Waste Management 105 (2020) 373–383

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

Transesterification of waste edible oils to biodiesel using calcium

oxide@magnesium oxide nanocatalyst
Rauf Foroutan a, Reza Mohammadi b, Hossein Esmaeili c,⇑, Fatemeh Mirzaee Bektashi b, Sajad Tamjidi d
a
Faculty of Chemical and Petroleum Engineering, University of Tabriz, Tabriz 5166616471, Iran
b
Polymer Research Laboratory, Department of Organic and Biochemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
c
Departments of Chemical Engineering, Bushehr Branch, Islamic Azad University, Bushehr, Iran
d
Department of Chemical Engineering, Shiraz Branch, Islamic Azad University, Shiraz, Iran

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

Article history: In the present research, application of waste edible oil (WEO) as a suitable and abundant source for bio-
Received 30 October 2019 diesel production using CaO@MgO nanocatalyst derived from waste chicken eggshells was studied. To
Revised 20 February 2020 this end, FT-IR, XRD, SEM, EDX, Map, and TEM analyses were performed to investigate characteristics
Accepted 23 February 2020
of the CaO@MgO nanocatalyst. Also, the physical properties of the biodiesel such as flash point, kinematic
viscosity, density, distillation point, cloud point, pour point, cetane number, oxidation stability, and acid
number were determined according to the international standards. In addition, FT-IR and HNMR analyses
Keywords:
were used to determine the biodiesel characteristics. Moreover, the produced catalyst was successively
Biodiesel
CaO@MgO nanocatalyst
reused for up to 6 cycles and the results showed that the catalytic activity of the catalyst produced
Waste edible oil was sufficient for biodiesel production from WEO for up to three cycles, beyond which its catalytic activ-
Waste chicken eggshell ity decreased. The present work further considered the effects of different parameters on biodiesel pro-
Optimization duction using central composite design to determine optimal conditions. According to the results, the
Calcination highest biodiesel conversion yield (98.37%) was achieved in a reaction time of 7.08 h, reaction tempera-
ture of 69.37 °C, methanol-to-oil ratio of 16.7:1, and catalyst concentration of 4.571 wt% which shows the
highest biodiesel conversion yield ever achieved from waste edible oil.
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction particles by combustion (Wen et al., 2010). Biodiesel is recognized

as the most abundant available source of liquid fluid which can be
Reduction of available reserves of fossil energy and simultane- produced from lipid material. Thanks to its similar characteristics
ous increase in the price of oil and oil derivatives, in one hand, to those of petroleum-derived fuels, biodiesel can be directly used
and escalated combustion-resulted environmental pollutions, on in diesel engines (Tran et al., 2016).
the other hand, have driven today’s societies toward the generation Biodiesel is mainly produced from renewable materials such as
of energy from renewable sources, so as to provide for lower envi- vegetable oils, animal fats, waste oils, microalgae, etc. (Tran et al.,
ronmental pollutions along with more affordable cost. Accordingly, 2016). Biodiesel production from edible oils increases the cost of
the use of biofuel has been largely regarded (Sitko et al., 2011). biodiesel production given that about 60–80% of the total cost of
Fatty acid methyl ester (FAME) is a type of biofuel, which has been biodiesel production is related to raw material. Therefore, it can
referred to as an alternative to fossil fuels (Yang et al., 2009). It has be stated that biodiesel production from edible oils is economically
gained great deals of attention thanks to its biodegradability, bio- inefficient as it gives rise to a competition between human con-
compatibility, non-toxicity, easy synthesis, safe operation (Soares sumption of such oils and biodiesel production market (Foroutan
et al., 2013, Liu et al., 2016), high cetane number, inherent lubric- et al., 2019). Accordingly, for the most part, the present and future
ity, free of sulfur, and high flash point (Fan et al., 2016, Baskar and research on biodiesel production is likely to focus on biodiesel pro-
Soumiya, 2016). In addition to the mentioned advantages, the bio- duction from low-cost, non-edible and biological sources in an
diesel has been recognized as a green fuel, because it emits very attempt to reduce the cost of biodiesel production while protecting
low amounts of gases such as SOx, COx, NOx, and suspended solid the environment (Foroutan et al., 2019). Waste edible oil (WEO)
has been acknowledged as a suitable renewable source for biodie-
sel production. Each year, large amounts of WEO, which is inappro-
⇑ Corresponding author.
priate for human use, are being produced in food industry,
E-mail address: Esmaeili.hossein@iaubushehr.ac.ir (H. Esmaeili).

https://doi.org/10.1016/j.wasman.2020.02.032
0956-053X/Ó 2020 Elsevier Ltd. All rights reserved.
374 R. Foroutan et al. / Waste Management 105 (2020) 373–383

