A Kinetic Model for the Epoxidation of Allyl Alcohol with Hydrogen Peroxide on Titanium Silicate TS-1

Article abstract of DOI:10.1134/S0023158417060118

The kinetic regularities of the oxidation of allyl alcohol into glycidol in the presence of titanium silicate are studied at varied initial concentrations of the reagents, products, and temperature. The probable mechanism is used as the basis to develop a substantial kinetic model, which adequately describes the obtained experimental data.

Full text of DOI:10.1134/S0023158417060118

ISSN 0023-1584, Kinetics and Catalysis, 2017, Vol. 58, No. 6, pp. 673–678. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © A.V. Sulimov, S.M. Danov, A.V. Ovcharova, V.R. Flid, L.G. Bruk, 2017, published in Kinetika i Kataliz, 2017, Vol. 58, No. 6, pp. 688–694.
A Kinetic Model for the Epoxidation of Allyl Alcohol
with Hydrogen Peroxide on Titanium Silicate TS-1
A. V. Sulimova, *, S. M. Danova, A. V. Ovcharovaa, V. R. Flidb, and L. G. Brukb
aAlekseev Nizhny Novgorod State Technical University, Nizhny Novgorod, 603950 Russia
bMoscow Technological University, Moscow, 119571 Russia
*e-mail: epoxide@mail.ru
Received April 3, 2017
Abstract—The kinetic regularities of the oxidation of allyl alcohol into glycidol in the presence of titanium sil-
icate are studied at varied initial concentrations of the reagents, products, and temperature. The probable
mechanism is used as the basis to develop a substantial kinetic model, which adequately describes the
obtained experimental data.
Keywords: epoxidation, allyl alcohol, hydrogen peroxide, titanium silicate, glycidol
DOI: 10.1134/S0023158417060118
Glycidol (1,2-epoxipropanol) is an important allyl alcohol with perbenzoic acid. However, these
product of basic organic synthesis. It readily reacts
with compounds of different classes due to its high
reactivity, which enables its application as a basis for
the synthesis of a number of products used in many
industrial branches (epoxide resins, lacquers, paints,
glues, synthetic fibers, ion-exchange resins, rubbers
characterized by a high level of grease- and thermal
resistance and gas proofness, etc.). Moreover, the
chlorine-free glycerin synthesis based on the hydroly-
sis of glycidyl alcohol was the basic synthetic glycerin
production method for a long time [1].
methods have a number of significant shortcomings,
including a low target product yield, the formation of a
great volume of hardly utilizable reaction byproducts,
and the contamination of waste waters. Hence, the
improvement of the existing glycidol production tech-
nologies and the development of new more advanced
methods are an urgent and relevant problem.
In our opinion, the most advanced glycidol (GD)
production method is the liquid-phase oxidation of
allyl alcohol (AA) with hydrogen peroxide represent-
ing an environmentally friendly oxidizer in an organic
solvent medium on a heterogeneous catalyst (titanium
Among the basic glycidol production methods are
glycerin monochlorohydrine dehydrohalogenation,
epichlorohydrine hydrolysis, and the reaction between silicate) [2]:
+ H2O
H2C CH CH2
+ H2O2
H2C CH CH2
(I)
O
OH
OH
АA
GD
Alcohols, ketones, and ethers may also be used as a medium. Under these conditions, a number of side
solvent. Our studies [3] have shown that the use of reactions leading to the formation of 1-methoxypro-
methanol provides the highest rates of the epoxidation panediol-2,3 (MPD), glycerin, and small amounts of
process at a satisfactory glycidol yield [4]; thus, its unidentifiable compounds occur in the system, along-
kinetic regularities were studied in a methanol side with the target glycidol formation reaction:
+
H2C CH CH2
H3C OH
H2C CH CH2
O
(II)
O
OH OH
MPD
OH
GD
CH3
673

674
SULIMOV et al.
+ H2O
H2C CH CH2
H2C CH CH2
OH OH OH
(III)
O
OH
GD
Moreover, reaction products were found to contain States). The obtained data were used to calculate the
oxygen formed by the reaction
parameters of the porous structure of the catalyst sam-
ples in automatic mode by the Brunauer–Emmett–
Teller (BET) method (specific surface area, 316.7 m2/g;
pore volume, 0.182 cm3/g; average pore size at the dis-
tribution maximum, 38 Å).
