Nanoheterogeneous Catalytic Cotransformation of Polyatomic Alcohols and Carbamides

Article abstract of DOI:10.1134/S0965544117140067

The interaction of ethylene glycol and glycerol with carbamide in the presence of nanosized cobalt oxide obtained by the decomposition of cobalt(II) acetylacetonate in diphenyl ether is studied. The average size of the nanosized catalyst particles is 8–10 nm. The effect of nanoheterogeneous catalysis on the cyclocondensation of polyatomic alcohols with carbamide is investigated. A high capacity of the nanosized catalyst in this process is found 150 g(cyclic carbonate)/(g(catalyst) h), which is more than 100 times higher than the capacity of conventional catalysts.

Full text of DOI:10.1134/S0965544117140067

ISSN 0965-5441, Petroleum Chemistry, 2017, Vol. 57, No. 14, pp. 1326–1330. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © A.S. Lyadov, A.A. Kochubeev, E.B. Markova, S.N. Khadzhiev, 2017, published in Nanogeterogennyi Kataliz, 2017, Vol. 2, No. 2, pp. 158–162.
Nanoheterogeneous Catalytic Cotransformation of Polyatomic
Alcohols and Carbamides
A. S. Lyadov*, A. A. Kochubeev, E. B. Markova, and S. N. Khadzhiev
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia
*
e-mail: lyadov@ips.ac.ru
Received July 10, 2017
Abstract⎯ The interaction of ethylene glycol and glycerol with carbamide in the presence of nanosized cobalt
oxide obtained by the decomposition of cobalt(II) acetylacetonate in diphenyl ether is studied. The average
size of the nanosized catalyst particles is 8–10 nm. The effect of nanoheterogeneous catalysis on the cyclo-
condensation of polyatomic alcohols with carbamide is investigated. A high capacity of the nanosized catalyst
in this process is found 150 g(cyclic carbonate)/(g(catalyst) h), which is more than 100 times higher than the
capacity of conventional catalysts.
Keywords: organic carbonate, ethylene carbonate, glycerol carbonate, ethylene glycol, glycerol, carbamide,
nanosized oxide, nanoheterogeneous catalysis
DOI: 10.1134/S0965544117140067
Cyclic organic carbonates belong to the class of uct, and carbamide is a commercially available com-
esters of carbonic acid and polyatomic alcohols; they pound [6–8].
are widely used in different fields of the economy as
The scheme illustrating the interaction of poly-
high-polarity solvents, disinfectants, and additives to atomic alcohols with carbamide is presented in Fig. 1.
The process proceeds at an elevated temperature and
reduced pressure and is mediated by a catalyst. At the
first stage, one hydroxyl group of polyatomic alcohol
interacts with a carbamide amino group, whereupon
the corresponding hydroxycarbomate is formed. Then
the intramolecular cyclization of hydroxycarbomate
proceeds in two ways to produce the target product
cyclic carbonate or oxazolidone derivative. Oxazoli-
fuels [1]. There are many approaches to producing
cyclic carbonates. The main industrial method to pro-
duce them is the catalytic carboxylation of epoxides
[
2]. This method is not environmentally benign;
therefore, the development of new effective methods
for production of cyclic carbonates is a topical prob-
lem. It was shown that the interaction of polyatomic
alcohols and carbamide makes it possible to effectively done derivatives are widely used as new-generation
obtain cyclic carbonates [3–5]. Moreover, this antibiotics against gram-positive bacteria.
It was shown in [5] that the cobalt-containing cat-
diesel production—glycerol—to a high-margin prod- alyst systems have the highest selectivity for ethylene
method enables conversion of the by-product of bio-
R1
O
O
O
(2)
(3)
–
NH3
O
NH2
O
R2
R1
R2
R1
R2
OH
OH
H N
2
T, P, kat
O
R1
R2
O
+
–NH3
H N
2
O
OH
1)
–H O
2
(
N
H
Fig. 1. Interaction of polyatomic alcohols with carbamide: (1) hydroxycarbomate, (2) organic carbonate, and (3) oxazolidone
derivative.
1326

