Energy Conversion and Management 74 (2013) 1723

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Energy Conversion and Management

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Biodiesel production using oil from sh canning industry wastes

J.F. Costa a,b, M.F. Almeida a, M.C.M. Alvim-Ferraz b, J.M. Dias a,
a
b

LEPAE, Departamento de Engenharia Metalrgica e de Materiais, Faculdade de Engenharia, Universidade do Porto, R. Dr. Roberto Frias, 4200-465 Porto, Portugal
LEPAE, Departamento de Engenharia Qumica, Faculdade de Engenharia, Universidade do Porto, R. Dr. Roberto Frias, 4200-465 Porto, Portugal

a r t i c l e

i n f o

Article history:
Received 8 February 2013
Accepted 23 April 2013
Available online 30 May 2013
Keywords:
Fish oil
Biodiesel
Acid esterication
Experimental planning

a b s t r a c t
The present study evaluated biodiesel production using oil extracted from sh canning industry wastes,
focusing on pre-treatment and reaction conditions. Experimental planning was conducted to evaluate the
inuence of acid catalyst concentration (13 wt.% H2SO4) in the esterication pre-treatment and the
amount of methanolic solution (6090 vol.%) used at the beginning of the further two-step alkali transesterication reaction. The use of a raw-material mixture, including waste oil obtained from olive oil
bagasse, was also studied. The results from experimental planning showed that catalyst concentration
mostly inuenced product yield and quality, the best conditions being 1 wt.% catalyst and 60 vol.% of
methanolic solution, to obtain a product yield of 73.9 wt.% and a product purity of 75.5 wt.%. Results from
a one-step reaction under the selected conditions showed no advantage of performing a two-step alkali
process. Although under the best conditions several of the biodiesel quality parameters were in agreement with standard specications, a great variation was found in the biodiesel acid value, and oxidation
stability and methyl ester content did not comply with biodiesel quality standards. Aiming to improve
fuel quality, a mixture containing 80% waste olive oil and 20% of waste sh oil was evaluated. Using such
mixture, biodiesel purity increased around 15%, being close to the standard requirements (96.5 wt.%), and
the oxidation stability was in agreement with the biodiesel quality standard values (P6 h), which are
promising results clearly showing the potential of using such wastes, of very low value, for biodiesel
production.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
A biofuel is, in simple terms, a combustible material obtained
from renewable biomass resources, commonly used as an alternative, cleaner fuel.
When properly produced, biodiesel can be used pure or in mixture in most current diesel vehicles, with minor adaptations. The
quality requirements for this automotive diesel substitute can be
found in standards. At present, the standard used in Europe for
100% fatty acid methyl esters (FAME) is the EN
14214:2008+A1:2009. In case of the produced biodiesel fail the
standard requirements, due to raw material characteristics, it
might be used in boilers for heat generation (depending on its
characteristics); alternatively, raw materials might be mixed or
the fuel blended with diesel to improve its quality [1].
Biodiesel production is generally made at a larger scale by a
transesterication reaction, using selected feedstock, normally virgin vegetable oils [2]. However, their high prices and use as food

Corresponding author at: LEPAE, Departamento de Engenharia Metalrgica e de

Materiais, Faculdade de Engenharia, Universidade do Porto, R. Dr. Roberto Frias,
4200-465 Porto, Portugal. Tel.: +351 22 5081422; fax: +351 22 5081447.
E-mail address: jmdias@fe.up.pt (J.M. Dias).
0196-8904/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.enconman.2013.04.032

resource (if edible) are limiting factors. Therefore, efforts have been
made to nd alternative raw materials.
The use of waste materials brings a valuable contribution, not
only in the reduction of biodiesel production costs but also in the
better waste management results, avoiding subsequent environmental impacts. Waste frying oils are deeply studied as alternative
raw materials [37]. The impact of this responsible application,
even though relevant, is limited, considering their availability.
Industrial waste oils and fats are however more abundant. When
compared with biodiesel from vegetable origin, biodiesel from fats
has the advantages of a higher caloric value and cetane number,
being however less stable to oxidation and presenting a higher cold
lter plugging point [8].
For countries with a considerable expression of the sh canning
industry there is the possibility to use oily sh discarded parts as
feedstock for the biodiesel production. The use of such alternative
raw material, that represents a challenging waste management
problem for the industries, is, however, still understudied.
The oil extraction is performed mainly in marine oily shes
such as mackerel, salmon, tuna and codsh, which present a considerable oil content [913]. The usable parts, that can represent
around 25 wt.% of the sh, are, in general, the viscera, head, ns,
and tails, amongst others [12]. On the other hand, considering

