Journal of Cleaner Production 372 (2022) 133739

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Journal of Cleaner Production

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

Green and fast biodiesel production at room temperature using soybean and
Jatropha curcas L. oils catalyzed by potassium ferrate
Adriana N. Gutiérrez-López a, b, Violeta Y. Mena-Cervantes a, b, Mario A. González-Espinosa a, b,
Fabiola S. Sosa-Rodríguez c, Jorge Vazquez-Arenas a, b, *, Ricardo Rodríguez-Ramírez d,
Raúl Hernández-Altamirano a, b, **
a
Centro Mexicano para la Producción más Limpia, Instituto Politécnico Nacional, Av. Acueducto s/n, Col. La Laguna Ticomán, Ciudad de México, 07340, Mexico
b
Laboratorio Nacional de Desarrollo y Aseguramiento de la Calidad de Biocombustibles (LaNDACBio), Instituto Politécnico Nacional, Ciudad de México, 07340, Mexico
c
Research Area of Growth and Environment, Metropolitan Autonomous University, Azcapotzalco (UAM-A), Av. San Pablo 180, Mexico City, 02200, Mexico
d
Unidad Profesional interdisciplinaria en Ingeniería y tecnologías avanzadas, Instituto Politécnico Nacional, Av. IPN No 2580, 07340, Ciudad de México, Mexico

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

Handling Editor: Zhen Leng The biodiesel production is typically conducted around 65 ◦ C (methanol’s boiling point), this study describes a
catalytic process at room temperature (25 ± 3 ◦ C) to shrink energy consumptions. In order to achieve this,
Keywords: potassium ferrate (K2FeO4) is used as a heterogeneous pseudo-catalyst in the transesterification reaction of two
Biodiesel different vegetable oils: refined soybean oil (SBO) and crude Jatropha curcas L. oil (JCO). Transesterification
Soybean oil
variables are optimized using a Box-Behnken design (BBD) to maximize the oil conversion to fatty acid methyl
Jatropha curcas L. oil
esters (FAMEs). Process variables such as stirring rate (125–700 RPM), K2FeO4 dosage (0.15–6 wt%), and
Heterogeneous catalysis
Methoxy radical methanol to oil molar ratio (6:1 to 16:1) are varied to obtain maximum conversion. The experimental results
K2FeO4 revealed that maximum conversion of 98.17% and 98.35% are produced in 1 h using the optimized conditions
determined with the response surface methodology (RSM) for JCO (357 RPM, 5.29 wt% K2FeO4 dosage, 14.89:1
MeOH: oil molar ratio) and SBO (700 RPM, 4.82 wt% K2FeO4 dosage, 14.28:1 MeOH: oil molar ratio), respec­
tively. The conversion percentage is quantified by Fourier Transform Infrared Spectroscopy (FTIR) and
corroborated by proton nuclear magnetic resonance (1H NMR). The fatty acid methyl esters produced under
optimized reaction conditions are characterized to obtain their density, viscosity, acid number, oxidative sta­
bility, flash point, heating value, cloud point, and pour point to determine the quality compliance with the
standard ASTM D6751. Additionally, conversion percentage is monitored at 0, 1, 5, 10, 15, 30, 45, 60, and 90
min of reaction. It is found that after 5 min of transesterification reaction, a conversion of 98.31% is reached
without significant variation over time using SBO. A similar conversion (98.07%) is generated at 30 min for JCO,
reaching its maximum conversion (98.65%) at 90 min. These fast reactions might occur due to the methoxy
radicals formed on K2FeO4, unlike the methoxy ions produced by other heterogeneous catalysts. X-ray diffraction
(XRD) and scanning electron microscopy (SEM) spectroscopy are used to characterize the K2FeO4 material.

1. Introduction such as global warming and climate change, whereby it is necessary to

Economic development and population growth have led to a rapid
increase in energy demand, which is mostly obtained from petroleum-
derived fuels. The combustion of fossil fuels significantly contributes
to the emission of greenhouse gases, causing environmental impacts
diversify the energy matrix by incorporating alternative sources of en­
ergy (Chozhavendhan et al., 2020). In this direction, biodiesel is a car­
bon neutral and biodegradable fuel obtained from renewable sources
that can be used pure or mixed with fossil diesel (Singh et al., 2018). Its
implementation can improve air quality as a consequence of reducing

* Corresponding author. Centro Mexicano para la Producción más Limpia, Instituto Politécnico Nacional, Av. Acueducto s/n, Col. La Laguna Ticomán, Ciudad de
México, 07340, Mexico.
** Corresponding author. Centro Mexicano para la Producción más Limpia, Instituto Politécnico Nacional, Av. Acueducto s/n, Col. La Laguna Ticomán, Ciudad de
México, 07340, Mexico.
E-mail addresses: jorge_gva@hotmail.com, jgvazquez@ipn.mx (J. Vazquez-Arenas), rhaltamirano@gmail.com (R. Hernández-Altamirano).