NANOHETEROGENEOUS CATALYTIC COTRANSFORMATION
1327
carbonate for the interaction of ethylene glycol and with a CP-Wax58 capillary column (50 m) and a flame
carbamide. But these catalysts do not always exhibit a ionization detector. Helium was used as a carrier gas.
high activity. It is known that transfer of the reaction to The concentration of the initial compounds and reac-
the nanoheterogeneous regime makes it possible to tion products was determined using the internal stan-
increase the catalyst capacity by several times [9]; dard method (n-butanol).
therefore, the investigation of polyatomic alcohol
interaction with carbamide under nanoheterogeneous
catalytic conditions is of both scientific and practical
interest.
The size of particles and the morphology of the
synthesized nanosized cobalt oxides were studied by
transmission electron microscopy (TEM) on a Tecnai
Spirit 120 kV microscope. The test samples were dis-
The purpose of the present work is to explore the persed in methanol using ultrasound, whereupon they
combined transformation of ethylene glycol or glyc- were deposited on a copper support and dried.
erol and carbamide in the presence of nanosized
The X-ray phase analysis was carried out on a
cobalt oxide obtained by the thermolysis of cobalt Rigaku X-ray diffractometer equipped with an Ultima
acetylacetonate in diphenyl ether.
IV theta-theta goniometer. CoK radiation with a
α
scanning step of 0.02° and an exposure time of 1 s
was used. The range of angle measurements was 2θ =
EXPERIMENTAL
30°–90°.
Commercial ethylene glycol, glycerol, and carbam-
ide were used as reagents in catalytic tests. The precur-
sor of nanosized cobalt oxide was cobalt(II) acetylac-
etonate synthesized as described in [10].
The X-ray patterns of the products obtained were
indexed by the homology method using the data taken
from the international database ICDD PDF-4. The
crystal lattice parameters were refined by means of the
Nanosized cobalt oxide was obtained by the XRD tabular processor (RTP) software program.
decomposition of cobalt(II) acetylacetonate in diphe-
nyl ether (DPE) in a manner similar to [11]. For this
RESULTS AND DISCUSSION
During the thermolysis of cobalt(II) acetylaceto-
purpose, 0.5 g of cobalt(II) acetylacetonate was dis-
solved in 10 mL of DPE. Forty milliliters of DPE was
heated to the required temperature under intensive nate in diphenyl ether used as a dispersion medium,
stirring by a magnetic stirrer in an oil bath in a two- spherical nanosized cobalt oxide with an average par-
neck round-bottom flask equipped with a reflux con- ticle size of 8–10 nm is formed. Figure 2 illustrates the
denser. Then the solution of cobalt(II) acetylacetonate TEM images of the nanosized cobalt oxide.
was rapidly added to the heated diphenyl ether using a
syringe. This mixture was intensely stirred for 2 h to
attain complete thermolysis and to form the nanosized
particles. Thereafter the mixture was cooled and ana-
lyzed. As reference catalysts, we used cobalt oxide,
which was obtained by the decomposition of cobalt
nitrate at 400°С in an air stream, and the supported
X-ray phase analysis showed that the thermolysis of
cobalt(II) acetylacetonate resulted in formation of
mixed cobalt oxide Co O which crystallizes in the
cubic syngony (Fd3m space group, refined unit cell
parameters: a = 6.9850 ± 0.0009). The X-ray pattern
of nanosized cobalt oxide (Fig. 3) is characterized by
the widening of diffraction peaks. This indicates that
the sizes of oxide crystallites are within the nanosized
range.
The influence of conditions of organic carbonate
synthesis from polyatomic alcohols and carbamide in
the presence of the nanosized carbon oxide was stud-
ied. All dependences obtained for ethylene glycol and
3
4
catalyst 15% Со O /SiO , which was produced by
3
4
2
incipient wetness impregnation of the KSKG trade-
mark silica gel by cobalt(II) nitrate solution followed
by calcination in an air stream at 400°С. The compar-
ative experiments were performed using these catalysts
with a particle size of 50–100 μm.
Cyclocondensation was carried out at a reduced glycerol have the same pattern (Fig. 4). In all catalytic
pressure in a flask equipped with a reflux condenser tests, selectivity for the target carbonates was almost
and an external jacket for heating of the reaction mix- 100%; in the case of ethylene glycol, ethylene carbon-
ture to the required temperature. The reduced pres- ate was obtained, and in the case of glycerol, glycerol
sure in the reaction system was formed using a vacuum carbonate was obtained.
pump and controlled by a mercury manometer. The
system was stirred by a magnetic stirrer. The cyclocon-
densation reaction conditions were as follows: 120–
As expected, a rise in temperature leads to an
increase in the conversion of polyatomic alcohol. The
conversion significantly increases in the temperature
range from 120 to 150°С; above 150°С, the alcohol
conversion changes insignificantly. It should be noted
that the interaction of glycerol with carbamide pro-
ceeds more intensely compared with ethylene glycol. A
1
80°С, 30–160 mmHg, reaction time of 1–4 h, and
polyatomic alcohol/carbamide ratio = 0.5–2. The
concentration of the nanosized cobalt oxide in all cat-
alytic tests was 500 ppm.
The initial components and cyclocondensation decrease in pressure in the reaction system favorably
products were analyzed by gas-liquid chromatography affects these processes, since ammonia, which is con-
on a Kristalyuks-4000M chromatograph equipped tinuously formed during the reaction, must be
PETROLEUM CHEMISTRY Vol. 57 No. 14 2017