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J.F. Costa et al. / Energy Conversion and Management 74 (2013) 1723

the 2006 Best Available Techniques in the Food, Drink and Milk
Industries Reference Document (BREF) [14], the expected range
for solid wastes generated during sh processing is 2060% of
the catch, comprising heads, viscera, skins and other parts.
Regarding Northern Portugals sea canning industry, the oily
shes transformed are mainly sardine, mackerel and tuna. Considering the information gathered from contact with the existing
plants (information given on a condential basis), it can be estimated that more than 150 t of sh oil are produced annually
and, also, that more than 40 t are, in addition, washed away by
the wastewaters. Currently, the reported sh oil that is extracted
is being, essentially, commercialized for incorporation in animal
feed or processed for use as a soil supplement. The energetic potential of such waste is however not being used by the industries.
Table 1 presents the characteristics of the raw oil extracted
from the discarded parts of various marine shes. The elementary
composition shows around 77 wt.% of carbon and 12 wt.% of
hydrogen [15]. The most common fatty acids found in these sh
oils, ordered by carbon chain increase, are: myristic (C14:0, up to
7 wt.%), palmitic (C16:0, up to 20 wt.%), palmitoleic (C16:1, up to
28 wt.%), stearic (C18:0, up to 7 wt.%), oleic (C18:1, up to
42 wt.%) and also signicant amounts of polyunsaturated fatty
acids (PUFA) such as arachidonic (C20:4, up to 3 wt.%), eicosapentaenoic (C20:5, up to 11 %), docosapentaenoic acid (C22:5, up to 15
%), and docosapentaenoic (C22:6, up to 39 wt.%) [9,10,12,16,17]. It
should be noted that the PUFA are considered benecial for feed
purposes [18]; regarding biodiesel production, uidity of the fuel
is improved compared to other raw materials, which might be an
advantage. On the other hand, the presence of PUFA might increase
fuel instability since degradation tends to be accelerated in more
unsaturated esters.
Biodiesel current production process includes several steps:
raw material pre-treatment (if necessary) to remove impurities
and undesirable characteristics, transesterication reaction, phase
separation and product purication (usually washing and drying)
[2].
Common feedstock characterization to evaluate pre-treatment
needs includes water content and acid value determination. In particular, the reduction of the acid value is an important pre-treatment as the removal of the excessive amount of free fatty acids
is vital, especially when using alkaline catalyzed transesterication. The idea is to prevent the formation of soaps and consequently avoid a poorer catalytic activity and emulsifying soap
effects that reduce biodiesel yield and quality [1,19].
Biodiesel transesterication reaction occurs between the triglyceride source and a short-chain alcohol (mostly methanol) to
produce a mixture of FAME and glycerol. The reaction might be
catalyzed by enzymes, acid or alkaline homogenous catalysts [20]
and heterogeneous catalysts [21]. The most commonly used are
the homogeneous alkaline catalysts [2,20] due to low cost and high

Table 1
Characteristics of sh oil extracted from marine wastes [10,15,16,20,25].
Parameter

Result

General characteristics

Dark brown, viscous liquid with a

distinctive smell
0.050.26
0.128.4
88a
875.3978.9
39.7140.21
156.0178.5
3.8834.360

Water content (wt.%)

Acid value (mg KOH g 1)
Iodine value (g I2/100 g)
Density (kg m 3)
Caloric value (MJ kg 1)
Flash point (C)
Kinematic viscosity at 40 C
(mm2 s 1)
a

Wiggers et al., 2009.