The allyl alcohol epoxidation process was studied on
a periodic laboratory setup in a temperature-controlled
glass reactor equipped with a magnetic agitator. At the
initial time moment, the reactor was loaded with allyl
alcohol, a solvent, and the catalyst in the calculated
amounts. Then the magnetic agitator drive was con-
nected and the reactor was attached to a thermostat and
thermostated for 10–15 min until a specified tempera-
ture was attained. Afterwards, the reactor was loaded
with Н2О2, and the starting time of the experiment was
recorded. Samples of the reaction mixture were taken
for analysis at certain time intervals with a capillary.
(IV)
2H2O2 → 2H2O + O2.
Several papers devoted to this glycidol synthesis
method have been published [5–12] in recent years.
However, these papers more often discuss the prob-
lems of the synthesis and application of different tita-
nium-containing zeolites (MWW, Ti-SBA-15, TS-1,
etc.), while the kinetic regularities of the allyl alcohol
epoxidation process are studied only in a very limited
number of works [9–12], in none of which titanium
silicate is considered as a catalyst. In this respect, the
objective of this study was to develop a substantial
kinetic model based on the probable mechanism of the
liquid-phase epoxidation of allyl alcohol with hydro-
gen peroxide in an organic solvent medium in the
presence of a heterogeneous catalyst, namely, tita-
nium silicate.
The components of the reaction mixture were ana-
lyzed by gas chromatography on a Khromos GKh-1000
(Russia) instrument equipped with a flame ionization
EXPERIMENTAL
The following reagents were used in this work: detector with a metallic column (2 m × 3 mm). The
methanol (pure grade), glycidol (pure grade, Techni- used phase was 15 wt % of Carbowax 6000 on the N-AW
cal Specifications (TU) 6-09-14-2635-79), 33–34-% chromatone. The carrier gas was nitrogen, whose flow
hydrogen peroxide (extra-pure grade, TU 2611-069- rate through the column was 50 mL/min. The tempera-
05807977-2006), allyl alcohol (TU 6-01-753-77), ture of the evaporator and columns’ thermostat were
tetrabutoxytitanium (TU 6-09-2738-89), tetraethox- 180 and 130°C, respectively.
ysilane (TU 2435-419-05763441-2003), and tetrapro-
pylammonium hydroxide synthesized by passing tet-
rapropylammonium bromide (98%, Acros) through
an anion-exchange column.
The content of Н2О2 was determined by iodometric
titration. The mean square error of the measurements
over the results of 5–7 parallel experiments was less
than 5%. The initial process rate was calculated from
the kinetic Н2О2 consumption curves via the differen-
tiation of the initial regions.
Powder titanium silicate synthesized according to
the works [13, 14] was used as the heterogeneous
epoxidation catalyst. The prepared catalyst was char-
acterized by X-ray diffraction on a Shimadzu LAB
XRD-6000 diffractometer (Japan) (CuKα radiation;
nickel filter; scintillation counter; voltage, 30 kV;
current, 30 mA) within the range of angles 2θ = 10°–
80° at a scanning rate of 2 deg/min and a step of
0.02 deg and IR spectroscopy (the spectra were
recorded in air at room temperature as KBr pellets in
the region of 400–4000 cm–1 on a Shimadzu IRAf-
finity-1 IR Fourier transform spectrometer).
The catalyst’s morphology was studied by scanning
electron microscopy (SEM) on a Hitachi S-2500 elec-
tron microscope (Japan) equipped with an Oxford
Instruments JNCA X-ray energy-dispersive micro-
analysis attachment (Britain) and low-temperature
nitrogen adsorption.
RESULTS AND DISCUSSION
The analysis of the IR spectra of the catalyst sam-
ples shows that the positions of the characteristic
reflections of the synthesized titanium silicate in the
regions of the bands at 540 and 960 cm–1 completely
coincide with the positions of the absorption bands in
the IR spectra presented in the literature [15–17].
The X-ray diffraction patterns of the catalytic sam-
ples are also in good agreement with the published
data [15–17].
To characterize the morphology of catalyst samples
in powder form, their microphotos were taken on a
scanning electron microscope. These photos were used
as the basis to plot the histograms of the size distribution
The specific surface area, the total volume of the of the catalyst particles (sampling incorporated more
pores, and the size distribution of their volume of the than 250 particles) and establish by statistical processing
powder catalyst were measured on a Micromeritics that the average size of catalyst particles in powder form
TriStar 3020 automatic gas adsorption analyzer (United is 255 nm at a distribution width of 25 nm.
