Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts
The gas-phase oxidation of ethylene glycol and methanol mixture into methyl glycolate С2H6O2+CH3OH+O2 = C3H6O3+2H2О over synthesized copper-containing catalysts was studied.  Methyl glycolate can be considered as raw material for obtaining biodegradable polygly...
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V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine
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Catalysis and petrochemistry| _version_ | 1872009046897197056 |
|---|---|
| author | Varvarin, Anatolii M. Levytska, Svitlana I. Mylin, Artur M. Zinchenko, Oleksii Yu. Brei, Volodymyr V. |
| author_facet | Varvarin, Anatolii M. Levytska, Svitlana I. Mylin, Artur M. Zinchenko, Oleksii Yu. Brei, Volodymyr V. |
| author_institution_txt_mv | [
{
"author": "Anatolii M. Varvarin",
"institution": "Institute for Sorption and Problems of Endoecology of the National Academy of Sciences of Ukraine, 13 General Naumov Str., Kyiv 03164, Ukraine"
},
{
"author": "Svitlana I. Levytska",
"institution": "Institute for Sorption and Problems of Endoecology of the National Academy of Sciences of Ukraine, 13 General Naumov Str., Kyiv 03164, Ukraine"
},
{
"author": "Artur M. Mylin",
"institution": "Institute for Sorption and Problems of Endoecology of the National Academy of Sciences of Ukraine, 13 General Naumov Str., Kyiv 03164, Ukraine"
},
{
"author": "Oleksii Yu. Zinchenko",
"institution": "Manufacturing Group Techinservice Limited, Makiivskyy Provulok, 1, Kyiv, 04114, Ukraine"
},
{
"author": "Volodymyr V. Brei",
"institution": "Institute for Sorption and Problems of Endoecology of the National Academy of Sciences of Ukraine, 13 General Naumov Str., Kyiv 03164, Ukraine"
}
] |
| author_sort | Varvarin, Anatolii M. |
| baseUrl_str | https://kataliz.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2023-01-20T10:00:52Z |
| description | The gas-phase oxidation of ethylene glycol and methanol mixture into methyl glycolate С2H6O2+CH3OH+O2 = C3H6O3+2H2О over synthesized copper-containing catalysts was studied.  Methyl glycolate can be considered as raw material for obtaining biodegradable polyglycolide. The CuO-containing samples were synthesized by impregnation of granular oxide-supports (γ-Al2O3, SiO2 and MgO-ZrO2) with the calculated amount of aqueous solution of Cu(NO3)2·3H2O followed by heat treatment at 400 °C. In such way the supported CuO-MexOy /Al2O3 (Me = Mg, Ti, Cr, Co, Zn, Zr, Ag) samples have been prepared. Catalytic experiments were performed in a stainless-steel flow reactor with a fixed bed of catalyst at 200-270 °C and atmospheric pressure. Oxygen of air was used as an oxidant. The reaction products were analyzed using 13C NMR spectroscopy and gas chromatography. It was found that СuO/Al2O3 catalyst provides ~ 100% ethylene glycol conversion with 56% selectivity towards methyl glycolate at 220 °С. The main by-products are methoxymethanol, 1,1-dimethoxymethane, methyl methoxyacetate, and methyl formate. Use of silica as catalyst support leads to a significant decrease of the ethylene glycol conversion to 57 % for CuO/SiO2, but methyl glycolate selectivity does not change significantly. Promotion of СuO/Al2O3 with MgO increases methyl glycolate yield to 64%. According to the scheme of ethylene glycol sequential oxidation the increase in selectivity for methyl glycolate over CuO-MgO/Al2O3 catalyst is caused by the basic sites that promote intramolecular Cannizzaro rearrangement of the intermediate reaction product – glyoxal hemiacetal to methyl glycolate. It’s found that mixed CuO-CrO3 oxide supported by γ-Al2O3 provides 80 % methyl glycolate selectivity with 95-100% ethylene glycol conversion at 200-210 °C. |
| doi_str_mv | 10.15407/kataliz2022.33.059 |
| first_indexed | 2026-03-12T15:50:15Z |
| format | Article |
| fulltext |
