Chemosphere 289 (2022) 133226

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Application of waste chalk/CoFe2O4/K2CO3 composite as a reclaimable

catalyst for biodiesel generation from sunflower oil
Rauf Foroutan a, Seyed Jamaleddin Peighambardoust a, *, Reza Mohammadi b,
Seyed Hadi Peighambardoust c, Bahman Ramavandi d, e, **
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
Department of Food Science, College of Agriculture, University of Tabriz, Tabriz, 5166616471, Iran
d
Department of Environmental Health Engineering, Faculty of Health and Nutrition, Bushehr University of Medical Sciences, Bushehr, Iran
e
Systems Environmental Health and Energy Research Center, The Persian Gulf Biomedical Sciences Research Institute, Bushehr University of Medical Sciences, Bushehr,
Iran

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• A catalyst was prepared from waste

chalk waste and its structure was
modified.
• Waste chalk/CoFe2O4/K2CO3 was used
to produce biodiesel from oil sunflower.
• The BET of waste chalk/CoFe2O4/K2CO3
were 5.8 m2/g.
• The catalyst had a good efficiency for
biodiesel production up to 6 stages.
• Ea (11.8 kJ/mol) and frequency factor
(0.78 min− 1) of the process was
obtained.

A R T I C L E I N F O A B S T R A C T

Handling Editor: Mathimani Thangavel This investigation aimed to produce a new composited catalyst from a waste chalk powder, a waste generated by the
construction industry, to produce biodiesel from sunflower oil. The waste chalk was modified by CoFe2O4 nanoparticles
Keywords: and K2CO3. The surface tests showed that the obtained catalyst has been successfully synthesized with desired surface
Waste chalk properties. The surface areas of waste chalk, waste chalk/CoFe2O4, and waste chalk/CoFe2O4/K2CO3 were determined
Biodiesel
20.8, 77.8, and 5.8 m2/g, respectively. This indicates that the waste chalk/CoFe2O4/K2CO3 catalyst has a lower surface
Heterogeneous catalyst
area due to K2CO3 being placed on the catalyst. Results showed the efficiency of RSM-CCD (R2 = 0.992) compared to ANN
Thermodynamic study
Artificial neural network (R2 = 0.974). It was shown that a contact time of 180 min, a temperature of 65 ◦ C, a waste chalk/CoFe2O4/K2CO3 mass of
2 wt%, and methanol to oil mole ratio of 15:1 gave the highest efficiency (98.87%) of biodiesel production at the labo­
ratory conditions. The kinetic results of the process showed the energy of activation and frequency factor of 11.8 kJ/mol
and 0.78 min− 1, respectively. Also, the values of ΔH◦ , ΔS◦ , and ΔG◦ at 65 ◦ C was calculated to be 9010.7 J/mol, − 256.3 J/
mol and 95.7 kJ/mol, respectively, indicating that the biodiesel production process is endothermic requiring high energy
for proceeding. The generated catalyst has an efficiency of over 90% up to 6 steps of reuse. The generated biodiesel was
met most of the international standard levels.

* Corresponding author.
** Corresponding author. Department of Environmental Health Engineering, Faculty of Health and Nutrition, Bushehr University of Medical Sciences, Bushehr, Iran.
E-mail addresses: [email protected] (S.J. Peighambardoust), [email protected] (B. Ramavandi).

https://doi.org/10.1016/j.chemosphere.2021.133226
Received 11 July 2021; Received in revised form 21 November 2021; Accepted 6 December 2021
Available online 11 December 2021
0045-6535/© 2021 Elsevier Ltd. All rights reserved.
R. Foroutan et al. Chemosphere 289 (2022) 133226

