ISSN 1070-4272, Russian Journal of Applied Chemistry, 2016, Vol. 89, No. 5, pp. 683í689. © Pleiades Publishing, Ltd.

, 2016.
Original Russian Text © E.V. Ovchinnikova, L.A. Isupova, I.G. Danilova, V.V. Danilevich, B.A. Chumachenko, 2016, published in Zhurnal Prikladnoi Khimii,
2016, Vol. 89, No. 5, pp. 545í552.
INORGANIC SYNTHESIS AND INDUSTRIAL
INORGANIC CHEMISTRY

Study of Acid-Modified Aluminum Oxides Produced

by Centrifugal Thermal Activation
in Dehydration of Ethanol
E. V. Ovchinnikova, L. A. Isupova, I. G. Danilova, V. V. Danilevich, and B. A. Chumachenko

Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences,

ul. Akademika Lavrent’eva 5, Novosibirsk, 630090 Russia
e-mail: evo@catalysis.ru

Received May 18, 2016

Abstract—Possibility of using products formed in centrifugal thermal activation of hydrargillite to obtain alumina
catalysts washed to remove admixtures of alkali metals was considered. A comparison of the physicochemical and
catalytic properties of the samples demonstrated that washing with water is more favorable than that with nitric
acid; the catalytic activity and acid-base properties of the catalyst surface are determined not only by the content
of Na, but also by the whole set of catalyst preparation conditions. The most active of the samples obtained in the
study has acidity close to that of industrial aluminum oxide produced by the reprecipitation method, but surpasses
it in activity: at 370°C, the total yield of ethylene and diethyl ether reaches a value of 88.8 mol %, which is 4%
higher than that for the reference sample.
DOI: 10.1134/S1070427216050013

Despite the endothermic effect, the dehydration of
ethanol to ethylene readily occurs on acid catalysts at
elevated temperatures, owing to which it is widely used as
a model reaction. Industrially, this reaction is performed
on alumina catalysts or those containing aluminum oxides
(AOs) in reactors of different types, including those of
tubular design [1].
At present, the interest in studying the properties of
aluminum oxides in dehydration of ethanol to ethylene
has noticeably increased [2–12]. This is due in no small
part to two main factors: (i) intensive development of low-
tonnage technologies for obtaining polyethylene-based
composites [13], which require shops for low-tonnage
production of ethylene, unattached to sources of petro-
chemical raw materials; and also (ii) high activity and
stability of AOs in operation in a high-concentration reac-
tion mixture [1, 6, 8], which is promising as regards their
practical application. It has been shown that temperature
strongly affects the pathways of ethylene synthesis both
directly from ethanol and via intermediate formation of
diethyl ether [3, 8]. The following issues are under discus-
sion: mechanisms of ethylene formation [3, 9], nature of
active centers [7, 9, 10], and effect of the AO morphology
on the activity and apparent activation energy [3, 11].
It has been found that the activity of AOs in the
dehydration of ethanol is mostly determined by the
optimal combination of surface Brɲnsted and Lewis
acid centers (LACs) [6]. Admixtures of Na in samples
are a kind of a catalytic poison because of changing the
surface properties and the morphology of AOs [4]. It has
been shown that the activity and selectivity of AOs in the
dehydration of ethanol to ethylene is favored by a high
concentration of weak and medium-strength acid centers,
which is observed in samples with the lowest content
of Na [7, 14, 15]. Therefore, AOs with the minimum
content of sodium, produced by reprecipitation and
hydrolysis of alcoholates, are commonly accepted as the
most active in the catalytic synthesis of ethylene from
ethanol [2, 6–8, 12]. However, the production of AOs
by these techniques necessarily involves utilization of a
large amount of wastewater or use of expensive reagents,
which makes larger the number of technological stages
in catalyst preparation and raises the production cost of
the manufactured products.

