Fuel 138 (2014) 143148

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Fuel
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Biodiesel production from used cooking oil and sea sand

as heterogeneous catalyst
Gabriel Galvn Mucio a, Rubi Romero a,, Armando Ramrez b, Sandra Luz Martnez a,
Ramiro Baeza-Jimnez a, Reyna Natividad a
a
Centro Conjunto de Investigacin en Qumica Sustentable UAEM-UNAM, Carretera Toluca-Atlacomulco Km 14.5, Unidad San Cayetano, Toluca, Estado de Mxico 50200, Mxico
b
Facultad de Qumica, Universidad Autnoma del Estado de Mxico, Paseo Coln esq., Paseo Tollocan s/n 50120, Toluca, Estado de Mxico, Mxico

h i g h l i g h t s

 Calcined sea sand is a highly active catalyst for biodiesel production.

 Biodiesel produced was over 95% methyl esters using rened and used cooking oil.
 Biodiesel from used cooking oil is enhanced with a two-step reaction system.
 Produced biodiesel fullls parameters of norm EN14214.

a r t i c l e i n f o a b s t r a c t

Article history: The aim of this study was to analyze the catalytic performance of sea sand as a nonconventional catalyst
Received 14 March 2014 in the transesterication reaction of used cooking oil and rened oil with methanol. The sea sand was
Received in revised form 16 July 2014 utilized as a source of calcium oxide. The main characteristic of this sea sand is the high content of CaCO3
Accepted 18 July 2014
which was transformed into CaO by calcination. The catalyst was characterized by X-ray diffraction
Available online 30 July 2014
(XRD), scanning electron microscopy (SEM), nitrogen adsorption/desorption (BET) and by Hammett
method (basicity determination). The produced biodiesel has 95.4% (polar + non polar methyl esters),
Keywords:
96.6% and 97.5% methyl esters content when employing used cooking oil, safower oil and soybean
Biodiesel
Used cooking oil
oil, respectively. The obtained biodiesel at these conditions (atmospheric pressure, reaction temperature
Safower oil of 60 C, 12:1 M ratio of methanol:oil and catalyst amount of 7.5%) met key parameters (viscosity:
Soybean oil 4.25.0 mm2/s and acid value: 0.050.011 mg KOH/g) of the European norm EN-14214 (viscosity:
Sea sand 3.55.0 mm2/g and acid value: max. 0.50 mg KOH/g).
2014 Elsevier Ltd. All rights reserved.

1. Introduction fossil fuels in four distinct markets: power generation, heating

Most of the energy produced in the world comes from fossil
fuels: oil, coal, natural gas. Unfortunately, these are non-renewable
resources and they could potentially be depleted in the future. In
contrast, it is estimated that the energy demand in the world will
increase by 40% between 2010 and 2030 [1]. Therefore, in recent
years the study of fossil fuels substitution by other energy sources
has become of paramount importance.
In 2010 renewable energy supplied an estimated 16.7% of nal
global energy consumption. Out of this total, an estimated 8.2%
came from modern renewable energy (hydropower, wind, solar,
geothermal, biofuels and biomass). These sources can substitute
Corresponding author. Tel.: +52 722 2766610x7721; fax: +52 722 2965541.
E-mail address: rromeror@uaemex.mx (R. Romero).
and cooling, transport fuels and rural/off-grid energy services [2].
In this sense, biodiesel is an alternative fuel that can be used
directly in commercial diesel engines. This biofuel has evident ben-
ets compared to fossil diesel fuel including enhanced biodegrada-
tion, reduced toxicity and a lower emission prole [3]. Biodiesel is
generally produced by the transesterication of triglycerides from
vegetable oils and animals fats with alcohol in the presence of an
alkali or acid catalyst to form a mixture of fatty acid alkyl esters
and glycerol.
The major disadvantages of producing biodiesel are the high
cost of raw material and the subsequent purication process of
the product, which results in an expensive nal product in compar-
ison to fossil diesel. Therefore, used cooking oils and fats offer a sig-
nicant alternative low-cost biodiesel feedstock. Additionally,
these raw materials can convert a problematic waste into an

http://dx.doi.org/10.1016/j.fuel.2014.07.053
0016-2361/ 2014 Elsevier Ltd. All rights reserved.
144 G.G. Mucio et al. / Fuel 138 (2014) 143148

ecological friendly fuel. However, it is necessary to consider that Table 2

the quality of the biodiesel will depend on the quality of the used Oil properties.

