Industrial Crops and Products 89 (2016) 416–424

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Industrial Crops and Products

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

Solid acid as catalyst for biodiesel production via simultaneous

esterification and transesterification of macaw palm oil
Leyvison Rafael V. da Conceição, Livia M. Carneiro, J. Daniel Rivaldi, Heizir F. de Castro ∗
Engineering School of Lorena, University of São Paulo, Estrada Municipal do Campinho s/n, 12602-810 Lorena, São Paulo, Brazil

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

Article history: Heterogeneous catalysis applied to esterification and transesterification of non-edible oil offers a strat-
Received 20 January 2016 egy to the clean synthesis of the biodiesel and is driving research interested into the development of
Received in revised form 22 May 2016 acid catalysts for efficient conversion of low quality vegetable oils into fuels to meet future societal
Accepted 24 May 2016
demands. Thus, sulfated niobium oxide catalyst was synthesized by the impregnation method and used
as a heterogeneous catalyst aimed at biodiesel production via macaw palm oil through high free fatty acid
Keywords:
content transesterification with ethanol. The effect of two reaction parameters, molar ratio of ethanol to
Biodiesel
macaw palm oil and reaction temperature, on ester content and viscosity was studied by the response
Macaw palm oil (Acrocomia aculeata)
Sulfated niobium oxide
surface methodology (RSM). The ester content was determined by GC. The catalyst shows excellent
Optimization activity (99.2% ester content and 4.5 mm2 /s viscosity) towards biodiesel production. Its optimum reac-
Ethanolysis tion conditions were: 120:1 molar ratio of ethanol to macaw palm oil at 250 ◦ C reaction temperature.
The catalysts characterization was carried out by using the X-ray Diffraction (XRD), Scanning Electron
Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR), and N2 Adsorption-desorption and
Surface Acidity Analyses.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
As traditional fossil fuels are not renewable and their depletion
is in the offing, probably in the next several decades, the search for
alternative fuels is becoming increasingly attractive (Fu et al., 2013).
In this context, biodiesel stands out as an alternative fuel which
produces low aromatic gases and CO2 emissions. Moreover, it is also
renewable, biodegradable, non-flammable, non-toxic, and sulfur-
free (Syazwani et al., 2015). Biodiesel consists of a mixture of fatty
acid alkyl esters, derived from renewable lipid feedstocks, such as
vegetable oils and animal fats, which are basically triacylglycerols
(Banković-Ilić et al., 2014).
Alcoholysis is the process that most frequently takes place,
which is an established method for the transformation of veg-
etable oils into biodiesel. The transesterification reaction can occur
in the presence of homogeneous or heterogeneous catalysts (acids
or bases) or enzyme (mostly lipases) with alcohol (methanol and
ethanol) (Avhad and Marchetti, 2015; Banković-Ilić et al., 2014).
Biodiesel production from non-edible oils has drawn the atten-
tion of researchers due to its high biodiesel yield and easy
∗ Corresponding author.
E-mail address: heizir@dequi.eel.usp.br (H.F. de Castro).
processing. However, edible oils for producing biodiesel is the sub-
ject of debate on its use as fuel or as food, thus these factors have
negatively affected its production from edible oils. Therefore, non-
edible vegetable oils have become more attractive for biodiesel
production (Ong et al., 2013). Hence, many resources have been
analyzed in order to explore non-edible feedstocks for biodiesel
production, such as Jatropha oil (Jatropha curcas L.) (Nizah et al.,
2014), Karanja oil (Pongamia pinnata L.) (Thiruvengadaravi et al.,
2012), Sea Mango oil (Cerbera odollam Gaertn.) (Kansedo and Lee,
2013), Rubber seed oil (Hevea brasiliensis Muell. Arg) (Reshad et al.,
2015), Moringa oil (Moringa oleifera Lam.) (Fernandes et al., 2015),
Kusum oil (Schleichera oleosa L.) (Silitonga et al., 2015), Andiroba oil
(Carapa guianensis Aubl.), Castanhola oil (Terminalia catappa L.) (Iha
et al., 2014), Mahua oil (Madhuca indica J.F. Gmel) and Simarouba
oil (Simarouba glauca DC) (Jena et al., 2010).
Macaw palm (Acrocomia aculeata (Jacq.) Lodd ex Mart.), com-
monly known in Brazil as Macaúba, is a native oleaginous palm tree
which grows abundantly in the Brazilian cerrado, located mainly
in the center of the country, but adapted from cooler subtropical
scenarios to drier semiarid ecosystems, and widely spread across
Mexico, Antilles, Argentina, Uruguay and Paraguay (Moura et al.,
2009). This palm tree can reach 15–20 m in height, with 20–30 cm
of trunk diameter and covered by dark thorns that are usually 10 cm
in length (César et al., 2015). Its fruits are spherical, with 2.5–5.0 cm