683
684 OVCHINNIKOVA et al.
The production of AO-based catalysts without repre-
cipitation by ecologically attractive thermal activation
techniques is of particular interest, including that in
commercial regard, because these techniques are simpler
and more-cost-effective. For example, a wide variety of
catalysts, supports, and adsorbents is manufactured on the
basis of an industrial product formed in thermal activation
of hydrargillite in a flow of fume gases. Recently, the tech-
nology of centrifugal thermal activation of hydrargillite
(CTA HG) in TsEFLARTM reactors has been under active
development at the Institute of Catalysis, Siberian Branch,
Russian Academy of Sciences [16–18]. This technology
makes it possible to obtain AO precursors without repre-
cipitation and without contamination of these by products
of incomplete combustion of fume gases.
However, a study of industrial AO samples produced
by thermal activation of hydrargillite in a flow of fume
gases demonstrated their insufficient activity for commer-
cial application in the process of ethanol dehydration [2].
The yield of ethylene at 370°C on AOK-63-22 alumina
catalyst was about 41 mol % at ethanol conversion of
74% [2]. The activity of AOs of this kind can be raised
via optimization of the acid properties of AO samples by
making lower the content of alkali metals (Na) and (or)
by acid modification of the active surface of the catalysts
[1, 19]. For example, the modification of AOs containing
an admixture of sodium with hydrochloric acid made it
possible to raise the activity of the catalysts [19]. At the
same time, modification with hydrochloric or sulfuric acid
may lead to a fast deactivation of the catalyst because of
the presence of the corresponding ions (Cl– and SO4–) on
its surface [7, 20, 21]. To preclude undesirable effects
cased by residual ions of a modifying acid agent, it may
be of interest to use a solution of nitric acid [20, 21],
which fully decomposes in the stage of thermal treatment
of aluminum hydroxide.
The goal of our study was to examine the possibility of
obtaining active alumina catalysts by the thermal activa-
tion technique via optimization of the acid properties of
samples by lowering their content of Na and modifying
the samples with hydrochloric and nitric acids.
We examined four catalysts produced by using prod-
ucts of a mild hydration of CTA HG, washed with water
or nitric acid solution to remove admixtures of alkali
metals. An additional acid modification was performed
by introduction of hydrochloric or nitric acid solutions in
the stage of preparation of moldable pastes.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 89 No. 5 2016
EXPERIMENTAL
As starting raw material for preparing catalysts served
hydrargillite (HG) manufactured by BazelTsement
Pikalevo OOO (Pikalevo). On being thermally activated
in a TsEFLARTM drum reactor, the product formed in
centrifugal thermal activation of hydrargillite (CTA HG)
has a specific surface area of 205 m2 g–1; according to
X-ray phase analysis data, its phase composition is the
following: 7.5% HG, 12.5% boehmite, and 80% disor-
dered Ȥ-like Al2O3 phase.
The hydration was performed in the course of 4 h
under permanent agitation in a reactor with a stirrer in an
aqueous solution of HNO3 at pH 4–5 and temperature of
75°C. A ground CTA HG product with average particle
size of 15 ȝm was used in the hydration. After the liquid
phase was removed, the hydration product was addition-
ally washed to remove the admixture of sodium ions with
distilled water (sample nos. 1 and 2) or a diluted 0.3%
solution of nitric acid (sample nos. 3 and 4). Further, the
product was dried at 120°C for 24 h and then ground in a
ball mill for 6 h to particles with average size of 15 ȝm.
The product of CTA HG hydration contained 55.5%
pseudoboehmite, 7% hydrargillite, and 37% disordered
Ȥ-like Al2O3 phase.
The mass for extrusive molding of the catalysts was
obtained in a 500-cm3 mixer with Z-shaped blades. The
peptization and modification were performed with solu-
tions of hydrochloric (sample nos. 1 and 3) and nitric
(sample nos. 2 and 4) acids. The thus prepared paste
was extruded through a die to give granules in the form
of a trefoil with a diameter of the circumscribed circle of
1.6 mm. On being dried in air, the granules were calcined
at 550°C for 4 h in a flow of dried air at a flow rate of
5000 h–1.
As a reference sample served the support of IK-
VGO-01 catalyst (sample no. 5) manufactured at
Promyshlennye Katalizatory ZAO (Ryazan) by the re-
precipitation method with water used for washing and
nitric acid solution for peptization. The finished catalyst
