The kinetic model of the combined heterogeneously catalyzed condensation and esterification of propionic acid and methyl propionate with formaldehyde and methanol
In this work we aim for developing a kinetic model for the methyl methacrylate and methacrylic acid synthesis by the combined condensation and esterification of methyl propionate and propionic acid with formaldehyde and methanol in the presence of the silica-supported boron-phosphorus-o...
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V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine
2022
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Catalysis and petrochemistry| _version_ | 1872009038252736512 |
|---|---|
| author | Ivasiv, Volodymyr V. Nebesnyi, Roman V. Maykova, Svitlana V. |
| author_facet | Ivasiv, Volodymyr V. Nebesnyi, Roman V. Maykova, Svitlana V. |
| author_institution_txt_mv | [
{
"author": "Volodymyr V. Ivasiv",
"institution": "Lviv Polytechnic National University, S. Bandery Str., 12, Lviv, 79013, Ukraine"
},
{
"author": "Roman V. Nebesnyi",
"institution": "Lviv Polytechnic National University, S. Bandery Str., 12, Lviv, 79013, Ukraine"
},
{
"author": "Svitlana V. Maykova",
"institution": "Ivan Franko National University of Lviv, Universytetska St, 1, Lviv, 79000, Ukraine"
}
] |
| author_sort | Ivasiv, Volodymyr V. |
| baseUrl_str | https://kataliz.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2023-01-20T09:50:05Z |
| description | In this work we aim for developing a kinetic model for the methyl methacrylate and methacrylic acid synthesis by the combined condensation and esterification of methyl propionate and propionic acid with formaldehyde and methanol in the presence of the silica-supported boron-phosphorus-oxide catalyst promoted by oxides of tungsten and zirconium. The dependencies of the formation rates of methyl methacrylate, methacrylic acid and diethyl ketone from the concentrations of methyl propionate, propionic acid, formaldehyde and methanol were studied, and reaction orders of every product formation with respect to each reagent were determined. Methacrylic acid is formed predominantly by condensation of methyl propionate with formaldehyde, and methyl methacrylate hydrolysis is insignificantly. The methyl methacrylate formation reaction rate is limited by the methyl propionate adsorption rate on the catalyst surface, and both reactions of methyl methacrylate and methacrylic acid formation are inhibited due to adsorption of formaldehyde, propionic acid and methanol. Based on obtained data, the reaction scheme was offered, which includes formation of intermediates such as 3-hydroxy-2-methylpropanoic acid, its methyl ester and 3,3-dihydroxy-2-methylpentanoic acid. From this reaction scheme the kinetic model was derived using steady state approximation. The reaction rate constants and their activation energies for this model were calculated from experimental data. Validity of the model was experimentally confirmed by the correlation between experimental and theoretically calculated data. Therefore, the developed kinetic model satisfactorily describes the process of the combined condensation and esterification of methyl propionate and propionic acid with formaldehyde and methanol as well as partial cases of condensation of methyl propionate with formaldehyde and propionic acid with formaldehyde, and is suitable for process optimization and technological calculations. |
| doi_str_mv | 10.15407/kataliz2022.33.031 |
| first_indexed | 2026-03-12T15:50:15Z |
| format | Article |
| fulltext |
Каталіз та нафтохімія, 2022, №33 31
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
UDC 541.128.13
https://doi.org/10.15407/kataliz2022.33.031
The kinetic model of the combined heterogeneously catalyzed condensation
and esterification of propionic acid and methyl propionate with
formaldehyde and methanol
Volodymyr V. Ivasiv1, Roman. V. Nebesnyi1, Svitlana V. Maykova2
1Lviv Polytechnic National University, S. Bandery Str., 12, Lviv, 79013, Ukraine; volodymyr.v.ivasiv@lpnu.ua
2Ivan Franko National University of Lviv, Universytetska St, 1, Lviv, 79000, Ukraine; svitl.majkova@gmail.com
In this work we aim for developing a kinetic model for the methyl methacrylate and methacrylic acid synthesis
by the combined condensation and esterification of methyl propionate and propionic acid with formaldehyde and
