Results in Engineering 22 (2024) 102202

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Results in Engineering
journal homepage: www.sciencedirect.com/journal/results-in-engineering

Preparation CaO/MgO/Fe3O4 magnetite catalyst and catalytic test for

biodiesel production
Widayat a, b, *, Hantoro Satriadi a, Prambudi Widi Setyojati a, Dimas Shihab a, Luqman Buchori a,
Hadiyanto Hadiyanto a, c, **, Faustina Alda Nurushofa a
a
Department of Chemical Engineering, Faculty of Engineering, Diponegoro University, 50275, Semarang, Central Java, Indonesia
b
Advanced Material Laboratory Central Laboratory for Research and Service Unit, Diponegoro University, 50275, Semarang, Central Java, Indonesia
c
Center of Biomass and Renewable Energy (CBIORE), Diponegoro Univerity, Indonesia

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

Keywords: Biodiesel is a promising renewable fuel with lower emissions and environmental friendly. This research inves­
Biodiesel tigated the potential of a CaO/MgO/Fe3O4 nanomagnetic catalyst synthesized from dolomite and iron sand for
CaO/MgO/Fe3O4 biodiesel production from waste cooking oil. The influence of catalyst loading, Fe3O4:CaO/MgO mass ratio, and
Magnetic catalyst
calcination temperature on biodiesel yield was investigated and the catalyst was characterized using XRD, SEM,
Simultaneous esterification-transesterification
and PSA techniques. The optimal reaction conditions were found at 1 % w/w catalyst loading, Fe3O4:CaO/MgO
weight ratio of 1:7.5 w/w, and 1000 ◦ C calcination temperature, which result in 95.640 % yield. The produced
biodiesel has fulfill the quality standards for density and viscosity. This work also demonstrates the effectiveness
of CaO/MgO/Fe3O4 nanomagnetic catalysts for sustainable biodiesel production from waste feedstock, offering a
promising approach for waste management and cleaner fuel alternatives.

1. Introduction required for the reaction, leading to a faster reaction rate and quicker
equilibrium attainment. The three main types of commonly used cata­
Global energy consumption is projected to increase by 28 % from lysts are acid catalysts, base catalysts, and biocatalysts [5]. However,
2015 to 2040 which isdriven by rapid industrialization (U.S. EIA, 2017). strong acid and base catalysts have several drawbacks, including being
This rising energy demand and reliance on fossil fuels have triggered corrosive to equipment, causing fatty acid saponification (soap forma­
energy crises and environmental degradation. Rising demand across tion), generating excessive waste, and potentially releasing hazardous
sectors and escalating oil prices are driving the depletion of fossil fuels waste into the environment [6].
[1]. Biodiesel, a renewable liquid fuel, offers a solution with lower Research on improving catalyst efficiency for biodiesel production is
emissions and environmental friendliness. still progressing especially in heterogenous catalyst. One promising area
Biodiesel is a renewable liquid fuel produced through the trans­ is nanomagnetic catalysts, which are essentially oxide-supported metal
esterification reaction of biomass such as vegetable and animal oils or catalysts. These minimize catalyst loss and simplify the purification
fats, including waste cooking oil [2]. Its use has proven advantages in process, making the catalyst reusable [7]. The large specific surface
reducing carbon monoxide (CO), nitrogen oxides (NOx), sulfur oxides area, a characteristic of nanomaterials, in nanomagnetic catalysts pro­
(SOx), hydrocarbons, and air particulates that cause adverse effects such vides more active sites for reaction to occur. The greater the surface
as ozone depletion, smog, acid rain, and global warming [3]. Catalysts area, the less catalyst is required [8].
play a crucial role in facilitating the transesterification reaction and Iron sand has the potential as a feedstock for Fe3O4 synthesis due to
achieving high biodiesel yields under milder conditions [4]. its dominant iron content, around 76.61 % before extraction and 78.60
The utilization of various catalysts has significantly increased in % after extraction [9–11]. Widayat et al. [10] developed iron as catalyst
recent years to enhance biodiesel production efficiency through trans­ in biodiesel production using used cooking oil as raw material. In this
esterification. Catalysts function by lowering the activation energy reserach, the biodiesel and Fatty Acid Methyl Ester (FAME) content l

