Fuel 315 (2022) 123246

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Fuel
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Full Length Article

The effect of process parameters and catalyst support preparation methods

on the catalytic efficiency in transesterification of sunflower oil over
heterogeneous KI/Al2O3-based catalysts for biodiesel production
Miloš Marinković a, Hadi Waisi a, b, Stevan Blagojević a, Aleksandra Zarubica c,
Radomir Ljupković c, Aleksandra Krstić c, Bojan Janković b, c, *
a
University of Belgrade, Institute of General and Physical Chemistry, Studentski trg 12/V, P.O. Box 45, 11158 Belgrade, Serbia
b
Faculty for Ecology and Environmental Protection, University Union-Nikola Tesla, Cara Dušana 62-64, 11000 Belgrade, Serbia
c
University of Niš, Department of Chemistry, Faculty of Science and Mathematics, Višegradska 33, 18000 Niš, Serbia
d
University of Belgrade, Department of Physical Chemistry, “Vinča” Institute of Nuclear Sciences – National Institute of the Republic of Serbia, Mike Petrovića Alasa 12-
14, P.O. Box 522, 11001 Belgrade, Serbia

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

Keywords: The essence of this study is synthesis of a newly developed and efficient heterogeneous catalyst based on
Heterogeneous catalysis aluminum oxide support promoted with potassium iodide (KI) as active dopant responsible for pronounced
Biodiesel production catalyst activity. Modified sol–gel, reflux and hydrothermal method were used for synthesis of aluminum-oxide
Potassium loaded alumina
support using aluminum isopropoxide as a precursor. The γ-Al2O3 support and KI/γ-Al2O3 catalyst samples were
Process parameters
Transesterification
examined by various experimental techniques. Effects of several operational parameters were considered and
those are: methanol to sunflower oil molar ratio, catalyst loadings, reaction time and reaction stirring rate. The
obtained results indicated that modified sol–gel method for synthesis of γ-Al2O3 catalyst support is the most
favorable for obtaining the catalyst with superior catalytic performances in transesterification of sunflower oil. A
maximum conversion (triglycerides to methyl esters) of 99.99% was achieved using the SG-KI/γ-Al2O3-770
catalyst under following optimal process parameters: 15:1 methanol to sunflower oil molar ratio, 2.5 wt% cat­
alysts loading, 600 rpm stirring rate and 4 h of the reaction run.

1. Introduction high yields under mild conditions and quite short reaction time are the
primary benefits of this process [1]. For the purpose of obtaining bio­
Human society, during the past few decades, has needed to incor­ diesel different oils, both edible and non-edible [5], such as soybean [6],
porate new green technologies for producing energy. Increased demand sunflower oil [7], and jatropha [8] have been transesterified. However,
for petroleum diesel can be overcome by replacing it with biodiesel. for industrial scale biodiesel production by homogeneously catalyzed
Biodiesel is an alternative renewable fuel that is obtained from tri­ transesterification the main hindrance was quality related problems
glycerides and offers a complementary strategy for sustainability [1–3]. encountered. In order to satisfy the prescribed quality numerous
Reaction of triglycerides with an alcohol to form esters and glycerol is washing and purification steps significantly increase the cost of obtained
called transesterification or alcoholysis. The extensively used technol­ biodiesel [5,9–13].
ogy for biodiesel production is transesterification of oils derived from Unlike homogeneously catalyzed transesterification, the heteroge­
plant sources [1]. This is the satisfactory starting material to produce neous catalysis is classified as a green technology for the following at­
biodiesel due to the fact the conversion to the fatty acid methyl ester tributes: much easier separation of biodiesel from glycerol, the catalyst
from triglyceride is excessive and the reaction time is quite short [4]. can be reused/recycled and quantity of wastewater generated during the
Base catalyzed transesterification reaction on industry level represents process is significantly reduced [14,15]. Moreover, heterogeneously
the process, which is based on the use of homogeneous catalysts (KOH or catalyzed transesterification overcomes problems to handle multiple
NaOH) and methanol to produce biodiesel from vegetable oils/fats. Very feedstocks because solid heterogeneous catalysts are immiscible with

* Corresponding author.
E-mail addresses: [email protected] (R. Ljupković), [email protected] (A. Krstić), [email protected] (B. Janković).

https://doi.org/10.1016/j.fuel.2022.123246
Received 20 September 2021; Received in revised form 25 November 2021; Accepted 9 January 2022
Available online 16 January 2022
0016-2361/© 2022 Elsevier Ltd. All rights reserved.
M. Marinković et al. Fuel 315 (2022) 123246