http://dx.doi.org/10.1016/j.indcrop.2016.05.044
0926-6690/© 2016 Elsevier B.V. All rights reserved.
 L.R.V. da Conceição et al. / Industrial Crops and Products 89 (2016) 416–424
in diameter. A single plant has 2–6 clusters, with a total number of
fruits ranging from 260 to 1270 per palm tree, producing estimated
yields of 4000 kg of oil/ha (Ciconini et al., 2013).
However, its oil presents high acidity and cannot be used
as feedstock for biodiesel production by a conventional alkaline
route (Aguieiras et al., 2014). In this case, the biodiesel synthesis
should be carried out via simultaneous esterification and transes-
terification process using acid catalysts, which enables the use of
low-quality raw materials with high concentrations of free fatty
acids (FFA).
The major focus of recent advances is on the rational devel-
opment of recyclable solid acids catalysts. These catalysts have
been established as being other alternatives to the heterogeneous
alkaline, unrecyclable-homogeneous acid and alkaline catalysts.
Several encouraging results described in literature have highlighted
the potentials of solid acid catalyzed-biodiesel production (Sani
et al., 2014). Among the most studied solid acids are mixed oxides
(Liu et al., 2015; Amani et al., 2014), ion-exchange resin (Fu et al.,
2015; Shibasaki-Kitakawa et al., 2015), heteropolyacid (Narkhede
et al., 2014; Gong et al., 2014), sulfated zirconia (Patel et al., 2013;
Saravanan et al., 2015) and zeolite (Vieira et al., 2015; Sun et al.,
2015).
The aim of the present work is to optimize the performance
of sulfated niobium (Nb2 O5 /SO4 ) as a heterogeneous catalyst in
a simultaneous esterification and transesterification for biodiesel
production using macaw palm oil with high free fatty acid con-
tent and ethanol as acylant agent. Ethanol has some advantages
when used in a process for biodiesel production. It has a supe-
rior dissolving power in vegetable oils and the ethyl esters (FAEE)
show lower smoke opacity, lower exhaust temperature and lower
pour point (Yusoff et al., 2014). The evaluation of exhaust gas emis-
sions (including nitrogen oxides, CO2 and smoke density) shows
that FAEE has a less negative environmental effect in comparison to
methyl esters (FAME) (Brunschwig et al., 2012; Stamenkovic et al.,
2011). Additionally, unlike methanol (which is generally derived
from fossil sources), ethanol is produced mainly from renewable
sources via fermentation processes, and because its large scale pro-
duction as a substitute fuel for gasoline already exists, the supply of
bioethanol for the industrial production of biodiesel can be easily
achieved (Brunschwig et al., 2012).
2. Material and methods
2.1. Materials
Macaw palm oil with high free fatty acid content was sup-
plied by Association of Small Farmers D’Antas (Minas Gerais,
Brazil). Hydrated niobium oxide HY340 (amorphous) with high
surface area (BET ∼170 m2 /g) containing 80% Nb2 O5 was supplied
by Companhia Brasileira de Metalurgia e Mineração—CBMM and
calcined at 500 ◦ C for 5 h before use. Sulfuric acid (98.0%) and anhy-
drous ethanol (98.0%) were purchased from VETEC® Sigma-Aldrich.
Anhydrous sodium sulfate, ethyl acetate (99.5%) and hexane (65.0%)
were supplied by Cromoline. Methanol (99.95%) and acetonitrile
(99.9%) were purchased from J.T. Baker. Internal standard methyl
heptadecanoate C17:0 (99.0%) was purchased from Sigma.
2.2. Catalyst preparation
The Nb2 O5 /SO4 catalyst was prepared with a mixture of 5 g
Nb2 O5 , 5 mL H2 SO4 solution (0.5 M) and 15 mL deionized water in a