* Corresponding author. Department of Chemical Engineering, Faculty of Engineering, Diponegoro University, 50275, Semarang, Central Java, Indonesia.
** Corresponding author. Center of Biomass and Renewable Energy (CBIORE), Diponegoro Univerity, Semarang, Indonesia
E-mail addresses: [email protected] (Widayat), [email protected] (H. Hadiyanto).

https://doi.org/10.1016/j.rineng.2024.102202
Received 5 October 2023; Received in revised form 26 April 2024; Accepted 28 April 2024
Available online 1 May 2024
2590-1230/© 2024 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
Widayat et al. Results in Engineering 22 (2024) 102202

obtained by using α-Fe2O3– Al2O3 catalyst could reached yield of 86.78 This includes the optimal ratio of CaO/MgO to Fe3O4, the impact of
% and FAME content of 87.88 %, respectively. Gardy et al. [12] con­ calcination temperature, and how the catalyst characteristics, analyzed
ducted an experiment using SO4/Mg–Al–Fe3O4 nanomagnetic catalyst using XRD, SEM, and PSA, affect biodiesel production from waste
and obtained a biodiesel yield of 98.5 % under operating conditions of cooking oil. Additionally, the research examined the characteristics of
95 ◦ C for 5 h. Research by Aleman-Ramirez et al. [13] using CaO/Fe3O4 the produced biodiesel and how catalyst treatment influences the yield.
catalyst achieve 95.33 % biodiesel yield under the best conditions of
soybean oil molar ratio of 12:1, a catalyst load of 4 wt%, a reaction 2. Material and methods
temperature of 65 ◦ C and a reaction time of 120 min. Widayat et al. [10]
also developed of MgO-Cao/SiO2 as catalyst in biodiesel production. The 2.1. Materials
result shows that the best variable to produce biodiesel is at the ratio of
MgO–CaO: SiO2 is 15:85. The conversion of biodiesel using this variable The materials used in this study were iron sand and dolomite as the
is 92.63 %. main ingredients for making catalysts, NH4OH as magnetite pre­
Biodiesel production relies heavily on catalysts, but finding cost- cipitants, methanol as the main ingredients for biodiesel, aquadest, and
effective and efficient options remains a challenge. This research HCl as solvent, waste cooking oil as the main ingredient for biodiesel.
explored a promising new avenue: utilizing dolomite (CaMg(CO3)2), a The equipment used is a three-neck flask, thermometer, heater, mag­
readily available mineral, as a nanomagnetic catalyst (CaO/MgO/ netic stirrer, furnace, 250 ml glass beaker, 1000 ml glass beaker, oven,
Fe3O4). While dolomite has applications in other catalyst types [14], its scales, dropper, stirrer, separating funnel, and Buchner filter. The
potential for biodiesel production with this specific nanomagnetic specification and model of the equipment used in this study were
structure is underexplored. The research investigated how various fac­ identical to Prameswari et al. (2022).
tors influence the performance of this novel dolomite-based catalyst.

Fig. 1. Schematic diagram of this research.

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Widayat et al. Results in Engineering 22 (2024) 102202