https://doi.org/10.1016/j.jclepro.2022.133739
Received 15 December 2021; Received in revised form 5 August 2022; Accepted 19 August 2022
Available online 24 August 2022
0959-6526/© 2022 Elsevier Ltd. All rights reserved.
A.N. Gutiérrez-López et al.
emissions of sulfur oxides, particulate matter, aromatics, carbon mon­
oxide, carbon dioxide, and unburned hydrocarbons (Rouhany and
Montgomery, 2019).
Biodiesel is comprised of a mixture of fatty acid alkyl esters produced
by transesterification of vegetable oils or animal fats with methanol
subjected to acid, basic or enzymatic catalysis (Gebremariam and Mar­
chetti, 2018). Currently, biodiesel is produced using homogeneous basic
catalysts such as sodium hydroxide due to its high commercial avail­
ability and affordable cost, however, it undesirably reacts with free fatty
acids to produce soaps (sodium carboxylates), thus, requiring additional
purification operations by removing impurities with water (Tacias-­
Pascacio et al., 2019). Recent efforts are focused on making biodiesel
production more environmentally friendly, preferentially selecting
heterogeneous catalysts to avoid the drawbacks of homogeneous base
catalysis, including null catalyst recovery and reuse for various reaction
cycles (Changmai et al., 2020). Heterogeneous catalysts are typically
made up of alkaline earth metal oxides such as CaO (Kouzu et al., 2017),
MgO (Rasouli and Esmaeili, 2019), and SrO (Roschat et al., 2018);
transition metal oxides including TiO2 (Carlucci et al., 2019), ZnO–SiO2
(Justine et al., 2021), and Na2ZnSiO4 (Rodríguez-Ramírez et al., 2020);
hydrotalcite (Navajas et al., 2018); mixed metal oxides containing Sr–Ce
(Banerjee et al., 2019), Sr–Ti (Sahani et al., 2020), and Ca–Mg (Sudsa­
korn et al., 2017); and biomass-based catalysts consisting of banana
trunk ash (Rajkumari and Rokhum, 2020) and eggshell (Yaşar, 2019),
among others. However, these materials still present some disadvan­
tages, such as deactivation due to moisture and free fatty acids (FFA),
slow reaction rate associated with diffusion limitations, high alcohol to
oil molar ratio, complex synthesis and fabrication, and leaching of active
catalyst sites (Changmai et al., 2020). And particularly, they are used at
around 65 ◦ C to promote the formation of a methoxide ion attacking the
triglyceride to form the biofuel, which is responsible of most of the
energy consumption of the process.
Potassium ferrate (K2FeO4) is a strong oxidizing agent widely used in
environmental applications such as water and waste-water treatment
because it does not form any harmful by-products, provides efficient
inactivation of microorganisms, degrades and oxidizes organic and
inorganic impurities, and removes suspended colloidal particles via
coagulation-flocculation process (Jiang et al., 2006). Also, potassium
ferrate has attracted attention in organic synthesis. The oxidation of
alcohols to form aldehydes or ketones by potassium ferrate has been
likewise reported (Bartzatt et al., 1985; Delaude et al., 1995). Recently,
methanol oxidation routes have been theoretically described, in which
methoxide radical (CH3O•) can be produced as an intermediate before
formaldehyde formation (Ohta et al., 2001). The methoxide radical
could lead to the production of methyl esters in a considerable shorter
time even at room temperature due to its high reactivity compared to the
methoxide ion (CH−3 ).
At present, soybean, palm oil, and rapeseed oil are the dominant
biodiesel feedstocks because of their high availability in many
geographical areas (Joshi et al., 2017). Jatropha curcas is another
promising inedible energy crop since it displays low irrigation re­
quirements and can be grown on land unsuitable for growing food. Also,
it is widely distributed in Mexico and Central America, Asia, and Africa,
and its seeds contain approximately 40–50% good quality oil (Ewunie
et al., 2021). The economic competitiveness of biodiesel against fossil
diesel is one of the determining factors promoting a sustainable energy
transition using renewable fuels. The price of this biofuel is determined
by feedstock, unit operations integrating the production process, pro­
duction volume, food prices, government incentives, as well as research
and technological development costs, etc. (Rouhany and Montgomery,
2019). Accordingly, it is of paramount importance to reduce the heating
consumption in the transesterification reaction producing biodiesel, in
order to favorably impact costs that benefit its profitability and appli­
cability. This has stemmed the development of these processes at room
temperature, although, there is a lack of information regarding this
issue. To this concern, Piker et al. (2016) obtained a conversion of 98 wt
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Journal of Cleaner Production 372 (2022) 133739
% and 97 wt% using SBO and waste cooking oil (WCO) respectively (1:6
oil: methanol molar ratio), and eggshells as catalyst (5.8% w/w) after
11 h at room temperature (25 ± 3 ◦ C). The eggshell was utilized during
10 and 5 cycles for SBO and WCO. Laskar et al. (2018) reported 98 wt%
conversion of SBO into methyl esters (1:6 oil to methanol molar ratio) at
room temperature (28 ◦ C) using waste snail shell as catalyst (3 wt%)
after 7 h. The catalyst was recycled 8 times. Recently, Laskar et al.
(2020) obtained 98 wt% conversion of SBO (1:6 oil to methanol molar
ratio) at 28 ◦ C using mango peel ash (6 wt%) after 4 h and the catalyst
was used for 4 cycles. Although low-cost catalysts are used and heating is
not required in the aforementioned studies, the reaction time is still
long, which implies high energy consumption due to stirring.
Therefore, the current study reports the pseudo-catalytic perfor­
mance of K2FeO4 at room temperature using refined SBO and crude JCO
for biodiesel production, with the aim of using a sustainable pseudo-
catalyst without heating in a short reaction time. A Box-Behnken
experimental design was employed to achieve the maximum conver­
sion through the interaction analysis of the following variables: stirring
rate (125–700 RPM), K2FeO4 dosage (0.15–6 wt%), and methanol to oil
molar ratio (6:1 to 16:1). Once obtained the optimized reaction condi­
tions, conversion was measured at 0, 1, 5, 10, 15, 30, 45, 60, and 90 min.
Additionally, physicochemical characterization of each oil and its
respective methyl esters was carried out. Likewise, the K2FeO4 is char­
acterized using XRD and SEM analysis.
2. Materials and methods
2.1. Determination of physicochemical properties of soybean oil and
Jatropha curcas L
The refined SBO from the Nutrioli brand was purchased from a local
market, while the raw JCO was obtained as mentioned below: The seeds
were collected in Zacatepec, Morelos, Mexico. Then, they were cracked
to carefully separate the kernels and shells. The crushed kernels were
placed in a round-bottom flask with ethanol in proportion 1:5 w/v. The
mixture was heated at 60 ◦ C under magnetic stirring at 700 RPM for 6 h,
and then, it was allowed to cool down to room temperature before being
vacuum filtered to remove the kernel. The ethanol/oil mixture was
placed in a rotary evaporator to recover the ethanol and the dry oil was
filtrated using Whatman filter paper (diameter of 125 mm) to separate
the residual fine fragments. It is important to mention that it was
decided to carry out the solid-liquid extraction using ethanol as solvent
instead of hexane, since this last one is toxic and harmful to human
health. By this method, an average of 40% vegetable oil was obtained.
Both, SBO and JCO were physicochemical characterized according to
the ASTM standard methods. Kinematic viscosity at 40 ◦ C and density
and were obtained from a single measuring cycle employing a SVM 3001
Stabinger viscosimeter (Anton Paar) in accordance with ASTM D-445
and ASTM D-4052, respectively. The acid number was measured as
described in the ASTM D-664 method. The oxidative stability was
quantified in a RapidOxy 100 oxidation stability tester (Anton Paar),
following the ASTM D7525 and ASTM D7545 methods. The infrared
spectra were recorded from 4000 to 400 cm− 1 using a PerkinElmer
Frontier infrared spectrophotometer.
2.2. Potassium ferrate characterization
Potassium ferrate (K2FeO4) was purchased from Jinan Huijinchuan
Chemical Industry Co. With ≥95% purity. The crystalline structure was
identified by XRD analysis using a PANalytical Empyrean powder
diffractometer with Cu Kα radiation (λ = 1.5417 Å) over the angular
range of 10–80◦ (2θ) with an interval of 0.05◦ s− 1. The surface
morphology of the material was studied using a scanning electron mi­
croscope JEOL JSM-6510LV with energy-dispersive X-ray spectroscopy
(EDX). After the transesterification reaction, the spent K2FeO4 resulting
from the reaction with SBO and JCO were washed several times with
A.N. Gutiérrez-López et al. Journal of Cleaner Production 372 (2022) 133739