restaurants, shops, and houses around the world (Ashok et al., BET analysis. In order to produce CaO@MgO catalyst, firstly, a
2018). It has been estimated that the European countries alone 1 M solution of magnesium in water was prepared and stirred
produce 100,000–700,000 tons of WEO per year (Patil et al., for 20 min to reach a thoroughly uniform solution. Subsequently,
2010). The use of WEO for biodiesel production can potentially an appropriate amount of the prepared CaO was added to the aque-
reduce the cost of this process by 60–90%. ous solution of magnesium and the mixture was ultrasonicated for
Biodiesel is produced via the transesterification reaction 50 min. One molar sodium hydroxide solution was added to the
between oils (i.e. waste edible oil) and alcohol (e.g. methanol, etha- CaO mixture in a dropwise fashion and the mixture was stirred
nol, propanol, and butanol) in the presence of an appropriate cata- at ambient temperature for 2 h. The resultant precipitate was sep-
lyst. In general, either homogenous or heterogeneous, and alkali or arated by centrifuging at 3000 rpm for 15 min followed by heating
acidic catalysts can be used in the transesterification reaction for at 100 °C for 24 h to have it completely dried. The resultant dry
improving the transesterification reaction performance and white mixture containing CaO@Mg(OH)2 was powdered and
enhance biodiesel production yield (Arumugamurthy et al., heated to 450-500 °C at 10 °C/min for 3 h, so that the Mg(OH)2
2019). Transesterification process in the presence of alkali catalysts in the catalyst structure was calcined to MgO.
(e.g. sodium hydroxide and potassium hydroxide) is a common
process for biodiesel production, because this reaction in the pres- 2.2. Design of experiment and statistical analysis
ence of alkali catalysts is some 4,000 folds faster than that in the
presence of acidic catalysts, making the process more economically In the present study, in order to investigate different parame-
feasible (Malhotra and Ali, 2019). There are several works on bio- ters on biodiesel production from WEO using heterogeneous
diesel production from alkali catalyst, which has been done in a CaO@MgO catalyst, response surface methodology (RSM) was uti-
reactor (Klofutar et al., 2010, Likozar et al., 2016). However, it is lized. The experiments were designed using central composite
worth noting that the use of alkali catalysts comes with several design (CCD) technique and 30 experiments were presented to
disadvantages as well, including the production of soap and water investigate four independent variables. The four independent
which necessitates a washing stage for removing the catalyst from variables considered in this work included reaction time (1–9 h),
the produced biodiesel (Esmaeili and Foroutan, 2018a, Seffati et al, reaction temperature (40-80 °C), methanol-to-oil molar ratio
2019). Accordingly, great deals of research have been performed on (6:1–18:1), and catalyst concentration (2–6 wt%). The mentioned
heterogeneous catalysts for biodiesel production given that these independent variables were examined at five levels (
a,
1, 0, 1,
catalysts can be easily separated from the reaction mixture, facili- +a), as detailed in Table S.1. In this study, experiments were per-
tate the biodiesel purification stage, and are reusable with easy formed with three replications and their average was reported as
separation (Kashyap et al., 2019). The reusability represents a the response. The experiments were designed by the Design Expert
unique property of heterogeneous catalysts and is known to signif- software and a quadratic polynomial model was proposed. This
icantly reduce the process cost. Among heterogeneous catalysts, model describes the relationship between dependent (Y) and inde-
calcium oxide (CaO) is a highly efficient catalyst for biodiesel syn- pendent variables (X1 to X4), as expressed in Eq. (1).
thesis, as approved in previous research works (Borah et al., 2019a,
X
n X
n X
n X
n
Keihani et al., 2018). Efficiency and effectiveness of calcium oxide Y ¼ b0 þ bi X i þ bij X i X j þ bii X 2i ð1Þ
as a catalyst can be attributed to its particular characteristics such i¼1 i¼1 j>1 i¼1
as strong basicity, easy synthesis, economic advantages, and
available in natural resources such as eggshell, snail shell, chicken where Y, b0, bis, bijs, and biis, are the biodiesel yield, the model con-
bone, crab shell, and oyster shell (Borah et al., 2019b). In stant, linear coefficients, interaction coefficients, and quadratic
previous investigations, various CaO-based catalysts such as coefficients, respectively. Also, Xi and Xj are independent variables,
Ni-CaO-montmorillonite, CaO/C, Li/CaO, and CaO/TiO2 have been which are evaluated in each experiment. Results of the model were
produced and used to produce biodiesel (Teo et al., 2019). analyzed using analysis of variance (ANOVA), correlation coefficient
In the present research, the transesterification process of WEO, (R2), F-values, and comparison to the corresponding experimental
as a raw material, with methanol in the presence of CaO@MgO data (Esmaeili and Karimi, 2018b). For each response, desirability
nanocatalyst was done for biodiesel production. The surface char- function (DF) provides for maximization of the response by setting
acteristics of the catalyst was evaluated using FT-IR, Map, EDX, the value of effective variables appropriately by taking into consid-
SEM, TEM, and XRD analyses. In addition, the effect of different eration their interactions. The DF gives values in the range of 0–1.
parameters (methanol/oil ratio, temperature, reaction time, and Accordingly, a DF value of 1 characterizes a desirable response,
catalyst concentration) was studied on the biodiesel production. while a DF value of 0 refers to a totally undesirable response with
Furthermore, the physical properties of biodiesel such as pour minimal applicability.
point, kinematic viscosity, density, flash point, cloud point, acid
number, cetane number, water content, and distillation point were 2.3. Biodiesel production experiment
calculated and compared to international standards.
Production of biodiesel from WEO in presence of heterogeneous
2. Materials and methods CaO@MgO catalyst was conducted in three-neck flasks (50 mL)
under different sets of conditions in terms of reaction time (1–
2.1. Synthesis of CaO@MgO nanocatalyst 9 h), reaction temperature (40–80), methanol-to-oil molar ratio
(6:1–18:1), and catalyst concentration (2–6 wt%). In the present
Firstly, eggshell was prepared from local restaurants, washed work, the WEO was initially filtered to remove remnants of food
several times with distilled water and fully dried in an oven at material. Subsequently, 25 mL of the resultant oil was preheated
105 °C for 24 h. The dried eggshell was then heated to 850- to the considered temperature for 30 min to adjust its temperature.
900 °C at 10 °C/min for 4 h, so as to provide for calcination process. To perform the transesterification reaction, an appropriate amount
The calcined eggshell was milled and then graded by sieving of methanol was mixed with the specified amount of CaO@MgO
through the sieve no. 25 (ASTM E11); the obtained white powder catalyst and added to the preheated WEO at the desired tempera-
(CaO) was stored at ambient temperature. The specific surface area ture. In all experiments, the transesterification reaction was done
and volume of pores for the calcined eggshell were determined in a mixing rate 600 rpm, which is reported according to a study
6.50 m2/g and 0.022 cm3/g, respectively, which determined by by Brásio et al. (2011); Elsheikh et al. (2014). Upon completion of
 R. Foroutan et al. / Waste Management 105 (2020) 373–383 375

