An Environmentally Friendly Catalyst for Aromatic Hydrocarbons
Alkylations with 1-alkenes
MICHAL HORŇÁČEK*, MIROSLAVA BÉREŠOVÁ, PAVOL HUDEC
Slovak University of Technology in Bratislava, Faculty of Chemical and Food Technology,
Radlinského 9, 812 37 Bratislava,
SLOVAKIA
*Corresponding Author
Abstract: - Nowadays, the alkylation of aromatic compounds using 1-alkenes is still conducted in industrial
applications using Friedel-Crafts alkylations. The most commonly used catalysts are aluminum chloride (AlCl3)
and hydrofluoric acid (HF), both of which pose significant environmental concerns. An alternative approach
involves the use of solid acid catalysts, specifically zeolites, which may offer a more environmentally
acceptable option. In this study, the alkylation of toluene with 1-decene was performed in a batch reactor under
autogenous pressure in the liquid phase at a temperature of 100 °C. Zeolite Y samples with varying sodium
content (molar ratio of Si/Al approximately equal to 2.27), were employed as the parent catalysts. These
zeolites underwent a dealumination process followed by the removal of residual sodium and the cationic form
of aluminum via ion exchange with ammonium nitrate. Accessible physical and chemical methods were used
for the characterisation of the prepared catalyst. The residues of sodium were found to influence the catalytic
activity in the alkylation reaction. The formation of a secondary mesoporous structure enhanced the selectivity
towards the production of 2-decyltoluene. Following the dealumination and ion exchange treatment, an
increased ratio of Brønsted to Lewis acid sites was observed, resulting in the suppression of dimerization
reactions in the alkylation products.
Key-Words: - Solid acid catalysts, Aromatics, Zeolites, Zeolite Y, Friedel-Crafts catalysts, Dealumination, 1-
alkenes, Linear alkyltoluenes.
Received: June 17, 2024. Revised: November 4, 2024. Accepted: November 26, 2024. Published: December 16, 2024.
1 Introduction
The alkylation of aromatics with various 1-alkenes
or alcohols is extensively utilized in the chemical
industry. The rate and mechanism of these reactions
are influenced by several factors, including the
structural characteristics of the alkylation agent, the
polarity and solvation capacity of the solvent, and
the nature of the catalyst employed. Traditionally,
Friedel-Crafts alkylation reactions involving
alkenes, chloroalkanes, or alcohols have been
catalyzed by liquid-phase catalysts such as
hydrofluoric acid and aluminum chloride, [1], [2].
The main issues of these catalysts are related to
corrosion and stringent requirements for feedstock
drying. The associated drawbacks of these
conventional catalysts underscore the necessity for
the development of alternative catalytic systems to
facilitate a cleaner petrochemical process for
detergent production, [3], [4], [5]. In this context,
zeolite catalysts, such as HY zeolites, have emerged
as the preferred choice for advancing this new
alkylation process, [6], [7], [8].
The alkylation of aromatics with long-chain 1-
alkenes using solid acid catalysts represents a
promising approach for the synthesis of linear
alkylaromatics. One of the examples of this type of
reaction is the synthesis of linear alkyltoluenes
(LATs). This process generally yields several
positional isomers of the desired LAT product, with
the 2-isomer being particularly advantageous due to
its favorable environmental attributes. Specifically,
the 2-isomer exhibits enhanced solubility, superior
biodegradability, and effective detergent properties,
[9].
Zeolites are microporous materials characterized
by their high surface-to-volume ratio. One unique
property of zeolites is that they have open channels,
or pores, and cavities distributed throughout their
lattice, [10]. They consist of three-dimensional
tetrahedral units (TO4) bonded by oxygen atoms.
The T atoms are mostly aluminum and silicon.
Through the combination of these units, zeolites
form unique arrangements that result in the creation
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Volume 20, 2024
of intra-crystalline channels and cavities. These
channels have molecular-scale dimensions ranging
from 0.3 to 2 nm, [11].
The faujasite (zeolite Y) has a primary structure
composed of tetrahedral units with aluminum
(AlO4) and silicon (SiO4) central atoms. Faujasite
zeolites are particularly known for their large cages
called "supercages," which have a diameter of 1.3
nm and a ball-shaped structure. These supercages
are approachable through a window with 12 rings
and a free aperture measuring 0.74 nm, making
them larger than most organic molecules, [11].