efciency. NaOH, KOH and their methoxydes are the commonly

used catalysts. Since it is a reversible reaction, an excess of alcohol
(usually 6:1 methanol to oil molar ratio) is usually used to force the
reaction towards the products.
When the sh oil presents high acidity, an acid esterication
pre-treatment might be performed. In a study by El-Mashad
et al. [10], an acid esterication using 1 wt.% H2SO4 and a reaction
temperature around 52 C, during 1 h, was performed (molar ratio
methanol:oil of 6:1, 600 rpm stirring) to reduce the acid value of a
salmon oil (3.5 or 12 mg KOH g 1) to values acceptable for alkaline
transesterication (considering a maximum of 2 mg KOH g 1).
The sh oil biodiesel synthesis, that follows pre-treatment, is
usually, but not exclusively, reported as single stage alkaline
transesterication process (methanolic route). Few studies have
been performed in biodiesel production from sh oil; however,
according studies found [913], common conditions include: (i)
NaOH (1 wt.%) or KOH (0.5 wt.%) as catalysts; (ii) 6:1 to 9:1 methanol to oil molar ratio; (iii) reaction temperature between 50 and
60 C; (iv) reaction time between 30 and 60 min; and, (v) stirring
from 600 to 6000 rpm. These are conditions conventionally used
in most alkaline transesterication reactions [2].
After phase separation, methyl esters/biodiesel purication is
usually performed. First, the methanol in excess is recovered by
distillation, water washing is used to remove the homogeneous
catalyst and drying is performed to remove residual water [10
13,16], as in general alkali transesterication processes.
Regarding the characterization of the obtained biodiesel, Table 2
reports data collected from the revised literature and compares it
with the general applicable requirements according to the European Biodiesel Standard EN 14214. The studies show that biodiesel
quality varies considerably and that it might be difcult to fulll
some of the required parameters. Therefore, further studies are required to evaluate and if possible improve biodiesel quality.
The biodiesel composition varies according to the sh oil characteristics and fatty acids found agree with the ones reported previously for oils. It should be, however, mentioned, that a greater
range of values were found for the composition of FAME due to
the great variability of sh oils and mixtures used as raw materials.
In order to improve product quality, pre-treatment conditions
should be studied and optimized. In a study by Dias et al. [1], the
catalyst concentration during the acid esterication pre-treatment
of a waste fat was found to be a key parameter.

Table 2
Quality parameters of biodiesel obtained from waste sh oil [913,16,17,20,27,28]
and European Biodiesel Standard (EN 14214) requirements.
Parameter

Result

EN
14214

Aspect

Transparent yellow, but varies depending

on the feedstock nature/condition and the
processing
619a

NA

0.261.19

60.50

860889

860
900
P51.0
P101 C
3.50
5.00

Water content
(mg kg 1)
Acid value
(mg KOH g 1)
Density (kg m 3)
Cetane number
Flash point (C)
Kinematic viscosity
at 40 C
(mm2 s 1)
Methyl ester
content (wt.%)
NA Not applicable.
a
Fan et al., 2010.
b
Lin and Li, 2009.

50.9
103220
4.07.2

95.74100.00

6500

P96.5

J.F. Costa et al. / Energy Conversion and Management 74 (2013) 1723

The purity of the product is a very important parameter and it is

generally difcult to achieve purities imposed by EN 14214
(>96.5 wt.%) using waste raw materials [1], even though according
to some of the revised studies, high purities could be obtained.
For the same raw material, higher purities are associated with
lower viscosities, because triglycerides have higher viscosities than
FAME. Using a two-step alkali transesterication, removing the
produced glycerol in the rst step, a biodiesel yield increase from
91% to 97% could be obtained by Ye et al. [22], through the reduction of reaction equilibrium constraints. Such process was however
not previously studied for the transesterication of waste sh oil.
Another way to improve fuel quality is the use of raw-material
mixtures, preferably by incorporation of other wastes [8].
Olive is one of the most important agricultural products of Mediterranean countries [23] and Portugal is widely known for its production; however, the waste management associated is still a
challenge. Olive bagasse is the solid residue obtained from the
mechanical oil extraction of olives. Such waste still presents relevant oil content; however, it usually has a high acidity, impairing
its application for food purposes. The olive oil presents high content of linoleic acid and lower content of PUFA [24] which makes
it a suitable raw material for mixture to balance quality issues
resulting from the use of sh oil.
According to what was previously stated, the goal of the present
work was to study the pre-treatment and reaction conditions to
produce biodiesel using oil extracted from Portuguese sh canning
industry wastes. With that purpose, the variation of the acid catalyst concentration in the esterication pre-treatment was studied
and a two-step alkali transesterication was after performed aiming to maximize FAME production and deal with the quality issues
previously referred. Finally, the use of a mixture, including waste
oil obtained from olive oil bagasse was studied aiming biodiesel
quality improvement.
2. Materials and methods
2.1. Experimental design
The present study was conducted using Design of Experiments
(DOE). This is a useful way to test factors and their interaction effects in the process response, within a limited range and a minimum of experiments and time. JMP 5.0.1 software was used,
considering the following approaches: Response Surface Design
(two factors, three levels) RSD 32, with Central Composite Design
(two central points, one replica).
Therefore, 20 experiments were due to be made in advance, in a
random way, to minimize undesirable disturbances or uncontrollable external factors effects. The chosen factors, or process variables,
were: catalyst concentration during esterication, ranging from 1
to 3 wt.%, and, the amount of methanolic solution used in the rst
transesterication stage, varying from 60 to 90 vol.%. Apart from
the biodiesel quality parameters selected as response variables,
product yield (weight of product/weight of oil  100) was also
used. The determination of product yield is important, because
one can have very high purities but low yields (less product, with
high purity), namely due to the formation of soaps when high catalyst concentrations are used [2]. For economical evaluations, the
product yield is very important.
2.2. Materials
Fish oil was donated by Savinor S. A. (Trofa, Portugal) and was
kept in the refrigerator at 4 C during the experimental period.
Waste oil, extracted from olive oil bagasse, was supplied by a local
company and kept under the same conditions as the sh oil. The