the methanol or ethanol. A great variety of heterogeneous catalysts for the solution was adjusted to 12 with an 0.1 M sodium hydroxide
the transesterification has been investigated so far, and these include: solution.
metal hydroxides, metal complexes, metal oxides, zeolites, hydrotalcites Synthesis of nanocrystalline Al2O3 by using modified hydrothermal
and supported catalysts [16–18]. The most commonly investigated base method [29] was done as follows: two previously made solutions (pre­
heterogeneous catalysts are alkaline earth metal oxides [19], transition cursor solution and isopropyl alcohol and water solution) were mixed
metal oxides and its derivatives [20], then mixed metal oxides and its drop by drop for 1 h on a magnetic stirrer with vigorous stirring
derivatives [21], basic zeolites, as well as alkali metal loaded alumina continuously, then the pH value of the solution was adjusted to 12 with
[22]. According to the recent studies, the base heterogeneous catalysts an 0.1 M sodium hydroxide solution. Then the generated gel was sub­
based on potassium iodide doped alumina have shown significant ac­ jected to the hydrothermal treatment in an autoclave for 2 h at a tem­
tivity in the transesterification reaction of edible oils and methanol perature of 200 ◦ C. Inside the autoclave, the pressure is spontaneously
[23,24]. generated by the pressure of water vapor. The prepared solids were
Xie and Li [25] have reported that the maximum conversion of 96 % separated from mother liquors by the filtration through membrane filter,
over KI promoted alumina (35 wt% KI on Al2O3, activated at 773 K) was using the vacuum filtration technique. Then the obtained solids were
achieved under following transesterification conditions (methanol washed with a solution of deionized water and isopropyl alcohol (1:1 vol
reflux temperature, 15:1 M ratio of methanol to oil, 2.5 wt% of catalyst ratio), and dried for 3 h at 120 ◦ C [26]. All samples obtained by each of
in mixture, and 8 h reaction time). Slightly lower activity and the three applied methods of synthesis were calcinated at the temperature of
maximum conversion of 95.2% in a similar catalytic system under the 550 ◦ C inside the horizontal tube oven in an air atmosphere, with a
same transesterification conditions (excluding of catalyst amount in heating rate of β = 10 ◦ C min− 1 for 3 h. The samples were labeled ac­
mixture 5 wt%) was reported by Evangelista et al. [23]. Marinkovic et al. cording to preparation method in a following order: (sol–gel) SG-
[26] have reported that there is a significant influence of the parameters γ-Al2O3-550, (reflux) RE-γ-Al2O3-550, and (hydrothermal) HT-γ-Al2O3-
of synthesis and activation of catalysts based on KI promoted alumina on 550.
its catalytic activity, and efficiency in the transesterification reaction.
Almost quantitative conversion of 99.99 % was achieved under rela­ 2.2. Preparation of potassium iodide γ-Al2O3-supported catalysts
tively mild reaction conditions (methanol reflux temperature, 12:1 M
ratio of methanol to oil, 2.5 wt% of catalyst in mixture, and 3 h reaction Impregnation of the obtained catalyst supports was performed by
time). incipient wet impregnation method. Impregnation of γ-Al2O3 to form
To the best of our knowledge, there isn’t any research reporting the KI/ γ-Al2O3 catalysts was carried out with calculated amounts of
synthesis of KI-doped alumina via modified sol–gel, reflux and hydro­ potassium iodide (Aldrich Co., Reagent Plus®, 99%) aqueous solutions
thermal methods using aluminum isopropoxide as a precursor, while to the nominal amount of KI 37 wt% in the rotary vacuum evaporator for
only a few studies considered the impact of doping KI on alumina and its 2 h. The obtained samples then were dried for 3 h at 120 ◦ C and then the
catalytic activity in transesterification reaction [23,26]. catalysts were activated by thermal heating in the horizontal tube oven
The main goal of this study is to synthesize the newly-developed at 770 ◦ C with a heating rate of β = 10 ◦ C min− 1 for 3 h. The samples
heterogeneous base catalyst by using improved, modified sol–gel, were labeled according to preparation method in a following order:
reflux and hydrothermal methods using aluminum isopropoxide as a (sol–gel) SG-KI/γ-Al2O3-770, (reflux) RE-KI/γ-Al2O3-770, and (hydro­
precursor. Moreover, this study reveals relationships between the thermal) HT-KI/γ-Al2O3-770.
physicochemical properties of the catalyst support as well as dernier Overall flow chart diagram for synthesis of KI promoted alumina
catalyst and its catalytic performance in the transesterification reaction. catalysts using aluminum isopropoxide precursor with different syn­
Additionally, the impact on the conversion of designated reaction con­ thesis path (sol–gel, reflux, hydrothermal) is presented in Fig. 1.
ditions was examined by the current study. Based on the previous ex­
periences, it is expected that the catalyst support as well as the final 2.3. Catalyst characterization
catalysts should have improved physicochemical properties, in terms of
obtaining the well-crystallized, nano-sized material. The surface basicity/surface properties of the catalysts were deter­
mined by Hammett indicators [30,31]. The following Hammett in­
2. Materials and methods dicators were used in this work as: bromothymol blue (H0- = 7.2),
phenolphthalein (H0- = 9.8), 2.4-dinitroamine (H0- = 15.0) and 4-nitro­
2.1. Preparation of nanocrystalline Al2O3 support by the modified sol–gel, aniline (H0- = 18.4). With the intention of estimating catalytically active
reflux and hydrothermal methods sites and their total strength, the additional FTIR (Fourier Transform
Infrared) analysis was performed. A detailed description of the applied
For each of the three applied methods of synthesis of the catalyst FTIR technique is described in our previous paper [24].
support the same precursor solution was prepared. Preparation of the Additionally, textural, structural and morphological properties of the
precursor solution was carried out at a temperature of 50 ◦ C in an ul­ examined samples, i.e., BET (Brunauer, Emmett and Teller) method (this
trasonic bath. The accurately measured amount of aluminum isoprop­ method is commonly applied to calculate the specific surface area on the
oxide (Aldrich Co., purity ≥ 98 %) was dissolved in isopropyl alcohol basis of nitrogen adsorption isotherm measurements at 77 K, using the
(Aldrich Co., 99.5 %). Synthesis of nanocrystalline Al2O3 by improved data in the relative pressure range from 0.05 to 0.3 and which was based
sol–gel method [27] was performed in the following way: two previ­ on the multilayer adsorption of gas on the adsorbent’s surface), XRD and
ously made solutions (precursor solution and isopropyl alcohol and SEM instrumental techniques were performed under identical experi­
water solution) were mixed drop by drop for 2 h on a magnetic stirrer mental conditions and on the identical instruments, which was
with vigorous stirring continuously, then the pH value of the solution described in the previous paper [24].
was adjusted to 12 with an 0.1 M sodium hydroxide (Aldrich Co., re­
agent grade, ≥98%, pellets (anhydrous)) solution and aging of sol was 2.4. Transesterification reaction
conveyed for 2 h at a temperature of 50 ◦ C.
Synthesis of nanocrystalline Al2O3 by using modified reflux method In this study, the sunflower oil from the manufacturer „Sunce” was
[28] was performed in a following manner: two previously made solu­ used. The detailed analysis of the oil and the fatty acid profile deter­
tions (precursor solution and isopropyl alcohol and water solution) were mined by GC–MS analysis was published in our previously paper [26].
mixed drop by drop for 2 h on a magnetic stirrer with vigorous stirring The transesterification reaction was carried out on the magnetic stirrer
continuously, under the reflux boiling temperature, then the pH value of in standard 250 mL glass flask equipped with a condenser, charged with