the transesterification reaction, the produced catalyst and glycerol samples, absorption peaks were observed in the range of 3400–
were separated from the biodiesel by centrifuging the mixture. In 3855 cm
1 and at around 1640 cm
1, indicating stretching vibra-
the next step, the produced biodiesel was heated in a rotary evap- tion of –OH in the structure of the materials or the adsorption of
orator at 80 °C for 40 min to separate methanol from produced bio- water molecules on the surface of the mentioned samples
diesel completely. Once finished with producing the biodiesel from (Foroutan et al., 2018). In the CaO structure, very small vibrations
WEO, biodiesel yield in each stage was determined via Eq. (2) were observed at 2517 cm
1, which can be attributed to the CaCO3
(Seffati et al., 2019): content in the eggshell (Tan et al., 2015). Moreover, absorption
peaks were observed at 1472 cm
1 and 878 cm
1 along the spectra
Weight of biodiesel recorded for the CaO; these were attributed to the vibration of the
Yield of biodiesel ð%Þ ¼  100 ð2Þ
Weight of oil CAO bond on the CaCO3 structure (Teimouri et al., 2018). Also, in
the structure of the CaO obtained from eggshell, vibrations were
observed at 1420, 1085, and 577 cm
1 bands, which could be
2.4. Characterization of biodiesel and catalyst
linked to alteration of carbonate to CaO (Seffati et al., 2020). In
addition, in the structure of the MgO nanoparticles, several absorp-
FT-IR analysis (Broker Victor 22 spectrometer apparatus) was
tion peaks with variable intensities were observed at 1630 and
performed to determine the functional groups on the considered
1428 cm
1, which can be attributed to the vibration of –OH bond
catalyst and produced biodiesel. The analysis was performed in
in water molecules and carbonate ions (CO2
3 ) in the atmosphere,
the range of 400–4000 cm
1. Two methods have been used to pre-
respectively (Mageshwari et al., 2013). Moreover, several peaks
pare oil and catalyst samples for measuring FTIR spectra. To mea-
in the structure of MgO nanoparticles were seen at 445, 692,
sure the functional group in the catalyst, 1 mg of the catalyst
869, and 1114 cm
1, which can be an indication of metal-oxygen
powder was initially mixed with completely dried potassium bro-
vibration and formation of MgO (Al-Hazmi et al., 2012). Following
mide (KBr). Then, a small amount of it was poured into a special
the formation of CaO@MgO, the results showed that the CaO@MgO
metal mold and pressed by hydraulic press device to obtain a
structure is composed of the existing functional groups on both
transparent tablet. Also, to measure the functional group in oil, a
CaO and MgO, suggesting a successful combination of metal oxides
droplet of oil was poured onto a KBr plate and then the second
on CaO and MgO.
plate was placed on top of the first plate (sandwich mode) to trans-
XRD analysis was also utilized to investigate the structure and
form the oil into a thin film. Afterwards, the FTIR analysis was per-
crystalline phases of CaO, MgO, and CaO@MgO, with the results
formed (Hollas, 2004, King et al., 2004). X-ray diffraction (XRD)
presented in Fig. 1(b). The results showed peaks of variable inten-
analysis was performed to see whether the CaO@MgO catalyst
sities along the spectra for the CaO and MgO metal oxides and
was crystallized or amorphous. The analysis was practiced using
CaO@MgO, implying that the mentioned compounds are crys-
a Siemens D500 apparatus irradiating Cu-Ka rays at 35 kV within
talline. The eggshell-derived calcium oxide (CaO) exhibited some
a 2h range of 5–80° at a scanning rate of 1°/min and wavelength
peaks at 2h values of 32.34, 37.36, 54.23, and 64.27°, indicating
of 1.5048 Å. Surface variations, elemental composition, and
(1 1 1), (2 0 0), (2 0 2), and (3 1 1) crystalline phases in the CaO
distribution of elements across the prepared catalyst surface were
structure, respectively (JCPDS 77-9574) (Pandit and Fulekar,
investigated using scanning electron microscope (SEM, TESCAN
2017). For the MgO structure, peaks were observed at 2h values
MIRA3-FEG), Energy Dispersive X-Ray (EDX/Mapping, TESCAN
of 37.1, 43.23, 62.41, 74.67, and 79.35°, referring to the (1 1 1),
MIRA3-FEG), and transmitted electron microscope (TEM, Zeiss
(2 0 0), (2 2 0), (3 1 1), and (2 2 2) crystalline phases in the cubic
LEO906) operating at 80 kV. The physical properties of the biodie-
structure of MgO, respectively (Al-Hazmi et al., 2012, Bindhu
sel (e.g. kinematic viscosity, density, flash point, cloud point, pour
et al., 2016). Following the reaction between the CaO and MgO
point, total acid number, and cetane number) were measured
metal oxides, the crystalline phases corresponding to the metal
according to ASTM D 6751 and EN 14214 standards.
oxides were fully appeared in the CaO@MgO structure although
the peaks were somewhat shifted, possibly due to the interaction
3. Results and discussion between crystalline phases of the CaO and MgO oxides. Therefore,
based on the XRD results, it can be stipulated that the CaO and
3.1. Characteristics of the nanocatalyst MgO oxides had interacted successfully.
In order to study surface variations, elemental composition, and
Fig. 1(a) shows the results of FT-IR analysis for the CaO, MgO, distribution of the elements on the surface of the CaO, MgO,
and CaO@MgO samples. In the structure of the aforementioned and CaO@MgO samples, SEM, EDX, and Map analyses were done,