19

waste olive oil presented an acid value of 21.85 mg KOH g 1 and

an iodine value of 71 cg I2 g 1.
The methanolic acid solution for the esterication reaction was
prepared with methanol min. 99.8% assay, AnalaR NORMAPUR
from VWR International S.A.S. and sulfuric acid 9597%, for analysis, EMSURE ISO from Merck. The methanolic solution prepared for
the transesterication reaction used the same methanol but sodium hydroxide 97%, reagent grade, from SigmaAldrich. The biodiesel washings were performed using distilled water and 0.2 wt.%
hydrochloric acid (prepared from hydrochloric acid 37%, A. C. S. reagent, from Aldrich).
For GC analysis, n-heptane (for analysis, Merck) was used as solvent and, as internal standard, methyl heptadecanoate, analytical
standard, Fluka Analytical, was used. A Supelco 37 Component
FAME Mix (10 mg/mL in methylene chloride) was also used as analytical standard.
2.3. Methods
2.3.1. Oil and biodiesel characterization
Oil properties measured were: (i) acid value, by volumetric
titration as reported in NP EN ISO 660:2002; (ii) water content,
by coulometric Karl Fischer titration, according to ISO 8534:996;
(iii) iodine value by volumetric titration using Wijs reagent,
according to the standard ISO 3961:1996; and (iv) oxidation stability at 110 C, according to EN 14112. Oil composition was obtained
from the methyl ester prole evaluated by GC analysis according to
NP EN 5508:1996 and EN 14103:2003.
Biodiesel quality was accessed by measuring: (i) density, by a
hydrometer method according to ISO 3675:1998; (ii) kinematic
viscosity, according to ISO 3104:1994; (iii) ash point, using a rapid equilibrium closed cup tester according to ISO 2160:1998;
(iv) methyl ester content, using GC analysis according to EN
14103:2003; and (v) acid value, as reported in EN 14104:2003.
Based on preliminary experiments, where all mentioned biodiesel quality properties were determined, and on a literature review
and previous work [1], only some biodiesel properties were selected for the experimental planning.
All parameters were measured in replicates and taking into account the error requirements imposed by each standard. Results
are presented as mean values.
2.3.2. Biodiesel production
The production process included dehydration, acid esterication and alkaline transesterication, divided in two steps.
Dehydration: Fish oil was dehydrated by heating at around
100 C until constant weight.
Esterication: Acid esterication was performed in a 250 mL
round-bottom glass reaction vessel, with three necks, immersed
in a temperature controlling bath and equipped with a watercooled condenser fed by a circulating cooling bath at 4 C. A thermometer was used to certify the reaction temperature. The vigorous stirring was performed using a magnetic stirrer, regulated to
900 rpm.
For the reaction, the dehydrated sh oil was fed to the reactor
followed by the homogeneous methanolic solution of methanol
and catalyst (sulfuric acid). The esterication conditions were:
90 g of oil, 1, 2 or 3 wt.% of catalyst relative to oil weight and
amount of methanol corresponding to a 6:1 methanol to oil molar
ratio. The reaction was conducted at 65.0 C, at ambient pressure,
during 1 h.
After reaction, excess methanol was removed from biodiesel in
a rotary evaporator and the product was washed four times using
distilled water (in equal volume). The nal product was dehydrated by heating at around 100 C, until constant weight was
achieved.