The molar ratio of Si/Al in the TO4 (T = Si, Al)
framework influences the hydrophilic and
hydrophobic properties of modified zeolites, which
in turn affects their sorptive and catalytic
capabilities. The principal methods for
dealumination of faujasite-type zeolite on a
commercial scale can be categorized into two main
approaches: thermochemical treatment of NH4Y
using steam (steaming) [12], [13], and the treatment
of NaY with SiCl4 (substitution), [14]. In the
steaming process, aluminum remains as extra-
framework aluminum (EFAL) on the surface of the
crystals, whereas the aluminum released from the
framework during the SiCl4 treatment dissolves in
the washing process and can be largely extracted
from the bulk of the zeolite.
During the hydrothermal treatment of the
ammonium form of zeolite Y, temperatures ranging
from 500 to 800 °C are utilized in a steam
atmosphere. The high-temperature steam induces
the dealumination of the zeolitic framework,
hydrolyzing the framework aluminum, which is then
partially substituted by silicon. The extracted
aluminum remains as extra-framework aluminum
within the zeolite structure. The types of extra-
framework aluminum can vary based on the
hydrothermal treatment conditions and the
properties of the zeolite. This aluminum plays a
significant role in influencing the catalytic
properties of zeolite Y, [15].
Zeolites Y in their original as well as modified
form are used in a wide range of chemical
processes. These processes include biomass
valorization [16], hydrocarbon cracking [17], VOC
oxidation [18], oxidative dehydrogenation [19], and
hydrocarbon adsorption [20].
In this work, new ecological catalysts for the
alkylation of toluene were prepared. They were
studied as a replacement for conventional
technology using non-environmentally friendly
catalysts. The novelty of the work lies in the
observation of the relation of sodium residues in
dealuminated zeolite Y in ammonium form on the
conversion, and selectivity for the desired product
and product composition.
2 Experimental
2.1 Catalysts Preparation
Zeolite NaY (Si/Al = 2.69; Na2O = 11.59 %) as a
parent zeolite used for further treatment and testing
was obtained from the Research Institute of
Petroleum and Hydrocarbon Gases, Bratislava
The parent catalyst was treated by
decationization at the Department of Organic
Technology, Catalysis, and Petroleum Chemistry.
Three zeolite catalysts were prepared by
decationization with different residues of sodium
after treatment. 10 ml of NH4NO3 solution on 1 g of
zeolite was used for all three zeolites. First zeolite Y
(Y-A) with sodium molar content of 2.69 % was
prepared by three-time repeated decationization
with a solution of NH4NO3 (1.5 M) at room
temperature. Second zeolite Y (Y-B) with a sodium
content of 1.27 % was prepared by four-time
repeated decationization with the same
concentration of NH4NO3 solution (1.5 M) at the
temperature of 90 °C. Third zeolite Y (Y-C) with
a sodium content of 0.76 % was prepared by eight-
time repeated decationization with NH4NO3 solution
at the temperature of 90 °C. Zeolites after
decationization were washed with distilled water
several times. Washed zeolites were dried in an
oven at a temperature of 80 °C and then
hydrothermally treated in a deep bed at different
temperatures of 560°C (NH4SY-4A, NH4SY-4B,
and NH4SY-4C) and 780 °C (NH4SY-2A, NH4SY-
2B, and NH4SY-2C). The last step of zeolite
modification was removing residual sodium and
extra framework aluminum by the solution of
NH4NO3 (2 M) three times at the temperature of 90
°C.
For alkylation testing H-forms of zeolites were
used. NH4-forms of zeolites Y were activated at
450°C (3 hours) to obtain H-form. Before reaction,
the formed H-form was let to cool down in a
desiccator.
2.2 Catalysts Characterization
The physical adsorption of nitrogen (–196 °C) was
used for the measurement of textural properties. The
used devise was ASAP-2400 (Micrometrics).
Measured zeolites were evacuated overnight
(350°C) under the vacuum (2 Pa) before analysis.
Conventional BET isotherm (p/p0 = 0.05–0.3)
method was used for specific surface area (SBET)
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calculation. For the external surface area with the
surface of mesopores (St) and the volume of
micropores (Vmicro) calculation, the t-plot using
Harkins–Jura master isotherm was used. The
volume of adsorbed nitrogen (p/p0 = 0.99) was used
for determination of total pore volume (Vp).