KINETICS AND CATALYSIS
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A KINETIC MODEL FOR THE EPOXIDATION OF ALLYL ALCOHOL
675
To estimate the noncatalytic component of the chemical system, have better predictability outside the
Н2О2 conversion process, several experiments were
studied factor space. In this respect, the information
performed without a catalyst in the reactor at a tem- about the most probable mechanism of the alkene
perature of 60°C. In this case, the Н2О2 conversion
was below 0.4%. This provided the possibility to con-
clude that the noncatalytic reactions (I) and (IV) may
be neglected under these conditions. The side reac-
tions (II) and (III) were studied under similar condi-
tions to establish that their rates are negligibly small
epoxidation process on titanium silicate catalysts was
taken as the basis for the developed kinetic model
It is well known [18–21] that an Н2О2 molecule
interacts with Ti-containing catalyst sites with the for-
mation of an active catalyst form, namely, a titanium
without a catalyst. Based on this fact, only the catalytic hydroperoxo complex stabilized by a solvent molecule.
component of this process was taken into account
during the further consideration.
The kinetic models developed, taking the internal
relations into consideration, which really exist in a (see Scheme 1).
The thus-formed five-membered complex (FC) fur-
ther participates in the allyl alcohol epoxidation pro-
cess with the formation of the target product (glycidol)
CH3
Si
O
O
Si
Si
OH
Si
H
O
O
O
+CH3OH, +H2O2
Ti
O
Si
+
Ti
−CH3OH, −H2O2
O
O
H
O
O
Si
Si
Si
FC
CH3
O
Si
Si
Si
O
O
OH
O
O
H
OH
+
+
Ti
O
Si
Si
Ti
H2C
CHCH2
OH
H2C=CH – CH2
−CH3OH,
−H2O2
O
H
O
O
O
H2C
O
Si
Si
Si
CH
CH2
OH
Scheme 1. Mechanism of allyl alcohol epoxidation with hydrogen peroxide in methanol medium.
We have experimentally established that the
formed glycidol decreases the target reaction rate,
while the change in the water concentration in the
reactio medium witihn the range of 2.1–12.6 mol/L
does not produce any appreciable effect on the process
rate. In all likelihood, glycidol is adsorbed on active
catalyst sites and thereby decreases the free surface
area and probability of the formation of the FC.
Cat ⋅ CH3OH + H2O2
KH
ꢀꢀꢀꢀꢀꢀꢁ
ꢂꢀꢀꢀꢀꢀꢀ
O
2
2
Cat ⋅ CH OH ⋅ H O ,
3
2
2
quickly
Cat ⋅ CH3OH ⋅ H2O2 + AA
k1
⎯⎯⎯→Cat ⋅ CH3OH ⋅ GD + H2O,
Cat ⋅ CH3OH ⋅ GD
KGD
⎯⎯⎯→Cat ⋅ CH3OH + GD.
Hence, the epoxidation process can conditionally be
presented in the form of three stages: the adsorption of
Н2О2 on active catalyst sites and the surface reaction
and desorption of glycidol (each of them may be a con-
trolling stage). Based on the set of available data, we
have proposed the probable mechanism of allyl alcohol
oxidation with an aqueous hydrogen peroxide solution
in the presence of a titanium-containing catalyst:
To find a specific form of the mathematical
description of the epoxidation process and calculate
the effective rate constants and activation energies of
reactions, we have made the following assumptions:
(1) The surface reaction is a controlling stage of the
process and all the adsorbed compounds are in equi-
librium;
(2) The reaction occurs between Н2О2 adsorbed on
the catalyst surface and allyl alcohol in a solution; and
(3) Side reactions occur on the catalyst surface.
KCH
ꢀꢀꢀꢀꢀꢀꢁ
ꢂꢀꢀꢀꢀꢀꢀ
OH
3
Cat + CH OH
Cat ⋅ CH OH,
3
3
quickly
KINETICS AND CATALYSIS Vol. 58 No. 6 2017

676
SULIMOV et al.
cidol adsorption equilibrium constants, respectively,
СGD, mol/L
L/mol (Eqs. (5)–(7)); m is the catalyst mass, g; and
V is the reaction mixture volume, L.