contained 80 ppm of Na and less than 20 ppm of K and
had the form of monodisperse Ȗ-Al2O3 with a specific
surface area of 205 m2 g–1, total mesopore volume of
0.7 cm3 g–1, and average pore diameter of 94 Å.
The phase composition of the samples was determined
by X-ray phase analysis on an HZG- 4 diffractometer
(Zeiss, Germany) at a wavelength of 1.54184 Å and point-
 STUDY OF ACID-MODIFIED ALUMINUM OXIDES
by-point scanning (scanning interval 10–75°, scanning
step 0.1°, accumulation at a point for 10 s).
The texture characteristics of the raw material and
samples were determined from isotherms of nitrogen
adsorption at 77 K. The specific surface area was
measured by the BET method; volume of micropores,
by the t-method; and volume of mesopores, by analysis
of the integral distribution curve of the volume of pores
over their radii (using the adsorption branch).
The content of Na and K in the samples was determined
by atomic-emission spectroscopy with inductively
coupled plasma on an Optima 4300DV instrument.
The acid properties of the AO surface were examined
by IR spectroscopy, with a CO probe molecule [22, 23].
The spectra were recorded on a Shimadzu FTIR-8300 IR
Fourier spectrometer with resolution of 4 cm–1. Before
the spectra were recorded, samples were compacted into
pellets without a binder (0.01–0.03 g cm–2), calcined
in air at 500°C, and trained in a vacuum at 550°C to a
residual pressure p < 10–3 Torr. The adsorption of CO
was performed at liquid nitrogen temperature, with the
CO pressure raised from 0.1 to 10 Torr. The strength of
LACs associated with aluminum-containing centers was
evaluated by the increase in the heat of CO adsorption,
calculated from the shift of the absorption band frequency
of adsorbed CO [Ȟ(CO)] by the formula QCO = 10.5 +
0.5(Ȟ CO – 2143). The concentration of LACs was
estimated from the integral intensity of the absorption
band of adsorbed CO in the range 2178–2235 cm–1, with
the integral absorption coefficients used [22, 23].
The activity of the catalysts in dehydration of ethanol
to ethylene was measured in a flow-through quartz reactor
on catalyst samples ground to a 0.25–0.5-mm fraction in
a concentrated reaction mixture of the following compo-
sition (mol %): 73.8 C2H5OH, 12.1 H2O, and 14.1 N2.
Medical ethanol served as the starting reagent, with mass
fractions of ethanol and water being, respectively, 94 and
6. Nitrogen was batched to determine the volume-increase
factor of the gas mixture. The content of the starting
substances and reaction products was determined by
chromatography. When a 1-mL sample was charged, the
contact duration was 0.28 s. Before the reaction mixture
was delivered, the catalyst was kept in a flow of nitrogen
at 550°C for 1 h.
The conversion of ethanol (X, %), selectivity with
respect to the main products (Si, mol %), and carbon
balance BC (mol %) were determined by the formulas
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 89 No. 5 2016
685
N2
N2
(1)
(2)
N2
N2
Bɋ (3)
where C 0C 2 H 5 OH , C 0N 2 , C kC 2 H 5 OH , and C kN 2 are the
concentrations of ethanol and nitrogen at the inlet and
outlet of the reactor, respectively (mol fractions); cki,
concentration of the reaction products at the outlet of the
reactor (mol fractions); Ȟi, stoichiometric coefficients; and
C0N2/CN2, volume-increase factor of the reaction mixture.
The carbon balance in the experiments was 98.7 ± 1.5%.
The total yield of useful products, ȈY, was chosen as
the activity parameter when the catalytic properties of
samples tested in formation of these products (ethylene
and diethyl ether).
RESULTS AND DISCUSSION
Table 1 lists the preparation conditions and the
texture characteristics of sample nos. 1–4. The activity
in dehydration of ethanol to ethylene and the acid
properties of the samples are presented in Tables 2 and
3, respectively. The sample numbering in all the tables
and figures is common.
The samples prepared by using CTA HG (Table 1,
sample nos. 1–4) have large specific surface area (208–
311 m2 g–1), micropores, large total volume of mesopores
(up to 0.35 cm3 g–1), and their bidisperse size distribu-
tion. The average pore diameter varied within the range
45–67 Å and depended on the preparation method.
The phase composition of sample nos. 1–4 corresponded
to a mixture of Ȗ- and Ȥ-Al2O3 phases: sample nos. 1 and
3, peptized with HCl, contained 31% Ȗ and 69% Ȥ; and
sample nos. 2 and 4, peptized with HNO3, 53% Ȗ and
47% Ȥ. The percentage ratio of the phases was affected
by the nature of the electrolyte used for peptization.
Presumably, introduction of HCl, instead of HNO3, in
the stage in which the moldable mass is prepared either
686 OVCHINNIKOVA et al.