Fig. 1. Results of (a) FT-IR analysis and (b) XRD analysis on CaO, MgO, and CaO@MgO samples.
376 R. Foroutan et al. / Waste Management 105 (2020) 373–383

and the results are shown in Fig. 2. The results show that the egg
shell-extracted CaO has a rough structure with numerous pores,
which may contribute to the biodiesel production process Fig. 2
(a). In addition, the Map and EDX analyses (Fig. 2(b, c)) showed
the presence of Ca (60.49%) and O (39.51%) on the surface of
CaO, indicating successful synthesis of CaO from eggshell and it
is in good agreement with the results of XRD analysis. Also, SEM
analysis on MgO nanoparticles is demonstrated in Fig. 2(d),
wherein the synthesized nanoparticles exhibit a heterogeneous
porous surface. The results also showed a uniform distribution of
Mg (59.81%) and O (40.19%) elements on the surface of the MgO
nanoparticles. Upon the formation of CaO@MgO, significant
changes were observed on the surface and particle size distribution
of the CaO@MgO composite, supposedly due to the interaction
between CaO and MgO species (Fig. 2(g)). The results obtained fol-
lowing the formation of CaO@MgO catalyst confirmed the presence
of calcium (26.03%), oxygen (41.93%), and magnesium (32.04%) in
the structure of the produced catalyst, which shows a favorable
interaction between CaO and MgO. These results were in good
agreement with the results of XRD and FT-IR analyses.
To investigate the morphology and particle size of the CaO,
MgO, and CaO@MgO, TEM analysis was used and the results are
shown in Fig. 3. Given the obtained results, the CaO particles pro- Fig. 3. Results of TEM analysis on (a) CaO, (b) MgO, and (c) CaO@MgO samples.

duced from eggshell were found to exhibit particulate morphology

with particle sizes smaller than 50 nm. Previous studies have catalyst, its structure was found to be composed of spherical parti-
reported similar results for CaO particles (Islam et al., 2014). It is cles with mesoporous structure, indicating a good arrangement of
worth mentioning that the CaO particles were seen to agglomerate CaO and MgO particles in the vicinity of one another. According to
to form larger and angular crystalline particles in particular sites the results shown in Fig. 3(c), the CaO@MgO catalyst is made up of
according to Fig. 3(a), confirming the results of XRD analysis. Also, crystals of various sizes in the range of 20–50 nm. However, CaO
TEM analysis on MgO particles (Fig. 3(b)) indicated that the MgO and MgO are agglomerated to form larger particles (beyond
particles possess a planar structure with meso-porosities, as 50 nm), so that the CaO@MgO catalyst does not show a regular
marked on the TEM image. After the formation of the CaO@MgO structure.

Fig. 2. Results of EDX, Map, and SEM analyses on (a)–(c) CaO, (d)–(f) MgO, and (g)–(i) CaO@MgO samples.
 R. Foroutan et al. / Waste Management 105 (2020) 373–383 377

3.2. Central composite design analysis impose adverse effects on the biodiesel production, while other
variables contributed to higher efficiency of biodiesel production.
CCD is a common technique for the design of experiments. This Results of ANOVA showed that the corresponding F-value to the
has root in the applicability of this model for investigating not only biodiesel production from WEO is 84.72 (Table S2). This high F-
the impacts of considered parameters separately, but also their value indicates the high importance and capability of the devel-
interaction effects on the response. This model involves the design oped model for producing biodiesel from WEO. Moreover, a low
of experiments, determination of coefficients in a mathematical and insignificant value of lack-of-fit characterizes a model with
form, prediction of responses, and the verification of the model high predictive power. The fact that the value of lack-of-fit for
(Sidik et al., 2016). In the present research, to produce biodiesel the biodiesel production process was 0.865 (insignificant since it
from WEO using heterogeneous CaO@MgO catalyst, the CCD was is larger than 0.05) confirmed that the developed model could well
adopted to study four factors at five levels. The experiment design predict the biodiesel production process and indicating good inter-
and their obtained responses are reported in Table 1. In order to actions between various variables. Another parameter measuring
obtain a reliable model for biodiesel production from WEO, ANOVA the importance of different variables in the biodiesel production
was used (Table S2). In Eq. (3), a quadratic polynomial model was process is the p-value. Accordingly, any p-value exceeding 0.05
developed to produce biodiesel based on the design of experiment. characterizes undesirability of the model in relation to the consid-
This equation expresses the correlation between response (biodie- ered variable, while p-values lower than 0.05 show desirability and
sel yield) and effective variables on the biodiesel production: significance of the variables and the model. The results reported in
Table S2 show that for the considered model, p-values lower than
Biodiesel yield ð%Þ 0.05 (p-value < 0.0001) were obtained, confirming the significance
¼
325:69 þ 11:29X 1 þ 7:76X 2 þ 9:32X 3 þ 9:36X 4 þ 0:096X 2 X 3 of the predicted responses and reliability of the model.