methanol in the presence of the silica-supported boron-phosphorus-oxide catalyst promoted by oxides of tungsten and
zirconium. The dependencies of the formation rates of methyl methacrylate, methacrylic acid and diethyl ketone from
the concentrations of methyl propionate, propionic acid, formaldehyde and methanol were studied, and reaction
orders of every product formation with respect to each reagent were determined. Methacrylic acid is formed
predominantly by condensation of methyl propionate with formaldehyde, and methyl methacrylate hydrolysis is
insignificantly. The methyl methacrylate formation reaction rate is limited by the methyl propionate adsorption rate
on the catalyst surface, and both reactions of methyl methacrylate and methacrylic acid formation are inhibited due to
adsorption of formaldehyde, propionic acid and methanol. Based on obtained data, the reaction scheme was offered,
which includes formation of intermediates such as 3-hydroxy-2-methylpropanoic acid, its methyl ester and 3,3-
dihydroxy-2-methylpentanoic acid. From this reaction scheme the kinetic model was derived using steady state
approximation. The reaction rate constants and their activation energies for this model were calculated from
experimental data. Validity of the model was experimentally confirmed by the correlation between experimental and
theoretically calculated data. Therefore, the developed kinetic model satisfactorily describes the process of the
combined condensation and esterification of methyl propionate and propionic acid with formaldehyde and methanol
as well as partial cases of condensation of methyl propionate with formaldehyde and propionic acid with
formaldehyde, and is suitable for process optimization and technological calculations.
Keywords: heterogeneous catalysis, kinetics, condensation, acrylates, esterification
____________________________________________________________________________________________________
Introduction
The condensation processes of carbonyl
compounds occupy a prominent place in the organic
synthesis industry, since they allow to produce a
multitude of valuable products, among which methyl
methacrylate (MMA) and methacrylic acid (MAA) are
especially important. These compounds are easily
polymerized, and therefore are widely used for the
production of various polymeric materials with
valuable properties. The wide scope of acrylate
monomers usage causes a significant annual growth of
world demand for them, and as result the need for a
new and improved methods for their production [1-3].
Combined condensation and esterification of methyl
propionate (MP) and propionic acid (PA) with
formaldehyde (FA) and methanol (M) is a prospective
method for acrylates production since it allows to use
either MP or PA or their mixture as raw materials
depending on the market availability, and to produce
both MMA and MAA with variable ratio depending on
the market demand [4-5]. In the previous research the
B–P–Zr–W–Ox/SiO2 catalytic system was found to be
efficient for this process, with total MMA + MAA
yield up to 96.3 %, with the sole by-product being
diethyl ketone (DEK) which is also valuable product
[5]. Further research is needed to establish the process
kinetics. Previously we have developed kinetic models
for a simpler cases of individual condensation
reactions of PA with FA [6] and MP with FA [7]. The
aim of this work is to develop a kinetic model for a
more complex case of combined condensation and
esterification of MP and PA with FA and methanol,
suitable for process optimization and technological
calculations.
Experiment
The catalyst was prepared by impregnating the
silica support with the solutions of boron acid,
diammonium hydrogen phosphate, phosphotungstic
acid and zirconium oxychloride, with further drying at
423 K for 8 h and calcinating at 673 K for 6 h. Atomic
ratio B:P:Zr:W = 3:1:0.15:0.15 was used as it was
previously determined as the optimum by the yield and
mailto:volodymyr.v.ivasiv@lpnu.ua
mailto:svitl.majkova@gmail.com
32 Каталіз та нафтохімія, 2022, №33
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
selectivity of acrylates [5]. Specific surface area of the
catalyst was 348 m2/g.
The kinetic was studied in the gas-phase flow
tubular reactor (200 mm × 16 mm) with fixed catalyst
bed at low (under 30%) reagents conversion to
maintain concentrations at quasi-stationary values.