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
The temperature dependence of the rate constants
of reactions (i = I–IV) and the adsorption equilibrium
constants of Н О (
) and glycidol (KGD) are
K
2
2
Н2О2
described by the Arrhenius and van’t Hoff equations,
respectively:
Ei
⎝ RT ⎠
i
⎛
⎞
⎟
(5)
(6)
(7)
k = k exp −
,
⎜
i
0
0
50
100
150
Time, min
200
Q
⎛
⎞
KH O = K0H O exp
,
H2O2
2
2
⎜
⎟
⎠
2
2
RT
⎝
Fig. 1. Glycidol concentration versus time at different stir-
ring speeds of (m) 200, (j) 400, and (r) 600 rpm. Reaction
Q
KGD = K0GD exp
.
⎛
⎜
⎞
⎟
GD
С0AA
С0Н О
2
2
conditions:
= 5.08 mol/L,
= 1.69 mol/L,
⎝ RT ⎠
С0СН ОН
3
= 11.01 mol/L, 40°C; catalyst mass, 21.43 g/L.
The material balance of a periodic isothermic reac-
tor applied for the synthesis of glycidol is described by
the following set of differential equations:
r0GD ×10−3, mol (g s)
dCAA
3.0
2.5
2.0
1.5
1.0
0.5
(8)
= −r1,
dt
dCH O
dt
2
(9)
(10)
(11)
(12)
(13)
(14)
(15)
= −r1 − 2r4,
dCH O
2
= r1 − r3 + 2r4,
dt
dC
CH3OH
= −r2,
dt
0
10
20
30
40
dCGD
dt
Catalyst content, g/L
= r1 − r2 − r3,
Fig. 2. Initial glycidol formation rate versus catalyst con-
tent in reaction mixture. Reaction conditions:
AA
dC
MPD
=
С0
= r2,
5.08 mol/L,
= 1.69 mol/L, СН ОН = 11.01 mol/L,
Н2О2
3
dt
С0
С0
40°C.
dCglycerin
= r3,
dt
dC
According to these assumptions, the sought kinetic
model must be the following:
O2
= r4.
dt
Equations (8)–(11) express the rates of allyl alco-
hol, hydrogen peroxide, water, and methanol con-
sumption in the formation of reaction products, and
Eqs. (12)–(15) are the formation rates of products
(glycidol, 1-methoxypropanediol-2,3, glycerin, and
oxygen, respectively). The accepted model does not
take into account the side reactions of the formation of
glycidol oligomers, as the consumption of Н2О2 in
these reactions does not exceed 1–2%, they may be
neglected when performing engineering calculations.
k1K
C
CAA
H2O2 H2O2
m
V
(1)
r1 =
,
1 + KH O
C
+ KGDСGD
2
2
H2O2
m
(2)
(3)
(4)
r2 = k2CGD
C
,
CH OH V
3
m
r3 = k3CGD
C
,
H O V
2
m
r4 = k4СH O
,
2 V
2
To determine the region of the reaction of allyl
alcohol epoxidation with an aqueous Н2О2 solution on
a titanium-containing silicate used as a catalyst in a
periodic reactor, we have performed a series of exper-
iments at the same initial content of the reagents and
catalyst and a different stirring speed (Fig. 1). At the
selected agitator revolution speeds of 200–600 rpm,
where r1 and r2–r4 are the rates of the target reaction
(Eq. (1)) and side reactions (Eqs. (2)–(4)), respec-
tively, mol/(s L); k1 is the target reaction rate constant,
L/(s g); k2 and k3 are the rate constants of side reac-
tions, L2/(mol s g); k4 is the Н2О2 decomposition rate
constant, L/(s g);
and KGD are the Н2О2 and gly-
K
Н2О2
KINETICS AND CATALYSIS
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A KINETIC MODEL FOR THE EPOXIDATION OF ALLYL ALCOHOL
677
different initial conditions, varying the temperature
(Fig. 3), the initial Н2О2 concentration (Fig. 4), the ini-
tial allyl alcohol concentration (Fig. 5), the glycidol con-
centration at the initial time moment (0–1.49 mol/L),
the methanol concentration (0–20.38 mol/L), and the
catalyst content (3.04–23.18 g/L).