2
M. Marinković et al. Fuel 315 (2022) 123246

Fig. 1. Overall flow chart diagram for synthesis of KI promoted alumina catalysts: left branch for SG-KI/γ-Al2O3-770, central branch RE-KI/γ-Al2O3-770, and right
branch for HT-KI/γ-Al2O3-770.

calculated volume of oil, and different volumes of anhydrous methanol transesterification reaction of sunflower oil was studied. The synthe­
(precisely, molar ratios from 6:1 to 21:1) and various quantities of sized catalysts ((sol–gel) SG-KI/γ-Al2O3-770, (reflux) RE-KI/γ-Al2O3-
freshly prepared catalyst, i.e., 0.5–3.0 wt%. Each mixture was heated at 770, and (hydrothermal) HT-KI/γ-Al2O3-770) were repeatedly used for
65 ◦ C for required reaction run of 5 h, and stirred at predetermined seven cycles. Between each cycle, the catalysts were recovered from the
mixing rates, i.e., 300–900 rpm. 1H NMR spectroscopy (Bruker, 400 reaction mixture by centrifugation, washed vigorously with n-hexane
MHz) (Bruker, Billerica, Massachusetts, US) was used for knoring the and dried at 110◦ C for reutilization.
progress of the reaction run. Procedure of preparing samples for analysis
is described in details in a previously published paper [26]. According to 3. Results and discussion
the method defined by Knothe, the conversion CME (in %) of vegetable
oil (sunflower oil - triglycerides) to biodiesel (methyl esters) can be 3.1. Textural properties
calculated from the integration values of the glyceridic and methyl ester
protons in 1H NMR by the Eq. (1): The nanocrystalline Al2O3 support and nanocrystalline KI/γ-Al2O3-
based catalysts textural properties (adsorption/desorption isotherms,
5 × IME
CME = 100 × (1) pore size distribution, BET specific surface area, mean pore diameter and
5 × IME + 9 × ITAG
pore volume) are shown in Figs. 2 and 3 and condense in Table 1. All
where CME is the conversion of triglycerides to methyl esters in %, IME is samples were activated at predefined temperatures (550 and 770 ◦ C)
the integration value of the methyl ester peak and ITAG is the integration with the purpose of incorporating the potassium iodide into/onto
value of the glyceridic peaks in the triacylglycerides (TAG) of the sun­ alumina, according to previously reported data [26,27]. As evidenced by
flower oil [32]. the data listed in Table 1, the surface area decreases from catalyst sup­
port nano-materials to KI/γ-Al2O3 catalysts in a following order of
applied synthesis methods: HT < RE < SG. Calcined γ-Al2O3 loaded
2.5. Catalyst recovery and reusability
materials at 770 ◦ C independently of applied synthesis route, show a
dramatic reduction in SBET values compared to γ-Al2O3 samples,
Under the optimum reaction conditions, reusability of the KI-
calcined at 550 ◦ C. The decrement of surface area can be attributed to
promoted alumina based catalysts (KI/Al2O3-based catalysts) in the