Catalyst load was 16 g. Analytical research grade
methyl propionate, propionic acid, methanol and
paraformaldehyde were used. 36 wt.% formaldehyde
water solution was prepared from paraformaldehyde
immediately before the experiments. MP, PA and
methanol concentrations in the gas phase were varied
in the range 3.74∙10-3 – 7.48∙10-3 mol/l, while FA
1.25∙10-2 – 2.49∙10-2 mol/l to account for its double
stoichiometric consumption. While varying the initial
concentration of one reactant, initial concentrations of
others were kept constant. Analysis was done on
Agilent 5890 SII gas chromatograph equipped with
FID and TCD detectors, using Supelcowax 10 column
(30 m × 0.53 mm) and helium as carrier gas.
Results and discussion
Generally, the investigated process can be
described by the following reactions:
CH3CH2COOH + CH2O → CH2=C(CH3)COOH + H2O
CH3CH2COOH + CH2O + CH3OH → CH2=C(CH3)COOCH3 + 2 H2O
CH3CH2COOCH3 + CH2O → CH2=C(CH3)COOCH3 + H2O
2 CH3CH2COOH → (CH3CH2)2CO + H2O + CO2
The dependencies of the products (MMA, MAA
and DEK) formation rates from the reagent (MP, PA,
FA and methanol) concentrations were studied in the
temperature range 593 – 683 K. The results at 653 K
are shown in the Fig. 1.
Fig. 1. Dependence of the initial formation rate of methacrylic acid (1), methyl methacrylate (2) and diethyl
ketone (3) from each individual reagent initial concentration: methyl propionate (a), propionic acid (b), methanol
(c) and formaldehyde (d) at reaction temperature 653 K
Каталіз та нафтохімія, 2022, №33 33
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
From experimental data, it has been established
that the MMA formation reaction in the presence of
the B–P–Zr–W–Ox/SiO2 catalytic system has the order
close to first (0.93 – 1) with respect to MP and a bit
less than one (0.8 – 0.9) with respect to PA (Fig. 1a–
1b, curve 1). The order of the MMA formation is
significantly lower than one and is 0.3 – 0.5 (Fig. 1c,
curve 1), which indicates the limiting of the MMA
formation reaction rate by the MP adsorption rate on
the surface of the catalyst, similar to the individual
condensation reaction of MP with FA [7]. The order of
MMA formation with respect to methanol is also
substantially smaller than one and is 0.2 – 0.4 (Fig. 1d,
curve 1).
The reaction of MAA formation has the order of
0.7 – 0.95 with respect to MP and 0.9 – 0.97 with
respect to PA, while the order with respect to FA is
around 0.7 – 0.8 (Fig. 1a–1c, curve 2). Similarly, to the
individual condensation reaction of MP with FA [7],
an increase in the FA concentration inhibits the MMA
formation rate, but increases MAA formation rate,
which indicates that MAA is formed predominantly by
condensation of PA with FA, and MMA hydrolysis is
insignificant. With respect to methanol, MMA
formation has the order a bit under zero (-0.1 – -0.2),
since methanol does not participate in the MAA
formation and inhibits this reaction (Fig. 1d, curve 2).
It should be noted that both reactions of MMA and
MAA formation are inhibited due to adsorption of FA,
PA and methanol on the surface of the catalyst.
The reaction of the formation of DEK has an
order of somewhat less than 2 with respect to MP (1.4
– 1.8) and PA (1.8 – 1.94) (Fig. 1a–1b, curve 3), which
confirms that the rate of DEK formation is limited by
the rate of interaction of PA molecules adsorbed on the
catalyst surface with free PA molecules from the
reaction volume, and in addition is slightly inhibited
by MP due to its adsorption on the catalyst surface.
Also the reaction of the DEK formation has the order a
bit under zero with respect to FA (-0.05 – -0,015) and
with respect to methanol (-0.1 – -0.2), and hence is
inhibited by both reagents (Fig. 1c–1d, curve 3).
Based on this data, the following reaction scheme
can be derived for the process of combined
condensation and esterification of MP and PA with FA
and methanol. PA molecules are adsorbed on active
sites of the catalyst surface with the formation of
activated methylene component, which are next
attacked by FA molecules from the reaction volume
with the formation of adsorbed 3-hydroxy-2-
methylpropanoic acid, which is next dehydrated to
MAA. In the case of the interaction of an adsorbed PA
molecule with another PA molecule, 3,3-dihydroxy-2-
methylpentanoic acid is formed, which is next
converted into DEK due to the splitting out of CO2 and
water. In the case of interaction of an adsorbed
molecule of PA with methanol from reaction volume,
the formation of an activated MP molecule occurs.