2.2. Methods Biodiesel viscosity was measured using an Oswald viscometer. The
viscosity was then calculated using the following equation:
2.2.1. Raw material preparation ρx . tx
Fe3O4 was synthesized from iron sand using a co-precipitation ηx = .η (2)
ρa . ta a
method in a hydroxide medium [15]. The chemical co-precipitation
began by adding 20 g of iron sand to 35 ml solution of 12 M HCl at where ηx represents the viscosity of biodiesel, ρx represents the density
70 ◦ C with constant magnetic stirring for 30 min (see Fig. 1). The of biodiesel, tx is the time taken for the biodiesel to flow from one point
resulting solution was then filtered using filter paper to remove any to another in the viscosimeter, ηa represents the viscosity of water, ρa
undissolved iron sand particles. Next, 50 ml of NH4OH was added to the represents the density of water, and ta is the time taken for water to flow
filtrate and stirred for 30 min at 70 ◦ C. This reaction yielded a dark from one point to another in the viscosimeter. Finally, the density of
precipitate, which was the newly formed magnetite. The precipitate was biodiesel was measured using a pycnometer and calculated using the
thoroughly washed with distilled water to remove any impurities and following equation:
finally dried in an oven at 70 ◦ C for 1 h.
Dolomite rock was ground using a mortar and pestle to achieve ρ=
(mass of pycnometer + biodiesel) − (mass of pycnometer)
(3)
uniform particle size. The resulting powder was then calcined at 700 ◦ C volume of picnometer
for 2 h in a tube furnace.
3. Result and discussions
2.2.2. Synthesis CaO/MgO/Fe3O4 catalyst
The synthesis of CaO/MgO/Fe3O4 catalysts involved varying weight 3.1. Catalyst characterization
ratios. Specifically, Fe3O4 and CaO/MgO were weighed in ratios of 1:7.5
w/w and 1:5 w/w. First, CaO/MgO was dissolved in 250 ml of distilled 3.1.1. XRD
water and stirred until homogeneous. Fe3O4 was then added to the so­ The X-ray Diffraction (XRD) analysis provides valuable information
lution and stirred using a magnetic stirrer on a hot plate. The stirring about the phases present in the CaO/MgO/Fe3O4 catalyst sample. The
process continued for 4 h at 70 ◦ C with a speed of 700 rpm. The resulting results are typically presented as a diffractogram, a graph with peaks on
slurry was dried in an oven at 105 ◦ C for 6 h to remove H2O and any the y-axis (diffraction intensity) corresponding to specific diffraction
residual HNO3. Finally, the dried slurry underwent calcination at vary­ angles (2θ) on the x-axis. This study employed XRD to analyze CaO/
ing temperatures: 700 ◦ C, 850 ◦ C, and 1000 ◦ C, for 4 h each. The syn­ MgO/Fe3O4 catalysts prepared under different conditions, varying
thesized catalysts were then characterized for further analysis. Fe3O4 content and calcination temperature. The following section pre­
sents the XRD results for these samples.
2.2.3. Catalyst characterization Fig. 2 shows the same diffraction peaks for each calcination tem­
The prepared catalysts were analyzed using X-ray diffraction (XRD), perature at variable mass ratios of Fe3O4:CaO/MgO 1:7.5 and 1:5 w/w.
scanning electron microscopy (SEM), and Particle Size Analysis (PSA) to Data regarding crystallinity are shown in Table 1 and data regarding
determine their composition, crystallinity, surface morphology, and lattice parameters and hkl are shown in Table 2.
particle size distribution. XRD was performed using a Shimadzu XRD- At a calcination temperature of 700 ◦ C there are the same peaks for
7000 instrument. The diffraction patterns were measured at 30 mA the CaO2 (portlandite, ICDD: 96-901-0902), CaCO3 (calcite, ICDD: 96-
current and 30 kV voltage using Cu radiation with a wavelength (λ) of 900-1299), and Fe3O4 (ICDD: 96-900-2027) phases. The CaO2 peaks
1.54 Å (Å). The diffraction pattern was observed at 2θ angles ranging were detected at 2θ = 18.51◦ , 34.55◦ , 47.52◦ , and 51.26◦ , while the
from 10◦ to 90◦ with a step time of 0.4 s. X’Pert HighScore software peaks belonging to CaCO3 were detected at 2θ = 23.51◦ , 29.85◦ , 36.41◦ ,
(copyright PANalytical 2024) was used to identify the components 39.85◦ , 47.54◦ and 48.93◦ . Additionally, low intensity peaks were
based on the obtained peak intensities. The SEM analysis was carried out observed at 2θ = 47.45◦ and 64.93◦ , corresponding to Fe3O4.
using a JEOL JSM6510LA SEM instrument at 20 kV accelerating voltage At a calcination temperature of 850 ◦ C there are the same peaks for
and 1.00000 nA probe current. Meanwhile, the PSA analysis was per­ the CaO2 phase (portlandite, ICDD: 96-901-0902) at 2θ = 18.36◦ ,
formed using a Laser Particle Analyzer LLPA-C10 with an ultrasonic time 29.05◦ , 34.42◦ , 47.35◦ , 51.16◦ , 54.68◦ , and 65.45◦ . The CaO phase
of 120 s and water as the dispersing medium. (lime, ICDD: 96-101-1328) was detected at 2θ = 32.56◦ , 37.7◦ , 54.18◦ ,
64.46◦ , and 67.67◦ . MgCO3 calcination occurs at a lower temperature
2.2.4. Biodiesel production and much faster than CaCO3 [16] so that at a temperature of 850 ◦ C
The performance of the synthesized CaO/MgO/Fe3O4 catalyst was MgO2 is formed. MgO2 (brucite, ICDD: 96-900-2349) peaks were
evaluated by producing biodiesel through a simultaneous esterification- detected at 2θ = 18.82◦ , 37.72◦ , and 50.39◦ . Additionally, low intensity
transesterification reaction. Methanol and waste cooking oil were peaks were observed at 2θ = 54.92◦ and 64.95◦ , corresponding to Fe3O4
combined in a three-neck flask at a ratio of 9:1 (methanol to oil). The (ICDD: 96-900-2027).
CaO/MgO/Fe₃O₄ catalyst was then added to the mixture in varying At a calcination temperature of 1000 ◦ C there are the same peaks for
amounts (1 % and 2 % w/w WCO). The mixture was heated to 60 ◦ C the CaO2 (portlandite, ICDD: 96-900-6833), CaO (lime, ICDD: 96-101-
under stirring at 1100 rpm. After a reaction time of 6 h, the mixture was 1328), and Fe3O4 (ICDD: 96-900-2027) phases. The CaO2 peaks were
separated. The magnet effectively removed the catalyst, while a sepa­ detected at 2θ = 18.39◦ , 29.08◦ , 34.46◦ , 47.41◦ , 51.19◦ , and 64.51◦ ,
rating funnel facilitated the separation of methanol from the biodiesel while the peaks belonging to CaO were detected at 2θ = 32.65◦ , 37.79◦ ,
product. 54.27◦ , and 64.55◦ . CaCO3 calcination occurs after MgCO3 is fully
calcined and decomposes into Calcium Oxide (CaO) [16]. Additionally,
2.2.5. Biodiesel characterization low intensity peaks were observed at 2θ = 38.24◦ and 61.87◦ , corre­
This study evaluated the performance of the CaO/MgO/Fe3O4 cata­ sponding to Fe3O4.
lyst by analyzing the yield, viscosity, and density of the biodiesel pro­ The confirmation of Fe3O4 in all catalyst variables shows that the
duced. Yield, defined as the mass ratio of the product (biodiesel) to the catalyst synthesis was successful. The formation of CaO2 and MgO2
raw material (waste cooking oil, WCO), was calculated using Equation phases caused by the calcination of dolomite (CaMg(CO3)2) was con­
(1): ducted in an open tube furnace. This method inadvertently exposed the
sample to ambient air with water vapor [17].
mass of biodiesel (g)
Yield = x 100% (1)
mass of WCO (g)