glass reactor at 90 ◦ C under reflux and constant agitation (500 rpm)
for 3 h. The solid was washed twice with deionized water, then
filtered and dried at 100 ◦ C for 12 h. The catalyst was calcined at
500 ◦ C for 5 h.
417
2.3. Catalyst characterization
2.3.1. X-ray diffraction (XRD)
X-ray powder diffractograms of the catalysts were collected
with a PANalytical Model Empyrean X-ray diffractometer at 40 kV
and 30 mA. Radiation of Cu K␣ (1.541874 Â) was employed with 2␪
of 8◦ –70◦ .
2.3.2. Scanning electron microscopy (SEM)
The morphology of the catalyst was analyzed by high-resolution
scanning electron microscopy in a LEO Model 1450 VP, operating
with accelerating voltage of 20 kV.
2.3.3. Fourier transform infrared spectroscopy (FT-IR)
The infrared spectra were recorded on a spectrum GX FT-IR sys-
tem Perkin Elmer spectrometer. The sample was pelletized with
KBr, and the spectrum was obtained from the accumulation of a
total of 32 scans in the range of 4000–400 cm−1 with resolution of
4 cm−1 .
2.3.4. N2 adsorption-desorption analysis
A sample of 0.2 g was added to a glass cell and heated at 200 ◦ C
for two hours under vacuum to remove impurities adsorbed on
the catalyst surface. Nitrogen adsorption isotherms were obtained
in a Nova 1000 mark Quantachrome. The surface area was calcu-
lated with the BET equation, and the mean pore size diameter was
calculated by the BJH method.
2.3.5. Surface acidity
The surface acidity of the catalyst was determined by using acid-
base titration. An aqueous suspension of 0.1 g of catalyst in 20 mL of
NaOH (0.1 M) was maintained under agitation for 3 h at room tem-
perature to allow ion exchange. The suspension was centrifuged
and the supernatant titrated with HCl (0.1 M) in the presence of
phenolphthalein. The surface acidity of the catalyst was expressed
in mmol H+ /g catalyst.
2.4. Catalytic reaction
The Nb2 O5 /SO4 catalyst was previously dried at 120 ◦ C for 2 h
before utilization. Its catalytic performance was analyzed in a
simultaneous esterification and transesterification reaction. Exper-
iments were conducted using different ethanol-to-oil molar ratios
and reaction temperatures. All experiments were conducted at
300 rpm for a maximal period of 4 h in a pressurized stainless steel
reactor (Parr Series 5000 Multiple Reactor System) equipped with
an electrical heating jacket covering the reaction vessel, and indi-
vidual temperature control.
At the end of the transesterification, the catalyst was separated
from the mixture containing products and reagents by centrifuga-
tion at 1570x for 15 min. The supernatant containing ethyl esters
was transferred to a separating funnel and washed with the same
volume of hot water for 12 h, allowing the decantation and sep-
aration of glycerol and the ethyl ester phase (higher phase). This
procedure was carried out three times to assure total glycerol
removal. The liquid phase containing ethyl esters was submitted to
evaporation in a vacuum rotary evaporator to remove the remain-
ing ethanol. Finally, the ethyl esters were dried with anhydrous
sodium sulfate to remove traces of water.
2.5. Experimental design
The effects of the process variables of ethanol-to-oil molar ratio
(X1 ) and reaction temperature (X2 ) on ester content (Y1 ) and kine-
matic viscosity (Y2 ) were verified using the experimental design.
The experiments were carried out and optimized following the
418 L.R.V. da Conceição et al. / Industrial Crops and Products 89 (2016) 416–424