Also activated MP molecules are formed as a result of
adsorption of MP from reaction volume on free active
sites on the catalyst surface. Interaction of activated
MP molecules with FA molecules from reaction
volume leads to the formation of adsorbed methyl ester
of 3-hydroxy-2-methylpropanoic acid, which due to
dehydration is next transformed into MMA. Taking
into account the practical irreversibility of dehydration
reactions in the reaction conditions [6, 7], the
following scheme was used to derive the kinetic
model:
where (*) – free active site on the catalyst surface,
(MP*) – adsorbed activated MP, (PA*) – adsorbed
activated PA, (MHMPA) – adsorbed methyl ester of 3-
hydroxy-2-methylpropanoic acid, (HMPA) – adsorbed
3-hydroxy-2-methylpropanoic acid, M – methanol,
(DHMPA) – adsorbed 3,3-dihydroxy-2-methyl
pentanoic acid.
Каталіз та нафтохімія, 2022, №33 34
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
Based on the above reaction scheme and using
steady state approximation, the following equations for
intermediates formation rates can be formulated:
dΘ1/dt = k1∙CPA∙(1 – Θ1 – Θ2 – Θ3– Θ4 – Θ5) – k2∙Θ1 – k3∙CFA∙Θ1 + k4∙Θ2 – k6∙CPA∙Θ1 + k7∙Θ3 + k10∙ Θ4 – k9∙Θ1∙CM =0
dΘ2/dt = k3∙CFA∙Θ1 – k4∙Θ2 – k5∙Θ2 = 0
dΘ3/dt = k6∙CPA∙Θ1 – k7∙Θ3 –k8∙Θ3 = 0
dΘ4/dt = k11∙CMP∙(1 – Θ1 – Θ2 – Θ3– Θ4 – Θ5) – k12∙Θ4 – k13∙CFA∙Θ4 + k14∙Θ5 – k10∙Θ4 + k9∙Θ1∙CM =0
dΘ5/dt = k13∙CFA∙Θ4 – k14∙Θ5 – k15∙Θ5 = 0
where:
Θ1 – surface concentration of activated PA molecules;
Θ2 – surface concentration of 3-hydroxy-2-
methylpropanoic acid;
Θ3 – surface concentration of 3,3-dihydroxy-2-
methylpentanoic acid;
Θ4 – surface concentration of activated MP molecules;
Θ5 – surface concentration of methyl ester of 3-
hydroxy-2-methylpropanoic acid;
(1 – Θ1 – Θ2 – Θ3– Θ4 – Θ5) – concentration of free
active catalytic sites;
CMP – concentration of MP in reaction volume;
CPA – concentration of PA in reaction volume;
CFA – concentration of FA in reaction volume;
CM – concentration of methanol in reaction volume.
Considering that total concentration of catalyst's
active sites is constant, and assuming Θ1, Θ2, Θ3, Θ4,
Θ5 << 1, we can simplify these equations:
dΘ1/dt = k1∙CPA – k2∙Θ1 – k3∙CFA∙Θ1 + k4∙Θ2 – k6∙CPA∙Θ1 + k7∙Θ3 + k9∙CMP – k10∙Θ1∙CM =0
dΘ2/dt = k3∙CFA∙Θ1 – k4∙Θ2 – k5∙Θ2 = 0
dΘ3/dt = k6∙CPA∙Θ1 – k7∙Θ3 –k8∙Θ3 = 0
dΘ4/dt = k11∙CMP – k12∙Θ4 – k13∙CFA∙Θ4 + k14∙Θ5 –k9∙Θ4 + k10∙Θ1∙CM =0
dΘ5/dt = k13∙CFA∙Θ4 – k14∙Θ5 – k15∙Θ5 = 0
from where we can derive Θ1, Θ2, Θ3, Θ4, Θ5 via
reagents concentrations and rate constants.