Fig. 1: Scheme of parent zeolite treatment
Temperature programmed desorption of
ammonia (TPD-NH3) method was used for the total
acidity determination. Zeolites (300 mg) were
treated in situ at 480 °C for 2 h (He flow) and then
cooled down to 220 °C (He atmosphere) right before
the adsorption. Ammonia was adsorbed at
a temperature of 220 °C by using an NH3/He
mixture. The desorption of NH3 was carried out at
the temperature from 220 to 700 °C (He flow).
During desorption, the effluent was led to the
solution of H2SO4 (0.05 M). Titration of NaOH
(0.05M) solution was used for the determination of
desorbed ammonia.
Brønsted (BAS) and Lewis (LAS) acidic sites
were measured by FTIR Genesis spectrometer
(Mattson-Unicam). Infrared spectroscopy of
pyridine adsorption was used for determination.
Zeolites with a surface density of ca. 8 mg/cm2 in
the form of wafers were activated at 450 °C under a
vacuum (10−4 Pa) for 3 h. The number of acid sites
was determined based on the integrated area
absorbances at 1550 (Brønsted) and 1450 cm−1
(Lewis), respectively, in correlation with their
extinction coefficients, [21]. KBr technique using
FTIR spectra was used for the molar ratio Si/Al
determination. the.
2.3 Catalytic Tests
All modified zeolites were tested in the alkylation
process at a temperature of 100 °C in a stirred batch
reactor (stainless-steel). Toluene p.a. (Mikrochem
Pezinok, 99.0 %) and 1-decene (Spolana
Neratovice, > 96 %) were used as feed of
hydrocarbons. For catalytic testing 80 g of reaction
mixture in a molar ratio of toluene to 1-decene 8.6:
1 was used for each experiment. An amount of 2.5
wt.% of calcined catalyst to the reaction mixture
was used. After reaching the reaction temperature of
100°C (30 min) first sample of reaction products
was taken. After that, every 30 minutes product
samples were taken until reaching 240 minutes of
reaction. Feed and reaction products were analyzed
with a gas chromatograph Hewlett-Packard 5890 A
(Series II) equipped with flame-ionisation detector.
Alkyltoluenes and olefins structures from products
were verified by GC-MS using MS25RFA Kratos,
Manchester equipment.
The 1-decene conversion was calculated as the
percentage of all products in sum with 1-alkenes to
all products. Selectivity of 2-decyltoluene was
calculated as a percentage of 2-decyltoluene in all
prepared products.
3 Results and Discussion
3.1 Zeolite Characterization
For testing modified zeolites in the alkylation
process, nine different samples of modified zeolites
were prepared by changing conditions of zeolite
treatment (Figure 1). As can be seen in Table 1, the
changes in decationization conditions had
a significant effect on catalyst properties. Especially
it is possible to see the correlation between the
molar ratio of Si/Al after the decationization process
and sodium content. With the decreasing sodium
content in treated zeolite, the molar ratio of Si/Al
increased. The same trend is possible to see in
relation to changes in hydrothermal treatment
temperature. With increasing decationization
temperature, the molar ratio of Si/Al is higher.
Different methods were used for obtaining
information about physical-chemical properties of
tested zeolites pretreated by different conditions.
Table 1. Content of Na and the molar ratio of Si/Al
in modified zeolites Y
Zeolite
Na2O
(wt.%)
Si/Al
Y-A
2.69
2.29
NH4SY-4A
> 0.05
4.25
NH4SY-2A
> 0.05
4.76
Y-B
1.27
2.26
NH4SY-4B
> 0.05
4.94
NH4SY-2B
> 0.05
6.65
Y-C
0.76
2.25
NH4SY-4C
> 0.05
5.28
NH4SY-2C
> 0.05
8.17
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In Table 2 it is possible to see the physical-
chemical properties of modified zeolites,
specifically textural properties. Hydrothermal
treatment as a last step of modifying zeolites at both
temperatures caused a decrease in the specific
surface area and volume of micropores in
comparison with zeolites without hydrothermal
stabilization.