Table 1. Preparation conditions and texture characteristics of AOs prepared by the CTA HG technique
Preparation
Sample no. Ssp, m2 g–1 ™Vpor, cm3 g–1 D, Å4
washing peptization
1 H2O HCl 311 0.35 45
2 H2O HNO3 208 0.35 67
3 HNO3 HCl 255 0.32 50
4 HNO3 HNO3 256 0.31 48

Table 2. Activity of AOs prepared by the CTA HG technique in dehydration of ethanol

Sample no. T, °C X, % YETEN, mol % ȈY, mol %
1 370 73.9 49.8 72.1
400 81.4 63.8 77.7
2 370 84.1 59.4 81.2
400 93.1 84.6 88.8
3 370 76.7 40.5 74.4
400 81.8 49.7 78.9
4 370 81.3 56.8 78.4
400 89.4 81.5 85.6

reduces the content of pseudoboehmite in the moldable
hydroxide (which is related to the content of Ȗ-Al2O3
in catalysts), or hinders formation of the Ȗ-Al2O3 phase
in thermal treatment of the modified catalysts due to the
higher removal temperature of Cl– anions.
The content of Na and K in the finished catalysts
(sample nos. 1–4) strongly decreased, compared with the
starting (unwashed) product formed in hydration of CTA
HG (1400 ppm of Na and 200 ppm of K), and, irrespective
of the electrolyte used for washing and(or) peptization,
was the same: 200 ppm of Na and 20 ppm of K.
The main product of ethanol dehydration at tempera-
tures of 370–400°C and contact duration of 0.28 s was
ethylene (ETEN) for all the catalysts, with other products
also observed in the course of the reaction: diethyl ether
(DEE), acetaldehyde (AA), and butylene (C4). Under the
reaction conditions, sample nos. 1–4 were characterized
by ethanol conversions X of 74 to 93% and yields of valu-
able products, ȈY, of 72 to 89 mol %. The highest activity
among the samples tested in the study was observed for
sample no. 2, washed and peptized with HNO3, ad the
lowest, for sample no. 1, washed with water and peptized
with HCl (Table 2).
A study of the hydroxy surface cover of sample
nos. 2, 4, and 5 demonstrated that the concentrations of
OH bridge groups exhibiting weak acid properties differ
insignificantly because the IR spectra in the range of
stretching vibrations of OH groups are close. The acid
properties of the least active sample no. 1 were not studied.
It was shown that modification leads to an increase in the
acid strength of bridge Al–O(H)–Al groups, compared
with similar groups of the unmodified Al2O3 whose IR
spectrum shows, upon low-temperature adsorption of CO,
a shift of the absorption bands of bridge hydroxy groups
to lower frequencies (ǻȞO–H…CO) by 130–140 cm–1 [22].
In the case of CO adsorption on sample no. 2, the shift is
ǻȞO–H…CO = 160–170 cm–1, whereas for sample nos. 3–5,
an insignificant amount of more acid bridge OH groups is
additionally observed (ǻȞO–H…CO = 190–200 cm–1). The
later is apparently due to the presence on the surface of
residual NO3– and Cl– ions, which may indicate that the
acidity of hydroxy groups in the catalysts increases upon
their modification with the acids. The concentrations of
isolated terminal OH groups exhibiting basic properties
are close on the surface of most of the samples: a decrease
in the concentration of Al–OH groups is observed for
sample no. 3 (peptized with HCl), presumably because
of the interaction with residual Cl– ions.
At the same time, the samples strongly differ in the
concentration of LACs. According to low-temperature
CO adsorption data, LACs of varied strength are present
on the surface of all the samples: super-strong (ȞCO =