Каталіз та нафтохімія, 2022, №33 59
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
УДК 544.47
https://doi.org/10.15407/kataliz2022.33.059
Vapor-phase oxidation of ethylene glycol methanolic solution into methyl
glycolate over CuO-containing catalysts
Anatolii M. Varvarin1, Svitlana I. Levytska1*, Artur M. Mylin1, Oleksii Yu. Zinchenko2, Volodymyr V. Brei1
1Institute for Sorption and Problems of Endoecology of the National Academy of Sciences of Ukraine, 13 General Naumov Str.,
Kyiv 03164, Ukraine; s_levytska@ukr.net
2Manufacturing Group Techinservice Limited, Makiivskyy Provulok, 1, Kyiv, 04114, Ukraine
The gas-phase oxidation of ethylene glycol and methanol mixture into methyl glycolate С2H6O2+CH3OH+O2 =
C3H6O3+2H2О over synthesized copper-containing catalysts was studied. Methyl glycolate can be considered as raw
material for obtaining biodegradable polyglycolide. The CuO-containing samples were synthesized by impregnation
of granular oxide-supports (γ-Al2O3, SiO2 and MgO-ZrO2) with the calculated amount of aqueous solution of
Cu(NO3)2·3H2O followed by heat treatment at 400 °C. In such way the supported CuO-MexOy /Al2O3 (Me = Mg, Ti,
Cr, Co, Zn, Zr, Ag) samples have been prepared. Catalytic experiments were performed in a stainless-steel flow
reactor with a fixed bed of catalyst at 200-270 °C and atmospheric pressure. Oxygen of air was used as an oxidant.
The reaction products were analyzed using 13C NMR spectroscopy and gas chromatography. It was found that
СuO/Al2O3 catalyst provides ~ 100% ethylene glycol conversion with 56% selectivity towards methyl glycolate at
220 °С. The main by-products are methoxymethanol, 1,1-dimethoxymethane, methyl methoxyacetate, and methyl
formate. Use of silica as catalyst support leads to a significant decrease of the ethylene glycol conversion to 57 % for
CuO/SiO2, but methyl glycolate selectivity does not change significantly. Promotion of СuO/Al2O3 with MgO increases
methyl glycolate yield to 64%. According to the scheme of ethylene glycol sequential oxidation the increase in
selectivity for methyl glycolate over CuO-MgO/Al2O3 catalyst is caused by the basic sites that promote intramolecular
Cannizzaro rearrangement of the intermediate reaction product – glyoxal hemiacetal to methyl glycolate. It’s found
that mixed CuO-CrO3 oxide supported by γ-Al2O3 provides 80 % methyl glycolate selectivity with 95-100% ethylene
glycol conversion at 200-210 °C.
Keywords: methyl glycolate, ethylene glycol, copper-containing catalysts, gas-phase oxidation
____________________________________________________________________________________________________
Introduction
Methyl glycolate (MG) - hydroxyacetic acid
methyl ester can be considered as raw material for
obtaining biodegradable polyglycolide [1,2]. The two-
step synthesis of MG by the carbonylation of
formaldehyde (24 MPa) in the presence of water and
acid catalysts (Nafion NR-50 or H3PW12O40) to obtain
at first glycolic acid and then its following
esterification with methyl alcohol was described in
[3,4]. Condensation of formaldehyde and methyl
formate to methyl glycolate using heteropolyacids was
proposed by authors [5]. In [6] p-toluenesulfonic acid
as a catalyst was used for this condensation. The
reaction was carried out in an autoclave at 140 °C,
with a molar ratio of formaldehyde/methyl formate =
0.65. The source of formaldehyde was trioxane. After
reaction time of 3 h MG yield was 31% [6].
MG can be obtained by the vapor-phase selective
hydrogenation of dimethyl oxalate using Ag/SiO2,
Ag/SBA-15, Ag/AC-N-3, Cu/RGO and others
catalysts [7-13]. It should be noted that this method
provides enough high selectivity for methyl glycolate
(96-99%). However, the low (0.4 vol. %) content of
dimethyl oxalate in the initial vapor-gas mixture
causes low productivity of the catalyst (about 0.02 g of
MG/Lcat/h) [12].