1328
LYADOV et al.
200 nm
80 nm
Fig. 2. TEM images of nanosized cobalt oxide obtained by the thermolysis of cobalt acetylacetonate in DPE.
removed from the reaction zone. In the case of glyc- rial conversion needs a substantially lower catalyst
erol, a decrease in pressure leads to an almost linear concentration in the reaction system.
rise in its conversion throughout the studied pressure
The interaction of the polyatomic alcohols by the
example of ethylene glycol and glycerol with carbam-
interval. For ethylene glycol, the conversion depen-
dence on pressure follows an S-shaped pattern. The
reaction time also affects the yield of the target prod- ide in the presence of the nanosized cobalt oxide
uct. With a rise in the contact time from 1 h to 3 h, the (Co O ) with an average particle size of 8–10 nm has
3
4
ethylene glycol or glycerol conversion increases lin- been studied in the present paper. It has been shown
early. Further rise in the contact time leads to insignif-
icant changes in conversion. Dependences illustrating
the effect of the molar ratio of the initial reagents on
polyatomic alcohol conversion show a maximum at
the molar ratio polyatomic alcohol/carbamide = 1.
This fact provides evidence for the stoichiometric
interaction of the reagents.
that temperature, pressure, contact time, and molar
ratio of the reagents affect the synthesis of ethylene
carbonate and glycerol carbonate under the conditions
of nanoheterogeneous catalysis, and the optimal con-
ditions for producing these products have been deter-
mined. The application of the nanosized cobalt oxide
as a catalyst in the synthesis of cyclic carbonate from
Taking into account the above data, we found that polyatomic alcohols and carbamide makes it possible
the optimum conditions of glycerol or ethylene glycol to implement this process with high efficiency and
interaction with carbamide are as follows: 150–160°С, selectivity for the target products, which may be syn-
3
0−50 mmHg, reaction time of 3 h, and polyatomic thesized with capacity above 150 g(cyclic carbon-
alcohol/carbamide molar ratio = 1. Under these con- ate)/(g(catalyst) h).
ditions the efficiency of the nanosized cobalt oxide
was comparable with the efficiency of micron-sized
cobalt oxide (50–100 μm) and cobalt oxide supported
on silica gel. The results of the comparative studies are
presented in Table 1.
2000
800
600
1400
200
000
00
600
00
1
1
Nanosized cobalt oxide
1
1
The interaction of polyatomic alcohols with carba-
mide can also proceed without catalysts; however, in
this case, the conversion does not exceed 30%, and the
selectivity for the target products is no more than 80%.
Introduction of the cobalt catalysts in the reaction sys-
tem makes it possible to selectively synthesize organic
carbonates. The traditional oxide or supported cata-
lysts have a capacity of about 1 g(cyclic carbon-
ate)/(g(catalyst) h). The capacity of the nanosized cat-
alyst is more than 100 times higher than the capacity of
traditional catalysts. This difference is caused exclu-
sively by a high activity of the nanocatalysts, where-
upon achievement of an acceptable level of raw mate-
8
4
1000
8
6
4
00
00
00
Co O , PD#80-1542
3
4
200
0
30
40
50
60
θ, deg
70
80
90
2
Fig. 3. X-ray pattern of nanosized cobalt oxide.
PETROLEUM CHEMISTRY Vol. 57 No. 14
2017

