5.3 mm2/s, 6.9 h and 3.7 C.

Therefore, the importance given to viscosity, IP and COM will

determine the selection of a single optimum solution from the Pareto
Front. It will dene the composition of the oil mixture (waste sh oil,
palm oil and waste frying oil) employed as raw material for the production of biodiesel.
4. Conclusion
The present study showed that biodiesel properties are highly
inuenced by the fatty acid composition of the oil mixture used as
feedstock. Viscosity, IP and COM are properties that depend on the oil
composition employed as raw material. From the response surface
methodology it was concluded that viscosity and COM are minimized
(4.3 mm2/s and 2.5 C, respectively) when waste sh oil is the biodiesel
feedstock, whereas IP is maximized (22.0 h) when palm oil is employed.
This is attributed to the SFA methyl ester content of the mixture, which
increases biodiesel viscosity, IP and COM. Consequently, the conicting
behavior of these variables (viscosity, IP and COM) suggests the use of
multi-objective optimization. This analysis reveals that although the
use of the pure oils studied (waste sh oil, palm oil and waste frying
oil) as feedstock showed more advantages to biodiesel properties, the
mixture of waste sh oil (42.1 wt.%) and waste frying oil (57.9 wt.%) is
benecial when the importance given to IP and COM is 20 and 80%,
respectively.
Acknowledgments
This work was supported by the Spanish National Plan I + D + I
(project CTQ2011-23009) and by the Andalusian Government (project
P12-AGR-1993). V. F. de Almeida acknowledges a grant from the
Science without Frontiers program, supported by CNPq, Brazil
(project 207461/2013-9).
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