Table 1
Macaw palm oil fatty acid composition and physico-chemical properties.

Property Value

Fatty acid (%)

Palmitic acid (C16:0) 18.7
Palmitoleic acid (C16:1) 4.0
Stearic acid (C18:0) 2.8
Oleic acid (C18:1) 53.4
Linoleic acid (C18:2) 17.7
Linolenic acid (C18:3) 1.5
Saturated total 21.5
Unsaturated total 78.5
Acid value (mg KOH/g) 39.0
Kinematic viscosity at 40 ◦ C (mm2 /s) 44.5
Density at 20 ◦ C (g/cm3 ) 0.902
Moisture content (%) 1.25

rate of 2.0 mL/min. The temperature setup was T1 = 150 ◦ C for 1 min,
heating up to T2 = 180 ◦ C at 7.5 ◦ C/min, holding for 2 min and heat-
Fig. 1. X-ray diffractograms (XRD) of a) Nb2 O5 , b) Nb2 O5 thermally treated at 500 ◦ C
and c) Nb2 O5 /SO4 catalyst.
ing up to T3 = 240 ◦ C for 3 min. The ester content, expressed as mass
fraction in percentage terms, is calculated by Eq. (2):

face centered central composite design (CCD) and the response sur-
A − API CPI
face methodology (RSM). The software Statistica (Statisoft, v.7) was EsterContent = × × 100 (2)
API Csample
used to analyze the results.

2.6. Statistical analysis Where,

The RSM is a set of mathematical and statistical techniques
which are useful for modeling and analyzing problems in which
a response of interest is influenced by several variables with the
purpose of optimizing this response (Montgomery, 1997; Hameed
et al., 2009). The first step of the RSM was to obtain a mathe-
matical model that describes the response variables (Y1 and Y2 )
as a function of the independent variables (X1 and X2 ). The equa-
tion obtained from it only considers the significant coefficients, as
shown in Eq. (1). Coefficient ˇ0 is the outcome (response) at cen-
tral point, and the other coefficients measure the main effects and
interactions of coded variables Xi on the response variable Y.
k k k
Y = ˇ0 + ˇi Xi + ˇii X 2 i + ˇij Xi Xj +e
i=1 i=1 i<1
The model obtained from the regression analysis was used to
generate the response surface and contour plots. For selecting the
significant terms from the model, the significance level was set at
95% and p < 0.05. The second step was to determine the quality of
the model, which was assessed by the analysis of variance (ANOVA)
using an F-test (Box et al., 1978).
A is the total peak area from the ethyl ester;
API is the peak area corresponding to methyl heptadecanoate;
CPI is the concentration of the methyl heptadecanoate solution;
Csample is the concentration of the sample solution.
The ethyl ester viscosity was determined according to the stan-
dard method ASTM D 445 with a LVDVII Brookfield viscosimeter
(Brookfield Viscometers Ltd., England) equipped with a CP 42 cone
at 40 ◦ C using 0.5 mL of sample. Its density value was determined
according to the standard method ASTM D 4052 with a DMA 35N
EX digital densimeter (Anton Paar) at 20 ◦ C using 2 mL of sample.
The remaining amount of glycerides after the transesterification
was determined in an Agilent 1200 Series liquid chromatograph
(Agilent Technologies, USA) equipped with an Evaporative Light
(1) Scattering Detector and a Gemini C-18 (5 ␮m, 150 × 4.6 mm, 110 Å)
column at 40 ◦ C. The mobile phase contained a mixture of acetoni-
trile (80%) and methanol (20%) at a flow rate of 1 mL/min for 6 min,
1.5 mL/min until 30 min, and 3.0 mL/min until 35 min. All samples
were dissolved in ethyl acetate-hexane (1:1, v/v), filtered through
0.22 ␮m membrane filters (Millipore) and injected in a volume of
10 ␮L. All solvents were of an HPLC grade, and the assays were
performed at least in duplicate.