Based on the reaction scheme the following equations
can be formulated for the formation rates of MMA,
MAA, PA and DEK:
WMMA = k15∙Θ5;
WMAA = k5∙Θ2;
WPA = k1∙CPA - k2∙Θ1 + k6∙CPA∙Θ1 – k7∙Θ3;
WDEK = k8∙Θ3.
Substituting here the values of Θ1, Θ2, Θ3, Θ4, Θ5,
with the values derived from steady state equations,
and simplifying the resulting equations by designating
specific expressions of rate constants k1 – k15 as
effective rate constants kef
1 – kef
10, we get the
following final kinetic model of combined
condensation and esterification of MP and PA with FA
and methanol:
ef ef
5 MP FA 7 PA FA M
MMA ef ef ef
6 FA 2 PA 8 M
K C C K C C C
W
1 K C K C K C
+
=
+ + +
(1)
ef
3 PA FA
MAA ef ef ef
1 FA 2 PA 8 M
K C C
W
1 K C K C K C
=
+ + +
(2)
ef 2
4 PA
DEK ef ef ef
1 FA 2 PA 8 M
K C
W
1 K C K C K C
=
+ + +
(3)
ef ef MMA
MP 9 MP 10
FA
W
W K C K
C
= − (4)
PA MMA MAA DEK MPW W W 2 W W= + + − (5)
FA MMA MAAW W W= + (6)
M MMA MPW W W= − (7)
Effective rate constants Kef
1, Kef
2, Kef
3, Kef
4 were
calculated from experimental data by linearization of
equation (2) in the coordinates 1/WMAA – 1/CPA with
stationary concentrations of FA and methanol (Fig.
2a):
ef ef ef
1 FA 8 M 2
ef ef
MAA PA3 FA 3 FA
K C K C 1 K1 1
W CK C K C
+ +
= +
and by linearization of equation (3) in the coordinates
1/WDEK – CFA with stationary concentrations of PA and
methanol (Fig. 2b):
ef efef
2 PA 8 M1
FAef 2 ef 2
DEK 4 PA 4 PA
K C K C 1K1
C
W K C K C
+ +
= +
Constants Kef
5, Kef
6, Kef
7, Kef
8 were calculated
from the equation (1), and constants Kef
9, Kef
10 – from
the equation (4) using data fitting by the least squares
method.
Activation energy of effective rate constants Kef
1
– Kef
10, were determined from the Arrhenius equation
linearization in the coordinates ln(K) – 1/T (Fig. 3).
Каталіз та нафтохімія, 2022, №33 35
ISSN 2707-5796. Kataliz ta naftohimia. 2022, 33
Fig. 2. Linearization of equation (2) in the coordinates 1/WMAA – 1/CPA (a) and equation (3) in the coordinates
1/WDEK – CFA (b).
Fig. 3. Linearization of the Arrhenius equation in the coordinates ln(K) – 1/T.
Resulting values of effective rate constants and
their activation energies are shown in the Table 1. The
correlation coefficient between the experimental data
of the reaction rates dependencies on the reagents
concentrations and theoretically calculated data from
the kinetic equations (1) – (7) is 0.95 – 0.99. Thus, we
can conclude that the developed kinetic model well
describes the process of gas-phase combined
condensation and esterification of MP and PA with FA
and methanol in the presence of a B–P–Zr–W–Ox/SiO2
catalyst, and can be used for technological calculation.
The kinetic model (1) – (7) also can be used for
the partial cases of the studied process. By equating
concentrations of methanol and MP to zero (CM = 0,
CMP = 0), the kinetic model transforms in the one for
the condensation of PA with FA to MAA described in
[6]. Similarly, by equating only the methanol
concentration to zero (CM = 0), the model describes the
process of condensation of MP with FA to MAA and
MMA [7]. Therefore, the kinetic model (1) – (7) can
be used as a general model for kinetics of various cases
of acrylic monomer synthesis by aldol condensation
reactions.
Каталіз та нафтохімія, 2022, №33 36
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
Table 1. Rate constants of the equations (1) – (7) and their activation energies.