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Widayat et al. Results in Engineering 22 (2024) 102202

Fig. 2. XRD analysis results of CaO/MgO/Fe3O4 catalyst at variations (a) Fe3O4:CaO/MgO weight ratio of 1:7.5 w/w; (b) Fe3O4:CaO/MgO weight ratio of 1:5 w/w.

Table 1
Crystallinity of CaO/MgO/Fe3O4 catalyst.
Catalyst Variation Crystallinity (%)

Fe3O4:CaO/MgO weight ratio of 1:7,5 w/w, 700 ◦ C 28,91

Fe3O4:CaO/MgO weight ratio of 1:5 w/w, 700 ◦ C 27,58
Fe3O4:CaO/MgO weight ratio of 1:7,5 w/w, 850 ◦ C 33,10
Fe3O4:CaO/MgO weight ratio of 1:5 w/w, 850 ◦ C 30,44
Fe3O4:CaO/MgO weight ratio of 1:7,5 w/w, 1000 ◦ C 24,04
Fe3O4:CaO/MgO weight ratio of 1:5 w/w, 1000 ◦ C 23,22

Table 2
Lattice parameter and hkl of CaO/MgO/Fe3O4 catalyst.
Compound Peak hkl Lattice parameter (Å) Crystal system

CaO2 (portlandite) 34.55 [011] 2,59 Hexagonal

CaCO3 (calcite) 36.41 [110] 2,47 Hexagobal
CaO (lime) 37.7 [002] 2.38 Cubic
MgO2 (brucite) 18.82 [001] 4.71 Hexagonal
Fe3O4 64.93 [144] 1,43 Cubic