1. Introduction resolve the limitations above, heterogeneous solid base catalysts have
been introduced with the additional advantage of rapid separation and
Depletion of fossil fuel resources in the world has raised the concerns recovery from the reaction mixture with no water or other solvents.
of many politicians and researchers. Therefore, the demand for renew­ Besides, these catalysts have less corrosive properties and cause safer
able and alternative energy is increasing today due to pressures on the operations, and are cheaper and more environmentally friendly (Borges
international community to supply energy as well as reduce environ­ et al., 2011b) than the homogeneous ones. However, from an industrial
mental pollution. Alternative fuels have to be acceptable from the perspective, heterogeneous catalysts should be non-volatile, non-cor­
technological point of view, should be economically competitive, envi­ rosive, non-toxic, ease of manufacture, suitable activity at outdoor
ronmentally friendly, and easily accessible (Sander et al., 2018). Among temperature, and high chemically stabile and reusable (Yang et al.,
biofuels, biodiesel can be derived from edible or non-edible sources and 2018). Today, nano-sized heterogeneous catalysts, in addition to these
is an important alternative biofuel (Abu-Jrai et al., 2017). Today’s properties, have high reactivity and durability, which is why they are of
policies around the world to support biodiesel production is related to interest to researchers (Baskar and Soumiya, 2016; Ambat et al., 2019).
subsidized and Tax exemption efforts (Fernandez et al., 2017). Calcium oxide (CaO) can be used as a base in producing heteroge­
Biodiesel possesses various benefits such as renewability, environ­ neous catalysts due to its high active surface area and high porosity. The
mental compatibility, non-toxicity, biodegradability, and good lubricant use of CaO by many researchers to produce heterogeneous catalysts
(Okumuş et al., 2019; Foroutan et al., 2021b). Furthermore, it has a justifies its high activity for biodiesel production (Lawan et al., 2020).
higher oxygen content compared to diesel fuel; thus, its application as Ca2+ in the structure of CaO during the reaction with methanol to
diesel engines fuel reduces air pollution by restricting the amount of produce biodiesel can react with the produced biodiesel, causing the
emitted hydrocarbons, carbon monoxide, sulfur, and polyaromatic generation of soap and inactivation of the catalyst. Hence, some re­
compounds, and particulate materials (Bhatti et al., 2008; Foroutan searchers tend to convert CaO to CaSO4 and overcome CaO deficiencies
et al., 2021a). In addition, biodiesel provides benefits of high compati­ (Ali et al., 2020). In addition, in recent years, most researchers have
bility with current diesel engines; thus, it can be satisfactorily used as a focused on the production of heterogeneous sulfonate catalysts like
cheap fuel in such engine systems (Chen et al., 2019). Despite to ad­ sulfonated carbohydrate-based catalysts and sulfonated carbon-based
vantages as mentioned earlier, biodiesel possesses certain disadvantages catalysts (Dehghani and Haghighi, 2019; Syazwani et al., 2019). The
that must be taken into account in its application. A significant concern waste chalk (CaSO4⋅2H2O) is a mineral found in nature as well as one of
in the application of biodiesel as car fuel is the incompatibility of this the wastes of the construction industry. Due to the presence of calcium
fuel with metal parts such as fuel tank, fuel pump, fuel injector, and and sulfate, this material can be a suitable option for producing het­
piston leading to unwanted corrosion of these parts (Rocabruno-Valdés erogeneous catalysts in the biodiesel generation process.
et al., 2019). In addition, biodiesel has high free fatty acids leading to According to scientific literature, the combination of metal oxides on
functional problems in vehicle pipes and filters at low temperatures. At highly active materials can accelerate catalytic activity and thus
low temperatures, biodiesel forms high viscous solid wax-like crystal improve the performance of biodiesel. In addition, the placement of
nuclei causing an interruption in the fuel flow from the tank to the en­ metal oxides on the material can increase the specific active surface area
gine (Doğan and Temur, 2013). and create a unique structure with large pores, which reduces the mass
In the process of biodiesel production, various oil sources can be transfer limit for the biodiesel production process (Ganesan et al., 2020).
used, such as animal fats, edible and non-edible vegetable oils, as well as The placement of magnetic metal oxides in the structure of heteroge­
waste oils. More than 70% of the cost of biodiesel is linked to the used neous catalysts can accelerate its separation from the reaction medium
raw materials in the process. To reduce competition in the food industry and reduce the total cost. CoFe2O4 nanoparticles in producing hetero­
and reduce the economic cost of biodiesel generation, non-edible and geneous catalysts, due to their high magnetic properties compared to
waste oils have received much attention. However, the use of vegetable Fe3O4 and CoFe2O4, can perform the separation in less time. Studies
oils in the biodiesel production process has advantages like reducing the have shown that K2CO3 has a high transesterification activity and can be
viscosity of the produced fuel (Borges et al., 2011b). The use of vege­ supported on various materials as a solid base and act as an activating
table and edible oils for biodiesel generation, however, is not entirely agent (Li et al., 2013).
possible. Still the production of a vast global volume of sunflower oil can Accordingly, in the current work, the waste chalk/CoFe2O4 catalyst
strengthen the hypothesis of fuel production from this source. In addi­ was modified by K2CO3 to improve the catalytic activity. Characteristics
tion, continuous sunflower planting can potentially contribute to energy of waste chalk/CoFe2O4/K2CO3, as a heterogeneous catalyst, were
sustainability potential. According to previous reports, the amount of analyzed by different techniques (FT-IR, EDX, SEM, Map, XRD, TEM,
sunflower crop has doubled on a global scale (going from 10 MnT for 9.6 TGA-DTA, VSM, BET, and AFM). An RSM-CCD and ANN were served to
million ha in 1975 to 52 MnT for 27 Mha in 2018), which indicates a assess the influence of parameters (temperature, time, catalyst quantity,
dynamic market and sustainable technical progress (John et al., 2021). and CH3OH to oil ratio) on biodiesel production from sunflower oil.
The increase in production has made sunflower oil a suitable candidate Catalyst reusability, process kinetics, and thermodynamics were also
for biodiesel generation that can play a significant role in the biodiesel investigated. Finally, FT-IR and HNMR methods were utilized to explore
market. Many studies have used sunflower oil as a qualified primary fuel properties.
source for biodiesel production (Banerjee et al., 2014; Calero et al.,
2014; Jalalmanesh et al., 2021). 2. Experimental part
Various methods such as supercritical flow, dilution technique, py­
rolysis, trans-esterification, and micro-emulsification have been stated 2.1. Materials
for biodiesel generation from different oil sources (Esmaeili and For­
outan, 2018; Ambat et al., 2019). Among these methods, trans-­ Methanol (purity: 99.9%), sodium hydroxide (purity ≥97%), iron
esterification using homogeneous catalysts is a common and commercial chloride (FeCl3), cobalt chloride (CoCl2. 6H2O), and K2CO3 were sup­
method that is widely used, because homogeneous catalyst materials (e. plied by Merck (Darmstadt, Germany). Waste chalk was collected from a
g., KOH, NaOH, H2SO4) exhibit high reaction rate and efficiency under local demolished building and was pulverized and sieved through a 710
normal reaction conditions (Zhao et al., 2018; Foroutan et al., 2019a). μm (sieve (no.25, ASTM E11). Commercial sunflower oil (molecular
However, homogeneous catalysts suffer disadvantages such as dissolu­ weight: 867.83 g/mol, acid value: 0.47 mg KOH/g, saponification value:
tion and neutralization, toxicity, non-recyclability, corrosiveness on the 194.4 mg KOH/g) was purchased from Behshahr Industrial Company
equipment, and high energy consumption that increase their production and used as a source of oil in the biodiesel generation process.
cost (Jookjantra and Wongwuttanasatian, 2017; Lv et al., 2019). To