NANOHETEROGENEOUS CATALYTIC COTRANSFORMATION
1329
1
9
00
(а)
90
80
(b)
2
0
0
0
0
0
0
0
0
8
7
6
5
4
3
2
70
60
50
40
30
20
1
2
10
1
10
0
0
1
20 130 140 150 160 170 180
30 50 70 90 110 130 150
Temperature, °С
Pressure, mmHg
(d)
9
8
7
6
5
4
3
2
0
0
0
0
0
0
0
0
(c)
2
80
7
6
5
4
3
2
0
1
0
0
0
0
0
2
1
1
0
10
0
0
1
2
3
4
0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9
Polyatomic alcohol/carbamide
Time, h
Fig. 4. Influence of reaction conditions on the conversion of polyatomic alcohols (1) ethylene glycol and (2) glycerol: (a) tem-
perature, (b) pressure, (c) time, and (d) polyatomic alcohol/carbamide molar ratio.
Table 1. Comparison of cobalt oxide catalysts in the interaction of ethylene glycol and glycerol with carbamide (synthesis
conditions: 140°С, 50 mmHg, 3 h, nanosized catalyst concentration of 0.1 wt %, micron catalyst concentration of 10 wt %)
Con. (EG), % S (EC), % Cap., g/(g(cat) h) Con. (Gl), % S (GC), % Cap., g/(g(cat) h)
OH
OH
OH
H N
OH
OH
2
Catalyst
H N
2
O
+
2NH3
+
O
O
O + 2NH3
+
O
O
H N
2
H N
2
O
OH
O
Without
20
76
–
24
76
33
52
80
100
100
100
–
162.2
Nano-Co O4
65
28
51
100
100
100
153.3
0.66
1.21
3
Co O4
0.71
1.11
3
1
5% Co O /SiO
3 4 2
Con.(EG) denotes ethylene glycol conversion; S(EC) denotes selectivity for ethylene carbonate; Cap. denotes catalyst capacity;
Con.(Gl) denotes glycerol conversion; S(GC) denotes selectivity for glycerol carbonate.
PETROLEUM CHEMISTRY Vol. 57 No. 14 2017

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LYADOV et al.
ACKNOWLEDGMENTS
6. J. R. Ochoa-Gómez, O. Gómez-Jiménez-Aberasturi,
C. Ramírez-López, and M. Belsué, Org. Process Res.
This work was supported by the Russian Founda-
tion for Basic Research and the Government of Mos-
cow, project no. 15-33-70018-mol_a_mos.
Dev. 16, 389 (2012).
7
8
9
. J. I. García, H. García-Marína, and E. Piresa, Green
Chem. 12, 426 (2010).
. D. Wang, X. Zhang, C. Liu, and T. Cheng, React.
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PETROLEUM CHEMISTRY
Vol. 57
No. 14
2017