The authors of [14] synthesized methyl glycolate
from the glyoxal (40% aqueous solution) and methanol
at 180°C for 0.5h in an autoclave using Al(NO3)3
9H2O, AlCl3 ∙ 9H2O and ZrOCl2 ∙ 2H2O. The MG
yield was in the interval of 85–87mol%. According to
[15], the MG synthesis was carried out by oxidation of
mannose and glucose in methanol at 100–120°С/1
MPa oxygen in the presence of MoO3 and Au/TiO2.
The maximum methyl glycolate yield of 39mol% was
achieved for mannose at 120 °C for 4 h. Authors [16]
described the liquid-phase oxidation of propylene
glycol-methanol mixture in autoclave under 3 MPa O2
pressure at 100°С. The supported Au/oxides were
used. On Au/ZnO the MG selectivity achieved 94
mol% at low 18% ethylene glycol conversion.
In this paper the results on vapor-phase oxidation
of ethylene glycol in the presence of methanol vapour
into methyl glycolate over supported copper-
containing catalysts are presented.
Experiment
Preparation of catalyst
mailto:s_levytska@ukr.net
60 Каталіз та нафтохімія, 2022, №33
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
The samples of Cu-containing oxides were
synthesized by impregnation of granular oxide-support
(fraction 0.5 – 2 mm) with calculated amount of aqueous
solution of Cu(NO3)2·3H2O. In such way the samples
of CuO-MexOy /Al2O3 (Me = Mg, Ti, Cr, Co, Zn, Zr,
Ag) have been prepared using a compatible solution of
copper nitrate with the corresponding metal salt:
Mg(NO3)2·6H2O, TiCl4, (NH4)2Cr2O7,
Co(NO3)2· 3H2O, Zn(NO3)2·6H2O, ZrO(NO3)2·5H2O,
AgNO3. The need solution volume was determined by
moisture absorption, as rule, 0.6 cm3 of solution on 1 g
of Al2O3 was used. Then samples were dried at 120 °C
and calcined at 400 °C for 4 h. As oxide-supports were
used γ-Al2O3 ( Ukraine, SBET = 280 m2/g, rav = 5.3 nm,
VΣ = 0.82 cm3/g, H0 ≤ +3.3, Cacid site = 1.1 ± 0.05
mmol/g), SiO2 (silica gel, China, SBET = 380 m2/g, rav =
4.9 nm, Vp = 0.97 cm3/g, H0 = +1.5, Cacid site = 1.2 ±
0.05 mmol/g) and mixed magnesium and zirconium
oxide (atomic ratio Mg: Zr = 7.5: 1, SBET = 70 m2/g,
rav = 7.3 nm, VΣ = 0.25 cm3/g, H_ ≤ +27.0, Cbasic site =
0.8 ± 0.05 mmol/g). The MgO-ZrO2 support was
synthesized by co-precipitation from Mg (NO3)2 and
ZrO(NO3)2 solutions according to [18]. A sample
marked 40CuO/Al2O3 means that the sample contains
40 wt.% CuO concerning to Al2O3.
The textural parameters of samples were determined
from the N2 adsorption-desorption isotherms by BET
method (Quantachrome Nova 2200e Surface Area and
Pore Size Analyzer). The X-ray powder diffraction
analysis of obtained samples was performed with a
DRON-4-07 diffractometer (CuKα).
Catalytic test
Methanol (Merk) and ethylene glycol (chemical
purity) were used. Catalytic experiments were
performed in a stainless-steel flow reactor (8 mm inner
diameter) with a fixed bed of catalyst (3 cm3) at 200-
270°C and atmospheric pressure. Oxygen of air use as
oxidant. 20% methanol solution of ethylene glycol
was fed into the evaporator using an Orion M-361
syringe pump. At that in evaporator need air flow was
fed also. The heated vapor-gas mixture flowed through
the reactor at space velocity GHSV= 320–1250 h– 1
that corresponded to contact time τ= 3–11 s. The molar
ratio of ethylene glycol: oxygen was 1: 1.5. The load
on a catalyst was varied from 0.9 to 3.5 mmol
EG/cm3
cat /h. The reaction products were condensed in
an ice-cooled receiver and analyzed using 13C NMR
spectroscopy (Bruker Avance-400) and gas
chromatography (Agilent 7820A). The conversion (X)
of ethylene glycol and selectivity (S) of products were
calculated in wt.% from chromatograms.