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 89 No. 5 2016

 STUDY OF ACID-MODIFIED ALUMINUM OXIDES 687

2241–2243 cm–1, QCO = 59.5–60.5 kJ mol–1), strong S, mol %

ETEN Ȉ(ETEN; DEE)

(ȞCO = 2231–2225 cm–1, QCO = 51.5–56.5 kJ mol–1),
medium-strength (ȞCO = 2216–2206 cm–1, QCO = 47–
43 kJ mol –1 ), and weak (Ȟ CO = 2197–2190 cm –1 ,
QCO = 37.5–34 kJ mol–1). LACs of medium and weak
strength are predominant on the surface of all the samples
under study (Table 3). It can be seen that washing with an
HNO3 solution leads to an increase in the total concentra-
tion of LACs (sample nos. 3 and 4), with the subsequent
peptization in HCl (sample no. 3) causing, compared
with HNO3 (sample no. 4), a rise in the concentration
of strong and super-strong centers. Among the samples

DEE
under study, produced by the CTA method, sample no. 2
has acid surface properties close to those of the reference
(sample no. 5). The data obtained indicate that the num-

AA, C4
ber of LACs is not directly dependent on the content of
alkaline ions, contrary to that observed in [7].
Ethylene is formed in the catalytic dehydration of
ethanol on alumina catalysts by the parallel-consecutive
scheme both directly from ethanol and via intermediate
formation of DEE [8]. At high conversions, the formation
of ethylene by the consecutive pathway from DEE can
be observed. Figure 1 presents the data obtained for the
activity of the samples at temperatures of 370 and 400°C
in the form of dependences of the selectivity with respect
to the products on the conversion of ethanol. Larger
values of the selectivity toward DEE are observed for
all the samples at lowered X, whereas with increasing X,
the selectivity with respect to DEE decreases due to its
consumption for ethylene formation, with the selectivity
toward ethylene accordingly becoming higher. An
additional evidence in favor of the ethylene formation
by the consecutive pathway is the invariable sum of the
selectivities toward the useful products, ȈS = (97.1 ±
1.7) mol %. In this case, the value of ȈS at 400°C is, on
average, 1% lower than that at 370°C due to the formation
of by-products (Fig. 1).
The selectivities with respect to the by-products AA
and C4, observed in the conditions of a concentrated
mixture and high conversions, were, on average, 1.5 and
2.2 mol %, respectively, for the samples tested in the
study. An exception is presented by sample nos. 1 and 2,
which have at 400°C somewhat increased selectivities
toward AA and C4, respectively (Fig. 1).
Thus, taking into account that ȈS varies only slightly
with X for different samples, we chose as an indication
of activity for comparing the catalytic properties of the
AOs tested in the study the total yield of useful products,
ȈY (Table 2).
X, %
Fig. 1. Correlation between the selectivities S with respect to
ethanol dehydration products and the conversion X of ethanol
for AOs produced by the CTA HG technique. Experimental
conditions: T = 370°C (crossed symbols), T = 400°C (full
symbols), IJ = 0.28 s, ethanol concentration 73.8 mol %. The
sample numbering corresponds to that in Table 1.
The highest activity among the catalysts prepared
by the CTA HG method is exhibited by sample no. 2
(Table 3) having the lowest total concentration of LACs,
whereas sample no. 3 having a higher total concentration
of LACs shows a lower activity. At the same time, sample
no. 4 also characterized by high concentration of LACs,
similarly to sample no. 3, demonstrated higher conversion
and yield of valuable products, and, therefore, the effect
of the concentration and strength of LACs on the activity
and selectivity of the catalysts invites an additional study.
It is noteworthy that the electrolytes used for peptization
(HCl or HNO3, Table 1) more strongly affect the yield of
useful reaction products, ȈY (Table 2), than the washing
solutions. Nevertheless, it can be seen that use of H2O
for washing is more favorable, compared with HNO3,
despite the same content of admixtures of alkali metals
in sample nos. 1–4.
The activity of the catalyst samples decreased to varied
extent on changing the reaction temperature from 400
to 370°C (Table 2). The process of ethanol dehydration
on an alumina catalyst in a tubular reactor is accompa-
nied by a decrease in temperature along the tube, with
a characteristic extremum, minimal temperature. For