2.7. Oil and biodiesel characterization

2.7.1. Macaw palm oil
The macaw palm oil fatty acid composition was determined by
gas chromatography (GC) according to the AOCS Ce 1-62 method.
The physico-chemical characterization was conducted according to
the following standard methods: acid value (AOCS Cd 3d-63), vis-
cosity (ASTM D 445), density (ASTM D 4052) and moisture content
(AOCS Ca 2b-38).
2.7.2. Macaw palm biodiesel
The ester content was determined by gas chromatography
according to Silva et al. (2007). The samples were analyzed on a
Varian CP 3800 chromatograph equipped with an auto injector,
and a FID. A TR FAME capillary column was used with the follow-
ing features: 30 m length, 0.25 mm internal diameter, and 0.25 ␮m
film thickness. Nitrogen gas was used as the mobile phase at a flow
3. Results and discussion
3.1. Properties of macaw palm oil
The fatty acid composition and physico-chemical characteriza-
tion of the macaw palm oil are shown in Table 1.
Macaw palm oil contains a large amount of unsaturated fatty
acids (78.5%) primarily, oleic acid (53.4%), and a lower amount
of saturated acid (21.5%), typically palmitic (18.7%). Its acidity
and moisture content was 39.0 mg KOH/g and 1.25%, respectively,
which was a determining factor in the choice of an acid catalyst
because the use of alkaline catalysts are recommended when the
oil has an free fatty acid (FFA) value of less than 3% and moisture
content lower than 1%, since the saponification reaction compro-
mises the transesterification reaction’s efficiency and hinders the
separation of ester and glycerol phases (Meher et al., 2006).
 L.R.V. da Conceição et al. / Industrial Crops and Products 89 (2016) 416–424 419

Fig. 2. SEM images of Nb2 O5 /SO4 catalyst.

Table 2 lack of peaks is also associated with its structure, water and impu-
Textural and acidic properties of Nb2 O5 and Nb2 O5 /SO4 .
rities (Nowak and Ziolek, 1999).
Sample Surface area (m2 /g) Pore volume (cm3 /g) Surface acidity (mmol H+ /g) The Nb2 O5 /SO4 spectrum showed pronounced peaks regarding
Nb2 O5 169.1 0.093 0.041 the crystalline phase in the region of 23, 28, 36, 51 and 56 (2␪) of
Nb2 O5 /SO4 63.1 0.143 2.764 the spectrum (Fig. 1c). These peaks are similar to those observed for
niobium oxide submitted to a thermal treatment at 500 ◦ C without
impregnation (Fig. 1b). Calcined Nb2 O5 usually shows a polycrys-
Table 3 talline structure (polymorphism), depending on the temperature
Experimental design matrix and results of the synthesis of macaw palm oil biodiesel
and the presence of oxygen during the thermal treatment (Melo
via esterification and transesterification.
et al., 2012). The formation of crystals in this oxide starts at 500 ◦ C,
Run Variable Response promoting structures of monoclinic, hexagonal and orthorhombic
Molar ratio Temperature Ester content (%) Viscosity (mm2 /s) systems (Nowak and Ziolek, 1999). As the calcination temperature
(◦ C) increases, the surface area decreases due to the crystal formation
1 60 −1 150 −1 34.65 20.00 and compaction. However, this arrangement reduces the number of
2 60 −1 250 1 86.80 6.15 available active acid sites for catalysis, and promotes greater struc-