Table 2. Characteristics of physical-chemical
properties of
modified zeolites Y
Zeolite
SBET
(m2/g)
St
(m2/g)
Vmicro
(cm3/g)
VP
(cm3/g)
Y-A
648
42
0.32
0.37
NH4SY-4A
617
53
0.29
0.35
NH4SY-2A
612
65
0.29
0.38
Y-B
690
30
0.35
0.38
NH4SY-4B
642
67
0.30
0.39
NH4SY-2B
611
77
0.28
0.41
Y-C
681
27
0.34
0.37
NH4SY-4C
630
71
0.30
0.39
NH4SY-2C
600
91
0.27
0.41
In the case of mesoporous volume and
mesoporous surface, the opposite trend was
observed, when hydrothermal treatment at both
temperatures slightly increased these values. These
results indicate, that after the dealumination, the
secondary mesoporous structure was formed for all
modified zeolites.
The acidic properties of modified samples from
FTIR adsorbed pyridine and TPDA measurement
are possible to see in Table 3. The impact of sodium
content on the total acidity of modified zeolites was
observed. The total acidity of zeolites
hydrothermally treated at both temperatures shows
lower total acidity with a lower molar ratio of Si/Al.
The highest content of Lewis active sites was
reached in NH4SY-4A. The high presence of LAS is
undesirable in context with the alkylation process,
due to the formation of coke and that leads to
catalyst deactivation. On top of that, the presence of
LAS leads to the formation of undesirable by-
products during the reaction, [22]. The higher molar
ratio of Si/Al caused a decrease in the ratio of
BAS/LAS. A higher BAS/LAS ratio positively
influences the alkylation process.
The content of LAS and BAS and its molar ratio
were determined by FTIR of desorbed pyridine. In
Figure 2, the FTIR spectra of desorbed pyridine on
modified catalysts by hydrothermal treatment at 560
°C in a deep bed are possible to see. The absorption
band at 1540 cm-1 belongs to Brøndsted acid sites
and the absorption band at 1450 cm-1 represents the
Lewis basic sites. The absorption band at 1490 cm-1
belongs to both acid types of acid sites, but this
band is commonly not evaluated, [22].
Table 3. Acidic properties of modified
zeolites Y from TPDA and FTIR
Fig. 2: FTIR spectra of desorbed pyridine on
hydrothermally treated zeolite Y at 560 °C
3.2 Alkylation of Toluene over Modified
Zeolites
Prepared modified zeolites before hydrothermal
treatment (Y-A, Y-B, Y-C) and after hydrothermal
treatment at 560°C (NH4SY-4A, NH4SY-4B, and
NH4SY-4C) and 780 °C (NH4SY-2A, NH4SY-2B,
and NH4SY-2C) were used in alkylation process.
Firstly, decationated zeolites without hydrothermal
treatment were tested in the alkylation of toluene.
The dependence of 1-decene conversion on TOS is
shown in Figure 3.
Fig. 3: Dependence of 1-decene conversion on TOS
over modified zeolites Y
Zeolite
BAS
(mmol/g)
LAS
(mmol/g)
Ratio
BAS/LAS
Acidity
(mmol/g)
NH4SY-4A
0.86
0.59
1.46
1.45
NH4SY-2A
0.79
0.25
3.22
1.04
NH4SY-4B
0.95
0.33
2.84
1.28
NH4SY-2B
0.77
0.18
4.24
0.95
NH4SY-4C
0.89
0.27
3.36
1.16
NH4SY-2C
0.72
0.15
4.72
0.87
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From the figure, it is possible to see, that
different sodium content significantly influenced the
course of the conversion of 1-decene. Even the first
taken sample at 30 minutes of reaction, showed
conversion over Y-C almost three times higher than
Y-A. The course of the whole reaction copies this
trend until almost the end of the reaction. These
results indicate, that lower sodium content improves
the catalytic activity in alkylation towards desired
products. After the end of the reaction at 240th
minutes of reaction, Y-C reached the highest
conversion (Table 4) among all tested zeolites. From
the view of selectivity to 2-decyltoluene (S2-DT), the
amount of sodium in tested zeolites did not show
any differences.
Table 4. Results of alkylation with 1-decene at 240th
minute of reaction
Zeolite
XC10
(wt.%)
S2-DT
(wt.%)
LAT
(wt.%)
BAT
(wt.%)
DIM
(wt.%)
DAT
(wt.%)
Y-A
94.7
29.6
91.3
8.3
0.2
0.2
Y-B
97.7
29.6
90.3
9.1
0.3
0.3
Y-C
99.4
29.6
89.7
8.1
0.8
1.4
The composition of products is formed by LAT
(Linear alkyltoluenes), BAT (Branched
alkyltoluenes), DIM (dimers of 1-decene), DAT
(dialkyltoluenes). 2-decyltoluene as a part of LAT is
in technology the most desired product
(biodegradable) for detergent production. The
composition of produced alkylaromates showed
small differences, where in the case of using Y-C
with the lowest sodium content, more undesirable
products were made during the reaction.