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R. Foroutan et al. Chemosphere 289 (2022) 133226

2.2. Preparation of catalyst 3. Results and discussion

The waste chalk/CoFe2O4/K2CO3 catalyst was synthesized using a 3.1. Catalyst characteristics
two-step co-precipitation chemical method. First, the waste chalk pieces
collected were rinsed using water and heated at 105 ◦ C for 1 day and The FT-IR technique was applied to characterize the chemical
then powdered and granulated. Then, an aqueous solution (100 mL) structure, functional groups, and possible interactions between the
containing cobalt ion (0.1 M, 2.379 g) and iron (0.2 M, 3.244 g) was components of waste chalk/CoFe2O4/K2CO3. FTIR spectra of the com­
provided in a 2:1 M ratio and 1 g of powdered waste chalk was added ponents of catalyst are presented in Fig. 1a waste chalk (CaSO4) showed
and stirred for 40 min. After thoroughly mixing, the mixture was heated characteristic low-vibration peak at 3616 cm− 1 and 1626 cm− 1 (the –OH
to 85–90 ◦ C, followed by NaOH (3 M, 50 mL) and stirring for 3 h. The group in water molecules) (Bartolomei and Wiebeck, 2019; Foroutan
waste chalk/CoFe2O4 was removed from the media, rinsed again with et al., 2019b), 1154 cm− 1, 672 cm− 1, 603 cm− 1 and 465 cm− 1 (vibra­
water, and adjusted to pH 6–7. The aqueous solution containing potas­ tions of sulfate (SO42− ) groups) (Ashfaq et al., 2020), and 1451 cm− 1
sium carbonate (2 wt%, 40 mL) was prepared and a certain amount of (C–– O vibrations). After the production process of waste chalk/CoFe2O4,
waste chalk/CoFe2O4 composite was added and stirred for 60 min. Then, the wavenumbers of the peaks in the waste chalk were considerably
it was dried at 105 ◦ C for one day to allow the water to evaporate changed by the appearance of new absorption peaks indicating the
completely. Potassium carbonate-modified composite was heated at incorporation/interaction of CoFe2O4 nanoparticles into/with waste
600 ◦ C for 5 h to be calcined and then utilized as a catalyst in the chalk structure. For example, waste chalk/CoFe2O4 magnetic composite
experiments. showed characteristic peaks at 1025-1109 cm− 1 attributing to Fe–O–Fe
vibrations (Foroutan et al., 2019c; Teo et al., 2019). By modification of
2.3. Generation of biodiesel waste chalk/CoFe2O4 magnetic composite with K2CO3 and calcination
process, the peak wavenumbers were changed, and a sharp peak with
Trans-esterification of sunflower in the presence of glycerol, waste high intensity has appeared at 1436 cm− 1 corresponding to C– – O vi­
chalk/CoFe2O4/K2CO3 catalyst, and excess methanol was performed to brations (Lukić et al., 2009).
produce biodiesel fuel. First, a certain quantity of the catalyst was mixed The XRD results (Fig. 1b) revealed that the prepared waste chalk has
with methanol by refluxed at 65 ◦ C. After adjusting the temperature of a bassanite crystalline phase (CaSO4.0.5H2O) with hexagonal structures
the mixture, the sunflower oil (@ 65 ◦ C) to the reaction medium under (Meireles et al., 2019) and is entirely consistent with the CaSO4⋅2H2O
magnetic stirring (600 rpm) for a specified time. After the compilations structure (Ahmed et al., 2004). It is also noteworthy to mention that the
of the trans-esterification, the waste chalk/CoFe2O4/K2CO3 was peaks in the 2θ (degree) range of 25.74, 33.54, 41.25, 52.36, and 55.85
centrifugally separated (5 min, 3500 rpm) and the mixture was decanted represented CaSO4 in the waste chalk (Teo et al., 2019). In the CoFe2O4
for one day to eliminate the glycerol. The biodiesel was finally heated at magnetic nanoparticles peaks appeared at 2θ (degree) range of 18.72,
80 ◦ C using a rotary evaporator for 1 h to evaporate the excess methanol. 29.98, 36.56, 42.76, 57.11, and 62.71 were corresponded to the crys­
The yield of biodiesel generation computed via Eq. (1): talline phases of (111), (220), (311), (222), (511), and (440), respec­
tively. This indicated that CoFe2O4 possesses a crystalline structure of
Weight of Biodiesel cubic spinel-type (Srivastava et al., 2016). After forming the waste
Yield of Biodiesel (%) = × 100 (1)
Weight of Oil chalk/CoFe2O4 magnetic composite, the intensity and range of the peaks
were altered compared to their components. The results showed that
2.4. Catalyst characterization methods both the waste chalk and the CoFe2O4 nanoparticles interacted well and
appeared in the resulting composite structure. Besides, modification of
SEM, EDX, and mapping tests were used to investigate the surface waste chalk/CoFe2O4 magnetic composite with K2CO3 followed by
changes, distribution of elements in the surface of waste chalk, waste calcification process led to a change in the range and intensity of the
chalk/CoFe2O4, and waste chalk/CoFe2O4/K2CO3 samples using scan­ peaks, indicating the incorporation of K2CO3 into the composite struc­
ning electron microscopy (SEM-TESCAN MIRA3-FEG). FTIR (Broker ture (Sengupta et al., 2014). Also, the peaks of CoFe2O4 and chalk in the
victor 22) device was used to determine the functional groups in the waste chalk/CoFe2O4/K2CO3 magnetic composite (target catalyst) were
sample. XRD spectra for waste chalk, waste chalk/CoFe2O4, waste well apparent, indicating that the target catalyst has been successfully
chalk/CoFe2O4/K2CO3, and CoFe2O4 were performed by Siemens-D500 generated.
with Cu-ka radiation in 35 kV in the range of 10 to 80◦ and scanning The results of the magnetic behavior of the CoFe2O4, waste chalk/
speed 1◦ /min and wavelength 1.5048 Å. Transmission electron micro­ CoFe2O4, and waste chalk/CoFe2O4/K2CO3 magnetic nanoparticles are
scopy (TEM) images were obtained for the case samples by the LEO 906 illustrated in Fig. 1c. The magnetic saturation values for the mentioned
transmission electron microscope at 80 kV. The thermogravimetric samples were 109.4, 36.2, and 2.2 emu/g, respectively, which reveals
analysis (TGA) method was used to evaluate the thermal stability. In this that the magnetic saturation field decreased with increasing non-
method, the weight change of the samples was determined as a function conductive portions in the composites. This may be due to the pres­
of temperature and under specific temperature programming condi­ ence of oxygen absorbed on the composite and non-magnetic content of
tions. To do this test, the TGA-PL device model TGA 1500, made in the particle (Foroutan et al., 2018a, 2018b).
England, was used. Atomic force microscope (AFM) (NanoScope III, Fig. 2 demonstrates the results of TGA to investigate the thermal
Digital Instruments Co., USA) was used to observe the morphologies of behavior of the catalyst and its components. These materials showed a
waste chalk, waste chalk/CoFe2O4, and waste chalk/CoFe2O4/K2CO3. weight loss percentage in three different temperature ranges. The first
Micrometrics/Asap2020 device made in the USA was used to measure weight loss was seen at 50–200 ◦ C, due to the evaporation of water
the surface area, porosity, and cavities in the structure of the samples. molecules adsorbed physically in the materials. The second one, at
The magnetic properties of CoFe2O4, waste chalk/CoFe2O4, and waste 200–700 ◦ C, was more intense than other stages of weight loss. This
chalk/CoFe2O4/K2CO3 were investigated using a vibrating magnetom­ second weight loss can be due to various factors such as thermal
eter sample (Lake-Shore 7400 VSM). decomposition of CaSO4 and K2CO3 as well as further removal of water
molecules from the said layers. The third one observed at 700–1000 ◦ C,
2.5. Experimental design was probably due to further degradation of oxygen functional groups,
carbon oxidation, and K2CO3 (Fang et al., 2014).
The experiments were designed based on RSM-CCD and ANN, which Specific surface area, pore size, and pore volume are other surface
are fully described in the Supplementary section (Table S1). properties of materials that can affect the properties and activity of