cooking oils. It is a fact that during the use of vegetable oils for fry- Properties Safower Soybean Used cooking
ing purposes, hydrolytic, thermal, oxidative and cracking reactions 2
Viscosity at 40 C (mm /s) 39.25 33.19 49.40
can potentially lead to chemical changes [4]. Actually, used cooking Acid value (mg KOH/g) 0.11 0.15 0.31
oils have a great amount of free fatty acids that can favor the Water content (wt%) 0.05 0.04 0.14
saponication reactions when using homogeneous catalysts.
Hence, the use of heterogeneous catalysts is better recommended
to conduct the transesterication reaction, especially if the raw Table 3
material is used cooking oil. The soap formed during the transeste- Glycerides content of oils used in the transesterication reaction.
rication reaction prevents the glycerol separation, which drasti- Properties Safower oil Soybean oil Used cooking oil
cally reduces the ester yield [5]. Currently, there are some
Triglycerides content (wt%) 98.5 98.2 75.5
studies that have reported the transesterication of waste oils
Diglycerides content (wt%) 1.4 1.7 1.5
using heterogeneous catalysts such as Sr/ZrO2, KOH/Al2O3, Others (wt%)a 22.9
ZnAl2O3, ferric sulfate, SO2 4 /SnO2SiO2 [69]. However, most of a
Polymeric triglycerides, oxidized glycerides and other polar compounds.
these catalysts require a complex synthesis. CaO has also been suc-
cessfully applied albeit using vegetable oil as raw material [1014].
Recently, some authors have used nonconventional catalysts for
2.2. Catalyst preparation
biodiesel synthesis such as enzymes [15], chicken eggs, waste
mud and crab and mollusk due to high content of calcium oxide
The sea sand was sieved (0.42 mm) to remove larger particles,
[1618]. The efforts of searching for less expensive and highly
which were crushed and the material passed through the same
active catalysts are justied by the necessity of lower biodiesel
sieve before being subjected to heat treatment in a furnace to
production costs. In this context, a material with high content of
transform the CaCO3 (sand major component) into CaO. The effect
calcium carbonate is sea sand so it is worth to explore it as noncon-
of heat treatment on catalyst crystallinity was studied. Three calci-
ventional catalyst in the transesterication reaction in order to
nation temperatures (700, 800 and 900 C) were evaluated. The
produce biodiesel. This was the main aim of this research work
time of calcination was kept constant (2 h) at all treatments.
and used cooking oil was employed as raw material. The inuence
of the methanol/oil molar ratio, the reaction time and the catalyst
amount on the nal methyl esters content was also studied. 2.3. Catalyst characterization