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 89 No. 5 2016

688 OVCHINNIKOVA et al.
Table 3. Acid properties of AOs prepared by the CTA HG technique (sample nos. 2–4) and industrial AO produced by the
reprecipitation method (sample no. 5)
Concentration of LACs, ȝmol g–1
Sample no.
super-strong
2 3
3 8
4 4
5 6
example, at a heat-carrier temperature of 390–450°C
in the intertubular space, the minimum temperature in
the catalyst base in the tube may be 330–385°C [8].
Consequently, an important characteristic of a catalyst
for the endothermic reaction of ethanol dehydration is
its activity at low temperatures. Let us compare sample
no. 2, the most active acid-modified AO produced in the
study by the CTA HG method, with industrial AO samples
produced by reprecipitation (sample no. 5, support for
IK-VGO-01 catalyst) and thermal activation (sample
no. 6, AOK-63-22, Special Design-Technology Bureau
SKTB Katalizator AO [2]). The activity of sample nos.
2, 5, and 6 characterized by comparable ȈY at the high
temperature, noticeably changes at the low temperature:
at 370°C ȈY decreases in the following order: sample
no. 2 > no. 5 > no. 6 (Fig. 2).
ȈY, mol % ȈY, mol %
Fig. 2. Comparison of the activities in ethanol dehydration of
acid-modified AOs (sample no. 2) and industrial AOs produced
by reprecipitation (sample no. 5, support for IK-GO-01) and
thermal activation (sample no. 6 [2], AOK-63-22 catalyst).
(ȈY) Total yield of useful products).
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 89 No. 5 2016
strong weak and medium-strength
20 876
28 1100
22 1042
15 815
Thus, the acid-modified alumina catalyst (sample
no. 2) produced by the CTA HG technique exceeds in
activity in the reaction of ethanol dehydration to ethylene
the industrial samples: AOK-63-22 catalyst formed by
a similar thermal activation method and IK-VGO-01
catalyst support formed by the reprecipitation technique.
It can be assumed that this catalyst is promising for
practical application.
It should be noted that, of the two samples, no. 2
(200 ppm of Na and 20 ppm of K) and no. 5 (80 ppm of Na
and <20 ppm of K) having close acid properties (Table 3),
but different contents of alkali metal admixtures, a higher
activity at the low temperature was exhibited by the
sample with higher content of Na. This fact gives reason
to conclude that the catalytic activity and the acid-base
properties of the catalysts are affected not only by the
content of sodium, but also by the whole set of catalyst
preparation conditions. Presumably, the whole set of these
conditions can determine the defect nature of the oxide
surface [4], which requires further analysis.
CONCLUSIONS
(1) Samples of alumina catalysts based on aluminum
hydroxide produced by hydration under mild conditions
of the product formed in centrifugal thermal oxidation of
hydrargillite in a TsEFLARTM reactor were examined.
The sample preparation procedure included the following
stages: (i) washing to remove admixtures of alkali metals
with water or nitric acid solution, (ii) peptization and
modification with hydrochloric or nitric acid, and (iii)