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R. Foroutan et al. Chemosphere 289 (2022) 133226

Fig. 2. The results of TGA-DTG analysis for waste chalk, waste chalk/CoFe2O4,
and waste chalk/CoFe2O4/K2CO3 composite samples.

the CoFe2O4 nanoparticles on the waste chalk particles. Modification of

waste chalk/CoFe2O4 with K2CO3 followed by calcification process led
to a decrease in the specific surface area of waste chalk/CoFe2O4/K2CO3
due to possible deposition of the K2CO3 between the particles and the
layers as well as the increased adhesion between the particles. Also, it is
Fig. 1. (a) The results of FT-IR, (b) XRD, and (c) VSM characterization for the
worth mentioning that the samples are classified as mesoporous by
experimental materials.
IUPAC classification (Foroutan et al., 2019c, 2020b).
Fig. S1 demonstrates SEM, dot-mapping, and EDX results of waste
catalysts. Brunauer – Emmett – Teller (BET) isotherm analysis was used
chalk, waste chalk/CoFe2O4, and waste chalk/CoFe2O4/K2CO3 magnetic
to evaluate the specific surface area, pore volume, and pore size of waste
composites to explore their surface morphology and the distribution of
chalk, waste chalk/CoFe2O4, and waste chalk/CoFe2O4/K2CO3 samples
components on the surface of composites. The results showed a rough
(Fig. 3). According to these results, the BET quantity for waste chalk,
surface containing different pores at the surface of waste chalk, which
waste chalk/CoFe2O4, and waste chalk/CoFe2O4/K2CO3 samples was
could be regarded as a suitable location for CoFe2O4 magnetic nano­
20.8, 77.8, and 5.8 m2/g, respectively. The increase in the BET quantity
particles (Fig. S1a). EDX and Map findings approved the presence of Ca,
of the waste chalk/CoFe2O4 sample compared to the chalk can be due to
O, Si, and S (SO4) in the prepared chalk with a uniform distribution at all

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R. Foroutan et al. Chemosphere 289 (2022) 133226

CoFe2O4 surface changed significantly due to the K2CO3 surface and

waste chalk/CoFe2O4 layers (Fig. S1g). The presence of K in waste
chalk/CoFe2O4 confirms the presence of K2CO3 in the desired catalyst
(Fig. S1h,i).
Results of TEM observation of waste chalk, magnetic CoFe2O4, and
waste chalk/CoFe2O4/K2CO3 samples are depicted in Fig. 4. These
findings showed that the waste chalk mainly has plate and particle
morphology, and in some parts, the particles have formed clusters
(Fig. 4a). The size of CoFe2O4 magnetic nanoparticles was in the range of
20–40 nm (Fig. 4b). K2CO3 modification and calcination process of
waste chalk/CoFe2O4 composite significantly increased particle size
(>50 nm) with particle aggregation in some parts, which was in good
agreement with SEM observation (Fig. 4c).
The results of AFM observation for waste chalk, waste chalk/
CoFe2O4 magnetic composite, and waste chalk/CoFe2O4/K2CO3 catalyst