Table 1 2.3. Transesterification reaction optimization via Box-Behnken

Physicochemical properties of soybean oil and Jatropha curcas L. oil. experimental design
Property SBO JCO
The Box-Behnken experimental design is used to analyze the inter­
Free fatty acids as oleic acid (%) 0.0225 3.6998
Acid number 0.0447 7.3626 action of reaction variables and allows to reduce the number of exper­
Oxidative stability (RANCIMAT) 5.78 10.30 iments in comparison to other methods without compromising the result
Kinematic Viscosity 40◦ C (mm2/s) 30.343 33.621 (Niju et al., 2020). A Box–Behnken experimental design was imple­
Density (g/cm3) 0.9056 0.9035 mented for maximizing the conversion in the transesterification reaction
for each SBO and JCO by optimizing three variables: oil molar ratio (6:1
ethanol to remove organic impurities, dried at 70 ◦ C for 3 h, and char­ to 16:1), K2FeO4 dosage (0.15–6 wt%), and stirring rate (125–700 RPM).
acterized as mentioned above to verify the decomposition of the initial In total, 15 experimental runs for each system were conducted,
compound. including three replications at the middle experimental region to
determine the experimental error.
The transesterification reactions were performed at room tempera­
ture (25 ± 3 ◦ C). The vegetable oil was fed into 50 mL round bottom

Fig. 1. X-ray diffraction pattern of K2FeO4 (a) and spent K2FeO4 from reaction using SBO (b) and JCO (c).

3
A.N. Gutiérrez-López et al.
Fig. 2. Scanning electronic microscopy images of K2FeO4 (a–b) and spent K2FeO4 from reaction using SBO (c–d) and JCO (e–f).
flasks placed on magnetic stirrers. The methanol and the K2FeO4 were
immediately added, and the flask was closed with a ground glass stop­
per. Note that it was not necessary to use a condenser and a water chiller
since there was no methanol evaporation caused by heating, as occurs in
conventional transesterification reactions. After 1 h, the reaction
mixture was directly transferred to centrifuge tubes to separate the
FAME, crude glycerol, and spent K2FeO4 using a Velab PRO-4 centrifuge
at 5000 RPM for 15 min. The non-reacted methanol was evaporated at
65 ◦ C for 3 h to completely dry the methyl esters phase.
The conversion was determined by a FTIR calibration curve previ­
ously made in the software Spectrum Quant Quantitative Analysis
(PerkinElmer), that associates the transmittance of the methyl ester peak
at 1435 cm− 1. The infrared spectrum of each FAME was recorded from
4000 to 400 cm− 1 using a PerkinElmer Frontier Fourier infrared spec­
trometer. The Minitab 17.0.1 software was used for the prediction of the
quadratic model and the obtention of a regression equation to analyze
the interaction between the reaction variables and their influence on the
response variable expressed as conversion.
2.4. Reaction time optimization
Optimized conditions obtained as described in section 2.3 were used
to determine the time wherein maximum conversions occur for each
SBO and JCO system. For these experiments, conversion over time was
independently evaluated through simultaneous reactions monitored at
1, 5, 10, 15, 30, 45, 60, and 90 min. FAMEs were separated by centri­
fugation and characterized by FTIR, as described in section 2.3.
4
Journal of Cleaner Production 372 (2022) 133739
2.5. Determination of physicochemical properties of fatty acid methyl
esters
The fatty acid methyl esters resulting from the optimized conditions
for each oil (SBO and JCO) were characterized through the following
analysis: Density, kinematic viscosity at 40 ◦ C, and acid number were
measured as mentioned in section 2.1. The flash point was obtained
using an Anton Parr PMA-5 flash point tester in compliance with ASTM
D93. The heating value was estimated using a Parr isoperibol calorim­
eter model 6200. The standard ASTM D6751 establishing standard
Specification for Biodiesel Fuel (B100) was taken as a reference to verify
if the results of the physico-chemical characterization are within the
permissible quality limits. Additionally, the JCO, SBO, and their
respective FAMEs were characterized by proton nuclear magnetic
resonance. 1H NMR was performed in a 60 MHz Anasazi Eft-60 spec­
trometer to confirm the vegetable oil conversion into methyl esters. 100
μL of each sample were dissolved in 500 μL of deuterated chloroform
(CDCl3) and placed in Wilmad® NMR tubes of 5 mm diameter. The
analysis was carried out at 25 ◦ C using a spectral width of 1000 Hz, 8.19
s acquisition time, 3 s relaxation delay, and 325 scans.
Ion chromatography was carried out to determine the amount of
potassium in the SBO and JCO FAMEs. The samples were extracted with
nitric acid (2 mM), dialyzed, and then injected into a Metrohm 930
compact ic flex. The column utilized was a Metrosep C 4–150/4.0. The
eluent (2 mmol L− 1 HNO3 with 10% acetone) was injected at 0.9 mL
min− 1; the column temperature was maintained at 30 ◦ C, and the sample
volume was 10 μL. The quantification was carried out through a
A.N. Gutiérrez-López et al.
Fig. 3. EDX analysis of K2FeO4 (a) and spent K2FeO4 from reaction using SBO (b) and JCO (c).
calibration curve using a certified Sigma-Aldrich multielement cation
standard solution (10 mg kg− 1).
3. Results and discussion
3.1. Determination of physicochemical properties of soybean oil and
Jatropha curcas L
The fatty acid composition of vegetable oils determines their physi­
cochemical properties. Several studies have reported that palmitic
(C16), oleic (C18:1) and linoleic acid (C18:2) are the major components
in SBO and JCO, which fluctuate depending on environmental condi­
tions (Ovando-Medina et al., 2013). The physicochemical properties of
both oils, SBO and crude JCO are summarized in Table 1. The acid
number is used to determine the free fatty acids (FFA) content in the oil,
and it is expressed as milligrams of potassium hydroxide required to
neutralize 1 g of sample. Acid number was 0.0447 and 7.3626 mg KOH
g− 1 of oil for SBO and JCO respectively. As observed in this Table 1, JCO
viscosity is higher than SBO. This parameter increases with the fatty acid
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Journal of Cleaner Production 372 (2022) 133739
alkyl chains chain lengths and decreases with decreasing degree of
saturation (Hellier et al., 2015), probably suggesting a higher percent­
age of saturated fatty acids such as palmitic acid in JCO. In this regard, it
has been also described that saturated fatty acid content improves the
oxidation stability of vegetable oils. Furthermore, non-saponifiable
components, such as tocopherols or phenol compounds, could also
significantly affect oxidative stability. The oxidation of vegetable oils is
the main cause of deterioration due to the loss of their nutritional value
and the formation of undesirable volatile compounds (Redondo-Cuevas
et al., 2018). The oxidative stability of crude jatropha oil was found to be
higher than refined soybean oil even though it contains Vitamin E,
which acts as an antioxidant to extend its shelf life. Further character­
ization is required to attribute this property to other possible compo­
nents present in JCO or the fatty acid composition.
3.2. Potassium ferrate characterization
The X-ray powder diffractogram of K2FeO4 and spent K2FeO4 are
shown in Fig. 1. The XRD pattern of the potassium ferrate (Fig. 1a)
A.N. Gutiérrez-López et al. Journal of Cleaner Production 372 (2022) 133739