3.1.2. SEM
Scanning Electron Microscopy (SEM) was employed to analyze the
surface morphology and shape of the CaO/MgO/Fe3O4 catalyst. SEM
works by capturing and processing secondary electrons emitted from the
catalyst surface, ultimately generating a high-resolution image that re­
veals the material’s morphology. The following results present the SEM
characterization of the CaO/MgO/Fe₃O₄ catalyst sample at 5000×
magnification.
Based on SEM analysis (Fig. 3), the surface morphology of the CaO/
MgO/Fe3O4 catalyst synthesized from dolomite and iron sand shows
uneven particle distribution and varying particle sizes, which indicates
Fig. 3. Morphology of the CaO/MgO/Fe3O4 catalyst with 5000× magnification
the formation of Fe3O4 on the catalyst [18]. Apart from that, there are at variations (a) Fe3O4:CaO/MgO 1:7.5 w/w; 700oC (b) Fe3O4:CaO/MgO 1:5 w/
voids and pores which indicate the presence of CaO in the catalyst [18], w; 700oC (c) Fe3O4:CaO/MgO 1:7.5 w/w; 850oC (d) Fe3O4:CaO/MgO 1:5 w/w;
and agglomeration of MgO and CaO particles from dolomite [18]. 850oC (e) Fe3O4:CaO/MgO 1:7.5 w/w; 1000oC (f) Fe3O4:CaO/MgO 1:5 w/
w; 1000oC.
3.1.3. PSA
The synthesized CaO/MgO/Fe3O4 catalysts were analyzed using a Fe3O4 catalyst in the variable d has an average of 49.536 μm, the particle
Particle Size Analyzer (PSA) to determine their particle size and distri­ size of the CaO/MgO/Fe3O4 catalyst in the variable e has an average of
bution. Water was used as the dispersing medium in this analysis. The 43.113 μm, and the particle size of the catalyst CaO/MgO/Fe3O4 in the
results of the PSA measurements will be presented as follows. variable f has an average of 37.279 μm.
The particle size distribution of the CaO/MgO/Fe3O4 catalysts, as The overall particle size of the catalyst with a Fe3O4:CaO/MgO mass
determined by PSA analysis (Fig. 4), reveals variations across the ratio of 1:5 w/w is larger than that of 1:7.5 w/w due to the addition of
different preparation conditions (see Fig. 3). The particle size of the more Fe3O4 mass to the catalyst. As the temperature increases, the
CaO/MgO/Fe3O4 catalyst in variable a has an average of 17.518 μm, the particle size of the catalyst also increases. This is due to the nano­
particle size of the CaO/MgO/Fe3O4 catalyst in variable b has an average sintering process caused by heating during the calcination process.
of 20.712 μm, the particle size of the CaO/MgO/Fe3O4 catalyst in var­ Sintering is easier on rougher surfaces than on flatter surfaces. This al­
iable c has the average of 35.595 μm, the particle size of the CaO/MgO/ lows multiple particles to merge and form larger sizes [19].

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Widayat et al. Results in Engineering 22 (2024) 102202

Fig. 4. Graph of PSA test results for CaO/MgO/Fe3O4 catalyst with variations (a) Fe3O4:CaO/MgO 1:7.5 w/w; 700oC (b) Fe3O4:CaO/MgO 1:5 w/w; 700oC (c) Fe3O4:
CaO/MgO 1:7.5 w/w; 850oC (d) Fe3O4:CaO/MgO 1:5 w/w; 850oC (e) Fe3O4:CaO/MgO 1:7.5 w/w; 1000oC (f) Fe3O4:CaO/MgO 1:5 w/w; 1000oC.

In the analysis using the Particle Size Analyzer method, the resulting
Table 3
particle size is still relatively large at a micro scale. This is because water
Biodiesel analysis results.
is used as a dispersing medium during the measurement, which allows
the agglomeration process to occur. The possibility of small particles Test parameters

joining together is caused by the very large size of water molecules. This Density Viscosity % %
is one possible explanation for the analysis results [19]. (kg/m3) (cSt) FFA Yield