The rate constants and the adsorption coefficients
of compounds were found from the condition of the
minimum for the function F determined as
Concentration, mol/L
T, °C
2.5
,
,
,
,
30
40
50
60
2.0
1.5
1.0
0.5
2
exp
calcd
⎛
⎞
Cij − Cij
1
(16)
F =
νij,
n∑∑⎜⎜
⎟
⎟
⎠
exp
0
2000 4000 6000 8000 10000
Time, s
C
ij
⎝
j
i
exp
where п is the number of experimental points,
Сij
Fig. 3. Change in concentration of Н О (black symbols)
2
2
calcd
and
are the experimental and calculated molar
concentrations of the compounds, respectively, and
Сij
and glycidol (white symbols) during reaction at different
temperatures: experiment (points), calculation (lines).
С0AA
С0Н О
2
2
is the weight coefficient. Summation was per-
νij
Reaction conditions:
= 5.73 mol/L,
=
formed over all the compounds (subscript i) and all the
С0СН ОН
3
1.91 mol/L,
5.08 g/L.
= 10.89 mol/L; catalyst mass,
experimental points of each experiment (subscript j).
At the first stage of estimating the unknown
Н2О2
parameters, we found k ,
Е , and
1
Calcu-
QН О .
K0
,
01
lation was performed by the initial region2s of the
kinetic curves of Н2О2 consumption in the experi-
ments performed at different initial Н2О2 concentra-
tions and temperatures. Such an approach provides
the possibility to minimize the effect of the formed
glycidol and the side reactions taking place. The found
Н2О2
2
the concentration of glycidol does not depend on the
stirring speed as long as all the other conditions are the
same; i.e., the reaction occurs in the kinetic region;
thus, the stirring speed of 200 rpm was used in the fur-
ther experiments. Moreover, as shown in Fig. 2, the
initial rate of the epoxidation process linearly depends
on the catalyst content, thus confirming the occur-
rence of this reaction in the kinetic region. Based on
the above facts, it is possible to assume that the allyl
alcohol epoxidation process is not controlled by diffu-
sion resistance.
constants (k ,
Е , and
) were further used
Н2О2
K0
,
Q
01
1
to determine the other unknown parameters. The pre-
exponents k –k , GD, the effective activation ener-
K0
02
04
gies E2–E4, and the glycidol adsorption heat QGD were
To determine the unknown parameters of the equa- thus calculated. The mathematical processing results
are given in Table 1.
tions, we performed several series of experiments under
Concentration, mol/L
Concentration, mol/L
4.0
AA/H2O2
AA/H2O2
,
,
,
,
,
,
1
2
3
4
5
6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
,
,
,
1
2
3
,
,
,
4
5
6
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
2000 4000 6000 8000 10000
Time, s
0
2000 4000 6000 8000 10000
Time, s
Fig. 4. Change in concentration of Н О (black symbols)
2
2
Fig. 5. Change in concentration of Н О (black symbols)
and glycidol (white symbols) during reaction at varied
initial allyl alcohol (AA) concentration: experiment
2
2
and glycidol (white symbols) during reaction at varied ini-
tial Н О concentration: experiment (points), calculation
2
2
AA
Н2О2
AA
(lines). Reaction conditions:
= 3.45 mol/L,
=
С0
С0
(points), calculation (lines). Reaction conditions:
=
=
С0
3
СН3ОН
С0Н О
С0СН ОН
2
2
0.57–3.45 mol/L,
mass, 5.08 g/L.
= 11.35–17.62 mol/L; catalyst
С0
1.14–6.86 mol/L,
= 1.43 mol/L,
10.66–20.27 mol/L; catalyst mass, 5.08 g/L.
KINETICS AND CATALYSIS Vol. 58 No. 6 2017

678
Table 1. Parameters of Arrhenius and van’t Hoff equations
Parameters of Arrhenius equation
SULIMOV et al.
k0i*
Ei, kJ/mol
Reaction (i)
(3.12 0.16) × 102
(9.09 0.45) × 10
(41.21 2.1) × 103
(57.30 2.9) × 103
(57.45 2.9) × 103
(50.86 2.5) × 103
(I)
(II)
(III)
(IV)
(5.02 0.25) × 10
(2.93 0.15) × 10
Parameters of van’t Hoff equation
K0Н О
K0GD
QGD
× 103
× 102
2
2
Q
Н2О2
L/mol
kJ/mol
3.16 0.16
74.95 3.75
14.69 0.73
9.27 0.46
2
* Dimensions of k , k and k , k are L/(s g) and L /(mol s g), respectively.