Table 2 that the initial hexavalent iron compound is reduced to a more stable
Optimization of transesterification variables via Box–Behnken design (BBD) oxidation state. To explain this decomposition, a proposed reaction
using potassium ferrate as pseudo-catalyst for soybean oil (SBO) and Jatropha mechanism is presented in section 3.6.
curcas L. oil (JCO).
Stirring rate K2FeO4 (wt. methanol: SBO JCO
3.3. Transesterification reaction optimization via Box-Behnken
(RPM) %) oil Conversion Conversion
molar ratio (%) (%) experimental design
412.50 3.075 11:1 91.21 81.40
412.50 3.075 11:1 91.35 83.91
As explained in section 2.3, 15 transesterification reactions were
700 0.15 11:1 4.64 0 carried out for each vegetable oil (SBO and JCO) to analyze the effect of
412.50 0.15 6:1 2.43 0 the reaction variables: methanol to oil molar ratio (6:1–16:1), stirring
412.50 6.00 16:1 96.61 92.15 rate (125–700 RPM), and K2FeO4 dosage (0.15–6%). The conversion,
125 3.075 16:1 96.04 91.09
which was considered as the response variable, was obtained by FTIR
700 3.075 16:1 96.15 83.90
700 6.00 11:1 96.77 94.91 spectroscopy. The software Minitab 17.0.1 software was used to perform
700 3.075 6:1 87.83 64.28 regression, variance analysis (ANOVA), optimization plots, and contour
412.50 6.00 6:1 95.18 93.58 plots. The experiments and the response variable (conversion) are listed
125 0.15 11:1 14.87 0
in Table 2. The mathematical correlation between the variables and
125 3.075 6:1 88.40 37.93
412.50 0.15 16:1 1.68 0
conversion is given by the following second-order polynomial equations
125 6.00 11:1 95.26 89.65 in terms of uncoded units for each oil, SBO (1) and JCO (2):
412.50 3.075 11:1 93.69 83.95
a conversion = − 2.8 − 0.0356 RPM + 43.13 cat% + 1.96 MeOH
700 4.82 14.28:1 98.35 –
a
357 5.29 14.89:1 – 98.17 : oil + 0.000024 RPM*RPM − 4.811 cat%*cat − 0.0778 MeOH
a
Optimized reaction conditions for each oil. : oil*MeOH : oil + 0.00349 RPM*cat% + 0.00012 RPM*MeOH
: oil + 0.037 cat%*MeOH : oil (1)
shows the main characteristic peaks according to the reference pattern
ICDD 01-075-2468, indicating that the solid sample has an ortho­
conversion = − 95.2 + 0.1363 RPM + 36.50 cat% + 10.46 MeOH
rhombic structure with a Pnam space group: a = 7.6900 Å, b = 10.3280
Å, and c = 5.8550 Å. No peaks of any other phases or impurities were : oil − 0.000080 RPM*RPM − 3.541 cat%*cat% − 0.286 MeOH
detected. The spent K2FeO4 obtained from the reaction with SBO : oil*MeOH : oil + 0.00156 RPM*cat% − 0.00583 RPM*MeOH
(Fig. 1b) and JCO (Fig. 1c) display the most intense peaks at 35.5◦ and : oil − 0.029 cat%*MeOH : oil (2)
62.84◦ in 2θ, having a good agreement with the JCPDS file No. 19–0629
corresponding to magnetite (Fe2+ Fe3+ 2 O4). This compound presents an From the analysis of variance (ANOVA) shown in Table 3, it is
inverse spinel structure with a cubic unit cell. possible to determine the effect that each design factor, and their in­
Fig. 2a and b shows SEM images of the potassium ferrate obtained at teractions possess on the conversion of biodiesel. The correlation co­
2500 and 5000X, respectively. The morphology of the K2FeO4 sample efficients for SBO and JCO experiments were R2 = 0.9969 and R2 =
consists of irregular granular particles in the range from 2.5 to 7.5 μm in 0.9701, respectively. Both results are closer to unity, indicating good
its most elongated regions. Furthermore, lamellar structures can be agreement between the prediction model and experimental data. On the
observed both on the surface and in the spaces between the grains. Spent other hand, ANOVA analysis reveals that K2FeO4 dosage (Cat%) presents
K2FeO4 obtained from the reaction with SBO (Fig. 2c and d) and JCO the most significant influence on maximizing conversion in both systems
(Fig. 2e and f) consist of octahedrons of magnetite in the range of 6–8 (SBO and JCO). As observed in the low p-value for SBO (0.000) and JCO
μm, along with some amorphous and jagged-edged crystals. Fig. 3 de­ (0.000), as well as a high F value for SBO (1153.14) and JCO (127.61).
scribes the EDX analysis of (Fig. 3a) pristine K2FeO4 and spent K2FeO4 The effect of K2FeO4 dosage is also reflected in the conversion drop for
obtained from the reaction with SBO (Fig. 3b) and JCO (Fig. 3c). These both oils when the lower limit of this independent variable (0.150 wt%)
evaluations provide the elemental compositions of the samples, which is employed (Table 2). The interaction between K2FeO4 dosage and
confirm the results obtained by XRD. In Fig. 3a, the weight compositions methanol to oil molar ratio is shown in Fig. 4, which includes 3 contour
of oxygen, potassium, and iron are 31.24, 37.83, and 28.23%, respec­ plots for each set of experiments for SBO (a, b, c) and JCO (d, e, f). The
tively. A small amount of carbon (2.7%) was also identified, possibly due stirring rate was fixed to low (125), medium (412.5), and high levels
to atmospheric carbon dioxide absorption. In Fig. 3b and c, the weight (700) since it is the factor that least affects the transesterification reac­
composition of oxygen is 12.91% and 17.01% respectively. Iron weight tion, as also noted in the analysis of variance.
percentages are 78.00 and 73.81%, respectively. Carbon (2.92 and As observed when SBO is used, the maximum conversion zone is
3.68%, respectively) and potassium (5.55 and 5.50%, respectively) were wider throughout the methanol to oil molar ratio range when the
also detected, indicating the presence of other decomposition products K2FeO4 dosage is higher than 4 wt% regardless of the stirring rate
containing potassium. The spent K2FeO4 characterization demonstrated applied. The reaction conditions according to the statistical model for
SBO (700 RPM, 4.82 wt% Cat, 14.28:1 MeOH: oil) were experimentally