3
M. Marinković et al. Fuel 315 (2022) 123246

pores that are near the micro-meso boundary in a size, and characteristic
mesopores, categorized with the mean pore diameter of approximately
5 nm (Fig. 3 a)). Depending on the applied method of synthesis, the
maxima of the pore size distribution curve is shifted towards larger
values of the mean diameter, as well as a slight increase in their volume
ratios in the following order: from hydrothermal via reflux to the sol–gel
(not shown). According to the BJH desorption isotherms, the KI-doped
γ-Al2O3 catalytic samples are characterized with bimodal distributed
pores. There are two main pore types according to the mean pore
diameter, pores with maxima in pore size in the range of 3 to 7 nm, and
pores with maxima in pore size in the range of 30 to 45 nm, with a mean
pore diameter around 34 nm in size. The interstices among γ-Al2O3
primary crystallites are probably presented as the pores that are near the
micro-meso boundary in size, and interstices among secondary crystal­
lites and relatively poorly dispersed dopant are probably associated with
mesopores, characterized with a mean pore diameter around 34 nm in
the size (Fig. 3 b)). The size of pores around 34 nm is big enough to
enable the diffusion of larger molecules in these pores such as triglyc­
eride molecules for an example. However, only a small fraction of the
surface area is accessible for these types of molecules (the reduced SBET
values for KI-doped γ-Al2O3 catalytic samples, Table 1).
However, the results presented in Table 1 indicate that there is a
relationship between the applied methods of synthesis of the pure
γ-Al2O3 support samples and the BET specific surface area of samples.
The largest BET specific surface area of 315.18 m2⋅g− 1 has the pure
γ-Al2O3 catalyst support sample which is prepared by modified sol–gel
synthesis method and calcinated at 550 ◦ C. The sample prepared by the
modified reflux method has a somewhat lower BET specific surface area
of 297.96 m2⋅g− 1, while the sample prepared by the modified hydro­
thermal method has the lowest BET specific surface area of 273.32
m2⋅g− 1. It is obvious that the impregnation of potassium iodide on the
γ-Al2O3 catalyst support samples and the increase of the activation
Fig. 2. N2 adsorption/desorption isotherms for: a) HT-γ-Al2O3-550 and b) HT-
temperature up to 770 ◦ C, result in the significant reduction of the BET
KI/γ-Al2O3-770 samples.
specific surface area, and a decreasing in the pore volume values of
catalysts. The observed reduction in pore volume, especially those of
the effect of catalyst deposition on the support (the reduction due to
smaller dimensions, is probably due to the formation of a layer or de­
covering alkaline compound on the porous surface of γ-Al2O3), which
posit of KI-based compounds or intermediate compounds on the surface
may also outcomes in a partial blocking of porous network. However,
of the catalyst support (which was preliminary assumed earlier – see
complete blocking is not observed, since that mean pore diameter (dp)
above). Additionally, due to the size of the pores for all KI-doped γ-Al2O3
significantly increases for all KI/γ-Al2O3 samples, where the high
catalytic samples prepared with different synthesis routes, no internal
calcined temperature has a crucial role (Table 1) in promoting this
diffusion restrictions are expected for the transport of molecules of both
effect.
reactants and reaction products according to the defined dimension of
All investigated catalyst support and catalytic samples exhibited type
methyl oleate molecule (around 2.5 nm in size [11]). These relatively
IV sorption isotherm curves (from the shape of nitrogen adsorption/
slight differences in textural properties of various KI/γ-Al2O3-based
desorption isotherm curves) (Fig. 2 a)). These findings indicate
catalysts may have (in synergy with other physicochemical properties of
adsorption on mesoporous solids followed by possible capillary
the catalyst) the influence on the final catalytic efficiency in trans­
condensation of adsorbent in gaseous and/or liquid phase. All pure
esterification reaction of sunflower oil. These assumptions are similar to
γ-Al2O3 support samples prepared by different methods of synthesis and
earlier report [26].
calcined at 550 ◦ C show typical S-shape behavior of type IV sorption
isotherm, with a type H4 hysteresis loop, while the KI-promoted γ-Al2O3
3.2. Microstructural characterization – XRD analysis
catalytic samples activated at 770 ◦ C were categorized with type IV
sorption isotherm, with a type H3 hysteresis loop according to IUPAC
The XRD patterns of the pure γ-Al2O3 support samples prepared with
classification [33]. The observed hysteresis loops suggest the presence of
different methods of synthesis and corresponding KI-doped γ-Al2O3
mostly narrow slit-like pores, particles with inner cavities of the uneven
catalytic samples are shown in Fig. 4 a) and b), respectively. In the case
shape and wide-ranging size distribution in the pure γ-Al2O3 support
of the pure γ-Al2O3 support samples (Fig. 4 a)), it can be noticed that
samples, while the KI-doped γ-Al2O3 catalytic samples have cracks-like
there are no clearly defined diffraction lines, but several shoulders can
and/or conical pores. The introduction of potassium iodide into/onto
be noticed which are characteristic for the amorphous phase. Low-
γ-Al2O3 and application of higher calcination temperatures for the KI-
intensity diffraction lines are observed at diffraction angles of 2θ =
doped γ-Al2O3 catalytic samples shifts isotherms downward, and leads
20.5◦ , 37.0◦ , 46.0◦ and 66.7◦ , which correspond to alumina tetragonal,
to a shift of the hysteresis loop towards higher values of relative pres­
mono-phase and amorphous phase structure, similarly to previously
sures (Fig. 2 b)).
reported results by other authors [23,25]. Formation of catalysts char­
The pore size distribution of the pure γ-Al2O3 support sample and KI-
acterized with higher structure order, occurred after the impregnation of
doped γ-Al2O3 catalytic sample are shown in Fig. 3 a) and b), respec­
KI onto γ-Al2O3 support samples. Well crystallized material with sharp/
tively. The pore system of all investigated catalyst support and catalytic
clearly defined intense XRD lines was obtained after grafting of KI onto
samples is within mesoporous range. All pure γ-Al2O3 support samples
γ-Al2O3 support samples (Fig. 4 b)). Additional diffraction lines in the
show bimodal pore sizes distributions consists of two kinds of pores:
case of all KI/γ-Al2O3 catalyst samples, which originate from KI residual