3 120 1 150 −1 32.10 19.00 tural stability. The impregnation with sulfuric acid did not affect
4 120 1 250 1 99.20 4.50
the crystalline structure of the niobium oxide after calcination, as
5 90 0 200 0 62.90 11.35
6 90 0 200 0 55.00 12.45
demonstrated by the same crystal spectrum observed for both the
7 90 0 200 0 54.85 11.00 catalyst and the calcined support (Fig. 1c).
8 60 −1 200 0 75.50 8.10 The catalyst SEM images are shown in Fig. 2(a) and (b). The
9 120 1 200 0 51.90 13.70 micrographs clearly show that the catalyst is not uniform and its
10 90 0 150 −1 20.50 24.60
particles do not present a single size.
11 90 0 250 1 92.30 5.85
The FT-IR spectra of Nb2 O5 and Nb2 O5 /SO4 are presented in
Fig. 3. The spectrum of the samples is predominated by a broad
Table 4 band at 675 cm−1 , which is typical for niobium oxides, and it is
Analysis of variance (ANOVA) of the response surface quadratic model. assigned to the vibrations of Nb O Nb bridges from slightly dis-
Sources Sum of squares Degree of freedom Mean squares F-value F0.05 torted octahedral NbO6 connected with sharing corners. The weak
band around 850 cm−1 can be assigned to the symmetric stretching
Ester model
Regression 5899.3 5 1179.86 13.05 5.05
mode of Nb O surface species, which is present in highly distorted
Residual 452.11 5 90.42 octahedral NbO6 structures (Stosic et al., 2014). At 1625 cm−1 , there
Lack of Fit 409.70 3 136.56 6.44 19.16 appears to be a peak which can be attributed to water molecules
Pure error 42.41 2 21.20 adsorbed on the surface of Nb2 O5 and Nb2 O5 /SO4 . There is also
Totals 6351.41 10
a shoulder at 3435 cm−1 , probably due to the hydroxyl moieties
Viscosity model (Nb OH) as well as from the water molecules themselves. In the
Regression 440.87 5 88.17 18.76 5.05 spectrum of Nb2 O5 /SO4 , the peak at 1125 cm−1 can be attributed
Residual 23.52 5 4.70
Lack of Fit 22.42 3 7.47 13.58 19.16
to the symmetric stretching of S O bonds (Ngee et al., 2014).
Pure error 1.10 2 0.55 Table 2 presents the values of surface area, pore volume and total
Totals 464.39 10 surface acidity of Nb2 O5 and Nb2 O5 /SO4 . The nitrogen adsorption-
desorption isotherms for Nb2 O5 and Nb2 O5 /SO4 are shown in Fig. 4.
The isotherms showed pronounced type IV characteristics with
3.2. Catalyst characterization hysteresis loop type H2, according to the IUPAC classification (Sing
et al., 1985). The hysteresis loop is associated with the capillary
The X-ray diffractograms of the Nb2 O5 support and Nb2 O5 /SO4 condensation taking place in the mesopores, which indicates the
catalyst were prepared by the impregnation method, which are existence of a mesoporous structure in the sulfated niobium. The
shown in Fig. 1. The spectrum of Nb2 O5 without any thermal treat- type H2 hysteresis loop is attributed to the pores shaped like ink
ment (Fig. 1a) showed a characteristic profile of a non-crystalline bottles (pores with narrow necks and wide bodies) (Deshmane and
material without peaks, corresponding to an amorphous solid. This Adewuyi, 2013). The sulfated niobium catalyst showed acidity of
420 L.R.V. da Conceição et al. / Industrial Crops and Products 89 (2016) 416–424