Results and Discussion
The nitrogen adsorption-desorption isotherms for
studied oxides belong to type IV as it’s shown for
40CuO/Al2O3 (Fig. 1). The isotherm is characterized
by a wide hysteresis loop in the range of relative N2
pressure 0.4–0.9, which indicates on a substantial part
of mesopores in the Al2O3 support. The calculated pore
size distribution confirms this fact also (Fig. 1). The
calculated from the adsorption-desorption isotherm
values of SBET, VΣ and rav for 40CuO/Al2O3 are equal
to 160 m2/g, 0.42 cm3/g and 5.4 nm respectively. It
should be noted, that the specific surface area and pore
volume of the supported oxides become almost half
smaller as to the initial γ-Al2O3 due to filling alumina
pores with CuO supported.
0.0 0.2 0.4 0.6 0.8 1.0
0
50
100
150
200
250
300
0 5 10 15 20
0.000
0.006
0.012
0.018
d
V
/r
r, nm
P/P
0
V
,
см
3
/г
Fig. 1. Nitrogen adsorption–desorption isotherm and
pore-size-distribution plot for 40CuO/Al2O3 catalyst
According to XRD analysis of 40CuO/Al2O3, CuO
supported is in the crystalline state. The peaks at 2θ =
32.5, 35.5, 38.7, 48.7, 53.5, 58.2, 61.5, 66.2, 68.1, 71.7
and 75.5° on XRD pattern of the sample (Fig. 2) are
correspond to the CuO phase (JCPDS). The average
calculated crystallite size of CuO, determined by the
peak (202) at 2θ = 48.7°, is 22–24 nm.
10 20 30 40 50 60 70 80 90
2,
o
2
1
Fig. 2. XRD patterns of γ-Al2O3 (1) and
40CuO/Al2O3 (2)
The EG conversion and MG selectivity values at
different temperatures for 40CuO/Al2O3 catalyst are
presented in Fig. 3. The conversion of ethylene glycol
at 210–240°С is at the level of 98–100%. Selectivity
Каталіз та нафтохімія, 2022, №33 61
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
towards methyl glycolate has maximum of 56% at
220°C (Fig. 3).
200 210 220 230 240
0
20
40
60
80
100
X
,
S
,
%
2
1
T,
o
C
Fig. 3. Ethylene glycol conversion (1) and methyl
glycolate selectivity (2) on 40CuO/Al2O3 catalyst at
different temperatures (L = 1.6 mmol ЕG/cm3
cat/h)
With increasing the load on 40CuO/Al2O3 catalyst
from 1.6 to 3.5 mmol EG/cm3
cat/h, ethylene glycol
conversion decreases from 98 to 75% (Fig. 4). The
selectivity for methyl glycolate is 56–58% at load
ranges from 1.6 to 2.5 mmol EG/mlсat/h, but at L = 3.5
mmol EG/mlсat/h the selectivity decreases to 47% (Fig.
4).
1.5 2.0 2.5 3.0 3.5
20
40
60
80
100
L, mmol EG/ml
cat
/h
2
1
X
,
S
,
%
Fig. 4. Ethylene glycol conversion (1) and methyl
glycolate selectivity (2) on 40CuO/Al2O3 at different
loads on catalyst (220 °С)
Therefore, the optimal temperature and load on
catalyst, that provide the highest 55% methyl glycolate
yield on 40CuO/Al2O3 catalyst, are 220°C and 1.6
mmol EG/mlcat/h, respectively.
The values of EG conversion and MG selectivity
for 40CuO/Al2O3 catalyst do not change significantly
for at least 12 hours’ reaction (Fig. 5). It should be
noted that initially, during 1-2 h, the catalyst provides
only 20-40% of MG selectivity. After 3 h work of
catalyst, the selectivity reaches ~55% and remains
constant (Fig. 5).
0 2 4 6 8 10 12 14
0
20
40
60
80
100
TOS, h
1
2
X
,
S
,
%
Fig. 5. Ethylene glycol conversion (1) and methyl
glycolate selectivity (2) with time on stream on
40CuO/Al2O3 (220°C, 1.6 mmol ЕG/cm3
cat/h).