SNI 850–890 Max 6 at <1

400C
3.2. Biodiesel characterization
Variable 1 (700oC, Fe3O4:CaO/ 883 5.50 0.289 93.641
MgO 1:7.5 w/w, 1%w/w CaO/
This study evaluated the characteristics of the produced biodiesel MgO/Fe3O4)
through three key parameters: density, viscosity, and free fatty acid Variable 2 (700oC, Fe3O4:CaO/ 874 5.69 0.292 90.527
MgO 1:5 w/w, 1%w/w CaO/
(FFA) content. Density and viscosity measurements served as a reference
MgO/Fe3O4)
for product conformity with the Indonesian National Standard (SNI) for Variable 3 (700oC, Fe3O4:CaO/ 882 5.41 0.290 85.653
biodiesel. Conversely, FFA content analysis aimed to assess the catalyst’s MgO 1:7.5 w/w, 2%w/w CaO/
performance in the waste cooking oil esterification reaction. Table 3 MgO/Fe3O4)
presents the results of the biodiesel, including density, viscosity, %FFA, Variable 4 (700oC, Fe3O4:CaO/ 888 5.86 0.288 84.407
MgO 1:5 w/w, 2%w/w CaO/
and %yield.
MgO/Fe3O4)
According to SNI 7182-2015, good quality biodiesel has a density of Variable 5 (850oC, Fe3O4:CaO/ 882 5.43 0.289 93.729
0.85–0.9 gr/ml and a viscosity of 2.3–6 cSt. The density and viscosity of MgO 1:7.5 w/w, 1%w/w CaO/
the biodiesel obtained in this study meet the quality standards of SNI MgO/Fe3O4)
7182-2015, indicating good quality. Variable 6 (850oC, Fe3O4:CaO/ 882 5.38 0.290 90.712
MgO 1:5 w/w, 2%w/w CaO/
MgO/Fe3O4)
3.3. Effect of catalyst treatment on biodiesel yield Variable 7 (850oC, Fe3O4:CaO/ 886 5.87 0.288 85.663
MgO 1:7.5 w/w, 1%w/w CaO/
MgO/Fe3O4)
This study investigated the effects of several factors on biodiesel Variable 8 (850oC, Fe3O4:CaO/ 884 5.80 0.289 85.819
yield. These factors included variations in calcination temperature MgO 1:5 w/w, 2%w/w CaO/
(700 ◦ C, 850 ◦ C, and 1000 ◦ C), the composition of Fe₃O₄ and CaO/MgO MgO/Fe3O4)
(1:7.5 and 1:5 w/w), and the amount of catalyst used during biodiesel Variable 9 (1000oC, Fe3O4:CaO/ 882 5.41 0.290 95.640
MgO 1:7.5 w/w, 1%w/w CaO/
production (1 % w/w and 2 % w/w). The results of the biodiesel yield
MgO/Fe3O4)
analysis are presented in Fig. 5. Variable 10 (1000oC, Fe3O4: 880 5.32 0.290 91.629
According to the presented graph, there is an inverse relationship CaO/MgO 1:5 w/w, 2%w/w
between catalyst loading and biodiesel yield. As the amount of catalyst CaO/MgO/Fe3O4)
Variable 11 (1000oC, Fe3O4: 880 5.78 0.290 86.084
used increases, the biodiesel yield decreases, and vice versa. The highest
CaO/MgO 1:7.5 w/w, 1%w/w
biodiesel yield was achieved with the addition of 1 % w/w CaO/MgO/ CaO/MgO/Fe3O4)
Fe3O4 catalyst with Fe3O4:CaO/MgO weight ratio of 1:7.5 w/w and a Variable 12 (1000oC, Fe3O4: 883 5.74 0.289 86.316
calcination temperature of 1000 ◦ C, resulting in a yield of 95.640 %. CaO/MgO 1:5 w/w, 2%w/w
This result exceeds that of Xie & Wang [20], who used a magnetic CaO/MgO/Fe3O4)

Fe3O4/SiO2 nanocatalyst functionalized with polymeric acidic IL. In

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Widayat et al. Results in Engineering 22 (2024) 102202

Fig. 5. Effect of catalyst treatment on biodiesel yield.