0:208X 2 X 4 þ 0:975X 3 X 4
1:296X 21
0:063X 22
0:62X 23 Fig. S1-a shows the cross plot of predicted values versus actual
ð3Þ data on the biodiesel production. Based on the obtained results,
one can conclude that the predicted values using the software tool
where X1, X2, X3, and X4 denote reaction time, reaction temperature, are in good agreement with the actual data. Also, the value of cor-
oil-to-methanol molar ratio, and the catalyst content (weight per- relation coefficient (R2) for the biodiesel production process was
cent), respectively. The resultant quadratic polynomial equation determined as 0.9875; i.e. 98.75% of the variations in the biodiesel
for biodiesel production showed that the variables with negative production process could be explained by the considered indepen-
coefficients impose adverse effects on the efficiency of biodiesel dent variables. In addition, the adjusted correlation coefficient
production, while the variables with positive coefficients favored (Adj-R2) using the prediction model was found to be 0.9759, indi-
the biodiesel production. Considering Eq. (3), it can be stipulated cating high degrees of correlation between the independent vari-
that the interaction between reaction temperature and the catalyst ables. As a measure of reproducibility of a model, the coefficient
concentration (X2X4) and also the interaction of squared variables of variance (CV) has been defined as the ratio of standard predic-

Table 1
Results of experimental design under coded conditions for biodiesel production from WEO in presence of CaO@MgO catalyst using the CCD.

Run Factors Biodiesel conversion yield (%)

X1 X2 X3 X4 Exp.a Pred.b Res.c
1 5 60 6 4 25.42 24.36 1.06
2 7 70 15 3 81.35 82.12
0.77
3 7 50 9 5 49.57 51.77
2.2
4 7 50 15 5 83.41 84.15
0.744
5 3 70 15 3 71.39 69.4 1.99
6 7 50 15 3 61.29 60.14 1.15
7 5 60 12 4 76.28 76.85
0.57
8 3 50 15 5 72.28 69.91 2.37
9 7 50 9 3 39.69 39.46 0.226
10 3 70 9 5 41.39 42.76
1.37
11 5 60 12 4 82.38 76.85 5.53
12 5 60 12 4 80.47 76.85 3.62
13 3 70 15 5 81.52 82.33
0.805
14 7 70 9 5 54.39 53.83 0.5596
15 3 50 9 3 34.48 32.37 2.11
16 5 60 12 4 74.73 76.85
2.12
17 5 60 12 2 61.28 62.25
0.969
18 7 70 9 3 47.27 49.86
2.59
19 5 80 12 4 65.14 62.96 2.18
20 7 70 15 5 95.47 97.8
2.33
21 5 60 12 4 73.58 76.85
3.27
22 5 60 12 4 73.66 76.85
3.19
23 3 50 15 3 47.5 48.64
1.14
24 1 60 12 4 42.67 44.82
2.15
25 9 60 12 4 70.34 67.39 2.95
26 5 60 12 6 89.25 87.48 1.77
27 5 60 18 4 84.33 84.59
0.265
28 3 70 9 3 41.71 41.55 0.165
29 5 40 12 4 38.76 40.14
1.38
30 3 50 9 5 42.12 41.93 0.191
a
Experimental values of response.
b
Predicted values of response by RSM proposed model.
c
Residual.
378 R. Foroutan et al. / Waste Management 105 (2020) 373–383