In order to improve the methyl glycolate
selectivity, the ethylene glycol oxidation, the
CuO/Al2O3 catalyst was promoted with magnesium,
titanium, chromium, cobalt, zinc, zirconium, silver
oxides. Also, the CuO/SiO2, CuO-MgO/SiO2, СuО/
MgO-ZrO2, CuO-ZnО-ZrO2-Al2O3 and CuO-ZnО-
Al2O3 (catalyst for methanol synthesis) were tested in
this reaction. The results are presented in Table 1.
The addition of zirconium, zinc or magnesium
oxides to copper oxide on γ-Al2O3 (20CuO-10ZnО
/Al2O3, 20CuO-20ZrO2/Al2O3, 20CuO-2.5MgO/Al2O3
samples) increases the methyl glycolate yield by 5–
9 % compared with 40CuO/Al2O3. Other tested
samples provide the target product yield at the level of
13–58 % (Table 1). It can be noted that methyl
glycolate selectivity is sufficiently high on CuO/MgO-
ZrO2 (74 %), CuO-ZnО-ZrO2-Al2O3 (76 %) and
20CuO-10MgO/Al2O3 (77 %) oxides, however, the
ethy- lene glycol conversion is much less than that
over other samples (Table 1).
The using of silica as catalyst support leads to a
significant decrease of the ethylene glycol conversion
from 98 % for 40CuO/Al2O3 to 57 % for 40CuO/SiO2
while the methyl glycolate selectivity does not change
significantly (Table 1). A similar situation is observed
when comparing of 20CuO-5MgO/Al2O3 and 20CuO-
5MgO/SiO2 samples (Table 1). Methyl glycolate yield
of 64 % is observed on CuO-MgO/Al2O3 catalyst con-
taining 20 wt. % of CuO and 2.5 wt. % of MgO at
220C (Table 1).
In Table 2 are presented the contents of EG
oxidation products (without methanol) on three suit-
able catalysts.
62 Каталіз та нафтохімія, 2022, №33
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
Table 1 Ethylene glycol oxidation over CuO-containing catalysts 1
Catalyst XEG, % SMG, wt. % Y MG, wt. %
40CuO/Al2O3 98 56 55
45CuO-0.44Ag2О/Al2O3 96 55 53
20CuO-10ZnО/Al2O3 90 67 60
15CuO-30ZrO2/Al2O3 95 52 49
20CuO-20ZrO2/Al2O3 99 64 63
20CuO-15ZrO2/Al2O3 96 57 55
20CuO-12TiO2/Al2O3 96 46 44
15CuO-1.5Co3O4/Al2O3 82 46 38
20CuO-1.5MgO/Al2O3 89 66 59
20CuO-2.5MgO/Al2O3 90 71 64
20CuO-5MgO/Al2O3 81 72 58
20CuO-10MgO/Al2O3 59 77 45
CuO-ZnО-ZrO2-Al2O3 63 76 48
CuO-ZnО-Al2O3 50 25 13
40CuO/SiO2 57 54 31
20CuO-5MgO/SiO2 65 63 41
35СuО/MgO-ZrO2 24 74 18
1 Reaction conditions: 20 wt. % EG methanol solution, T = 220°C, L = 1.6 mmol EG/mlcat/h, molar ratio
ЕG : О2 = 1 : 1.5.