Fig. 3. Adsorption-desorption curve nitrogen isothermal for waste chalk, waste

chalk/CoFe2O4, and waste chalk/CoFe2O4/K2CO3 samples.

points on the surface of the composite material (Fig. S1b,c). The for­
mation of waste chalk/CoFe2O4 nanocomposites resulted in significant
changes in its structure and surface, where particles with different sizes
of CoFe2O4 particles were deposited on the surface of composite chalk
(Fig. S1d). EDX and dot-mapping characterization confirmed the pres­
ence of cobalt and iron ions in the waste chalk (Fig. S1e,f), which cor­
responded to the formation of CoFe2O4 nanoparticles in the waste chalk.
After modifying the waste chalk/CoFe2O4 magnetic composite using
Fig. 4. TEM observations of (a) waste chalk, (b) CoFe2O4 magnetic nano­
K2CO3 and performing the calcification process, the waste chalk/ particles, and (c) waste chalk/CoFe2O4/K2CO3 catalyst samples.

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R. Foroutan et al. Chemosphere 289 (2022) 133226

are shown in Fig. S2. AFM analysis showed that the waste chalk particles sunflower oil was determined to be 99.27%. The results showed no
had a roughness of 33.47 nm, which was increased to 135.03 nm after significant difference between the experimental data and those proposed
preparing waste chalk/CoFe2O4 magnetic composite. The growth of by the model, which confirms that CCD successfully determined the
roughness value of the waste chalk surface can be linked to the depo­ optimal conditions of the process. More details about RSM-CCD and
sition of CoFe2O4 nanoparticles on the waste chalk surface, which is ANN are provided in the Supplementary section (Table S2-S6; Fig. S3-
consistent with the output of SEM analysis. K2CO3 modification and S5).
calcination process of waste chalk/CoFe2O4 composite decreased sur­
face roughness of the prepared catalyst due to the incorporation of 3.3. Comparison of used catalysts with other catalysts
K2CO3 particles in the pores and layers of waste chalk/CoFe2O4 and
possible aggregation of the particles (Fig. S2), which is also evident in Today, the production of catalysts with high catalytic activity and
the results of SEM and TEM tests. high production efficiency has been considered, so the ability and cat­
alytic activity of waste chalk/CoFe2O4/K2CO3 have been compared with
3.2. Effect of factors and their interaction in the production process of other heterogeneous catalysts used in biodiesel production from sun­
biodiesel flower oil. The results showed that the heterogeneous waste chalk/
CoFe2O4/K2CO3 catalyst had significant catalytic capacity and activity
Various factors, including the time of reaction, the content of compared to many of the catalysts used (Table 1). Thus, it can be stated
composited catalyst, temperature, and the methanol to oil ratio, are that the heterogeneous waste chalk/CoFe2O4/K2CO3 catalyst can be
important in the generation of biodiesel fuel. These parameters were successfully used in the biodiesel production process from sunflower oil
considered as input variables whose impact on the process output and other oil sources.
(biodiesel production efficiency) was investigated by plotting the three- The ability and catalytic activity of waste chalk and waste chalk/
dimensional curves as depicted in Fig. 5. In transesterification, the time CoFe2O4 were also investigated under laboratory conditions such as
of reaction is one of the important parameters, as prolonged heating will contact time of 180 min, temperature 65 ◦ C, catalyst content of 2 wt%,
reverse the process and reduce the efficiency of biodiesel production by and methanol to w/w 0.578. The results are shown in Table 1. The
destroying inhomogeneous catalysts (Nongbe et al., 2017). The results maximum efficiency of biodiesel was determined using waste chalk and
of the P-value showed that the time of reaction was the most positive waste chalk/CoFe2O4 61.57% and 82.38%, respectively. This showed
influencing parameter on the performance of biodiesel production that the catalytic activity of these two catalysts is low and requires high
compared to other factors. Process temperature was another important temperature and reaction time. When waste chalk/CoFe2O4 was modi­
factor in biodiesel production. The increasing temperature might fied using K2CO3, the maximum efficiency of the biodiesel production
enhance the overall catalyst activity and reaction performance due to process increased to about 99%, indicating that the number of active
decreased oil viscosity, which leads to higher rates of catalyst penetra­ sites for the biodiesel production process increased.
tion in the oil chain (Afsharizadeh and Mohsennia, 2019). By increasing
the temperature from 45 to 75 ◦ C the level of the produced biodiesel was 3.4. Kinetic study
initially increased and then decreased (Fig. 5). Increasing efficiency with
increasing temperature represents that triglycerides and free fatty acids There are many ways to generate biodiesel from different oils, such
are present in sunflower oil. These compounds require high tempera­ as trans-esterification, micro-emulsion, pyrolysis, and dilution, most of
tures to activate carboxylic or carbonyl groups (Dai et al., 2015). In which are commercially produced biodiesel produced by trans-esterifi­
contrast, reduced efficiency at high temperatures is linked to the evap­ cation. In transesterification, triglycerides are converted to monoalkyl
oration of CH3OH and a decrease in the rate of trans-esterification ester in the presence of methanol as the reactant. This process is per­
reaction. formed in three consecutive steps, including (i) conversion of tri­
By increasing the quantity of catalyst composite, the production glycerides (TG) to diglyceride (DG), (ii) conversion of DG to
percentage increased. It may be related to the growth of the BET and monoglyceride (MG), and finally, (iii) conversion of monoglyceride to
active sites of the catalyst for proceeding the reaction (Xie et al., 2018; monoalkyl ester and glycerol (GL), and their successive reactions are as
Kashyap et al., 2019). In the trans-esterification process, the molar ratio follows:
of CH3OH to oil has a significant effect, and more methanol must be used Step by step reactions:
to drive the forward reaction (biodiesel fuel) because the trans­
esterification process is reversible (Nisar et al., 2017). Also, it has been TG + R’OH ↔ kk1− 1 DG + R’ COOH
reported in previous studies that each mole of oil requires 3 mol of
CH3OH for the trans-esterification reaction, and this excess quantity of DG + R’OH ↔ kk3− 3 GL + R’ COOH
CH3OH will drive the reaction to produce biodiesel (methyl ester)
(Wang et al., 2012; Takase et al., 2014). Increasing CH3OH to oil mole MG + R’OH ↔ kk3− 3 GL + R’ COOH
ratio from 9:1 to 15:1 increased the efficiency of biodiesel production,
Final reaction:
followed by a decrease at a mole ratio of 21:1. This decrease can be due
to various factors, among which difficulty of biodiesel separation from TG + 3R’OH ↔ catalyst GL + 3R’ COOH
glycerol, reduction of reaction rate, dilution, and inactivation of the
To investigate the kinetic behavior, the equilibrium constant is not
catalyst by the use of excess methanol (Chen et al., 2015).
dependent on the methanol concentration, and the final trans-esterifi­
The RSM-CCD optimizes and determines the conditions for biodiesel
cation reaction is performed in one step, which allows pseudo-first-order
production. According to RSM-CCD, the maximum production efficiency
kinetics. Therefore, the rate of trans-esterification reaction can be
of 99.86% was obtained in biodiesel production at a reaction time of
determined from Eq. (2):
177 ± 0.31 min, a temperature of 67 ± 1 ◦ C, a catalyst value of 2.65 wt
%, and methanol to oil mole ratio of 15.87, which were considered as d[TG]
(2)
′