Table 3
Analysis of variance (ANOVA).
Source Analysis of variance

df Sum of squares Mean square F-value P-value

SBO JCO SBO JCO SBO JCO SBO JCO SBO JCO

Model 9 9 22656.1 21441.5 2517.3 2382.4 178.99 18.04 0.000 0.003

RPM 1 1 10.5 74.6 10.5 74.6 0.75 0.56 0.426 0.486
K2FeO4 1 1 16218.4 16850.6 16218.4 16850.6 1153.14 127.61 0.000 0.000
MeOH: oil 1 1 34.6 693.4 34.6 693.4 2.46 5.25 0.178 0.071
Lack of fit 3 3 66.5 656 22.2 218.7 11.45 102.95 0.081 0.010
Pure error 2 2 3.9 4.2 1.9 2.1

6
A.N. Gutiérrez-López et al.
Fig. 4. Contour plots showing the effects of K2FeO4 dosage (wt.%) and methanol: oil molar ratio on conversion at fixed stirring rate of 125, 412.5 and 700 RPM.
tested obtaining 98.35% of conversion. The area of maximum conver­
sion is reduced if the stirring rate is low when JCO is used, even if the
K2FeO4 dosage and methanol to oil molar ratio are increased. However,
a high stirring rate also generates a negative impact on conversion.
Accordingly, a medium stirring rate is required to minimize any mass
transfer limitation without affecting the reaction. The model suggested
the following reaction conditions for JCO: 357 RPM, 5.29 wt% Cat,
14.89:1 MeOH: oil, which were experimentally tested obtaining 98.17%
of conversion. The differences in behavior between the SBO and JCO
systems could be possibly due to the high viscosity of JCO and the im­
purities inherent to raw and unrefined vegetable oil. However, a similar
maximum conversion was achieved after optimization. It has been re­
ported that low amounts of methanol cause insufficient reagent mixing
and lead to poor conversion, on the contrary, excess of methanol in­
creases polarity and glycerol goes into the ester phase, producing a shift
in the equilibrium to the opposite direction and reducing the conversion
as a consequence (Hossain et al., 2021).
As mentioned before, the conversion was determined by a FTIR
calibration curve. The FTIR spectra of fatty acid methyl esters produced
using the optimized conditions for each SBO and JCO are shown in
Fig. 5. The peak located at 1435 cm− 1 corresponds to the asymmetric
7
Journal of Cleaner Production 372 (2022) 133739
bending of methyl ester group (CH3–O-). The peak at 1197 cm− 1 is
related to the H–C–O vibration. These two peaks appear in both SBO and
JCO FAMEs but not in the oils. Additionally, a peak corresponding to the
O–CH2–C bond can be observed at 1098 cm− 1 in both vegetable oils, but
it does not appear in the FAMEs. Confirming the oil conversion into fatty
acid methyl esters. No signals were detected at 1570 cm− 1 corre­
sponding to carboxylates (COO− ), confirming the absence of soaps.
3.4. Reaction time optimization
The conversion was monitored at 1, 5, 10, 15, 30, 45, 60, and 90 min
in the transesterification reactions for each type of oil, using the opti­
mized conditions obtained for each system: SBO (700 RPM, 4.82 wt%
Cat, 14.28:1 MeOH: oil) and JCO (357 RPM, 5.29 wt% Cat, 14.89:1
MeOH: oil). Through these experiments, it was possible to observe the
reaction progress to determine the minimum time in which maximum
conversion is achieved. The conversion over time is shown in Fig. 6 for
a) SBO and b) JCO. As observed, maximum conversion is obtained at 5
min of reaction, and it fluctuates over time without significant variation
using SBO. Using JCO, the reaction takes place quickly within 5 min and
then, conversion increases slowly, reaching the maximum conversion in
A.N. Gutiérrez-López et al. Journal of Cleaner Production 372 (2022) 133739

Fig. 5. FTIR spectra of SBO, JCO, and their respective fatty acid methyl esters.