Table 2. Product content of ethylene glycol conversion 1
Catalyst Content of reaction products, mol. % 2 XEG,
%
SMG,
mol. % EG MG MA MF MM DMM ME
40CuO/Al2O3 1 65 4 13 8 2 7 99 66
CuO-ZnО-ZrO2-Al2O3 42 51 2 0 5 0 0 58 88
20CuO-5MgO/Al2O3 18 50 0 6 20 0 6 82 60
1 Reaction conditions: 20 wt. % EG methanol solution, 220°C, 1.6 mmol EG/mlcat/h, molar ratio ЕG : О2 = 1 : 1.5; 2 EG – ethylene
glycol, MG – methyl glycolate, MA – methyl methoxyacetate, MF – methyl formate, MM – methoxymethanol, DMM – 1,1-
dimethoxymethane, ME-1-methoxyethanol
Sequential oxidation of propylene glycol to
methyl glycolate is described by sum reaction С2H6O2
+ CH3OH + O2 = C3H6O3 + 2H2О and includes at least
three stages. In opinion authors [16], ethylene glycol is
oxidized on the Au/ZnO catalyst initially to
glycolaldehyde that forms the hemiacetal with
methanol. Next, this hemiacetal is oxidized to methyl
glycolate. According to another scheme, proposed for
the propylene glycol and glycerol oxidative este-
rification into alkyl lactates [18, 19], the EG con-
verting to MG could be include the sequential oxi-
dation to glyoxal via glycolic aldehyde, the formation
of glyoxal hemiacetal with methanol. Then the
hemiacetal rearrangements into MG by Cannizzaro on
basic sites of catalyst:
Каталіз та нафтохімія, 2022, №33 63
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
The process follows Mars - van Krevelen’s
scheme, that the oxidant is atomic oxygen of copper
oxide lattice: 2CuO = Cu2O + O. Copper oxide (I) is
oxidized to CuO by air oxygen. The increase of methyl
glycolate yield on basic CuO-MgO/Al2O3 catalyst, and
twice decreasing one on CuO-MgO/SiO2 with more
acidic support – silica, confirms the Cannizzaro
intermolecular rearrangement (Table 1).
The by-products of studied EG oxidation are
methyl methoxyacetate, methyl formate, hemi- and full
acetals of formaldehyde and acetaldehyde with
methanol (methoxymethanol, 1,1-dimethoxymethane,
1-methoxyethanol, 1,1-dimethoxyethane). It should be
noted that methyl formate, methoxymethanol and 1,1-
dimethoxymethane are formed from formaldehyde,
producing by aldol decondensation of glycolaldehyde.
According to the calculations using Aspen HYSYS
program of equilibrium OHCH2CHO ↔ 2HCHO, the
formaldehyde content may be 36 mol. % at 240 °C.
That is, the reaction rate of glycolaldehyde de-
condensation competes with its oxidation into glyoxal.
The acetaldehyde is formed at dehydration of ethylene
glycol.
At testing various supported oxides in the TPR
oxidation of cyclohexanol to cyclohexane, we have
found a promising CuO-CrO3/Al2O3 sample that
catalyzes the oxidation without cyclohexanol
dehydration to cyclohexene in fact [20]. This sample
turned out to be active and selective in studied EG
oxidation: 80% methyl glycolate selectivity is obser-
ved at 2000C with 100% ethylene glycol conversion.
Also, CuO-CrO3/Al2O3 catalyst provides 95-100%
ethylene glycol conversion at higher load on a catalyst,
up to 2.3 mmol EG/cm3
cat/h, in comparison with other
studied samples (Fig. 6).
1.6 2.0 2.4 2.8 3.2
20
40
60
80
100
X
.
S
,
%
1
2
L, mmol EG/ml
cat
/h
Fig. 6. Ethylene glycol conversion (1) and methyl
glycolate selectivity (2) on CuO-CrO3/Al2O3 catalyst at
different loads on catalyst (200 C)
Conclusion
Thus, it’s found that mixed CuO-CrO3 oxide
supported by γ-Al2O3 may be a suitable catalyst for the
vapor-phase ethylene glycol oxidative esterification
with methanol into methyl glycolate at 200-2100C. The
catalyst provides 80 % methyl glycolate selectivity
with 95-100% ethylene glycol conversion at loads on
the catalyst up to 2.3 mmol EG/cm3
cat/h.
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Надійшла до редакції 07.04.2022 р
Каталіз та нафтохімія, 2022, №33 65
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
Парофазне окиснення метанольного розчину етиленгліколю до метилгліколату
на мідьвмісних каталізаторах
Анатолій М. Варварін1, Світлана І. Левицька1*, Артур М. Милін1,
Олексій Ю. Зінченко2, Володимир В. Брей1
1Інститут сорбції та проблем ендоекології НАН України, вул. Генерала Наумова, 13; Київ , 03164, Україна;
s_levytska@ukr.net
2ТОВ «Виробнича група Техінсервіс», Макіївський провулок, 1, Київ, 04114, Україна
В роботі наведено результати парофазного окиснення етиленгліколю в метанолі С2H6O2+CH3OH+O2 =
C3H6O3+2H2О на оксидних мідьвмісних каталізаторах в проточному реакторі для одержання метилгліколату.