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M. Marinković et al. Fuel 315 (2022) 123246

Fig. 3. Pore size distribution: a) HT-γ-Al2O3-550 and b) HT-KI/γ-Al2O3-770 samples.

surface, which can play a significant role in catalytic activity in trans­

Table 1
esterification reaction. Dispersion and decomposition of KI to form
Textural properties (specific surface area SBET, mean pore diameter dp, pore
strong basic sites in the activation process, is directly accelerated by
volume Vp) of alumina-based catalysts samples.
inserting the K+ ions of KI into oxygen vacancies of alumina. This phe­
Sample SBET(m2 g− 1) dp(nm) Vp(cm3 g− 1)
nomenon results in the surface enrichment with alkaline species (i.e.,
SG-γ-Al2O3-550 315.18 5.12 0.401 potassium-based) which are significant for base-catalyzed reactions
RE-γ-Al2O3-550 297.96 4.99 0.397 including transesterification [26]. Variations in the catalytic activity of
HT-γ-Al2O3-550 273.32 4.71 0.392
SG-KI/γ-Al2O3-770 10.58 35.78 0.195
catalysts prepared by various methods of synthesis may be in agreement
RE-KI/γ-Al2O3-770 9.17 33.62 0.197 with the differences in the total number of catalytic active basic sites.
HT-KI/γ-Al2O3-770 7.74 32.94 0.172 Therefore, differences of the total mass fractions of K2O and K3AlI6
species between a catalysts prepared by various methods of the syn­
thesis, could be correlated with their different catalytic performance in
crystals, are observed at the following diffraction angles: 2θ = 21.0◦ ,
transesterification reaction.
25.0◦ and 35.0◦ . Probably, the spontaneous dispersion capacity of KI on
alumina was exceeded; therefore, the remaining bulk phase of potassium
iodide persisted on the composite. During the catalyst preparation 3.3. Topographic characterization – SEM analysis
procedure, the formation of catalytically active species occurs, namely
K2O species and alkaline iodine compounds. Presence of a new phase Fig. 5 shows the scanning electron microscopy (SEM) images that
characteristic for K2O species in all catalyst samples was determined by represent morphological properties of the pure γ-Al2O3 support sample
distinctive diffraction lines at 2θ = 51◦ , 56◦ , 69◦ and 76◦ (Fig. 4 b)). (Fig. 5 a)), prepared by hydrothermal synthesis route and corresponding
Additionally, the presence of a newly formed intermediate structure KI/γ-Al2O3 catalyst sample (Fig. 5 b)). In the case of the pure γ-Al2O3
K3AlI6 can be confirmed by diffraction lines at 2θ = 42◦ , 44◦ , 58◦ and 64◦ support sample, on the analyzed material surface, it can be observed the
[26]. Moreover, impregnation and dispersion of alkaline iodine com­ minor number of primary particles in sizes up to 100 nm, and a greater
pounds on/into the surface of alumina is consistent with strong MSI number of secondary particles, characterized with diameter from 0.2 to
(metal/salt-support interaction) due to the presence of a large number of 3.75 μm distributed as aggregates (Fig. 5 b)).
crystal defects and many potential oxygen vacancies onto catalyst sur­ Despite the loading of KI into/onto γ-Al2O3, the bulk morphology of
face (KI/γ-Al2O3). Besides, as a consequence of strong MSI interactions, the KI/γ-Al2O3 catalyst remains globally unchanged. The impregnation
the formation of Al-O-K groups is most likely to occur on the catalyst of the potassium iodide on the γ-Al2O3 catalyst support and the increase

5
M. Marinković et al. Fuel 315 (2022) 123246

Fig. 4. XRD patterns: a) γ-Al2O3-550 and b) KI/γ-Al2O3-770 samples.