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J.F. Costa et al. / Energy Conversion and Management 74 (2013) 1723

Reaction conditions were selected according to the literature review. Preliminary experiments were performed to evaluate the
progress of the esterication reaction with time and support the
selection of the reaction period. For that, two experiments were
conducted using 120 g of oil, 2 wt.% catalyst and 65 C during 5 h
of esterication. Around 2 mL were sampled at 0.5, 1, 2, 3, 4 and
at the end of the reaction. Samples were treated and acid value
was determined at each sampling, according to Dias et al. [1].
The product obtained after 5 h was subjected to alkaline transesterication, described below, to evaluate the FAME quality in advance and select key quality parameters.
Alkaline transesterication: The same apparatus as for the esterication reaction was used. The following reaction conditions were
selected: 1 wt.% NaOH, methanol amount corresponding to a 6:1
methanol to oil molar ratio, temperature of 65 C and 1.5 h of reaction. Two steps of 45 min each were performed. The amount of
methanolic solution used in the rst step varied from 60 to
90 vol.% (corresponding to the addition of 40% to 10% of solution
in the second step, respectively) according to the experimental
planning previously described (Section 2.1). After the rst reaction,
the glycerol was separated and the rest of the methanolic solution
was added to perform the second stage of reaction for another
45 min.
The nal product was decanted overnight. The biodiesel purication consisted on distillation under vacuum to remove excess
methanol followed by washing once with a hydrochloric acid solution (0.2 wt.% (m/m)) and after three times with distilled water (in
equal volume). The remaining water was nally removed by heating at around 100 C, until constant weight.

Table 3
Waste sh oil properties.
Property

Result
1

Acid value (mg KOH g )

Water content (wt.%)
Iodine value (cg I2 g 1)
Oxidation stability @ 110 C (h)

10.04
0.28
164
0.1

Methyl ester prole, wt.%

Myristate (C14:0)
Palmitate (C16:0)
Palmitoleate (C16:1)
Stearate (C18:0)
Oleate (C18:1)
Linoleate (C18:2)
Linolenate (C18:3)
Eicosenoate (C20:1)
Eicosapentanoate (C20:5)
Docosenoate (C22:1)
Docosadienoate (C22:2)
Docosapentanoate (C22:6)
Mean molecular weight (g mol

6.6
21.6
8.0
4.1
17.3
1.7
2.9
4.2
13.3
3.8
1.7
14.8
882.6

1 a

Obtained from the methyl ester composition.

3. Results and discussion

3.1. Raw material properties
The resume of the sh oil properties is presented in Table 3.
Regarding the acid value, the values agree with the range reported
in previous studies (between 0.1 [20] and 28.4 mg KOH g 1 [25]).
Taking into account the high value found, it is clear the need of a
pre-treatment to allow alkali transesterication (usually less than
2 mg KOH g 1 is demanded).
The iodine value of many sh oils is in fact higher than
150 cg I2 g 1 [26], as it was found for the present oil, although in
the study by Wiggers et al. [25], the acid value of the waste oil
was determined as being 88 cg I2 g 1. The differences relate mostly
to the type of sh but also to the source of the oil and the conditions at which the oil was exposed. The water content was not very
high, as found in revised studies [25].
The composition of sh oil agrees with the values generally reported, described in the introduction chapter. As previously stated,
sh oil differs considerable from other oils, namely due to its content of PUFA [18]. However, due to its high content, these oils are
very prone to oxidation. In fact, results from the present study indicate that this oil presents very low oxidation stability. From the
point of view of nutrition, this is a very important subject. Considering the use for biodiesel production, raw material oxidation is
also detrimental, as it increases the acid value and reduces the
quality of the oil. The results show that a great care is required during the storage of such oil to prevent oxidation.

Fig. 1. Evolution of waste oil acid value during the esterication reaction (mean
values of two experiments, differences below 5%; reaction conditions: 65 C, 2 wt.%
H2SO4, 6:1 M ratio of methanol to oil).