Метилгліколат можна розглядати як сировину для одержання гліколіду – мономеру для виробництва
біодеструктуючого полігліколіду. Зразки нанесених мідьвмісних каталізаторів синтезували просочуванням
гранул вибраного оксиду-носія (γ-Al2O3, SiO2 та MgO-ZrO2) розрахованою кількістю водного розчину
Сu(NO3)2 · 3H2O, а для зразків CuO-МеxОy/Al2O3 (Ме = Мg, Тi, Cr, Co, Zn, Zr, Ag) сумісним розчином нітрату
міді з сіллю відповідного металу з наступною термообробкою для утворення нанесеної оксидної фази.
Каталітичні експерименти здійснювали в проточному реакторі з нерухомим шаром каталізатору за температур
200–270 °С і атмосферного тиску. Окиснювачем слугував кисень повітря. Продукти реакції аналізували з
використанням 13С ЯМР спектроскопії та газової хроматографії. Виявлено, що СuO/Al2O3 каталізатор
забезпечує майже 100 % конверсію етиленгліколю із 56% селективністю за метилгліколатом при 220°С.
Основними побічними продуктами окиснення етиленгліколю є метоксиметанол, 1.1-диметоксиметан,
метилметоксиацетат та метилформіат. Використання кремнезему як оксиду-носія призводить до значного
зниження конверсії етиленгліколю (57 % для CuO/SiO2 каталізатора), тоді як селективність за метилгліколатом
істотно не змінюється. Введення до складу СuO/Al2O3 каталізатора оксидів цирконію, цинку і магнію сприяє
перебігу цільової реакції. Встановлено, що найбільший вихід метилгліколату - 64 % з 90 % конверсією
етиленгліколю спостерігається на CuO-MgO/Al2O3, що містить 20 мас. % оксиду міді і 2.5 мас. % оксиду
магнію. Згідно наведеної схеми послідовного окислення етиленгліколю збільшення селективності за
метилгліколатом на CuO-MgO/Al2O3 каталізаторі зумовлюють основні центри, які сприяють
внутрішньомолекулярному перегрупуванню Канніццаро проміжного продукту реакції – напівацеталю
гліоксалю у метилгліколат. Знайдено, що змішаний CuO-CrO3 оксид, нанесений на γ-Al2O3, забезпечує 80 %
селективність за метилгліколатом при 95-100% конверсії етиленгліколю за температур 200-210 °C.
Ключові слова : метилгліколат, етиленгліколь, мідьвмісні каталізатори, газо-фазне окиснення
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| id | oai:katalizorgua:article-82 |
| 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/6b/a02627db6f66246b1aced06fef32e06b.pdf |
| spelling | oai:katalizorgua:article-822023-01-20T10:00:52Z Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts Varvarin, Anatolii M. Levytska, Svitlana I. Mylin, Artur M. Zinchenko, Oleksii Yu. Brei, Volodymyr V. methyl glycolate, ethylene glycol, copper-containing catalysts, gas-phase oxidation метилгліколат, етиленгліколь, мідьвмісні каталізатори, газо-фазне окиснення The gas-phase oxidation of ethylene glycol and methanol mixture into methyl glycolate С2H6O2+CH3OH+O2 = C3H6O3+2H2О over synthesized copper-containing catalysts was studied.  Methyl glycolate can be considered as raw material for obtaining biodegradable polyglycolide. The CuO-containing samples were synthesized by impregnation of granular oxide-supports (γ-Al2O3, SiO2 and MgO-ZrO2) with the calculated amount of aqueous solution of Cu(NO3)2·3H2O followed by heat treatment at 400 °C. In such way the supported CuO-MexOy /Al2O3 (Me = Mg, Ti, Cr, Co, Zn, Zr, Ag) samples have been prepared. Catalytic experiments were performed in a stainless-steel flow reactor with a fixed bed of catalyst at 200-270 °C and atmospheric pressure. Oxygen of air was used as an oxidant. The reaction products were analyzed using 13C NMR spectroscopy and gas chromatography. It was found that СuO/Al2O3 catalyst provides ~ 100% ethylene glycol conversion with 56% selectivity towards methyl glycolate at 220 °С. The main by-products are methoxymethanol, 1,1-dimethoxymethane, methyl methoxyacetate, and methyl formate. Use of silica as catalyst support leads to a significant decrease of the ethylene glycol conversion to 57 % for CuO/SiO2, but methyl glycolate selectivity does not change