The crystalline phases of calcined and uncalcined sand were

2. Experimental
2.1. Materials
Safower oil and soybean oil were purchased from a local gro-
cery store. The used cooking oil was obtained from a restaurant.
The fatty acid composition of the employed oils is summarized in
Table 1. The viscosity, acid value and water content of the oils were
determined according to the European Union Quality Standard
(EN-14214). The resulting values are shown in Table 2. The glycer-
ide contents are shown in Table 3. Chemical analyses were carried
out according to standard methods (norm EN 14105).
Anhydrous methanol (99.9%) and sulfuric acid (97.3%) were
supplied by Productos Qumicos Monterrey. The gas chromatogra-
phy reference standard for fatty acid methyl esters was obtained
from Supelco; and methyl heptadecanoate supplied by Sigma
Aldrich (puriss. p.a., standard for GC, P99.7%) was used for quan-
tifying methyl esters.
The sea sand for this study was collected from Puerto Telchac at
21200 2600 N/89150 4700 W. The sand was taken directly from the
upper surface. It is worth mentioning that Puerto Telchac is in
the State of Yucatan, Mxico. Generally speaking, the sea sand
and soil from that region have been reported to have a high content
of calcium carbonate [19].
analyzed by X-ray diffraction and the analysis was conducted in
a Bruker D8 Advance diffractometer. The patterns were obtained
using Cu Ka radiation at 30 kV and 25 mA. Data were collected in
the scanning angle (2h) range of 2080 with step time of 0.3 s
and step of 0.03.
The surface morphology of the catalysts was obtained in a JEOL
JSM-6510LV scanning electron microscope (SEM) coupled with an
energy dispersive X-ray spectrometer employed to perform ele-
mental analysis of the catalysts.
Pore size distribution and BET surface area were determined by
nitrogen adsorption data acquired with a Quantachrome Quadra-
sorb SI apparatus. Prior physisorption, the samples were degassed
under vacuum of 8  103 Torr at 120 C for 15 h.
The base strength was determined by using Hammett indica-
tors. In this method, the catalyst is titrated with benzoic acid. By
doing this, a change in color is expected when the added acid is
enough to electrically neutralize the basic sites onto the catalytic
surface [20].
The sand was also analyzed by Thermo-gravimetric/differential
thermal analyzer (SDT Q600 Simultaneous TGA/DSC, TA Instru-
ments) under nitrogen ow condition with a heating rate of
10 C/min.
2.4. Pretreatment of used cooking oil

Due to the type of employed oil in this study, it cannot be

Table 1 directly used and a pre-treatment process is required. First, the
Fatty acid compositions (wt%) of vegetable oils. used cooking oil was ltrated by using a ne screen cloth in order
Fatty acid Safower Soybean Used cooking to remove all food debris and other suspended solid particles. After
Palmitic 5 10.1 11.8
that, the oil was heated at 80 C and placed in a separating funnel
Stearic 1.9 4.5 5.4 to be washed with water at 80 C (approximately 10% of the oil vol-
Oleic 76 23.5 26.3 ume). The resulting mixture was centrifuged at 600 rpm during
Linoleic 15.7 53 48.6 10 min to separate water soluble salt impurities and nally the
Linolenic 0.1 7.8 5.9
organic phase was placed in a glass vessel and kept under vacuum
Others 1.3 1.1 1.4
at 80 C for 30 min in order to remove water.
 G.G. Mucio et al. / Fuel 138 (2014) 143148 145

2.5. Reaction tests 5

0.17%
100 1.25%
2.5.1. Esterication 42.87 %
When the transesterication of used cooking oil was carried out 0

a fatty solid product was obtained. This is due to the high saturated 90
791 C
fatty acid content inherent to used cooking oil. Therefore, in order
565 C

DSC (Wg )
-5

Weight (%)