01 04
02 03
5. Fajdek, A., Wroblewska, A., and Milchert, E., React.
Kinet. Mech. Catal., 2011, vol. 103, no. 2, p. 451.
6. Harvey, L., Kennedy, E., Dlugogorski, B.Z., and
Stockenhuber, M., Appl. Catal. A. General, 2015,
vol. 489, p. 241.
The obtained mathematical model was estimated
for adequacy using the Fischer criterion. The pro-
posed kinetic model adequately describes our experi-
mental data (Figs. 3–5) and can be used for engineer-
ing calculations.
7. Wroblewska, A. and Makuch, E., J. Adv. Oxid. Technol.,
2014, vol. 17, no. 1, p. 44.
CONCLUSIONS
8. Wroblewska, A., Makuch, E., Dzieciol, M., Jedrzejew-
ski, R., Kochmanski, P., Kochmanska, A., and
Kucharski, L., Polish J. Chem. Technol., 2015, vol. 17,
no. 4, p. 23.
9. Agrawal, G.L., Singh, J.V., and Mishra, K., Oxid. Com-
mun., 2002, vol. 25, no. 1, p. 87.
The proposed kinetic model provides the possibility
to predict the reaction mixture composition at different
temperatures, initial ratios of reagents, and Н2О2 con-
versions. The set of differential equations (8)–(15) most
completely reflects the real liquid-phase process of allyl
alcohol epoxidation with an environmentally friendly
hydrogen peroxide solution in the presence of titanium
silicate and can be used in engineering calculations for
designing an epoxidation reactor.
10. Beg, M.A. and Ahmad, I., Indian J. Chem., 1977,
vol. 15, no. 7, p. 656.
11. Achrem, A.A., Timoscht, T.A., and Metelitz, D.I., Tet-
rahedron, 1974, vol. 30, no. 17, p. 3165.
12. Raciszewski, Z., J. Am. Chem. Soc., 1960, vol. 82, no. 6,
p. 1267.
13. US Patent 4410501, 1983.
ACKNOWLEDGMENTS
This work was financially supported by the Russian
Ministry of Education and Science (subsidy grant
agreement no. 14.577.21.0093, unique applied research
identifier RFMEFI57714X0093).
14. Ovcharova, A.V., Danov, S.M., and Sulimov, A.V.,
Khim. Interesah Ustoich. Razvit., 2010, no. 18, p. 767.
15. Ko, Y.S. and Ahn, W.S., Micropor. Mesopor. Mater.,
1999, vol. 30, p. 283.
16. Grieneisen, J.L., Kessler, H., Fache, E., Le Govic, A.M,
Micropor. Mesopor. Mater., 2000, vol. 37, p. 379.
17. Li, G., Wang, X., Guo, X., and Liu, S., Mater. Chem.
Phys., 2001, vol. 71, p. 195.
REFERENCES
1. Lebedev, N.N., Khimiya i tekhnologiya osnovnogo
organicheskogo i neftekhimicheskogo sinteza (Chemistry
and Technology of Main Organic and Petrochemical
Synthesis), Moscow: Khimiya, 1975.
18. Luchinskii, G.P., Khimiya titana (Chemistry of Tita-
nium), Moscow: Khimiya, 1971.
19. Beck, C. and Mallat, T., Catal. Lett., 2003, vol. 88,
2. Wroblewska, A. and Milchert, E., Chem. Pap., 2002,
nos. 3-4, p. 203.
vol. 56, no. 3, p. 150.
20. Wroblewska, A., Fadjdek, A., Wajzberg, J., and
3. Danov, S.M., Sulimov, A.V., Ryabova, T.A., Suli-
mova, A.V., and Sesorova, O.A., Zhurn. Khim. Tekh-
nologiya, 2011, vol. 12, no. 5, p. 270.
4. Sulimov, A.V., Danov, S.M., Ovcharov, A.A.,
Ovcharova, A.V., and Flid, V.R., Izv. Akad. Nauk, Ser.
Khim., 2014, no. 12, p. 2647.
Milchert, E., J. Hazard. Mater., 2009, vol. 170, p. 405.
21. Wroblewska, A. and Fadjdek, A.J., J. Hazard. Mater.,
2010, vol. 179, p. 258.
Translated by E. Glushachenkova
KINETICS AND CATALYSIS
Vol. 58
No. 6
2017