optimal conditions. To investigate the accuracy of the RSM-CCD method − ra = = k (TG)(ROH)3

dt
in designing and determining the optimum reaction conditions, the
experimental test of biodiesel generation from sunflower oil was per­ Where ḱ is the reaction constant, TG is triglyceride concentration and
formed using the catalyst in the optimum conditions reported using [ROH] methanol concentration. By assuming that the chemical reaction
RSM-CCD. Under the proposed conditions offered by RSM-CCD, the is only in the oil phase and, k = k (ROH)3 the equation for the trans-
′

maximum experimental efficiency of biodiesel generation from esterified reaction rate can be rewritten as follows:

6
R. Foroutan et al. Chemosphere 289 (2022) 133226

Fig. 5. Effects of time, catalyst quantity, temperature, methanol to oil ratio and their interactions on the biodiesel generation.

7
R. Foroutan et al. Chemosphere 289 (2022) 133226

Table 1
Comparison of the ability and performance of waste chalk/CoFe2O4/K2CO3 catalyst with other catalysts used in the biodiesel production process from different
feedstocks.
Catalyst type Feedstock Catalyst load (%) Transesterification Yield of biodiesel (%) Reference

M/O Time(h) Temp. (◦ C)

CaO Sunflower oil 3 13:1 1.66 60 94 Granados et al. (2007)

Ca–Mg–Al Sunflower oil 2.5 15:1 6 60 95 Dahdah et al. (2020)
K2CO3/alumina–silica sunflower oil 2 15:1 0.33 120 97 Lukić et al. (2009)
Ca/Al-MCM-41 Sunflower oil 10 12:1 8 70 84.2 Vardast et al. (2019)
K-pumice Sunflower oil 20 18:1 2 55 95.6 Borges et al. (2011a)
Fly ash-based solid Sunflower oil 15 15:1 8 179 87.5 Kotwal et al. (2009)
CaSO4/Fe2O3–SiO2 core-shell Jatropha oil 12 9:1 4 120 94 Teo et al. (2019)
Barium cerate Karanja oil 1.2 19:1 1.66 65 98.3 Sahani et al. (2019)
K2CO3/γ-Al2O3 sunflower oil 5 12:1 4 80 99.3 Junior et al. (2019)
PEG encapsulated ZnOMn2+ Microalgae oil 3.5 15:1 4 60 87.5 Raj et al. (2019)
CaO/MgO composite Waste cooking oil 6 15:1 2 90 96.47 Rabie et al. (2019)
Co doped ZnO Mesua ferrea oil 2.5 9:1 3 60 98.03 Borah et al. (2019)
Waste chalk/CoFe2O4/K2CO3 Sunflower oil 2.65 15.2 2.95 80 99.27 Current study
Waste chalk/CoFe2O4 Sunflower oil 2.65 15.2 2.95 80 82.38 Current study
Waste chalk Sunflower oil 2.65 15.2 2.95 80 61.57 Current study