90 min (98.65%). However, conversions greater than 98% can be ach­ simpler and more environmentally friendly reaction system.
ieved from 45 min in order to avoid increased energy expenditure due to
prolonged stirring times.
3.5. Determination of physicochemical properties of fatty acid methyl
Heterogeneous catalytic processes for transesterification are usually
esters
not as fast due to mass transfer limitations, and there are only a few
studies in this regard that achieve high conversions in a short time. A
The results of the physicochemical characterization of the JCO and
SBO conversion of 98.8% was obtained in 15 min using 1 wt%
SBO FAMEs are shown in Table 4. The permissible limits of the quality
Cs–Na2ZrO3 as catalyst at 65 ◦ C and 30:1 methanol: oil ratio (Torres-­
standard ASTM D6751 are also included. As observed, both FAMEs meet
Rodríguez et al., 2016). Another investigation achieved 100% of SBO
quality requirements. Kinematic viscosity is crucial for proper transport
conversion in 2 min using 3.33 wt% lithium-modified kalsilite as cata­
of fuel from the tank to the engine. Transesterification reduces the vis­
lyst at 120 ◦ C (Wen et al., 2010). However, these studies have limitations
cosity of vegetable oils to improve combustion, reduce emissions and
associated with the cost and scarcity of the elements of which the
prevent filter clogging (Ayetor et al., 2015). Viscosity increases with
catalyst is composed, as well as the high reaction temperatures required
increasing hydrocarbon chain length, and it is reduced with unsatura­
(i.e. heating consumption). No studies of fast heterogeneous catalytic
tion. JCO FAMEs present a higher viscosity than SBO FAMEs due to the
transesterification were found at room temperature. Therefore, this
physicochemical characteristics of the oil from which they are produced.
work represents an important contribution to reduce energy consump­
Flash point indicates the amount of unreacted alcohol remaining in the
tion due to the fact that high conversions were achieved in a short time,
biofuel. It is related to safety concerns involved in fuel handling and
no heating is required, neither the methanol condensation system nor
storage. In addition, flash point is reduced with the increment of unsa­
long periods of stirring. This implies the reduction of production costs, a
turation and increases with the hydrocarbon chain length (Carareto
greater competitiveness compared to other conventional processes and a
et al., 2012). This value is similar for both FAMEs but slightly lower for

8
A.N. Gutiérrez-López et al. Journal of Cleaner Production 372 (2022) 133739

more stable and less susceptible to oxidation. A high acid number, as a

measurement of free fatty acids, is undesirable since it can cause
corrosion of the internal combustion engine. Even though Jatropha
curcas L. oil has a high acid number, the resulting JCO FAMEs have an
acid number as low as SBO FAMEs. From the characterization, it can be
inferred that SBO FAMEs have a lower content of saturated fatty acids,
which results not only in lower viscosity, lower oxidative stability but
also in a lower cloud point and pour point, as expected. Potassium fer­
rate is a strong oxidant that can cause triglyceride oxidation; however,
the oxidative stability values meet the quality standard, and no other
negative effects can be observed in the JCO. The SBO FAMEs have lower
oxidative stability compared to its starting oil, so strategies such as
reducing the amount of K2FeO4 without significantly affecting conver­
sion should be considered, or even the addition of antioxidants to pre­
vent oxidation of unsaturated aliphatic chains.
The 1H-NMR spectra of (a) SBO, (b) SBO FAMEs, (c) JCO, and (d)
JCO FAMEs are shown in Fig. 7. Peaks located at 0.84–0.96 ppm regions
correspond to the terminal methyl protons (CH3) of the hydrocarbon
chain. Peaks between 1.28 and 2.33 ppm are associated with the
methylene (CH2) protons in the aliphatic chains and the peaks of
methylene bonded to carbon-carbon double bond appear at 2.63–2.79
ppm. The characteristic peak area corresponding to the methyl ester
protons (OCH3) appears at 3.62–3.63 ppm. These peaks can be observed
in both JCO and SBO FAMEs but are not detected in the vegetable oil
(Galvan et al., 2020). Likewise, Fig. 7 (b) and 7 (d) reveal that the
glyceride signal (CHCH2 proton coupling) usually appearing at
4.07–4.23 ppm is completely absent (referenced from the SBO and JCO
oils NMR spectra in Fig. 7), indicating that yield is similar to conversion
described in Table 2, with high purity of the reaction FAMES for both
oils (Ng and Yung, 2019). At 5.19–5.44 ppm, the vinyl group (HC– – CH)
of the unsaturated chains can be observed.