tion error to the average value of the observed response. Accord- activity of the catalyst. Appropriate dosage of catalyst not only
ingly, CV values below 10% characterize reproducible models improves the biodiesel conversion yield, but also inhibits the soap-
(Bagheri et al., 2017). Based on the obtained results, the value of ing reaction during the biodiesel production process (Seffati et al.,
CV for biodiesel production from WEO was found to be 4.37%, 2020). Based on the obtained results, with increasing the catalyst
which shows the reproducibility of the model. In this research, dosage from 2 wt% to 6 wt%, biodiesel conversion yield was
the value of Adequate Precision (AP) for biodiesel production was enhanced. This enhancement could be due to increase in the num-
calculated as 34.96, suggesting the good signaling effect of the used ber of active sites on the catalyst surface in the transesterification
model. Fig. S1-b represents normal probability distribution func- reaction, which is reported in previous studies (Bora et al., 2018).
tion versus internally studentized residuals for the biodiesel pro- Reaction temperature also affects the efficiency and performance
duction process. According to the obtained results, one can of the biodiesel production process. In order to investigate the
conclude that the obtained results are distributed along a straight effect of temperature on the conversion yield of biodiesel produc-
line, i.e. are normally distributed (Shi et al., 2019). Box-Cox dia- tion from WEO, the transesterification reaction was examined at
gram serves as a tool for identifying the most appropriate power various temperatures in the range of 40–80 °C. The results indicate
transform for applying to the response. Accordingly, the lowest an increase in the biodiesel conversion yield with increasing the
point along the Box-Cox diagram identifies the lambda value at reaction temperature to up to 65 °C, beyond which temperature
which residual sum of squares of the transformed model is mini- a drop of efficiency was observed. Indeed, an increase in tempera-
mized. In cases where the ratio of maximum response value to ture is supposed to attenuate the diffusion stability across the
minimum response value exceeds 3, there are larger potentials three phases of methanol, oil, and catalyst while improving the
for improving the model using the power transform function. performance and catalytic activity of the catalyst, thereby increas-
Box-Cox diagram of the biodiesel production process is shown in ing the biodiesel conversion yield. However, when the temperature
Fig. S1-c. According to the obtained Box-Cox diagram, the lowest is too high, methanol changes from liquid phase to gas phase; this
point along the Box-Cox diagram was found to be 5.12, indicating phase change results in only poor contact and hence interaction
that the power transform function has more potential to improve between the methanol gas and oil, so that the overall reaction effi-
the model. Pareto diagram was further used to investigate the ciency decreases (Xue et al., 2014). On the other hand, the increase
effect of different parameters on the biodiesel conversion yield in temperature to values above 65 °C decreases the biodiesel con-
from WEO and the results is shown in Fig. S1-d. The Pareto diagram version yield because of saponification effect of triglyceride before
showed that the biodiesel production process is positively affected performing the transesterification process. This phenomenon can
by such variables as reaction time (X1), temperature (X2), be attributed to the methanol evaporation. An increase in the reac-
methanol-to-oil ratio (X3), and catalyst concentration (X4). Not to tion temperature above the boiling point of methanol is likely to
mention that the effect of reaction time, among other variables decrease the methanol to oil ratio, which results in a decrease in
considered in this study, imposes the largest contribution into bio- the biodiesel conversion yield (Seffati et al., 2020; Dhawane
diesel production. Putting the Pareto diagram aside, another et al., 2016). Methanol/oil ratio is another factor imposing signifi-
parameter indicating the effect of variables on biodiesel production cant contributions to the efficiency of biodiesel production. In gen-
is the p-value. Accordingly, p-values lower than 0.05 were eral, excessive methanol dosage leads the transesterification
obtained for reaction temperature, reaction time, and methanol- process toward biodiesel production, i.e. enhancing the efficacy
to-oil ratio, and catalyst concentration, proving the significance of the transesterification process. The effect of methanol/oil ratio
of the effects of these parameters and confirming the results pre- is displayed in Fig. 4. The results showed that an increase in the
sented on the Pareto diagram. methanol-to-oil ratio from 6:1 up to 15:1 increases the biodiesel
conversion yield, beyond which a lower biodiesel conversion yield
is expected. This decrease in efficiency can be attributed to various
3.3. Effects of different parameters on biodiesel production causes, including (1) excessive dissolution of glycerol in methanol
which inhibits the reaction of methanol with the catalyst and other
Various parameters affect the process of biodiesel production, reactants (Obadiah et al., 2012), and (2) excessive accumulation of
such as reaction time and temperature, catalyst dosage, and methanol on the catalyst surface and reduced number of active
methanol-to-oil ratio. Fig. 4 presents the 3D plots developed via sites on the catalyst (Baskar et al., 2018), which are known to
CCD for the purpose of investigating the effects of interactions attenuate the process efficiency.
between different variables on the conversion yield of biodiesel
from WEO in presence of CaO@MgO as a heterogeneous catalyst.
Reaction time is one of the most important parameters affecting 3.4. Optimization of effective variables
the conversion yield of biodiesel. The findings indicated that with
increasing the reaction time, biodiesel conversion yield exhibited To investigate and determine optimal conditions for biodiesel
an initially increasing trend followed by a decreasing trend. The production from WEO in the presence of CaO@MgO catalyst,
decrease in biodiesel conversion yield with increasing the reaction Design Expert 11.0 was used, and the results are shown in
time could be attributed to the formation of emulsion and gel Fig. S2. Based on the results, the maximum conversion yield of bio-
throughout the biodiesel production process, thereby increasing diesel from WEO was found to be 98.45%. In order to investigate
the viscosity of the reaction product which is known to cause dif- the predicted optimal conditions, biodiesel production was actu-
ficulties in purification and catalyst separation stages (Seffati et al., ally conducted in the laboratory under the optimal conditions.
2020). Another reason for reducing biodiesel conversion yield is The optimal conditions included reaction time of 7.08 h, a reaction
the reversible nature of the transesterification process. If the reac- temperature of 69.37 °C, methanol-to-oil ratio of 16.7:1, and the
tion time exceeds some optimal value, thereby reducing the overall catalyst dosage of 4.571 wt%. Under these optimal conditions, a
biodiesel conversion yield. In other words, excessive reaction time maximum biodiesel production yield of 98.37% was achieved
reduces biodiesel conversion yield because of the backward reac- experimentally. The results indicate a good agreement between
tion, which leads to a loss of esters as well as causing more fatty the experimental data from the actual biodiesel production exper-
acids to form soap (Seffati et al., 2019; Keihani et al., 2018). The iments and the predicted results, so that CCD can be seen as an effi-
concentration of catalyst is also a factor affecting the biodiesel pro- cient technique for investigating and optimizing the variables
duction process as it contributes to the performance and catalytic affecting the biodiesel production process.
 R. Foroutan et al. / Waste Management 105 (2020) 373–383 379

Fig. 4. Effects of different parameters and their interactions on the process of biodiesel production from WEO.