their study, the highest biodiesel yield of 93.3 % was obtained through form inactive compounds, and can also form complexes with free fatty
simultaneous esterification-transesterification with reaction conditions acids in the oil, blocking access to active sites. Fe3O4 also suffers from
of substrate molar ratio 35:1, catalyst loading 9 wt%, reaction time 6 h, leaching in methanol and oil, especially under acidic conditions. Dis­
and reaction temperature 120 ◦ C. solved Fe3O4 reacts with water and methanol to form inactive species,
The use of 1 % w/w catalyst allows for the simultaneous and can be reduced by waste cooking oil components into less active
transesterification-esterification reaction and influences the resulting forms. This leaching phenomenon has detrimental consequences. It re­
biodiesel yield. However, the addition of 2 % w/w catalyst did not in­ duces the catalyst’s ability to speed up the reactions, leading to lower
crease the biodiesel yield. According to Xia et al. [21], this can occur biodiesel yields. Leached metals can also contaminate the biodiesel,
because diffusion between methanol, oil and catalyst is limited. The increasing its color and lowering its quality.
addition of excessive catalyst will increase the viscosity of the mixture,
consequently inhibiting the mass transfer of reactants to the catalyst 4. Conclusion
surface, causing diffusion problems. This increase in catalyst concen­
tration also results in saponification because the FFA in the oil raw This study successfully produced and characterized an CaO/MgO/
material reacts with the excess catalyst to form a very thick product and Fe3O4 catalyst for biodiesel production. XRD analysis confirmed the
makes the separation of the desired product difficult so that the resulting presence of both CaO/MgO and Fe3O4, while SEM and PSA analysis
biodiesel yield is also low [22]. revealed spiky clusters with an average size of 33.959 μm. Higher
Apart from the use of 1 % w/w and 2 % w/w CaO/MgO/Fe3O4 cat­ calcination temperatures increased the Fe3O4 content and decreased
alysts with Fe3O4:CaO/MgO weight ratios of 1:7.5 and 1:5 w/w, CaO/MgO due to material dehydration. The Fe3O4:CaO/MgO weight
respectively, there is a decrease in the biodiesel yield. Conversely, ratios of 1:7.5 w/w yielded more biodiesel compared to 1:5 w/w because
increasing the calcination temperature increases the biodiesel yield with excessive support material in the 1:5 w/w Fe3O4:CaO/MgO mass ratio
increasing temperature. The addition of Fe3O4 support to the MgO disrupts active sites. Increasing catalyst use lowered the yield due to
catalyst aims to modify the catalyst in hopes of obtaining CaO/MgO/ higher viscosity hindering reactant-catalyst contact. Optimal conditions
Fe3O4 catalysts with better catalytic activity. However, excessive addi­ for biodiesel production from waste cooking oil were found to be 1 % w/
tion of support will lower catalytic activity as the performance of the w catalyst loading, Fe3O4:CaO/MgO weight ratio of 1:7.5 w/w, and
main catalyst is disrupted by the addition of excess support catalyst. The 1000 ◦ C calcination temperature, resulting in a 95.640 % yield. The
increase in biodiesel yield due to the increase in calcination temperature produced biodiesel met quality standards for density and viscosity ac­
will make the catalyst activation process faster and more complete, so cording to SNI 7182-2015. This study highlights the potential of CaO/
that the catalytic activity of CaO/MgO/Fe3O4 becomes greater with MgO/Fe3O4 catalysts for efficient biodiesel production from waste
increasing temperature during the calcination process [23]. cooking oil, promoting sustainable energy and waste management
practices.

3.4. Catalyst leaching Funding

Leaching is the loss of active components from a solid catalyst into This work was supported and funded by World Class Research
the liquid where the reaction takes place. This causes deactivation of the Diponegoro University Year 2023 grant (grant no. 609-124/UN.7D2/
catalyst, thereby reducing its ability to speed up the reaction. Leaching is PP/VIII/2023).
a serious problem because of its irreversible nature. The main causes of
leaching include the solubility of some of the active species of the CRediT authorship contribution statement
catalyst in the liquid, especially water, as well as chemical reactions
between the solvent or other components in the liquid and the catalyst, Widayat: Data curation, Formal analysis, Methodology, Supervision.
producing dissolved substances that are carried away by the liquid [24]. Hantoro Satriadi: Methodology, Project administration. Prambudi
Leaching is a major concern for CaO/MgO/Fe3O4 catalysts used in Widi Setyojati: Investigation. Dimas Shihab: Validation, Visualization.
biodiesel production [25]. Both CaO/MgO and Fe3O4 components can Luqman Buchori: Investigation. Hadiyanto Hadiyanto: Methodology.
leach out, negatively impacting catalyst performance. CaO/MgO Faustina Alda Nurushofa: Investigation.
leaching occurs due to its slight solubility in methanol and waste
cooking oil, which increases with temperature and methanol concen­
tration [9,26]. Dissolved CaO/MgO reacts with methanol and water to

6
Widayat et al. Results in Engineering 22 (2024) 102202

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interests or personal relationships that could have appeared to influence A core-shell SO4/Mg-Al-Fe3O4 catalyst for biodiesel production, Appl. Catal. B
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