of activation temperature up to 770 ◦ C, resulted in a additional which is consistent with the results obtained from XRD patterns, and
agglomeration of materials particles (Fig. 5 b)), which indicates that the additionally confirms the presence of K2O phase (independently on the
sintering process occurs under these thermal conditions [34]. The calcination temperature, considering FTIR spectra results for various
above-stated sintering process leads to a significant reduction of the BET synthesis methods, passing from SG through RE up to HT method; the
specific surface area during the activation process of the catalyst sam­ last one exhibits more smoother and narrower vibration bands related to
ples (Table 1). Despite the sintering process, the additional textural CO2 (Fig. 6)). Moreover, intensive broad vibration bands in the region of
properties, the pore volume and especially pore diameter, persisted 3400–3480 cm− 1 (at approximately of 3440 cm− 1) in all KI/γ-Al2O3
suitable for the non-hindered diffusion of reactants to catalytically catalyst samples can be assigned to OH groups which are directly
active species into the catalyst. Results obtained for identified attached to the γ-Al2O3 (νOH stretching vibration). However, during the
morphological properties are consistent with textural properties derived activation process on the surface of totally hydroxylated alumina, the
by using BET surface evaluation (Table 1). protons of isolated hydroxyl groups could be replaced with K+ ions to
form Al-O-K groups. The additional confirmation of the strong MSI is the
presence of the broad band at around 3480–3500 cm− 1, ascribed to the
3.4. Spectroscopic characterization – FTIR spectroscopy analysis
Al-O-K groups stretching vibrations [26].
The dominant alkali species/catalytically active sites in the base-
The FTIR spectra of the KI/γ-Al2O3 catalyst samples prepared by
catalyzed transesterification of sunflower oil with methanol over KI/
modified sol–gel (SG), reflux (RE) and hydrothermal (HT) synthesis
γ-Al2O3 catalyst are probably K2O derived from decomposition of KI
routes are shown in Fig. 6. The surface properties are important catalytic
along with the surface Al-O-K groups (by surface hydroxyls), thus dif­
features for transesterification of sunflower oil. Therefore, FTIR tech­
ferences in the values of the transmittance between the investigated
nique was applied to determine whether the different catalytic activities
catalyst samples (Fig. 6) indicate a difference in the quantitative
of the samples are associated with the differences in their surface
amounts of the basic species/catalytically active sites on the surface of
properties. In that manner, to further understand the interactions be­
catalysts.
tween KI and the support γ-Al2O3 and between the metal K and KI/
These claims are consistent with the results obtained for a catalytic
γ-Al2O3 during catalyst activation, the characterization by the FTIR
activity of the investigated catalyst samples prepared by various
technique was carried out. The physically adsorbed water on the KI/
methods of synthesis (e.g. SG-KI/γ-Al2O3 99.99 %, RE-KI/γ-Al2O3 85.24
γ-Al2O3 catalyst samples was detected and characterized by δOH
% and HT-KI/γ-Al2O3 69.14 %).
bending vibration mode of H2O molecules at about 1638 cm− 1 [35].
Further, two vibration bands at 1540 and 1410 cm− 1 are attributed to
carbonates [36]. During the activation, the reaction occurs between K2O
and CO2 from the air leading to the formation of potassium carbonate,

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M. Marinković et al. Fuel 315 (2022) 123246

Table 2
Hammett basicity of the catalyst samples.
Sample Calcination temperature Basic Strength Conversion
(oC) (H0-) (%)

SG-γ-Al2O3-550 550 <7.2 –

RE-γ-Al2O3-550 550 <7.2 –
HT-γ-Al2O3-550 550 <7.2 –
SG-KI/γ-Al2O3- 770 15.0–18.4 99.99
770
RE-KI/γ-Al2O3- 770 15.0–18.4 85.24
770
HT-KI/γ-Al2O3- 770 15.0–18.4 69.14
770

oil with methanol (Table 2). It is evident that impregnation of potassium

iodide on the γ-Al2O3 catalyst support samples and the increase of the
calcination temperature up to 770 ◦ C, resulting in a significant increase
in the basic strength of corresponding KI/γ-Al2O3-based catalysts. These
catalyst samples quickly change the colour of 2,4-dinitroaniline (H0- =
15.0) from yellow to pale purple, but failed to convert the colour of 4-
nitroaniline (H0- = 18.4), therefore, their base strength could be in the
range from H0- = 15.0 to H0- = 18.4. Moreover, it is assumed that the
relatively high catalytic activity of the KI/γ-Al2O3-based catalysts are
directly related to their surface basic strength (Table 2), where these
samples can be regarded as strong solid bases, agreeing to Tanabe’s
definition [37].

3.6. Catalytic activity in transesterification of sunflower oil

3.6.1. Influence of several operational parameters on the transesterification

reaction
Influence of the molar ratio (methanol to the sunflower oil) on the
transesterification reaction conversion over KI/γ-Al2O3-based catalysts
prepared by modified sol–gel, reflux, and hydrothermal methods of
Fig. 5. SEM micrographs: a) HT-γ-Al2O3-550 and b) HT-KI/γ-Al2O3- synthesis is presented in Fig. 7 a). As reported before, the molar ratio of
770 samples.
alcohol to triglyceride is one of the most significant variables affecting
the conversion of the reactants to the final product(s) in the biodiesel
synthesis [26,38]. The transesterification reaction is a process consisting
of three consecutive reversible reactions, and stoichiometrically, for
each mole of triglyceride three moles of methanol are required. In order
to obtain a higher conversion of triglycerides, a higher molar ratio of
methanol to sunflower oil are tested in this study, since an excess of
methanol will promote the total conversion of TG [39]. As shown in
Fig. 7 a), with an increase in the methanol molar ratio the conversion
was increased noticeably. The maximum conversions were derived
when the molar ratio was 15:1, for the each of tested catalysts. However,
futher increase in molar ratio over 15:1 had no significant effect on the
conversion or resulted in the slightly decrease of conversions. Therefore,
the optimum molar ratio of methanol to sunflower oil was exactly 15:1.
The influence of the catalyst amounts on the conversion was exam­
ined under the following reaction parameters: 15:1 M ratio of methanol
to sunflower oil, reflux of methanol and the reaction run 5 h. The cat­
alysts amounts were varied in the range of 0.5–3.0 wt%. The reaction
profile for each of tested catalysts (Fig. 7 b)) indicates that the trans­
esterification of sunflower oil was highly dependent upon the catalyst
loadings. It is evident from Fig. 7 b) that a significant increase in the
Fig. 6. FTIR spectra of investigated catalyst samples. reaction rate is a direct consequence of the increased amount of catalyst
in the reaction mixture. When catalysts amounts were increased from
3.5. Total Hammett basicity 0.5 % to 2.5 wt%, the conversions to final product(s) were increased, as
increasing the weight of the catalyst is proportional to the increase in the
The basic strengths of the pure γ-Al2O3 samples used as a support and rate of the reaction. A possible explanation for this pattern is that larger
KI/γ-Al2O3-based catalysts are summarized in Table 2. The pure γ-Al2O3 amounts of catalyst in the reaction mixture lead to more efficient con­
samples prepared by different methods of synthesis and calcined at tacts of the reactants due to the increased number of catalytically active
550 ◦ C, could not change the color of the indicator bromothymol blue, sites. It is assumed that further increasing the amount of catalyst in the
indicating that their basicity is less than (H0- < 7.2), therefore, does not reaction mixture could shorten the reaction time and increase the re­
exhibit catalytic activity in the transesterification reaction of sunflower action rate to achieve the same conversion, or even reduce the