3.5. Comparing the results with previous studies washed with methanol and hexane to remove the biodiesel and
glycerol residues. The reusability of the catalyst was studied for
The maximum biodiesel conversion yield in this study was up to 6 cycles of reuse (Fig. S3). The results showed that the afore-
compared to previous studies and the results are presented in mentioned catalyst can be reused for up to three successive cycles
Table 2. As shown in this table, the highest biodiesel yield was while maintaining the biodiesel conversion yield above 90% of the
achieved in this study using CaO@MgO nanocatalyst (98.37%), original yield. After three cycles, the conversion yield of biodiesel
which was more than previous studies. using the aforementioned catalyst decreased significantly. The
reduction in the biodiesel conversion yield shows that the active
3.6. Reusability of the catalyst sites on the catalyst surface were damaged upon reacting with
humidity and CO2 content of air, converting CaO and MgO contents
Reusability represents one of the most important advantages of in the catalyst to Ca(OH)2 and Mg(OH)2, respectively, and hence
heterogeneous catalysts used in the biodiesel production process. attenuating the catalyst activity (Roschat et al., 2018).
In the present study, to investigate the reusability of the CaO@MgO
catalyst, the biodiesel production process was performed under the 3.7. Characteristics of the biodiesel
optimal conditions predicted by Design Expert 11 Software. In
order to evaluate reusability of the catalyst, after each cycle of reac- Results of FT-IR analysis on the WEO and produced biodiesel are
tion, the catalyst was separated from the reaction mixture and presented in Fig. 5. For the WEO, an absorption peak is observed at
380 R. Foroutan et al. / Waste Management 105 (2020) 373–383

Table 2
Comparing the biodiesel production yield from waste edible oil using different catalysts.

Ref. Biodisel conversion Time (h) Amount of Alcohol:Oil ratio Temperature (°C) Catalyst
yield (%) catalyst (Wt %)
Dhingra et al. (2016) 96.33 1.28 0.99 9.05 57.31 KOH
Degfie et al. (2019) 96 1.5 1 8:l 50 CaO
Balakrishnan et al. (2013) 88 3 3 6:1 65 Ba/CaO
Gurunathan and Ravi (2015) 97.71 0.833 12 8:1 55 Copper/Zinc oxide
Mansir et al. (2018) 92.1 3 3 15:1 80 4Mn-6Zr/CaO
Ashok et al. (2018) 93.3 1 2 24:1 65 MgO
Gupta et al. (2015) 93.5 0.5 1 9:1 60 Calcium diglyceroxide
Mohadesi et al. (2019) 97.45 0.223 8.1 2.25:1 65 KOH/Clinoptilolite
Gardy et al. (2018) 96 2.5 3 10:1 90 SO4/Fe-Al-TiO2
Ullah et al. (2015) 95.65 1 5 15:1 160 Butyl-methyl imidazolium
hydrogensulfate
Peng et al. (2018) 87.8 2.75 5 9:1 65 Waste eggshell
This study 98.37 7.08 4.571 16.7:1 69.37 CaO@MgO

3473 cm
1, which is attributed to stretching vibration of AOH 1161 cm
1 along the FT-IR spectrum of the produced biodiesel
bond in the water molecules. Also, an absorption peak is evident from WEO could be attributed to the –OCH3 group on the pro-
at 2912 cm
1, characterizing the vibration of CAH bond in CH2 duced biodiesel (Degirmenbasi et al., 2014).
and CH3 groups. Moreover, a sharp strong peak is seen at Also, to investigate characteristics of the WEO as raw material
1742 cm
1, which is due to stretching vibrations of the C@O bond and the produced biodiesel from the WEO in the presence of
in the carbonyl group on the triglyceride structure (Nisar et al., CaO@MgO catalyst, HNMR analysis was performed. Fig. 6 shows
2017). Vibrations of variable intensities were observed along the the results of the HNMR analysis for both of them. Vegetable oils
absorption spectrum of WEO at different wavenumbers ranging are commonly composed of various compounds including palmitic
from 1000 to 1300 cm
1 because of stretching vibrations of CAO acid, linolenic acid, oleic acid, etc. Results of the HNMR analysis on
bond in the structure of the WEO. Given the presence of triglyc- the WEO were similar to those of many other vegetable oils, as
eride and ester in the composition of the produced biodiesel, its reported in previous studies, indicating that the WEO used in this
FT-IR spectrum was comparable to that of WEO. In the FT-IR spec- study resembled other vegetable oils closely. In the structure of
trum of the produced biodiesel, an absorption peak of very low WEO, multiple peaks were observed in the range of 4.11–
intensity was observed at 3474 cm
1. This peak refers to the 4.305 ppm, possibly due to the presence of glyceride protons in
stretching vibrations of the –OH group in water molecules and the structure of the WEO. These peaks were disappeared in the
confirms low moisture content in the biodiesel. Following the bio- structure of the produced biodiesel. It should be mentioned that
diesel production process, the ranges and intensities of the peaks several peaks with variable intensities were observed in the range
along the FT-IR spectrum changed from those in the WEO, possibly of 1.0–3.0 ppm on the spectra recorded from the WEO and pro-
due to the transesterification process and production of ester. After duced biodiesel; these could be attributed to the protons along
the biodiesel production process, the absorption peaks at 2912, the hydrocarbon chains in the structures of the WEO and biodiesel,
1742, 1460, 1369, and 1263 cm
1 were shifted to 2924, 1744, as reported in previous investigations (Akhlaghi et al., 2015). On
1456, 1366, and 1234 cm
1, respectively. Moreover, after biodiesel the spectra recorded from the WEO and produced biodiesel, a par-
production from WEO, new absorption peaks were appeared at ticular peak appeared at about 5.4 ppm, possibly due to protons
2858, 1161, and 719 cm
1, clearly indicating the production of bio- bonded to the unsaturated carbons of the methylene groups on
diesel from WEO (Nisar et al., 2017). The absorption peak at fatty acid esters and the WEO (Kaur and Ali, 2011). Comparing
the HNMR spectra of the WEO and produced biodiesel, differences
were observed between the two. In this respect, after biodiesel
production, the multiple peaks characterizing the presence of pro-
tons of glycerides in the WEO structure disappeared while a new
peak appeared at 3.663 ppm. The new peak was caused by the
hydrogens of the methoxy group on the methyl ester (- OCH3)
formed after biodiesel production from WEO (Samart et al.,
2010). HNMR analysis can also be used to evaluate biodiesel qual-
ity during the transesterification process, as reported in previous
studies (Kaur and Ali, 2011). Accordingly, the yield of WEO conver-
sion to methyl ester is determined by the ratio of signals at
3.66 ppm (hydrogen of the methoxy group on the methyl ester)
and 2.30 ppm (hydrogen of methylene group on fatty acids)
(Samart et al., 2010). According to the determination results, under
the predicted optimal conditions, the conversion yield of WEO to
biodiesel was estimated to be 96.24%.
After the purification stage, the physical properties of the bio-
diesel produced under optimal conditions were analyzed, which
included kinematic viscosity, density, flash point, cloud point, acid
number, cetane number, water content, and distillation point. The
physical properties were then evaluated according to ASTM D-
Fig. 5. Results of FT-IR analysis on the used WEO and the WEO-derived biodiesel.
6751 and EN 14214, and the results are reported in Table S3.
 R. Foroutan et al. / Waste Management 105 (2020) 373–383 381