-1
to reduce this content, an esterication of the used cooking oil was 80
conducted prior transesterication. This reaction was conducted in H =1907 J/g
a 250 ml spherical reactor connected to a reux system. The reac- -10
tion mixture was mechanically agitated by a magnetic stirrer. The 70 745 C
reactor was immersed in a constant-temperature bath. The oil was
preheated inside the reactor at 60 C and atmospheric pressure -15
60
before the addition of the mixture of catalyst (H2SO4) and metha-
nol. Experiments were performed with different methanoloil
molar ratios (6:1, 9:1, 12:1 and 15:1) and 0.35 wt% catalyst in ref- 50 -20
0 100 200 300 400 500 600 700 800 900 1000
erence to the mass of oil. After the esterication, the reaction mix-
Temperature (C)
ture was washed with water at 50 C to remove the alcohol and the
catalyst from the oil phase. To achieve good separation of phases, Fig. 1. TGA curve for sea sand sample.
the mixture was centrifuged 15 min at 600 rpm and water was
completely removed in a rotary evaporator.
the remained CaCO3. This is in agreement with the endothermic
2.5.2. Transesterication decomposition of calcium carbonate observed at 745 C in the
The batch reactor used to carry out the transesterication reac- DSC curve. This result is also consistent with that reported by Boey
tion was the same one used previously for the esterication reac- et al. [16] and Nakatani et al. [22], who indicated that the optimal
tion. After heating the oil up to the reaction temperature (60 C), temperature to convert CaCO3 from eggshell and oyster shell to
the alcohol and catalyst (calcined sand) were added and mixed at CaO is above 700 C. Therefore, it was decided to evaluate the effect
approximately 600 rpm. Multiple experiments were performed of calcination temperature at 700 C and above (800 and 900 C) on
modifying methanoloil molar ratios (6:1, 9:1, 12:1 and 15:1), the produced crystalline phases. These were established by X-ray
the amount of catalyst respect to the mass of oil (5%, 7.5% and diffraction. Fig. 2 depicts the X-ray diffraction patterns of calcined
10%) and the reaction time (4, 6 and 7 h). After the transesterica- and uncalcined sea sand. As can be seen, the principal components
tion reaction, the catalyst was separated from the products (glyc- of uncalcined sea sand are CaCO3 (calcite and aragonite), (Ca,
erin and methyl esters) by centrifugation. The residual methanol Mg)CO3 (calcite, magnesian) and MgCO3 (magnesite). After calcina-
was separated via vacuum evaporation. tion treatment at 700 C for 2 h, it was found that the aragonite
was completely transformed into calcite, another part of CaCO3
was transformed to CaO (calcia) and the MgCO3 (magnesite) was
2.5.3. Biodiesel characterization
completely transformed to MgO (periclase). Because CaCO3 was
The quantity of methyl esters was determined according to bio-
not fully transformed into CaO after calcining the sea sand at
diesel test method UNE-EN14103, using a Varian CP3800 gas chro-
700 C, it was decided to not further characterize or test the corre-
matograph equipped with a ame ionization detector and a
sponding sample in the transesterication reaction. After calcina-
capillary column CPwax with a length of 30 m, lm thickness of
tion at 800 and 900 C for 2 h, it was found that the CaCO3 was
0.25 lm and internal diameter of 0.32 mm. Kinematic viscosity
completely transformed to CaO. Characteristic CaO peaks were
was measured with a Canon-Fenske capillary viscometer
obtained at 32.2, 37.3, 53.8, 64.1, 67.3, 79.6, 88.5 and 91.4.
immersed in a constant temperature bath (40 C) following the
The signals of MgO were identied in the XRD patterns at 36.8,
European norm EN ISO 3104. Acid value is expressed in mg KOH
required to neutralize the existent free fatty acids in one gram of
fatty acid methyl esters and is set to a maximum value of 0.5 mg
KOH/g in the European norm (EN 14214). The acid value was deter-
mined in a potentiometric titrator (877 Titrino Plus-Metrohm)
using potassium biphthalate as primary standard to evaluate the 900 C
concentration of the titration solution (KOH). This technique was
developed according to norm UNE-EN 14104.
Intensity (a.u.)

800 C
3. Results and discussion

3.1. Catalyst characterization 700 C

In order to establish the adequate calcination temperature to

obtain CaO, the sea sand sample was analyzed by DSC/TGA. The Uncalcined
TGA curve of the sea sand is presented in Fig. 1. As can be seen,
the sample lost weight in three steps. The rst step at around 20 30 40 50 60 70 80 90
110 C is due to the loss of physically adsorbed water from the sur- 2
face of the porous sample. The second step, at around 400 C, can
be attributed to the change of aragonite to calcite. This result is Fig. 2. XRD patterns of uncalcined and calcined sea sand at different activation
temperatures. (4 CaCO3 (aragonite) [JCPDS #760606], N CaCO3 (calcite) [JCPDS
in agreement with that reported by Yoshioka and Kitano [21], #240027], (Ca, Mg)CO3 (calcite, magnesian) [JCPDS #430697], } MgCO3
who reported the change of these polymorphs at 380470 C. (magnesite) [JCPDS #020871],  MgO (periclase) [JCPDS #711176], d CaO (calcia)
The third step observed at 670 C is due to the decomposition of [JCPDS #371497]).
146 G.G. Mucio et al. / Fuel 138 (2014) 143148