3.2.1. Progress of the esterication reaction

Fig. 1 shows the evolution of the acid value with time during the
acid esterication of the oil. According to the results, the time required for the esterication was selected as 1 h. The acid values
are high due to the presence of H2SO4 in the reaction media. The
results agree with what has been reported for the esterication
of acid waste lard [1].
3.2.2. FAME quality
The product from the esterication reaction was further transesteried (according to Section 2.3.2) and the quality of the FAME
obtained was analyzed. Results are presented in Table 4.
Table 4
Biodiesel quality in preliminary experiments, using waste sh oil, and European
biodiesel quality requirements (results outside the standard presented in bold).
Property

3.2. Preliminary experiments

Preliminary experiments were conducted to evaluate the progress of the esterication reaction as well as the quality of the produced FAME to support the selection of the conditions for the
design of experiments.

Acid value (mg KOH g )

Density (kg m 3)
Kinematic viscosity (mm2 s 1)
Flash point (C)
Methyl ester content (wt.%)
a

Resulta

EN 14214

0.90
891.8
4.41
162
78.2

60.50
860900
3.505.00
P101 C
P96.5

Mean values, differences always less than 5%.

J.F. Costa et al. / Energy Conversion and Management 74 (2013) 1723

Table 5
Resume of results obtained regarding yield, biodiesel quality parameters and
comparison with European biodiesel quality requirements (results outside the
standard presented in bold).
Parameter

Result

EN 14214

Yield
Kinematic viscosity at 40 C (mm2 s
Acid value (mg KOH g 1)
Methyl ester content (wt.%)

66.473.9
4.324.59
0.320.85
73.075.5

NA
3.505.00
60.50
P96.5

NA Not applicable.

Fig. 2. Product yield obtained varying the concentration of the H2SO4 catalyst
during esterication and the volume of the methanolic solution used in the rst
transesterication stage (mean of relative percentage differences around 6%).

The preliminary quality results showed that the acid value of

FAME was still higher than the one imposed by the European quality standard. The ash point was considerably higher than the minimum imposed and the density and viscosity of biodiesel were
within the standard requirements. The methyl ester content was
below the minimum required value. Taking into account the preliminary results, the experimental plan considered the evaluation of
the acid value, methyl ester content and kinematic viscosity. The
kinematic viscosity was still evaluated as it is closely related with
the methyl ester content and could help to evaluate specic trends.
3.3. Experimental planning
According to the planning described in Section 2.1, 20 experiments were performed aiming to evaluate the impact on product

21

quality of the acid concentration during esterication and the

two step transesterication using different ratios of the methanolic
solution at each step.
Table 5 presents the resume of the results obtained for the analyzed variables in all conditions studied. It can be seen that the
parameters concerning the yield and the acid value presented
some degree of variation within the experimental range whereas
the viscosity and methyl ester content presented small variation.
In addition, some of the parameters were not in agreement with
the biodiesel standard. Considering the preliminary experiments,
the results differ on the acid value; the maximum purity obtained
was in agreement with the values found previously (differences
less than 3%); however, under different reaction conditions.
In order to understand the inuence of the studied variables in
each parameter, an individual discussion of the results will be performed in more detail from now on.
3.3.1. Product yield
The variation of the product yield with the studied variables is
presented in Fig. 2.
In general, the higher yields were obtained for the lowest catalyst amount (1 wt.%) and the increase in catalyst concentration led
to a decrease in product yield. This is probably related with the fact
that, as it was observed experimentally, at higher catalyst concentrations the purication of the lipid phase during washing leads to
the formation of emulsions, responsible for high product losses.
The highest yield was obtained at the lowest catalyst concentration and 60 vol.% of the methanolic solution in the rst stage
(73.9 wt.%). The lower yield was obtained for 3 wt.% catalyst and
90 vol.% of the methanolic solution (66.4 wt.%).
The results also showed that biodiesel yield generally decreased
when the amount of methanolic solution used in the rst step increased. The results relate to the amounts in the rst step of 60, 75
and 90 vol.% of solution at the different catalyst concentrations,
which results in the addition of 40, 25 and 10 vol.% in the second
step, respectively. Therefore, it seemed to be more relevant, considering this parameter, to use more methanolic solution in the
second step (in this case the maximum was 40 vol%.) to allow
greater product conversion (note that the difference between the
highest and lowest yield was 7.5 wt.%).
3.3.2. Kinematic viscosity and biodiesel purity
The kinematic viscosity of biodiesel presented a small variation
among experiments, ranging between 4.32 and 4.60 mm2 s 1. The
lower viscosities were generally obtained at the lowest catalyst
concentration (Fig. 3A), except when 75 vol.% solution was used
in the rst step, where the lowest viscosity was obtained at

Fig. 3. (A) Kinematic viscosity @ 40 C, and (B) purity obtained varying the concentration of the H2SO4 catalyst during esterication and the volume of the methanolic
solution used in the rst transesterication stage (mean of relative percentage differences less than 4%).