Based on the reaction course of conversion
during reaction time, the 60th minute was chosen to
demonstrate other dependencies. This time was
chosen based on the fact, that after this time the
reaction course was stabilized and there were not
that significant differences. Figure 4 demonstrates
the dependence of 1-C10 conversion on sodium
content in prepared zeolites before hydrothermal
treatment. The conversion of 1-decene is
significantly influenced by sodium content. With
higher sodium content, the conversion of 1-C10 at
the beginning of the reaction is lower. This
observation could be explained by the blocking of
active sites by sodium.
The impact of sodium content in the first steps
of modification of parent zeolite was observed. To
see, if the next step of modifications, hydrothermal
treatment, can further influence catalyst activity and
selectivity in alkylation, decationated zeolites
hydrothermally treated at 560°C and 780°C were
tested in alkylation. During hydrothermal treatment
at both temperatures in a deep bed, residual sodium
is removed from the catalyst. Firstly, zeolites
treated at 560°C were tested (Figure 5).
Fig. 4: The dependency of C10 conversion on sodium
content in the 60th minute of the reaction
Fig. 5: Dependence of C10 conversion on TOS over
zeolites treated at 560 °C
The hydrothermal treatment at a lower
temperature 560°C, improved catalyst activity in
reaction. Even at first sight is possible to see at the
beginning of the reaction (30 min), that is the
conversion notably higher than in catalysts without
hydrothermal treatment and sodium residue
removal. While without hydrothermal treatment, the
conversion at 30 minutes was between 20-55 %
(Figure 3), after treatment at 560°C all tested
zeolites reached conversion above 85 %. In the
comparison of treated zeolites with different sodium
content, the trend is the same, where the reaction
course over zeolite with the lowest sodium content
is significantly lower. The composition of products
and final conversion of 1-C10 is possible to see in
Table 5.
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Table 5. Results of alkylation with 1-decene at 240th
minute of reaction over zeolites treated at 560 °C
Zeolite
XC10
(wt.%)
S2-DT
(wt.%)
LAT
(wt.%)
BAT
(wt.%)
DIM
(wt.%)
DAT
(wt.%)
NH4S
Y-4A
99.5
31.8
86.4
10.6
0.1
2.9
NH4S
Y-4B
99.6
31.6
84.5
12.0
0.0
3.5
NH4S
Y-4C
99.9
31.5
83.3
12.5
0.0
4.2
From the composition of final products, the
content of sodium influenced mostly the formation
of LAT and BAT and the higher formation of DAT.
This observation could be explained by a lower
amount of Lewis acid sites, which could cause the
formation of “liquid coke”, [23]. In comparison with
zeolites without hydrothermal treatment, the
formation of LAT is notably lower over zeolites
treated at 560°C. Lower production of LAT and
higher BAT production is related to the secondary
mesoporous structure formation (St in Table 2).
The dependence of selectivity to 2-decyl-
toluene on 1-C10 conversion over hydrothermally
treated zeolites at 560°C is shown in Figure 6. With
the increasing conversion of 1-decene, the
selectivity to the desired product (2-DT) decreased,
with the formation of by-products. But overall
selectivity at the end of the reaction is higher in
comparison with zeolites without hydrothermal
treatment. This is caused by the formation of
the secondary mesoporous structure after
dealumination.
Fig. 6: The dependence of 2-DT selectivity on 1-
C10 conversion over zeolite Y treated at 560 °C.
Zeolites Y modified with the last step of
hydrothermal treatment at 780°C were also tested in
the alkylation process (Figure 7). In comparison
with lower treatment temperatures, there are some
differences.
Fig. 7: Dependence of C10 conversion on TOS over
zeolites treated at 780 °C
While at the beginning of the reaction (30 min),
conversion reached a lower value, at the 60th minute
all tested catalysts reached conversion higher than
95%. After 90 minutes, conversion reached 99 %
and further did not change. It can be stated, that the
higher temperature of hydrothermal treatment
improves the diffusion properties of zeolite Y. This
allowed reactants to easily enter active sites, where
product formation takes place. Product
composition and selectivity to desired 2-DT over
zeolite treated at 780°C are listed in Table 6.