7
M. Marinković et al. Fuel 315 (2022) 123246

Fig. 7. a) The impact of methanol to oil molar ratio on the conversion, b) The impact of the catalyst amount on the conversion, c) The impact of the reaction time on
the conversion, and d) The impact of the stirring speed on the conversion.

conversion due to possible mixing problems involving reactants, prod­ Fig. 7 d). It is obvious that conversion to methyl-esters was largely
ucts and solid catalyst [25]. For the catalytic system investigated in this affected by stir rate when it was<600 rpm, for each of tested catalysts.
work, similar to authors who examined the K2CO3/Al2O3 catalyst, due to Conversions to methyl-esters for SG-KI/γ-Al2O3, RE-KI/γ-Al2O3, and HT-
favorable physicochemical properties, we do not expect internal and KI/γ-Al2O3 catalysts substantially increased respectively, from 79.99,
external diffusion constraints and mass transfer resistance [40]. The 68.19 and 53.17 % at 300 rpm to 99.99, 85.24, 69.14 % at 600 rpm.
optimum catalyst amount for each of the tested catalysts was 2.5 wt% However, conversion became practically invariant with further increase
(Fig. 7 b)). This can be correlated with the fact that SG-KI/γ-Al2O3-770 of the stir rate from 600 rpm to 900 rpm, only slightly decreased for each
possesses a larger BET surface area than RE-KI/γ-Al2O3-770 and HT-KI/ of the investigated catalyst samples. This trend indicates that trans­
γ-Al2O3-770, hence, it provides more accessible basic sites than other esterification reaction of sunflower oil with methanol over KI/γ-Al2O3
two catalysts. based catalysts is the diffusion-controlled process. The effect of external
The effect of elapsed reaction time on the conversion of triglycerides diffusion limitation on the catalysis is significantly eliminated at 600
to methyl esters at the following reaction parameters (notes: 15:1 M ratio rpm, for each of investigated catalyst samples, which is in consistency
of methanol to sunflower oil, reflux of methanol, and the reaction run 5 with the results of other authors [41].
h) was also investigated in this study. Conversion to methyl esters was In contrast to the previously obtained results, for the catalytic effi­
monitored by taking an aliquot every 20 min., for a period of 300 min., ciency in transesterification of sunflower oil with methanol over KI/
for each of the tested catalysts (Fig. 7 c)). As it can be seen from Fig. 7 c), γ-Al2O3 based catalyst [26], the investigated catalyst samples prepared
reactions rates were somewhat higher in the initial hour of the reaction, by various methods of synthesis in presented study showed slightly
and thereafter remained nearly constant until reaching the maximum/ inferior catalytic performance. These facts can be explained with
equilibrium conversions in the fourth hour. The maximum conversions different preparation procedures (such as sol–gel, reflux and hydro­
of sunflower oil were achieved after 4 h of the reaction run, for inves­ thermal processes for producing of porous solid materials; the selection
tigated catalyst samples prepared by various methods of synthesis (e.g., of the chemical approach relies upon the possibility to manage the re­
SG-KI/γ-Al2O3 99.99 %, RE-KI/γ-Al2O3 85.24 %, and finally, HT-KI/ action rates for activation/condensation processes, which determine the
γ-Al2O3 69.14 %). Among all studied catalysts, it is obvious that SG-KI/ textural properties of materials, matching precursors cost and avail­
γ-Al2O3-770 has a much higher catalytic activity compared to others, if ability, and their ease of handling) for the catalyst support and dissimilar
we take into account the results shown in Table 2, and in previous sub- calcination temperatures applied. In addition, authors of this study also
sections (relatively large BET surface area and basicity). suggest that the catalytic efficiency of KI/γ-Al2O3 based catalysts in
The effect of mass transport for the investigated catalyst samples transesterification reaction of sunflower oil is significantly dependent on
prepared by various methods of synthesis on the conversion to methyl- physicochemical properties of the catalyst support as well as the cor­
esters was evaluated by varying the stirring rate. Results are presented in responding KI/γ-Al2O3 catalyst. Synergism of different physicochemical