Т, К
Kef
1·10-2,
Kef
2·10-2,
Kef
3·106,
Kef
4·105,
Kef
5·105,
Kef
6·10-2,
Kef
7·107,
Kef
8·10-3,
Kef
9·10-2,
Kef
10·10-3,
593
623
653
683
1.348
2.126
3.294
4.118
2.624
3.458
4.955
5.725
1.924
3.268
5.371
8.983
0.0457
0.2044
0.6817
1.2452
0.464
1.045
2.341
4.487
0.384
0.962
2.957
7.276
0.694
1.347
2.354
3.629
1.853
2.729
3.924
5.172
0.678
1.082
1.419
2.041
1.527
2.321
3.486
4.743
Ea,
kJ/mol
42.7 30.3 57.4 125.6 85.5 111.4 62.1 38.7 40.2 42.7
Conclusions
In this work we developed the kinetic model for
the gas-phase combined condensation and
esterification of methyl propionate and propionic acid
with formaldehyde and methanol in the presence of a
B–P–Zr–W–Ox/SiO2 catalyst. The kinetic model well
describes the process as whole as well as partial cases
of condensation of methyl propionate with
formaldehyde and propionic acid with formaldehyde.
Validity of the model was experimentally confirmed
by the correlation between experimental and
theoretically calculated data.
References
1. Mamoru A., Hideyuki F., Sanae H., Akiyo Y. Pro-
duction of methacrylic acid by vapor-phase aldol
condensation of propionic acid with formaldehyde
over silica-supported metal phosphate catalysts.
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191.
2. Koichi N. New developments in the production of
methyl methacrylate. Applied Catalysis A: General,
2001, 221 (1-2), 367-377.
3. Nebesnyi, R., Pikh, Z., Sydorchuk, V., Khalameida,
S., Kubitska, I., Khyzhun, O., Pavliuk, A., Voron-
chak, T. Aldol condensation of acetic acid and for-
maldehyde to acrylic acid over a hydrothermally
treated silica gel-supported B-P-V-W oxide. Ap-
plied Catalysis A: General, 2020, 594, art. no.
117472.
4. Dmytruk, Y., Ivasiv, V., Nebesnyi, R., Maykova, S.
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lyst. Eastern-European Journal of Enterprise
Technologies, 2015, 4 (6), pp. 4-7.
5. Lapychak, N., Ivasiv, V., Nebesnyi, R., Pikh, Z.,
Shpyrka, I. Synthesis of acrylates from methyl pro-
pionate, propionic acid and formaldehyde in the gas
phase on solid catalysts. Eastern-European Journal
of Enterprise Technologies, 2016, 5 (6), 44-48.
6. Nebesnyi, R., Ivasiv, V., Pikh, Z., Zhyznevskyi, V.,
Dmytruk, Y. The kinetics of the gas phase aldol
condensation reaction of propionic acid with for-
maldehyde on B2O3-P2O5-WO3/SiO2 catalyst.
Chemistry and Chemical Technology, 2014, 8(1),
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Надійшла до редакції 27.04.2022 р.
Каталіз та нафтохімія, 2022, №33 37
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
Кінетична модель сумісної гетерогенно-каталітичної конденсації та естерифікації
пропіонової кислоти та метилпропіонату з формальдегідом та метанолом
Володимир В. Івасів1, Роман В. Небесний1, Світлана В. Майкова2
1Національний університет "Львівська політехніка", вул. С. Бандери, 12, Львів, 79013, Україна;
volodymyr.v.ivasiv@lpnu.ua
2 Львівський національний університет імені Івана Франка, вул. Університетська, 1, Львів, 79000, Україна;
svitl.majkova@gmail.com
Метою даної роботи є розробка кінетичної моделі синтезу метилметакрилату та метакрилової кислоти
шляхом комбінованої конденсації та естерифікації метилпропіонату та пропіонової кислоти з формальдегідом
та метанолом у присутності нанесеного на силікагель бор-фосфор-оксидного каталізатора, промотованого
оксидами вольфраму та цирконію. Встановлено залежності швидкостей утворення метилметакрилату,
метакрилової кислоти та діетилкетону від концентрацій метилпропіонату, пропіонової кислоти,
формальдегіду та метанолу, а також порядки реакцій формування кожного продукту за кожним з реагентів.