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J.F. Costa et al. / Energy Conversion and Management 74 (2013) 1723

2 wt.%. Under all the reaction conditions studied, none of the products reached the minimum purity imposed by the EN 14214, of
96.5 wt.% (Fig. 3B).
The results seem to indicate that no advantage regarding the
viscosity occurs using higher catalyst concentrations, since higher
viscosities can many times be attributed to lower purity of the
product. The trend veried for the viscosity was conrmed and validated by the purity results, which clearly present an inverse trend.
In fact, the highest purity was achieved generally at the lowest catalyst concentration, except when 75 vol.% solution was used in the
rst step, where the highest purity was obtained at 2 wt.%.
Although trends were identied, the differences between the results for purity, as for the viscosity, were not relevant (the differences between the maximum and minimum values were overall
less than 3%).

3.3.3. Acid value

The general applicable requirements according to the European
Biodiesel Standard EN 14214 state that the fuel should present a
maximum acid value of 0.50 mg KOH g 1. The experimental results
showed a great variation of this parameter (between 0.32 and
0.85 mg KOH g 1) and also, a difculty in obtaining low relative
percentage differences between replicates. In fact, using the different amounts of methanolic solution and also different acid catalyst
amounts in esterication, it was possible to obtain a product that
either complied or was very far from the standard limit.
These results are even so relevant, as they seem to indicate that
differences occurred not by changing the studied variables but by
variations during the purication procedures, when using such
waste oil. As this is a raw material with high degree of PUFA, the
results indicate that the acid value of the product depends upon
the purication procedures and storage, and that minor variations,
for instances during washing procedures and storage period prior
to analysis might result in changes in this parameter. This study
shows, therefore, that this is a parameter that requires additional
care when designing the biodiesel production process using waste
sh oil.
According to the results obtained from the experimental planning, and taking into consideration the preliminary results, it
seems that using such waste sh oil as raw material, the use of a
catalyst concentration of 1 wt.% H2SO4 during the esterication
leads to better results regarding the product yield and quality.
However, the use of a two-step transesterication, using different
amounts of the methanolic solution in each step does not seem
to bring advantages in terms of the results found.
To conrm this hypothesis, an experiment was conducted by
performing an acid esterication using the selected catalyst concentration (1 wt.% catalyst) followed by an alkali one step transesterication under the conditions previously described, during
1.5 h. The results are presented in Table 6, together with the results
retained from experimental planning and preliminary results, for

comparison. The oxidation stability of the product was also measured, being very low (0.1 h).
From the results, it is clear that for such raw-material, there is
no advantage of performing a two-step alkali transesterication,
since results obtained using a one-step reaction showed that the
same product yield and quality is achieved.
Therefore, the best conditions were selected as 1 wt.% H2SO4 for
the esterication reaction followed by a one step alkali transesterication, considering all the other conditions previously
described.
However, it should not be ignored that using such raw material,
the methyl ester content is signicantly below the minimum required to be used as automotive fuel in 100% and also that oxidation stability is very low.
The methyl ester content was in fact a very difcult parameter
to fulll and such challenge has been reported for acid raw materials and other wastes [1,8].
The FAME content obtained was less than expected according to
the revision performed (95.74100.00 wt.%). The analysis of such
studies conrms that different sh oils were used. Behet [9] used
a anchovy sh oil with low acidity; El-Mashad et al. [10] used salmon oil, with lower acid value (3.47 mg KOH g 1); Fan et al. [16]
used a sh oil with a much lower acidity, 0.28 mg KOH g 1; Lin
and Li [13] used a rened mixture of marine sh oil obtained from
discarded parts of various marine shes (after the crude sh oil
production, a renement process followed, removing water, sh
residue, saline compounds and others); Parente et al. [17] used
commercial sh oil. These last two studies used only alkali transesterication due to low acidity.
Apparently, the waste sh oil used in the present study lacked
the optimum qualities required to achieve the high methyl ester
contents reported. Therefore, it seems that this type of sh oil cannot be used pure as raw material for biodiesel production. Ideally, a
mixture of such sh oil with other lipid waste of high acid value
(presenting low commercial value and management difculties)
should be used, aiming to attenuate the quality issues found.
3.4. Mixture of waste sh oil and waste olive oil for biodiesel
production
For the present work, and as a preliminary study to access potential, a mixture containing 80 wt.% waste olive oil and 20 wt.%
of waste sh oil was evaluated. The selection of the mixture composition was performed according to the amount of available raw
material and expected impact on product quality; namely the need
to increase fuel stability and methyl ester content. Regarding the
fatty acid composition, the results showed that the waste olive
oil presented a high content of oleic acid (C18:1, 72.9 wt.%) and
the other most relevant acids found were the palmitic (C16:0,
13.9 wt.%) and the linoleic acid (C18:1, 8.6 wt.%). Small contents
of stearic, palmitoleic and linolenic acid were also found (2.2, 1.4
and 0.9 wt.% respectively).