molding in the form of a trefoil. The texture, acid, and
catalytic properties in ethanol dehydration of the resulting
acid-modified aluminum oxides were studied.
(2) It was found that the catalytic activity and the
acid-base properties of the surface of the catalysts are
 STUDY OF ACID-MODIFIED ALUMINUM OXIDES
determined not only by the content of sodium, but also
by the whole set of catalyst preparation conditions, which
presumably predetermine the defect nature of the oxide
surface.
(3) It was shown that the thermal activation technique
yields catalysts with higher activity at low temperatures,
compared with catalysts produced by the reprecipitation
method.
ACKNOWLEDGMENTS
The study was supported by the Ministry of Education
and Science of the Russian Federation, unique project
identifier RFMEFI60714X0046.
REFERENCES
1. Yakovleva, I.S., Banzaraktsaeva, S.P., Ovchinnikova, E.V.,
et al., Catal. Ind., 2016, vol. 8, no. 2, pp. 152–167.
2. Chumachenko, V.A. and Ovchinnikova, E.V., Catal. Ind.,
2016, vol. 8, no. 2, pp. 134–138.
3. Phung, T.K. and Busca, G., Chem. Eng. J., 2015, vol. 272,
pp. 92–101.
4. Phung, T.K., Herrera, C., Larrubia M A., Garcia-
Dieguez, M., et al., Appl. Catal. A, 2014, vol. 483,
pp. 41–51.
5. Phung, T.K., Lagazzo, A, Crespo, M.Ȼ.R., et al., J. Catal.,
2014, vol. 311, pp. 102–113.
6. Ivanova, A.S., Kinet. Catal., 2012, vol. 53, no. 4, pp. 425–
439.
7. Zotov, R.A., Molchanov, V.V., Volodin, A.M., and
Bedilo, A.F., J. Catal., 2011, vol. 278, pp. 71–77.
8. Kagyrmanova, A.P., Chumachenko, V.A., Korotkikh, V.N.,
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 89 No. 5 2016
689
et al., Chem. Eng. J., 2011, vol. 176–177, pp. 188–194.
9. Phung, T.K. and Busca, G., Catal. Commun., 2015, vol. 68,
pp. 110–115.
10. Hu, J.Z., Xu, S., Kwak, J.H., et al., J. Catal., 2016, vol. 336,
pp. 85–93.
11. Lee, J., Jeon, H., Oh, D.G., et al., Appl. Catal. A, 2015,
vol. 500, pp. 58–68.
12. Garbarino, G., Travi, I., Pani, M., et al., Catal. Commun.,
2015, vol. 70, pp. 77–81.
13. Queiroz, A.U.B. and Collares-Queiroz, F.P., Polym. Rev.,
2009, vol. 49(2), pp. 65–78.
14. Ross, R.A. and Bennett, D.E.R., J. Catal., 1967, vol. 8,
pp. 289–292.
15. Narayanan, C.R., Srinivasan S., Datye, A.K., et al.,
J. Catal., 1992, vol. 138, pp. 659–674.
16. Pinakov, V.I., Stoyanovsky, O.I., Tanashev, Yu.Yu., et al.,
Chem. Eng. J., 2005, vol. 107, pp. 157–161.
17. Danilevich, V.V., Lakhmostov, V.S., Zakharov, V.P., et al.,
Kataliz Prom–sti, 2016, vol. 16, no. 1, pp. 13–28.
18. Isupova, L.A., Tanashev, Yu.Yu., Kharina, I.V., et al., Chem.
Eng. J., 2005, vol. 107(1–3), pp. 163–169.
19. RF Patent 2 438 775 (publ. 2012).
20. Chesnokov, V.V., Paukshtis, E.A., Buyanov, R.A., et al.,
Kinet. Catal., 1987, vol. 28, no. 3, pp. 566–570.
21. Prokudina, N.A, Chesnokov, V.V., Paukshtis, E.A., and
Buyanov, R.A., Kinet. Catal., vol. 30, no. 4, pp. 835–839.
22. Paukshtis, E.A., IK spektroskopiya v geterogennom
kislotno–osnovnom katalize (IR Spectroscopy in
Heterogeneous Acid-Base Catalysis), Novosibirsk: Nauka,
1992.
23. Soltanov, R.I., Paukshtis, E.A., and Yurchenko, E.N., Kinet.
Catal., 1982, vol. 23, no. 1, pp. 135–141.