significantly. Promotion of СuO/Al2O3 with MgO increases methyl glycolate yield to 64%. According to the scheme of ethylene glycol sequential oxidation the increase in selectivity for methyl glycolate over CuO-MgO/Al2O3 catalyst is caused by the basic sites that promote intramolecular Cannizzaro rearrangement of the intermediate reaction product – glyoxal hemiacetal to methyl glycolate. It’s found that mixed CuO-CrO3 oxide supported by γ-Al2O3 provides 80 % methyl glycolate selectivity with 95-100% ethylene glycol conversion at 200-210 °C. The gas-phase oxidation of ethylene glycol and methanol mixture into methyl glycolate С2H6O2+CH3OH+O2 = C3H6O3+2H2О over synthesized copper-containing catalysts was studied.  Methyl glycolate can be considered as raw material for obtaining biodegradable polyglycolide. The CuO-containing samples were synthesized by impregnation of granular oxide-supports (γ-Al2O3, SiO2 and MgO-ZrO2) with the calculated amount of aqueous solution of Cu(NO3)2·3H2O followed by heat treatment at 400 °C. In such way the supported CuO-MexOy /Al2O3 (Me = Mg, Ti, Cr, Co, Zn, Zr, Ag) samples have been prepared. Catalytic experiments were performed in a stainless-steel flow reactor with a fixed bed of catalyst at 200-270 °C and atmospheric pressure. Oxygen of air was used as an oxidant. The reaction products were analyzed using 13C NMR spectroscopy and gas chromatography. It was found that СuO/Al2O3 catalyst provides ~ 100% ethylene glycol conversion with 56% selectivity towards methyl glycolate at 220 °С. The main by-products are methoxymethanol, 1,1-dimethoxymethane, methyl methoxyacetate, and methyl formate. Use of silica as catalyst support leads to a significant decrease of the ethylene glycol conversion to 57 % for CuO/SiO2, but methyl glycolate selectivity does not change significantly. Promotion of СuO/Al2O3 with MgO increases methyl glycolate yield to 64%. According to the scheme of ethylene glycol sequential oxidation the increase in selectivity for methyl glycolate over CuO-MgO/Al2O3 catalyst is caused by the basic sites that promote intramolecular Cannizzaro rearrangement of the intermediate reaction product – glyoxal hemiacetal to methyl glycolate. It’s found that mixed CuO-CrO3 oxide supported by γ-Al2O3 provides 80 % methyl glycolate selectivity with 95-100% ethylene glycol conversion at 200-210 °C. 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/82 10.15407/kataliz2022.33.059 Catalysis and petrochemistry; No. 33 (2022): Catalysis and petrochemistry; 59-65 Каталіз та нафтохімія; № 33 (2022): Каталіз та нафтохімія; 59-65 2707-5796 2412-4176 10.15407/kataliz2022.33 en https://kataliz.org.ua/index.php/journal/article/view/82/71 Copyright (c) 2022 Catalysis and petrochemistry |
| spellingShingle | метилгліколат етиленгліколь мідьвмісні каталізатори газо-фазне окиснення Varvarin, Anatolii M. Levytska, Svitlana I. Mylin, Artur M. Zinchenko, Oleksii Yu. Brei, Volodymyr V. Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts |
| title | Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts |
| title_alt | Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts |
| title_full | Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts |
| title_fullStr | Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts |
| title_full_unstemmed | Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts |
| title_short | Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts |
| title_sort | vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over cuo-containing catalysts |
| topic | метилгліколат етиленгліколь мідьвмісні каталізатори газо-фазне окиснення |
| topic_facet | methyl glycolate ethylene glycol copper-containing catalysts gas-phase oxidation метилгліколат етиленгліколь мідьвмісні каталізатори газо-фазне окиснення |
| url | https://kataliz.org.ua/index.php/journal/article/view/82 |
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