Table 6
Results comparing the yield and quality parameters, obtained using one-step transesterication (OST) and two-step transesterication (TST) after
acid esterication of sh oil under selected catalyst concentration.
Parameter
Yield (wt.%)
Kinematic viscosity @ 40 C (mm2 s
Acid value (mg KOH g 1)
Methyl ester content (wt.%)

1 wt.% catalyst, OST

1 wt.% Catalyst, TSTa

2 wt.% Catalyst, OSTb

73.5
4.27
0.55
75.0

73.9
4.32
0.62
75.5

NA
4.41
0.90
78.2

NA Not applicable.
a
Results from experimental planning, where 60 vol.% of methanolic solution was used in the rst stage.
b
Results from preliminary experiments.

J.F. Costa et al. / Energy Conversion and Management 74 (2013) 1723

The conditions under which biodiesel production was performed were the ones selected according to the previous results
(1 wt.% H2SO4 for esterication followed by one step alkali transesterication). The results of the quality of the fuel obtained showed
a methyl ester content of 90.2 wt.% (compared to 75 wt.% using the
sh oil alone) and an oxidation stability of 6.2 h (compared to 0.1 h
obtained using the sh oil alone).
These results clearly show the potential of using such wastes, of
very low value, in mixture for biodiesel production. Biodiesel purity increased 15.2 wt.% and the oxidation stability is in agreement
with the biodiesel quality standard values (P6 h). Results are
promising; however, it is a fact that biodiesel purity, although
much higher, is still slightly lower than the one required for use
100% as automotive fuel. The application of such fuel might be
done for heating purposes (boilers) but the impact of its use in diesel motors will depend upon the blending percentages with diesel
and also on long hour engine operation behavior. Accordingly, detailed studies are being conducted regarding the impact of using
such fuel in a diesel motor, pure, and in mixture with fossil diesel
fuel.

4. Conclusions
The present study showed that it is possible to produce biodiesel using acid oil extracted from the sh canning industry wastes.
The process established comprised an acid esterication pre-treatment followed by a basic transesterication.
The results from experimental planning showed that catalyst
concentration during esterication mostly inuenced product
yield and quality, the best conditions being 1 wt.% catalyst and
60 vol.% of methanolic solution. Under such conditions, a product
yield of 73.9 wt.% and a product purity of 75.5 wt.% was obtained.
With the selected catalyst concentration, results from a one-step
reaction showed that no signicant improvement occurs by using
two steps (a product yield of 73.5 wt.% and product purity of
75.0 wt.% was obtained).
Although several quality parameters were in agreement with
standard specications, a great variation was found in the biodiesel
acid value, which showed a high sensitivity of the product to purication and storage, due to the low oxidation stability; in addition,
methyl ester content was always below the minimum required for
use as 100% diesel fuel (96.5 wt.%).
Due to the fact that the waste sh oil used in the present study
lacked the optimum qualities required to achieve the high methyl
ester content and oxidation stability, a mixture containing 80 wt.%
waste olive oil and 20 wt.% of waste sh oil was evaluated using
the reaction conditions previously selected. Using such mixture,
biodiesel purity increased to 90.2 wt.% and the oxidation stability
was in agreement with the biodiesel quality standard values
(P6 h), which are promising results.

Acknowledgments
The authors thank the Project ValorPeixe (QREN 13634) and
J.M. Dias thanks the FCT for the fellowship SFRH/BPD/73809/2010.

23

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