Fig. 6. Results of HNMR analysis for the WEO and the biodiesel produced from WEO under optimal conditions in the presence of CaO@MgO catalyst.

According to the reported results, the flash point of the produced standards, proving that the produce biodiesel meets all standard
biodiesel was higher than the standard values, indicating that the specifications and hence can be used as a biocompatible alternative
produced biodiesel is safer and easier to transport compared to to conventional diesel in which it can power conventional diesel
conventional diesel (Dhawane et al., 2016), making it appropriate engines without any modification to the engines. Various analyses
for countries with hot or cold climates (Seffati et al., 2019). Kine- were conducted to investigate the characteristics of the produced
matic viscosity of the produced biodiesel was found within the catalyst. The results showed that the heterogeneous CaO@MgO
range of standard, indicating that it can be used to feed conven- catalyst possesses a crystalline structure with meso porosity, mak-
tional diesel engines without modification to the engines. There- ing it exhibit appropriate catalytic activity for biodiesel production.
fore, based on the obtained results, it can be stipulated that the As an important issue encountered with heterogeneous catalysts,
physical properties of the biodiesel produced from WEO in pres- the reusability of the catalyst in the biodiesel production process
ence of heterogeneous CaO@MgO nanocatalyst falls within the was investigated for up to 6 cycles. The findings showed that the
respective standard ranges so that the WEO-derived biodiesel considered catalyst can be used for up to three successive cycles
can be used as a suitable alternative to petroleum-derived fuels. while keeping the biodiesel conversion yield above 90% of the orig-
inal yield. However, lower conversion yields were observed for fur-
ther cycles of catalyst reuse.
4. Conclusion
Declaration of Competing Interest
In the present study, biodiesel production from WEO, as a raw
material, in presence CaO@MgO, as a heterogeneous nanocatalyst, The authors declare that they have no known competing finan-
was examined. The Response surface methodology with central cial interests or personal relationships that could have appeared
composite design was utilized to investigate the effect of different to influence the work reported in this paper.
parameters such as reaction time and temperature, catalyst
dosage, and methanol-to-oil ratio and also interactions of these
Acknowledgement
parameters on biodiesel conversion yield. The results showed that
the maximum yield of biodiesel production from WEO (98.37%)
Authors would like to acknowledge the staff at Polymer
was achieved at a reaction time of 7.08 h, reaction temperature
Research Laboratory at University of Tabriz and TEM Laboratory
of 69.37 °C, methanol-to-oil ratio of 16.7:1, and the catalyst con-
at the Center for Pharmaceutical Research at Tabriz University of
centration of 4.571 wt%. This is the best yield of biodiesel ever
Medical Science for their collaborations and contributions to this
obtained from waste edible oil. One of the main advantages of this
project.
work was the use of waste edible oil, which could convert to bio-
diesel with a remarkable yield. Another advantage of this work
was the use of experimental design method to optimize the effec- Appendix A. Supplementary material
tive factors on biodiesel production with the correlation coefficient
of 0.987, showing high accuracy of the experimental data. The pro- Supplementary data to this article can be found online at
duced biodiesel was characterized against respective international https://doi.org/10.1016/j.wasman.2020.02.032.
382 R. Foroutan et al. / Waste Management 105 (2020) 373–383

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