Результати показали, що метакрилова кислота утворюється переважно конденсацією метилпропіонату з
формальдегідом, а гідроліз метилметакрилату є незначним. Швидкість реакції формування метилметакрилату
лімітується швидкістю адсорбції метилпропіонату на поверхні каталізатора, а обидва реакції утворення
метилметакрилату та метакрилової кислоти гальмуються через адсорбцію формальдегіду, пропіонової
кислоти та метанолу на поверхні каталізатора. Виходячи з отриманих даних, запропоновано схему реакцій,
яка включає утворення проміжних сполук, таких як 3-гідрокси-2-метилпропанова кислота, її метиловий ефір,
та 3,3-дигідрокси-2-метилпентанова кислота. З цієї схеми реакцій була виведена кінетична модель з
використанням методу стаціонарних концентрацій. Константи швидкості реакції та їх активації для цієї
моделі були розраховані з експериментальних даних. Дійсність моделі експериментально підтверджено
кореляцією між експериментальними та теоретично розрахованими даними. Таким чином, розроблена
кінетична модель добре описує процес комбінованої конденсації та естерифікації метилпропіонату та
пропіонової кислоти з формальдегідом та метанолом, а також часткові випадки конденсації метилпропіонату з
формальдегідом та пропіонової кислоти з формальдегідом, і підходить для оптимізації процесу та
технологічних розрахунків.
Ключові слова: гетерогенний каталіз, кінетика, конденсація, акрилати, еcтерифікація
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| id | oai:katalizorgua:article-79 |
| institution | Catalysis and petrochemistry |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-03-12T15:50:15Z |
| publishDate | 2022 |
| publisher | V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine |
| record_format | ojs |
| resource_txt_mv | katalizorgua/d5/5b563dcbba8af1878875c189b9de9bd5.pdf |
| spelling | oai:katalizorgua:article-792023-01-20T09:50:05Z The kinetic model of the combined heterogeneously catalyzed condensation and esterification of propionic acid and methyl propionate with formaldehyde and methanol The kinetic model of the combined heterogeneously catalyzed condensation and esterification of propionic acid and methyl propionate with formaldehyde and methanol Ivasiv, Volodymyr V. Nebesnyi, Roman V. Maykova, Svitlana V. heterogeneous catalysis, kinetics, condensation, acrylates, esterification гетерогенний каталіз, кінетика, конденсація, акрилати, еcтерифікація In this work we aim for developing a kinetic model for&nbsp;the methyl methacrylate and methacrylic acid synthesis by the combined condensation and esterification of methyl propionate and propionic acid with formaldehyde and methanol in the presence of the silica-supported boron-phosphorus-oxide&nbsp;catalyst promoted by oxides of tungsten&nbsp;and&nbsp;zirconium. The dependencies of the formation rates of methyl methacrylate, methacrylic acid and diethyl ketone from the concentrations of methyl propionate, propionic acid, formaldehyde and methanol&nbsp;were studied, and reaction orders of every product formation with respect to each reagent were determined. Methacrylic acid is formed predominantly by condensation of methyl propionate with formaldehyde, and methyl methacrylate hydrolysis is insignificantly. The methyl methacrylate formation reaction rate is limited by the methyl propionate adsorption rate on the catalyst surface, and both reactions of methyl methacrylate and methacrylic acid formation are inhibited due to adsorption of formaldehyde, propionic acid and methanol. Based on obtained data, the reaction scheme was offered, which includes formation of intermediates such as 3-hydroxy-2-methylpropanoic acid, its methyl ester and 3,3-dihydroxy-2-methylpentanoic acid.&nbsp;From this reaction scheme the kinetic model was derived using steady state approximation. The reaction rate constants and their activation energies for this model were calculated from experimental data.