Fig. 3. Infrared spectra of the Nb2 O5 and Nb2 O5 /SO4 catalyst.

Fig. 4. N2 adsorption-desorption isotherms of Nb2 O5 and Nb2 O5 /SO4 catalyst.

2.764 mmol H+ /g which is 67 times greater than that of the niobium
oxide used as support. This confirms the impregnation of sulfate
groups on the crystalline structure of the niobium oxide.

3.3. Optimization of the reaction conditions to produce biodiesel
from macaw palm oil
In the present work, the relations between ester content (Y1 )
and kinematic viscosity (Y2 ) responses and two reaction variables,
ethanol-to-oil molar ratio (X1 ) and reaction temperature (X2 ), were
analyzed by using the RSM, as shown in Table 3.
By applying a multiple regression analysis of Table 3 data, the
experimental results of the centered face factorial design were fit-
ted to the polynomial Eq. (2). The models obtained for ester content

Fig. 5. Pareto charts for a) ester content and b) viscosity, and predicted vs. actual values for c) ester content and d) viscosity.
 L.R.V. da Conceição et al. / Industrial Crops and Products 89 (2016) 416–424
Fig. 6. Response surface and contour plots for (a) the ester content and (b) the
viscosity vs. molar ratio and temperature.
(Y1 ) and viscosity (Y2 ), as a function of the most significant inde-
pendent variables, are shown in Eqs. (3) and (4).
Y1 = 57.76 + 30.82X2 (3)
Y2 = 12.22 − 2.22X1 2 − 8.3X2 + 2.11X2 2 (4)
The fit of models Y1 and Y2 were verified by the coefficients of
determination R2 (Y1) = 0.9288 and R2 (Y2) = 0.9493, indicating that
approximately 93% and 95% of the responses variability could be
explained by these models, thus confirming the good correlations
between the independent variables.
The analysis of variance (ANOVA) in Table 4 demonstrates that
the empirical models can be considered statistically significant
according to the F-test at 95% confidence level. The F-values of Y1
and Y2 are 13.05 and 18.76, respectively, greater than F0.05 = 5.05.
Fig. 5 shows the student’s t-distribution values in a Pareto chart
and plots of predicted versus actual values. According to Fig. 5(a),
variable X2 Temperature(L) has the greatest effect on the ester con-
tent. The value of 16.4 was the greatest among the determined
421
values. Notably, an increase in the reaction’s temperature from the
lowest to the highest level yielded an average increase of 61.6% in
ester content. In Fig. 5(b), variables X2 Temperature(L), X1 Molar
ratio(Q) and X2 Temperature(Q) were found to be significant for
the biodiesel’s viscosity. Their values were 27.64, −4.78, and 4.53,
respectively. A variation from the lowest to the highest level of
reaction temperature and molar ratio produced a 16.7% and 4.4%
decrease in the biodiesel’s viscosity, respectively.
Fig. 5(c) and (d) compares the observed experimental ester con-
tent and viscosity with the predicted values. The determination
coefficient (R2 ) value of ester content (Fig. 5c) is 0.9288, indicating
approximately 93% variability in the data accounted by the model.
Meanwhile, as regards its viscosity (Fig. 5d), the R2 value is 0.9494,
indicating approximately 95% of variation in the data explained by
the model.
Generally, the 3D response surface plots are graphical repre-
sentations of the regression equation for optimizing the reaction
variables. Fig. 6 shows the response surface and contour plots for
the effects of temperature and molar ratio on ester content (Fig. 6a)
and viscosity (Fig. 6b). Fig. 6(a) shows that any molar ratio value
(within the studied range) can be used to obtain samples with high
ester content (greater than 95%), provided that the reaction temper-
ature is higher than 230 ◦ C. A decrease in the reaction temperature
originated samples with low ester content, indicating once again
the statical significance of the variable temperature. Such behavior
can be confirmed in Fig. 6(b) which indicates that the biodiesel vis-
cosity was absolutely dependent on temperature, and values below
5.0 mm2 /s were obtained at any molar ratio for reaction tempera-
tures higher than 230 ◦ C.
As the fitted models presented in Eqs. (3) and (4) offered a good
estimation of experimental conditions, they were employed to pre-
dict the best conditions for the variables so as to attain samples
having maximum ester content with the lowest viscosity. The opti-
mal conditions for the selected transesterification variables were a
molar ratio of 120:1 and reaction temperature of 250 ◦ C, with an
actual macaw palm biodiesel ester content of 99.2% and viscosity
of 4.5 mm2 /s.
3.4. Effects of reaction time and catalyst concentration on the
response variables
In order to determine the effect of reaction time on ester content
and viscosity of macaw palm biodiesel, experiments were carried
out at various reaction times, ranging from 2 to 4 h, at molar ratio of
120:1, reaction temperature of 250 ◦ C and catalyst concentration of
30 wt.% Nb2 O5 /SO4 . The experimental results are shown in Fig. 7(a).
As it can be seen, the ester content increases as the reaction time
increases, and with a reaction time of 2 h, the biodiesel ester content
reaches 91.9%. When the reaction took 3 h to be complete, the ester
content reached the value of 98.8%, and a maximum of 99.2% ester
content was achieved when it took 4 h.
The reaction time also influences the viscosity of biodiesel. The
experimental results are shown in Fig. 7(b). By increasing the reac-
tion time of the process, the viscosity values tend to decrease. For
biodiesel synthesized in a reaction time of 2 h, its viscosity was
6.15 mm2 /s, while for the transesterification reaction that occurred
for 4 h, it was 4.5 mm2 /s. This fact is justified by the increased for-
mation of ethyl esters along the reaction time, hence decreasing
the amounts of intermediates, such as monoacylglycerol and dia-
cylglycerol. Such compounds are partly responsible for increasing
the viscosity of biodiesel (Veljkovic et al., 2015).
The catalyst concentration is an essential parameter for process
optimization, thus making it feasible. In this part of the process, a
molar ratio of 120:1, reaction temperature of 250 ◦ C and reaction
time of 4 h were maintained as constant by varying the catalyst
concentrations (5–30 wt.% of macaw palm oil) for the production of
422 L.R.V. da Conceição et al. / Industrial Crops and Products 89 (2016) 416–424

Fig. 7. Effects of reaction time and catalyst concentration on the ester content and viscosity.