8
M. Marinković et al. Fuel 315 (2022) 123246

properties of catalyst support and corresponding catalyst properties,

such as greater specific surface area, greater pore diameter and pore
volume, greater total mass fractions of K2O, K3AlI6 and Al-O-K species,
absence of internal and/or external diffusion constraints at selected
process parameters, and above all higher total basicity and potentially
higher number of alkali active sites, is the essential for the catalytic
performance of KI/γ-Al2O3 based catalysts. Also, it can be concluded
that the modified sol–gel method for the synthesis of γ-Al2O3 catalyst
support is the most favorable for obtaining the catalyst with a superior
catalytic performances in transesterification of sunflower oil. The
described heterogeneous catalyst can be easily separated from reaction
mixture and re-used for many times, as well as being environmentally
friendly and easy to use in continuous processes.
Table 3 shows comparison of results obtained in this work with other
results from literature, for the production of the 1st and 2nd generation
biodiesel, where different alumina supported composite catalysts were
used.
From results reported in Table 3, it can be noticed that our elabo­
rated reaction conditions seem most advanced in the comparison with
other cases, where the highest yield of biodiesel was obtained. On the Fig. 8. Catalysts recovery cycles test.
other hand, if we compare our used feedstock system with the same or
similar feedstock systems, the superior conditions were achieved (see can be observed in the case of all tested catalysts (conversions to methyl-
Table 3). Since that sol–gel method represents most applicable prepa­ esters for SG-KI/γ-Al2O3, RE-KI/γ-Al2O3, and HT-KI/γ-Al2O3 catalysts
ration technique widely used in the material science for biofuels pro­ respectively 89.99, 75.31, 55.3 Fig. 8.). This is in agreement with the
duction, our proposed experimental technique which prefers modified results of previous researchers who investigated Zn-Ce/Al2O3 catalyst in
sol–gel synthesis route undoubtedly shows very well-balanced reaction transesterification of palm oil [52]. These findings indicate catalysts
conditions for transesterification, in order to make the biodiesel pro­ durability and stable activity in the sunflower oil transesterification
duction with high efficiency. reaction for at least six consecutive reaction cycles. Similar to the
findings of other authors [53,54], the decrease in catalytic performance
3.6.2. Catalyst recovery and reusability is due to the leaching of catalytically active sites into the reaction
Reusability of the KI-promoted alumina based catalysts (KI/Al2O3- mixture and a decrease in the total number of surface-active sites. The
based catalysts) in the transesterification reaction of sunflower oil overall differences in catalyst stability, compared to other studies, result
through seven cycles is shown in Fig. 8. In the case of all examined from differences in the catalytic system and differences in intercycle
catalysts ((sol–gel) SG-KI/γ-Al2O3, (reflux) RE-KI/γ-Al2O3, and (hydro­ processing of the catalyst.
thermal) HT-KI/γ-Al2O3), the obtained results indicate that there is no The prospects of using heterogeneous catalysts in commercial bio­
significant reduction in the conversion and activity of the catalysts until diesel production are in overcoming the disadvantages and limitations
the seventh cycle. The reduction in conversion in the case of all syn­ of the use of homogeneous catalysts such as saponification and separa­
thesized catalysts in the first six cycles is<5%, however, in the seventh tion of glycerol from methyl esters. In addition, these catalysts show
cycle a significant decrease in catalytic performance (higher than 5%)

Table 3
Comparison of the results where the different alumina supported composite catalysts was used for the production of the first and the second generation biodiesel from
various feedstocks.
Catalyst Preparation of catalyst Feedstock Yield The reaction conditions References
(%)
Reaction Methanol to Catalyst Reaction
temperature (oC) oil ratio amount (wt. %) time (h)

KI/γ-Al2O3 Modified sol–gel method Sunflower oil 99.99 50 15:1 2.5 4 This study
CaO/Al2O3 Impregnation and Palm oil 98.64 65 12:1 6 5 [42]
precipitation
K2CO3/Al2O3 Wet impregnation method Canola oil 84.60 50 6:1 2 4 [43]
CaO/Al2O3 Sol-gel method Sunflower oil 96.60 50 9:1 6 4 [44]
K2O/γ-Al2O3 Grinding calcining method Rapeseed Oil 94.00 70 12:1 3 3 [45]
with some modification
CaO-MgO/Al2O3 Co-precipitation method Cottonseed 92.45 95.8 8:5 12.5 3 [46]
KF/Al2O3 Impregnation method Soybean Oil 85.80 Methanol reflux 15:1 2 6 [25]
temperature
LiNO3/Al2O3 Impregnation method Palm Kernel Oil 91.60 60 6:5 10 3 [47]
CaO-La2O3- Co– precipitation method Crude Palm Oil 97.81 170 9:1 5 3 [48]
Al2O3
Mg(NO3)2/ Impregnation method Palm Kernel Oil 10.40 60 6:5 10 3 [47]
Al2O3
CaO/KI/Al2O3 Impregnation and Waste Cooking Oil 83.08 65 15:1 6 5 [49]
precipitation
Anthill-eggshell- Impregnation method Waste Frying Oil 90.23 70 12:1 3 2 [50]
Ni-Co
CaO/KI/Al2O3 Heating a mixture of alumina Rubber Seed Oil 91.60 65 9:1 2 5 [42]
and salt
CaO Precipitation method Algal (Chlorella 67.00 80 9:0.6 4 4 [51]
nanocatalyst vulgaris) oil

9
M. Marinković et al. Fuel 315 (2022) 123246

significant activity under relatively mild reaction conditions [55]. The 14/200124 for Faculty of Science and Mathematics, Niš, 451-03-9/
results obtained in the presented study indicate a significant activity of 2021-14/200017 for „Vinča” Institute of Nuclear Sciences - National
the heterogeneous catalyst obtained by the sol gel process, which is Institute of the Republic of Serbia, Belgrade).
higher than the similar catalytic system of the second group of authors
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