Table 6. Results of alkylation with 1-decene at 240th
minute of reaction over zeolite treated at 780 °C
Zeolite
XC10
(wt.%)
S2-DT
(wt.%)
LAT
(wt.%)
BAT
(wt.%)
DIM
(wt.%)
DAT
(wt.%)
NH4S
Y-2A
99.5
34.7
87.7
9.1
0.0
3.2
NH4S
Y-2B
99.6
34.9
87.8
8.9
0.0
3.3
NH4S
Y-2C
99.9
34.8
87.9
8.7
0.0
3.4
Selectivity is notably higher in comparison with
alkylation over zeolites treated by the last step of
modification at 560°C. LAT production is slightly
higher at the expanse of the reduced formation of
BAT. On the other hand, the formation of DIM as
an undesirable by-product, was not observed in both
modification temperatures. In the case of
hydrothermal treatment at 780°C, the impact of
sodium content on product composition was not
observed. The increase of 1-decene conversion
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caused a slight decrease in selectivity to 2-
decyltoluene (Figure 8).
Fig. 8: The dependence of 2-DT selectivity on 1-
C10 conversion over Zeolite Y treated at 780 °C
4 Conclusion
The main disadvantage of currently used
technologies of alkylation process of aromatics is
nonecological catalyst. Zeolites could be one of the
possible replacements as an environmentally
friendly catalyst. The results confirm the good
activity of modified zeolites in toluene alkylation
with 1-decene as an model reaction of aromatics
alkylation. Steps of modification of parent zeolite Y
showed a significant impact on catalyst activity in
reaction. Zeolites Y after decationization without
hydrothermal treatment confirmed their activity in
the alkylation reaction. But in comparison with
hydrothermally treated zeolites Y, the conversion of
1-decene and selectivity to 2-decyltoluene were
notably lower. Another thing is the stability and
regenerability of the prepared catalyst, where
zeolites after hydrothermal treatment are more
stable and could be regenerated and reused.
The achieved 1-decene conversion was the same
as for commercial catalysts and the selectivity to 2-
decyltoluene was higher by about 13%, while the
amount of linear alkyltoluenes was retained. The
amount of sodium left after decationization showed
a notable effect on physical-chemical properties.
Decationization followed by hydrothermal treatment
at both temperatures (560 °C and 780°C) caused
the formation of a secondary mesoporous structure,
which enhanced the diffusion properties of zeolite Y
in the alkylation process. Improvement of diffusion
properties and accessibility of active sites in
catalysts led to higher conversion of 1-decene and
the selectivity to 2-decyl toluene. Prepared catalysts
could be used as a potential replacement for
commercial alkylation catalysts such as HF or AlCl3
in industry.
Acknowledgement:
This article was written thanks to the generous
support under the Operational Program Integrated
Infrastructure for the project:” Support of research
activities of Excellence laboratories STU in
Bratislava”, Project no. 313021BXZ1, co-financed
by the European Regional Development Fund.”
Declaration of Generative AI and AI-assisted
Technologies in the Writing Process
During the preparation of this work the authors used
chat GDP in order to grammar check. After using
this tool/service, the authors reviewed and edited the
content as needed and take full responsibility for the
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WSEAS TRANSACTIONS on ENVIRONMENT and DEVELOPMENT
DOI: 10.37394/232015.2024.20.78
Michal Horňáček,
Miroslava Bérešová, Pavol Hudec
E-ISSN: 2224-3496
842
Contribution of Individual Authors to the
Creation of a Scientific Article (Ghostwriting
Policy)
Dr. Michal Horňáček, Dr. Miroslava Bérešová and
Assoc. Prof. Pavol Hudec equally contributed in the
present research, at all stages from the formulation
of the problem to the final findings and solution.
Sources of Funding for Research Presented in a
Scientific Article or Scientific Article Itself
This article was written thanks to the generous
support under the Operational Program Integrated
Infrastructure for the project:” Support of research
activities of Excellence laboratories STU in
Bratislava”, Project no. 313021BXZ1, co-financed
by the European Regional Development Fund.”
Conflict of Interest
The authors have no conflicts of interest to declare
that are relevant to the content of this article.
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WSEAS TRANSACTIONS on ENVIRONMENT and DEVELOPMENT
DOI: 10.37394/232015.2024.20.78
Michal Horňáček,
Miroslava Bérešová, Pavol Hudec
E-ISSN: 2224-3496
843