d[TG] and EN14214 standards (see Table S7). The flash point is one of the pa­
− ra = = k[TG] (3)
dt rameters affecting fuel properties, and it is noteworthy to mention that
although it does not directly affect engine performance, but is vital in
By assuming the concentration of triglyceride at moment t = 0 is
terms of safety in transporting and storing fuel. The flash point of the
equal to TGo, and by integrating from Eq. (3), we have:
desired biofuel was determined to be 154 ◦ C, which complies with in­
ln[TG0 ] − ln[TG] = k.t (4) ternational standards, showing that the biodiesel is easy to handle (Dha­
wane et al., 2016). Density is also an important property of fuel that,
Also using the mass balance:
unlike the flash point, directly affects the performance of engine charac­
[TG] teristics such as cetane number and the level of energy are related to the
XME = 1 − (5)
[TG0 ] biofuel density (Alptekin and Canakci, 2011). Fuel viscosity can affect its
atomization, droplet size, and injection speed, and thereby, the engine
[TG] = [TG0 ](1 − XME ) (6) combustion quality. High fuel viscosity will negatively influence its at­
omization during spraying leading to sediment build-up in the engine.
− ln(1 − XME ) = k . t (7) Besides, the high viscosity of fuel will reduce engine performance and
Here, XME reflects the conversion rate of TG to methyl ester, which increase smoke emissions (Ramírez-Verduzco et al., 2012). The other two
was quantified using the H NMR test. To determine the activation energy important parameters that confirm fuel use at low temperatures are the
(Ea), the Arrhenius equation was used where the relation between re­ pour point and the cloud point. The cloudiness point is the temperature
action constant (k), Ea, and absolute temperature (T) is as follows: caused by the decrease in fuel temperature to create a wax-like state in the
fuel, and the pour point reflects the temperature drop that fuel still can
k = ko exp(
− Ea
) (8) move (Saydut et al., 2008). Cetane number is another characteristic of
RT fuel, and the high level of fuel cetane will benefit combustion and engine
In this equation, k0 reflects the frequency factor, and R (8.314 J/mol. performance. The results showed that biodiesel produced from sunflower
K) is the global constant of gases. To quantify the activation energy of oil using heterogeneous waste chalk/CoFe2O4/K2CO3 catalyst has desir­
the process, the Arrhenius equation is rewritten as follows, and the able properties according to international standards. It can be used as a
linear relationship between lnk versus 1/T is determined: viable option to diesel fuel in diesel engines.
Fig. S7a shows the FTIR test for sunflower oil and biodiesel samples
Ea
lnk = lnk0 − (9) using the heterogeneous waste chalk/CoFe2O4/K2CO3 catalyst. In the
RT
sunflower oil and biodiesel, 2880-2931 cm− 1 strong adsorption peaks
The linear relationship of lnk vs. 1/T is depicted in Fig. S6. The were observed due to symmetric C–H vibrations and asymmetric C–C
constant rate of k at temperatures of 45 ◦ C, 55 ◦ C, 65 ◦ C, 75 ◦ C, and 85 ◦ C vibrations. Also, a sharp peak at 1744 cm− 1 and 1742 cm− 1 in the
were 0.0083 min− 1, 0.0077 min− 1, 0.022 min− 1, 0.0133 min− 1 and sunflower oil and biodiesel was observed, which could indicate the C– –O
0.0115 min− 1, respectively. Due to the free fatty acids available in the group in TG (Nisar et al., 2017). The major changes in the structure of
media, the operational conditions for biodiesel generation can vary, as sunflower oil occurred after the desired process in 1000–1500 cm− 1.
reported in previous studies (Teo et al., 2016). Also, the amount of These could be due to the replacement of the CH2O-groups in the TG
activation energy and frequency factor was 11.815 kJ/mol and 0.784 structure with CH3O- groups in the methyl ester structure. In the sun­
min− 1, respectively, and it can be noted that the level of free fatty acids flower oil structure, a low-intensity peak at 1451 cm− 1 has been
in the oil can be effective on the process Ea. Also, the presence of satu­ observed, which has changed to 1448 cm− 1 after the biodiesel genera­
rated free fatty acids reduces the reaction rate, and the higher the Ea tion, indicating the conversion of oil to methyl ester (biodiesel) (Sala­
factor, the slower the trans-esterification reaction and more adverse heldeen et al., 2015). Another peak that can confirm biodiesel
reactions that cause soap formation (Teo et al., 2016). production from sunflower oil is 1015 cm− 1, while the peak does not
exist in the sunflower oil structure. The vibrations at 1015 cm− 1 in the
biodiesel structure can be due to the presence of formed glycerol (San­
3.5. Study of biodiesel properties
tiago-Torres et al., 2014).
One of the analyses used to identify and characterize biodiesel
The optimization of desired variables on the efficiency of the trans-
properties is nuclear proton magnetic resonance (H NMR). For this
esterification process was also done. The obtained biodiesel after the
analysis, the samples of oil and biodiesel produced in the CDCl3 solvent
separation of glycerol and catalyst was tested according to ASTM D6751

8
R. Foroutan et al. Chemosphere 289 (2022) 133226

were dissolved. The results of the H NMR analysis for sunflower oil and
biodiesel are provided in Fig. S7b. In the sunflower oil, 4.13–4.30 ppm
multi-branch peaks have been observed, which is due to the glyceride
protons in the oil. Moreover, in the sunflower oil and generated bio­
diesel in the span of 1–3 ppm, different intensities and branches
appeared due to the hydrocarbon chain protons in the material structure
(Kaur and Ali, 2011). Also, in the biodiesel structure produced from
sunflower oil in the range of 5.274–5.372 ppm, a multi-branch peak is
linked to the unsaturated protons in the biodiesel. It is worth mentioning
that the biodiesel produced in the range of 0.841 ppm–2.763 ppm ap­
pears to be due to the protons of α-carbonyl methylene, allylic hydrogen,
bis-allylic, hydrogen olefinic, methylene, methyl-terminal, and carbonyl
group is and has been reported in previous studies (Parkar et al., 2012).
In addition to the peaks mentioned, in the range of 0.841 ppm–2.763
ppm, a sharp peak appeared in the biodiesel structure at 3.639 ppm,
while there was no peak sunflower oil mentioned. The peak at 3.639
ppm is related to protons in the methyl ester (Foroutan et al., 2020a),
which approves the success of produced biodiesel from sunflower oil by
the heterogeneous waste chalk/CoFe2O4/K2CO3 catalyst. Another case
that indicates the production of the desired compound (biodiesel) is the
lack of a peak of 4.2 ppm.