3.6. Transesterification mechanism catalyzed by potassium ferrate

Potassium ferrate has been known for decades as an effective oxidant

for the formation of aldehydes and ketones from primary (Delaude and
Laszlo, 1996) and secondary alcohols (Norcross et al., 1997). One of the
first theoretical studies on the oxidation of alcohols, alkanes, and al­
Fig. 6. Conversion over time using the optimized reaction conditions for (a) kenes by chromyl chloride (CrO2Cl2) was carried out by Rappe and
SBO, and (b) JCO obtained from the Box-Behnken experimental design. Goddard (1982) utilizing the Generalized Valence Bonds (GVB) calcu­
lations, concluding that oxidation of alcohols by high valent transition
metal oxides is initiated by addition of a metal oxo double bond to a
Table 4 α-C-H or an O–H bond followed by different reaction steps where radical
Physicochemical properties of soybean oil (SBO) and Jatropha curcas L. (JCO) species can be produced.
methyl esters produced at room temperature. Lee and Chen (1991) proposed a mechanism of mandelic acid and
Limits ASTM SBO JCO cyclobutanol oxidation by potassium permanganate This mechanism is
D6751 FAMEs FAMEs supposed to be comparable to how other high valent metal oxides react
Density (g cm− 3) 0.82–0.9 0.8665 0.8631 with alcohols (C–H or O–H activation), and the type of cleavage of
Kinematic Viscosity 40 ◦ C (mm2 1.9–6.0 4.0786 4.2512 metal-carbon or metal-oxygen bond (heterolytic or homolytic). The
s− 1 )
hexavalent iron contained in potassium ferrate is expected to have a
Flash point (◦ C) 130 min. 164 160
Heating Value (MJ kg− 1) – 39.4663 40.1968
similar performance in the oxidation of alcohols. Further investigations
Oxidative stability (h 3.0 min. 2.53 3.75 concluded that potassium ferrate oxidizes 2-propanol and mandelic acid
RANCIMAT) by a 2 + 2 addition between a metal-oxo double bond and an α-C-H
Acid number (mg KOH g− 1) 0.5 max. 0.0897 0.0897 bond, followed by homolytic cleavage of the resulting carbon-iron bond
Cloud point (◦ C) Report 1 2
under basic conditions. Furthermore, it is assumed that free radicals are
Pour point (◦ C) – − 2 − 1
formed as intermediate species in the reaction (Lee and Gai, 1993).
Kamachi et al. (2016) studied the methanol oxidation by ferrate ion
JCO FAMEs. The heating value refers to the amount of energy released (FeO2−4 ) and protonated ferrates (HFeO4 , H2FeO4) in aqueous solution
−

during combustion. This value is lower compared to fossil diesel as a
result of the oxygen incorporated in the biodiesel (Rahman et al., 2021).
The ASTM D6751 standard does not specify a minimum heating value
for biodiesel; however, a high heating value is desirable. Oxidative
stability refers to the susceptibility of biodiesel to degrade in the pres­
ence of oxygen due to the degree of unsaturation of fatty acids (Mairizal
et al., 2020). The oxidative stability of JCO FAMEs is higher than SBO
FAMEs possibly due to the high saturated fatty acid content, which are
from DFT calculations, focusing on a direct abstraction mechanism that
begins with the activation of the O–H or C–H bonds of alcohol by an oxo
group of monoprotonated and diprotonated ferrates, followed by the
subtraction of a hydrogen atom to form a methoxy radical (CH3O•).
Subsequently, the activation of a C–H bond of the radical by an oxo or
hydroxo ligand occurs to form formaldehyde.
In recent investigations, Ohta et al. (2001) described the methanol
oxidation mediated by protonated and no protonated ferrates in water