Fig. 8. Reusability of the Nb2 O5 /SO4 catalisty in simultaneous esterification and transesterification of macaw palm oil: a) Ester content and b) Viscosity.

ethyl ester. As shown in Fig. 7(c), increase in the catalyst concentra- tents higher than 98.0% were attained for catalyst concentrations
tion produces high ester content. The value of 92.8% ester content over 10%. The highest ester content was achieved from the biodiesel
was obtained using a concentration of 5% catalyst, and ester con- synthesized with catalyst concentration at 30%. The catalyst con-
 L.R.V. da Conceição et al. / Industrial Crops and Products 89 (2016) 416–424
centration in the transesterification reactions causes a decrease in
the viscosity of biodiesel. As shown in Fig. 7(d), only the reaction
carried out with 30% catalyst concentration results in biodiesel with
viscosity level that is below 5.0 mm2 /s.
Data reported from the optimization of reaction parameters pre-
sented in this work suggest that the ester content and viscosity can
be predicted by the models proposed herein.
The physico-chemical properties of macaw palm biodiesel pro-
duced under optimum conditions were determined to assess its
quality. The ester content was 99.2%, which shows a high level
of product purity. Other important properties that demonstrated
the quality of the synthesized fuel are its monoacylglicerol content
(0.61%) and diacylglicerol content (0.44%). Its kinematic viscosity
(4.5 mm2 /s) and density (872.6 kg/m3 ) also demonstrate its quality.
3.5. Catalyst recycle assays
Heterogeneous catalysts rather than homogeneous ones are
recommended for industrial applications after considering their
performance in activity, separation, and recycling. The recycling of
catalysts is important from economic and environmental points of
view. When supported and bulk catalysts are used in liquid-phase
reactions, there is a possibility that active species are leaching away
into the liquid phases (Zhao et al., 2000).
The stability of the Nb2 O5 /SO4 catalyst was assessed for
sequential recyclability in the simultaneous esterification and
transesterification of macaw palm oil to the corresponding ethyl
esters by recycling and reuse of the catalyst under the opti-
mized reaction conditions. After the completion of the reaction and
between each cycle, the catalysts was recovered from the reaction
mixture by simple filtration, washed with tert-butyl alcohol, dried
at 120 ◦ C and subjected to the next cycle. Five recycle runs were
carried out and the results attained at the end of each cycle are
displayed in Fig. 8.
The recycling experiments for simultaneous esterification and
transesterification reactions resulted in 98.65, 98.55, 96.05, 94.95
and 93.70% successive ester content (Fig. 8a). For all the five runs,
the rate of reaction was very high at the end of the 3 h reaction
period (with the esters content exceeding 90%). In all about 5.0% of
total esters was reduced at the end of the fifth run, suggesting that
the catalyst was stable and no linking of the active specie observed.
The viscosity results (5.25, 5.30, 5.65, 5.85 and 6.10 mm2 /s) (Fig. 8b)
revealed that the viscosity slowly increased with recycling exper-
iments, which are consistent with the corresponding to the ester
content decreased.
4. Conclusion
In this study, by optimizing the reaction parameters, macaw
palm biodiesel was produced with ester content of over 99%
and viscosity level which is below 5.0 mm2 /s. These values were
obtained with the following reaction conditions: molar ratio of
120:1, reaction temperature of 250 ◦ C, reaction time of 4 h and 30%
catalyst concentration. There are few reports in literature regard-
ing the use of Nb2 O5 /SO4 as catalyst for biodiesel production. Based
on the obtained experimental results, it can be concluded that the
application of Nb2 O5 /SO4 is promising and could be used as an
effective heterogeneous acid catalyst for a simultaneous esterifica-
tion and transesterification in biodiesel production from reactions
involving low-quality raw materials and ethanol as acylating agent.
The catalyst could be reused for five consecutive provided the excel-
lent yield of the desired products. The lowering of the yield of the
product after the fifthy recycle may be due to the handling loss of
the catalyst in successive recycles.
423
Acknowledgements
The authors gratefully acknowledge the financial support
of CNPq (Conselho Nacional de Desenvolvimento Científico e
Tecnológico-Process Number 404812/2013-9). Leyvison Rafael V.
da Conceição would especially like to thank the support of
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
(CAPES).
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