&nbsp;Validity of the model was experimentally confirmed by the correlation between experimental and theoretically calculated data. Therefore, the developed kinetic model satisfactorily describes the process of the combined condensation and esterification of methyl propionate and propionic acid with formaldehyde and methanol as well as partial cases of condensation of methyl propionate with formaldehyde and propionic acid with formaldehyde, and is suitable for process optimization and technological calculations. In this work we aim for developing a kinetic model for&nbsp;the methyl methacrylate and methacrylic acid synthesis by the combined condensation and esterification of methyl propionate and propionic acid with formaldehyde and methanol in the presence of the silica-supported boron-phosphorus-oxide&nbsp;catalyst promoted by oxides of tungsten&nbsp;and&nbsp;zirconium. The dependencies of the formation rates of methyl methacrylate, methacrylic acid and diethyl ketone from the concentrations of methyl propionate, propionic acid, formaldehyde and methanol&nbsp;were studied, and reaction orders of every product formation with respect to each reagent were determined. Methacrylic acid is formed predominantly by condensation of methyl propionate with formaldehyde, and methyl methacrylate hydrolysis is insignificantly. The methyl methacrylate formation reaction rate is limited by the methyl propionate adsorption rate on the catalyst surface, and both reactions of methyl methacrylate and methacrylic acid formation are inhibited due to adsorption of formaldehyde, propionic acid and methanol. Based on obtained data, the reaction scheme was offered, which includes formation of intermediates such as 3-hydroxy-2-methylpropanoic acid, its methyl ester and 3,3-dihydroxy-2-methylpentanoic acid.&nbsp;From this reaction scheme the kinetic model was derived using steady state approximation. The reaction rate constants and their activation energies for this model were calculated from experimental data.&nbsp;Validity of the model was experimentally confirmed by the correlation between experimental and theoretically calculated data. Therefore, the developed kinetic model satisfactorily describes the process of the combined condensation and esterification of methyl propionate and propionic acid with formaldehyde and methanol as well as partial cases of condensation of methyl propionate with formaldehyde and propionic acid with formaldehyde, and is suitable for process optimization and technological calculations. V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine 2022-10-26 Article Article application/pdf https://kataliz.org.ua/index.php/journal/article/view/79 10.15407/kataliz2022.33.031 Catalysis and petrochemistry; No. 33 (2022): Catalysis and petrochemistry; 31-37 Каталіз та нафтохімія; № 33 (2022): Каталіз та нафтохімія; 31-37 2707-5796 2412-4176 10.15407/kataliz2022.33 en https://kataliz.org.ua/index.php/journal/article/view/79/74 Copyright (c) 2022 Catalysis and petrochemistry |
| spellingShingle | гетерогенний каталіз кінетика конденсація акрилати еcтерифікація Ivasiv, Volodymyr V. Nebesnyi, Roman V. Maykova, Svitlana V. The kinetic model of the combined heterogeneously catalyzed condensation and esterification of propionic acid and methyl propionate with formaldehyde and methanol |
| title | The kinetic model of the combined heterogeneously catalyzed condensation and esterification of propionic acid and methyl propionate with formaldehyde and methanol |
| title_alt | The kinetic model of the combined heterogeneously catalyzed condensation and esterification of propionic acid and methyl propionate with formaldehyde and methanol |
| title_full | The kinetic model of the combined heterogeneously catalyzed condensation and esterification of propionic acid and methyl propionate with formaldehyde and methanol |
| title_fullStr | The kinetic model of the combined heterogeneously catalyzed condensation and esterification of propionic acid and methyl propionate with formaldehyde and methanol |
| title_full_unstemmed | The kinetic model of the combined heterogeneously catalyzed condensation and esterification of propionic acid and methyl propionate with formaldehyde and methanol |
| title_short | The kinetic model of the combined heterogeneously catalyzed condensation and esterification of propionic acid and methyl propionate with formaldehyde and methanol |
| title_sort | kinetic model of the combined heterogeneously catalyzed condensation and esterification of propionic acid and methyl propionate with formaldehyde and methanol |
| topic | гетерогенний каталіз кінетика конденсація акрилати еcтерифікація |
| topic_facet | heterogeneous catalysis kinetics condensation acrylates esterification гетерогенний каталіз кінетика конденсація акрилати еcтерифікація |
| url | https://kataliz.org.ua/index.php/journal/article/view/79 |
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