9
A.N. Gutiérrez-López et al.
Fig. 7. Proton nuclear magnetic resonance (1H-NMR) of (a) SBO, (b) SBO FAMEs, (c) JCO and (d) JCO FAMEs.
using the hybrid B3LYP DFT method. The oxidation is initiated by
activation of C–H and O–H bonds through two different mechanisms:
The addition-elimination and the direct abstraction mechanisms. The
first one involves the activation of C–H and O–H bonds of methanol and
cleavage for a hydrogen atom subtraction for an oxo or hydroxo ligand
of diprotonated ferrate, being the cleavage of the O–H bond the most
favorable initial step. In the second mechanism, the oxidation reaction
starts by a direct hydrogen atom abstraction from the C–H or O–H bond,
splitting in separate pathways until the methanol conversion to
10
Journal of Cleaner Production 372 (2022) 133739
formaldehyde. It was determined that the first steps in both mechanisms
are likely to occur due to the similarity in activation energy.
This previous theoretical evidence on the production of methoxide
radicals during the methanol oxidation by potassium ferrate could mean
that transesterification reactions carried out in the current study is not
fully governed by the conventional heterogeneous catalysis mechanisms
known to date, Langmuir-Hinselwood and Eley-Rideal (Marinković
et al., 2016), rather a variation is possible where methoxy radicals play a
fundamental role in the formation of methyl esters since methanol is not
A.N. Gutiérrez-López et al.
Fig. 8. Radical formation by partial oxidation of methanol by solid potassium ferrate.
completely oxidized to formaldehyde.
No experimental evidence has been found to support the reaction
pathways of theoretical studies mentioned above, also, these analyzes
were simulated in the aqueous phase and cannot be completely com­
parable with the conditions of the present study, which involve the use
of solid and dry potassium ferrate in an organic medium formed by a
mixture of oil and methanol. Thus, the current hypothesis is based on
how the methoxide radical is formed by the oxidation of methanol in
potassium ferrate (Fig. 8) and how these species carry out the formation
of methyl esters by reacting with triglycerides (Fig. 9). In Fig. 8, the
ferrate anion is completely solvated by interaction with the protons of
the methanol via hydrogen bonding and forming the diprotonated fer­
rate (Equation (1)). It is known that ferrate ion is more stable in alkaline
media than in acidic media, therefore, diprotonated ferrate initiates a
reduction chain reaction, releasing two methoxy anions to the bulk and
changing its oxidation state to a highly unstable and highly reactive
ferrate IV through a strong attraction of the resonant electrons of its
3K2 FeO4 + 12 CH3 OH + 4 JCO (or SBO)triglycerides → 3Fe(OH)2 + 12 FAMEs + 4 Glycerol (salts) + 3 O2 + 6K +
double bonds of oxygen (equation (2)). This may cause a chain pull
through hydrogen bonding with the methanol molecule, releasing two
methoxy radicals to the solution. FeIV is more reactive and unstable than
FeVI (Schmidbaur, 2018), so it will be reduced to iron (II) hydroxide
releasing two peroxy radicals (equation 3). Reduction of dry potassium
ferrate due to methanol oxidation would result in the formation of the
peroxy radical, the methoxy radical, and the methoxide anion. The
global reaction is shown in equation 4.
In Fig. 9, the transesterification reaction via free radicals is
11
Journal of Cleaner Production 372 (2022) 133739
presented. Free radicals are strong electrophiles and can easily attack
the oxygen double bond of the triglyceride, forming an intermediary
compound (equation 5). The free radical can reverse this reaction or can
continue with the reaction by breaking the C–O bond of the ester group
of triglycerides, forming a fatty acid methyl ester (FAME) and a
diglyceride free radical (equation 6). This free radical reaction can
proceed only limited by existing free radicals in the solution (equation
7).
During the transesterification experiments, oxygen bubbles were
observed. This can be explained by an attack of the peroxy radicals to the
living radicals of the glyceride molecule, extracting the electron, form­
ing the dioxygen molecule, and leaving its protons in the solution,
possibly forming the glycerol molecule. Finally, the methoxide anion
formed in equation (1) (Fig. 8) carries out the conventional trans­
esterification reaction. This reaction mechanism has been comprehen­
sively described elsewhere (Rodríguez-Ramírez et al., 2020).
The global chemical equation can be expressed as follows:
(10)
The oxidation state of hexavalent iron in potassium ferrate is reduced
during the transesterification reaction, thus, it can be considered as a
pseudo-catalyst since it is irreversibly involved in the reaction. Never­
theless, the cost of K2FeO4 is moderate, it does not require long residence
times, heating, or methanol condensing systems. Also, potassium ferrate
achieves high conversions and the methyl esters produced have no
carboxylate impurities. These considerations make it affordable to use it
A.N. Gutiérrez-López et al.
Fig. 9. Transesterification reaction via free radical mechanism.
on a larger scale to produce biodiesel in a single cycle at competitive
prices compared to conventional homogeneous processes using NaOH.
Analysis of ion chromatography for potassium ions in SBO and JCO
FAMES revealed concentrations of 0.796 and 0.758 mg kg− 1, respec­
tively. The EN 14 214 and ASTM D 6751 allow a maximum total po­
tassium concentration of 5 mg kg− 1, thus, confirming that potassium
leaching in the FAMEs is not occurring during the transesterification
reaction, even though the K2FeO4 is undergoing decomposition.
The formation of CH3O• could explain the fast catalysis at room
temperature. This radical is possibly the result of the high oxidation
potential of the FeO2− / 3+
4 Fe redox couple (2.2 V vs Standard Hydrogen
Electrode). High oxidation potentials above 2 V achieved with redox
pairs formed at low cost are not easy to find in materials science, which
is a requirement in the present system. Even though qualitative exper­
imental evidence exists, DFT simulation and experimental detection of
radical species involved in this hypothesis are needed to fully demon­
strate the validity of this unexplored transesterification reaction variant,
which may offer a new approach to quicker and cleaner biodiesel pro­
duction. This will be the motivation of a forthcoming analysis due to the
complexity involved to detect these radicals, and reactive intermediates
(short-lived) during the transesterification mechanism using K2FeO4 as
heterogenous pseudo-catalyst.
4. Conclusions
Potassium ferrate has been successfully shown to catalyze the
transesterification reaction at room temperature of SBO and JCO.
Maximum conversion under optimized reaction conditions of 98.35%
and 98.17% were obtained in 1 h, respectively. However, kinetic ex­
periments revealed that conversion of 98.31% is reached without
12
Journal of Cleaner Production 372 (2022) 133739
significant variation over time using SBO after 5 min. On the other hand,
a conversion of 92.63% was obtained at 5 min for JCO, reaching its
maximum conversion (98.65%) at 90 min, indicating that the K2FeO4
displays a different performance when it is applied to refined commer­
cial vegetable oil and crude vegetable oil, which may contain compo­
nents that interfere with the reaction such as tocochromanols
(tocopherols and tocotrienols), phytosterols, amino acids or saccharides
(Thi et al., 2018). Further characterization is necessary to identify these
components and their effect on K2FeO4 performance.
Through this method, the energy consumption of the reaction is
decreased by avoiding heating and reducing the stirring time due to its
fast kinetics; also, no water-cooled condenser is needed. During the
transesterification reaction, the K2FeO4 is reduced to Fe2+ Fe3+ 2 O4,
however it is a low-cost pseudo-catalyst that achieves high conversion in
a short time at room temperature. Also, the methyl esters produced do
not contain carboxylate impurities. The energy savings can be reflected
in the reduction of the production cost. These factors make potassium
ferrate a good candidate for producing environmentally friendly bio­
diesel on a large scale in a single cycle, which makes it competitive
against the conventional transesterification reaction with NaOH. From
biodiesel characterization, it can be inferred that due to the strong
oxidizing power of potassium ferrate, the oxidative stability of the bio­
diesel is reduced. It is recommended to add antioxidants to vegetable
oils before the transesterification reaction to avoid fatty acid chains
oxidation. Other quality parameters are not affected and comply with
the ASTM D6751.
The high conversions achieved and the short reaction times even at
room temperature indicate that the catalytic process herein studied
presents low energy consumption, thus, reducing the overall production
cost using green environmental conditions.
A.N. Gutiérrez-López et al.
CRediT authorship contribution statement
Adriana N. Gutiérrez-López: Investigation, Funding acquisition,
Experimental data acquisition, Data treatment, Data curation. Violeta
Y. Mena-Cervantes: Conceptualization, Formal analysis, Collection and
Discussion of XRD and SEM analyses. Mario A. González-Espinosa:
Determination of physicochemical parameters of biodiesel. Fabiola S.
Sosa-Rodríguez: Formal analysis, Collection and Discussion of Chro­
matography analysis. Jorge Vazquez-Arenas: Methodology, Writing –
original draft, preparation, Writing – review & editing. Ricardo
Rodríguez-Ramírez: Catalyst characterization; Mechanism of methoxy
radical formation. Raúl Hernández-Altamirano: Conceptualization,
Collection and discussion of FT-IR analysis and 1H-NMR spectrum.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
The authors thank the Consejo Nacional de Ciencia y Tecnología de
México for the financial support through the Project No. 315787.
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