3.6. Mechanism of biodiesel production reactions

In the biodiesel generation process, various vegetable oils and animal

fats can be used, a mixture of free fatty acids (FFA) and triglycerides that
can play a role in the biodiesel production process or fatty acid methyl
ester (FAME). In addition, in the heterogeneous waste chalk/CoFe2O4/
K2CO3 catalyst structure, there are K2CO3 and CaSO4 segments, consid­
ered active Lewis and Brønsted acid-base sites, respectively, and can play
an important role in the biodiesel production process. The mechanism of
the biodiesel production process from sunflower oil using the waste
chalk/CoFe2O4/K2CO3 heterogeneous catalyst is fully presented in Fig. 6.
In the reaction of producing biodiesel from sunflower oil, two mechanisms
of transesterification (Fig. 6a) and esterification (Fig. 6b) are involved,
which take place simultaneously and increase the efficiency of the pro­
cess. In the production of biodiesel using the waste chalk/CoFe2O4/K2CO3
catalysts, lattice oxygen (O2− ) derived from K2CO3 is considered as Lewis
base sites. The ability to link Lewis positive and basic species is related to
the basicity of oxygen species (Liu et al., 2019). As shown in Fig. 6a, in the
first step of the interaction between methanol and K2CO3, a nucleophilic
Fig. 6. (a) Transesterification process and (b) sunflower oil esterification pro­
methoxide anion forms on the surface of the waste chalk/CoFe2O4/K2CO3
cess using waste chalk/CoFe2O4/K2CO3 catalyst.
catalyst, which then attacks the carbonyls of the triglyceride molecule and
creates an intermediate compound. The next step is to form a diglyceride
molecule with anionic and methyl ester properties. At the end of the waste chalk/CoFe2O4, and waste chalk/CoFe2O4/K2CO3 were 20.815
transesterification reaction, the positive charges created by methanol on m2/g, 77.761 m2/g, and 5.839 m2/g, respectively. The VSM analysis
the surface of the catalyst (H+) are added to the anion in the glyceride, revealed that the synthesized catalyst had a magnetic property, but its
forming a diglyceride molecule. At this point, the catalyst is regenerated. magnetic saturation was lower than that of CoFe2O4 and waste chalk/
After diglyceride formation, the transesterification reaction continues CoFe2O4 nanoparticles. The synthesized catalyst had an efficiency of
until glycerol, and 3 mol of FAME are produced, and the reaction is over 90% through six steps of reuse. Based on the kinetic study, the
completed. Fig. 6b also fully describes the process of esterification of free values of Ea and frequency factor for the process were attained at 11.815
fatty acids with the anionic species of waste chalk as Brønsted acid sites kJ/mol and 0.784 min− 1, respectively. Besides, the study of thermody­
(SO42− ). It is noteworthy that in the first stage, free fatty acid reacts with namic parameters showed that the biodiesel production process is
Brønsted acid sites and after the interactions that take place, a molecule of endothermic and non-spontaneous, and sufficient energy is required to
water and fatty acid methyl ester is formed and the desired catalyst is perform the process. The produced biodiesel complied with interna­
rearranged and can participate in the biodiesel production cycle. tional standards. The catalytic activity of waste chalk/CoFe2O4/K2CO3
was compared with other catalysts, which showed that the synthesized
4. Conclusions catalyst has an acceptable ability to produce biodiesel.

In this work, a new composited catalyst of waste chalk/CoFe2O4/ Credit author statement
K2CO3 was synthesized to generate biofuel from sunflower oil. The effect
of temperature, time, catalyst quantity, and CH3OH to oil ratio on the R. Foroutan: Formal analysis, Methodology. S.J. Peighambardoust:
biodiesel generation efficiency was investigated using RSM-CCD and Methodology, Supervision. R. Mohammadi: Funding acquisition,
ANN methods. The results revealed that the RSM-CCD method can Conceptualization. S.H. Peighambardoust: Methodology. B. Ramavandi:
design experiments and determine the best conditions for biodiesel Supervision, Conceptualization, Methodology, Writing-review& editing.
generation than ANN. It was shown that BET surfaces of waste chalk,

9
R. Foroutan et al. Chemosphere 289 (2022) 133226

Declaration of competing interest Fang, F., Kong, L., Huang, J., Wu, S., Zhang, K., Wang, X., Sun, B., Jin, Z., Wang, J.,
Huang, X.-J., 2014. Removal of cobalt ions from aqueous solution by an amination
graphene oxide nanocomposite. J. Hazard Mater. 270, 1–10.
The authors declare that they have no known conflict of interest that Fernandez, I.A.P., Liu, D.-H., Zhao, J., 2017. LCA studies comparing alkaline and
may obscure or affect their judgment to influence the work reported in immobilized enzyme catalyst processes for biodiesel production under Brazilian
this paper. conditions. Resour. Conserv. Recycl. 119, 117–127.
Foroutan, R., Ahmadlouydarab, M., Ramavandi, B., Mohammadi, R., 2018a. Studying the
physicochemical characteristics and metals adsorptive behavior of CMC-g-HAp/
Appendix A. Supplementary data Fe3O4 nanobiocomposite. J. Environ. Chem. Eng. 6, 6049–6058.
Foroutan, R., Esmaeili, H., Mousavi, S.M., Hashemi, S.A., Yeganeh, G., 2019a. The
physical properties of biodiesel-diesel fuel produced via transesterification process
Supplementary data to this article can be found online at https://doi. from different oil sources. Phys. Chem. Res. 7, 415–424.
org/10.1016/j.chemosphere.2021.133226. Foroutan, R., Mohammadi, R., Esmaeili, H., Bektashi, F.M., Tamjidi, S., 2020a.
Transesterification of waste edible oils to biodiesel using calcium oxide@
magnesium oxide nanocatalyst. Waste Manag. 105, 373–383.
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