42.8, 62.2, 74.5 and 78.5. The obtained XRD spectra were con-
trasted with the Joint Committee on Powder Diffraction Standards
(JCPDS) le and the corresponding numbers are given in Fig. 2.
Sea sand calcined at 800 and 900 C was characterized by the
Hammett indicator method in order to obtain information of its
basic properties. The parameter determined by Hammett indicator
method conrmed the presence of strong basic sites that are
believed to be responsible for the increase in methyl esters con-
tent. The catalyst basic strength was designated as 9.3 < H_ < 15.
The basicity of calcined sea sand at 800 and 900 C was 0.61 and
0.60 mmol/g, respectively. This result was consistent with that
reported by Viriya et al. [18], who mentioned that the basic prop- 10 m
erty of the catalysts that should be expected from CaO species is
considered a key factor yielding biodiesel.
Fig. 3. SEM image of calcined sea sand sample.
The measured BET area and pore volume of the uncalcined and
calcined sea sand are shown in Table 4. As can be seen, this catalyst
is a low porosity material. The increase in BET surface area for cal- Table 5
cined sea sand may be caused by the increase of crystallinity (see Acid values for used cooking oil after the esterication reaction.
Fig. 2). The calcination also induced an increase of pore volume
Experiment number Methanol/oil molar ratio Acid value (mg KOH/g)
value which can be attributed to the development of porosity in
1 6:1 0.29
the calcined sea sand.
2 9:1 0.20
Fig. 3 is a representative scanning electron micrograph of the 3 12:1 0.16
calcined sea sand sample. This is observed to be amorphous and 4 15:1 0.08
some aggregates are also observed. According to the EDS chemical
mapping (not included), the calcined sea sand contains Ca and Mg
(traces) (Table 4). This result is in agreement with the XRD study. conducted with a 12:1 methanol:oil molar ratio, a catalyst loading
of 7.5% and 6 h of reaction time.
The effect of calcination temperature was studied at 800 C and
3.2. Esterication reaction
900 C. The temperature of 700 C was not tested since the forma-
tion of CaO is not complete at this temperature (see Fig. 2). The
Dorado et al. [23] mentioned that the in order to produce bio-
resulting no polar and polar methyl esters contents were similar
diesel from used cooking oil, this should be pretreated due to its
when using the sea sand calcined at 800 C and 900 C. For the cat-
high free fatty acid level, i.e. free fatty acids amount larger than
alyst calcined at the former temperature, the calculated no polar
1 mg KOH/g results in high amounts of undesirable soap. In order
methyl esters content was 86.3% while the polar methyl esters
to determine the effect of alcohol to oil ratio in the acid value,
content was 9.13%. When using the catalyst calcined at 900 C,
the esterication reaction of used cooking oil (acid value 0.31 mg
the non polar and polar methyl esters contents were 87% and
KOH/g) was carried out at 60 C, atmospheric pressure, reaction
9.13%, respectively. This similarity of results obtained with both
time of 3 h and 0.35 wt% of H2SO4 as catalyst. These parameters
calcination temperatures was expected since their basicity is alike
were selected based upon previous results in other studies
too. Therefore, the calcination temperature of 800 C was elected to
[24,25]. The methanol/oil molar ratios used were 6:1, 9:1, 12:1
further evaluate the performance of the sea sand as catalyst of the
and 15:1. Table 5 shows the acid values with different alcohol/oil
transesterication reaction.
molar ratio. When the alcohol/oil ratio increases, the acid values
Another important variable that usually affects the biodiesel
were observed to decrease. This is due to the esterication reaction
production is the methanol/oil molar ratio. In this study an excess
and therefore the transformation of free fatty acids being favored
of methanol was used to obtain a higher biodiesel yield. The
by the amount of methanol.
essayed methanol/pretreated cooking oil molar ratios were 6:1,
9:1, 12:1 and 15:1. The methyl esters content was 85.2%, 86.2%,
3.3. Transesterication reaction 86.3% and 86.4%, respectively. The difference in the methyl esters
content is not signicant between these four methanol/oil molar
The effect of four variables on the nal methyl esters content ratios. However, when using molar ratios of 6:1 and 9:1, it was also
was studied when performing the transesterication of pretreated observed that the difculty to separate the catalyst and the prod-
used cooking oil (produced by esterication at methanol:oil molar ucts of reaction increased. This difculty lies on the nature of the
ratio = 15:1). These variables were calcination temperature of the raw material. When transesterifying used cooking oil the appear-
catalyst, methanol:oil molar ratio, catalyst loading and reaction ance of a solid (presumably saturated fat) was observed. This mate-
time. Unless otherwise specied these experiments were rial trapped the catalyst and complicated its recovery. At high
methanol:oil ratios, however, the solid was diluted into the liquid
phase thus eliminating the difculty of recovering the catalyst.
Table 4
BET surface area, total pore volume and composition of the sea sand catalyst. Thus the optimum methanol/oil molar ratio was established to
be 12:1 for the transesterication reaction.
Catalyst BET area Total pore volume Composition (%)a
In order to investigate the inuence of the catalyst amount, 5%,
(m2/g) (cm3/g)
Ca Mg 7.5% and 10% values related to the initial oil weight (Fig. 4) were
Sea sand 3.1 0.002 98.7 1.3 tested. It was observed that by increasing the catalyst amount
Calcined sea sandb 4.6 0.009 the methyl esters content also increases when using a catalyst
Calcined sea sandc 5.1 0.011
loading of 5% and 7.5%. This increase is not important though.
a
Determined by EDS analysis. For a catalyst loading of 10%, it can be observed a slight decrease
b
Calcined at 800 C for 2 h. of the methyl esters content, however the difference is not signif-
c
Calcined at 900 C for 2 h.
icant with respect to the methyl esters content obtained with a

100
Methyl esters content (%)
80
60
40
20
0 the high temperature, exposure to air and light produce reactions
5 7.5
Catalyst amount (wt %)
Fig. 4. Inuence of catalyst loading on the biodiesel production.
catalyst loading of 7.5%. Kim et al. [26] suggested that a higher cat-
alyst dosage may increase the viscosity of the reacting mixture and
this would lead to an increase of the mass transfer resistance in the
multiphase system. Several reaction studies using heterogeneous
catalysts agree that the limiting steps in the transesterication of
vegetable oil can be either the liquidsolid mass transfer or the
surface reaction [27,28]. Therefore, the use of large amounts of
catalyst is not advised.
The effect of reaction time on methyl esters content was exam-
ined employing a methanol/oil molar ratio of 12:1, 7.5 wt% of cat-
alyst (calcined sea sand), 600 rpm stirring rate and atmospheric
pressure. A reaction time of 4 h was tested, and only 84% of methyl
esters content was achieved. An increase in reaction time from 6 to
7 h resulted in only a slight improvement of methyl esters content
from 86.3% to 86.8%. Thus, the selected reaction time was 6 h.
Besides, it was also observed that the difculty to separate the
catalyst increased with reaction time. This can be ascribed to the
formation of a suspensoid in the methanoloil mixture. This has
also been previously observed by other researchers [29].
3.4. Transesterication reaction of rened soybean and safower oil
The transesterication of rened soybean and safower oils was
conducted using calcined sea sand as catalyst in order to contrast
these results with those obtained when employing used cooking
oil. An important quality parameter is the amount of triglycerides.
In related literature, 96% of triglycerides has been reported for veg-
etable oils, which is related to the expected methyl esters content.
The glyceride content is shown in Table 3 and it can be observed
that used cooking oil has the lowest amount of triglycerides.
The same reaction conditions used with used cooking oil were
applied to the transesterication reaction of rened oil (6 h of reac-
tion time, atmospheric pressure, methanol/oil molar ratio 12:1,
7.5 wt% of catalyst and 600 rpm stirring rate). Samples of the prod-
ucts of these reactions were obtained and analyzed according to
standard methods to determine the content of methyl esters
(UNE-EN 14103), viscosity (ISO 3104) and acid number (UNE-EN
14104). The results of these analyses are shown in Table 6 and
Table 6
Characterization of biodiesel obtained in the transesterication of esteried cooking oil, safower oil and soybean oil.
Raw materials
Used cooking oil (esteried)
Non polar methyl esters
Polar methyl esters
Total methyl esters
Safower oil
Soybean oil
EN 14214
G.G. Mucio et al. / Fuel 138 (2014) 143148 147
are compared with those obtained when used cooking oil is the
raw material.
A high methyl esters content was obtained when rened oils
were used in the reaction (96.697.5%). This is expected from oils
containing over 95% of triglycerides [30]. A lower viscosity pro-
motes mixing of the reactants and the catalyst thus improving
the yield of reaction.
With used cooking oil a lower yield than with rened oils was
obtained. This may due to its lower content of triglycerides with-
out chemical modication. During the use of the oils for cooking
10 of oxidation, polymerization and hydrolysis. These reactions pro-
duce polymers, dimers, oxidized triglycerides, diglycerides and
monoglycerides, compounds with a higher polarity than triglycer-
ides in rened oils and their transesterication reaction products
are identied with different procedures than those proposed by
the norms UNE EN 1410314105 [31]. With the used cooking oil
(22.89% polar compounds), a product with 86.3% of methyl esters
was obtained. This is in agreement with literature that reports
the transesterication of oils with 2327% content of polar com-
pounds formed by the degradation of oil [25].
Ruiz-Mndez et al. [30] have proposed a correlation to calculate
the percentage of polar methyl esters (FAMES) produced by the
transesterication of compounds with higher polarity. In this case,
% polar FAMES 0:46  % of polar compounds  1:4
% polar FAMES 0:46  22:89% of polar compounds  1:4
9:1%
Thus the total content of methyl esters from used cooking oil
(polar + non polar) is 95.4%.
4. Conclusions
Production of biodiesel from used cooking oil, soybean oil and
safower oil can be catalyzed by calcined sea sand, which is rich
in CaO. After calcination at 800 C for 2 h, CaCO3 (principal compo-
nent of sea sand) was transformed to CaO. This oxide is a source of
strong basic sites, resulting in an increased reactivity.
To obtain methyl esters from used cooking oil, a two-step reac-
tion system was performed. First, an esterication reaction was
conducted to reduce the amount of free fatty acids in order to avoid
saponication in the subsequent transesterication reaction.
The effect of methanol:oil molar ratio on the nal methyl esters
content was not signicant when used cooking oil was the raw
material. However, a 12:1 ratio (methanol:oil) facilitated the sepa-
ration and cleaning of the products. The use of 7.5% catalyst
amount and 6 h of reaction time were the best conditions to obtain
95.4% (polar + non polar), 96.6% and 97.5% of methyl esters content
using used cooking oil, safower oil and soybean oil, respectively.
Methyl esters content (%) Viscosity (mm2/s) Acid value (mg KOH/g)
5.0 0.10
86.3
9.1
95.4
96.6 4.8 0.05
97.5 4.2 0.11
96.5 3.55.0 Max. 0.50
148 G.G. Mucio et al. / Fuel 138 (2014) 143148
Acknowledgments
The authors are grateful for the help provided with the catalyst
characterization to Dr. Marina Vega Gonzlez from Centro de
Geociencias UNAM, Dr. Susana Hernndez Lpez from Facultad
de Qumica UAEM, and Dr. Ivn Garca Orozco from Centro Conjun-
to de Investigacin en Qumica Sustentable UAEM-UNAM. The
nancial support of Universidad Autnoma del Estado de Mxico
through Project 3446/2013CHT is also acknowledged.
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