Direct Carbonation of Glycerol with CO2 Catalyzed by Metal Oxides

Article abstract of DOI:10.1002/cphc.201700579

Five metal oxides (ZnO, SnO₂, Fe₂O₃, CeO₂, La₂O₃) were produced by the sol–gel method and tested in the direct carbonation of glycerol with CO₂. Initial tests with Fe₂O₃ showed that the best reaction condition was 180 °C, 150 bar, and 12 h. The other oxides were evaluated at these conditions and were all active to the formation of glycerol carbonate. Zinc oxide was the most active catalyst, with a yield of 8.1 % in the organic carbonate. The catalytic activity decreased upon washing and drying the ZnO catalyst between the runs. Nevertheless, the activity is maintained if the ZnO is washed and calcined at 450 °C between the runs. FTIR and TGA results indicated the formation of ZnCO₃ as the main cause of catalyst deactivation, which may be decomposed upon calcination of the material. No appreciable leaching of Zn was observed, indicating a truly heterogeneous catalysis.

Full text of DOI:10.1002/cphc.201700579

Accepted Article
Title: Direct carbonation of glycerol with CO2 catalyzed by metal oxides
Authors: Claudio J. A. Mota and Leonardo Ozório
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ChemPhysChem
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Direct carbonation of glycerol with CO2 catalyzed by metal oxides
Leonardo P. Ozorio,[a] Claudio J. A. Mota*[a],[b],[c]
Abstract: Five metal oxides (ZnO, SnO2, Fe2O3, CeO2, La2O3)
were produced by the sol-gel method and tested in the direct
carbonation of glycerol with CO2. Initial tests with Fe2O3 showed that
the best reaction condition was 180 °C, 150 bar and 12 h. The other
oxides were evaluated at these conditions and were all active to the
formation of glycerol carbonate. Zinc oxide was the most active
catalyst, with a yield of 8.1% in the organic carbonate. The catalytic
activity decreased upon washing and drying the ZnO catalyst
between the runs. Nevertheless, the activity is maintained if the ZnO
industrial process of carbon dioxide chemical transformation
may be energy intensive and requires the use of catalysts.
Products such as hydrocarbons, methanol and organic
carbonates are among those of potential interest to be
synthesized using carbon dioxide as feedstock.[6-8]
Cyclic carbonates with five-membered rings are used as aprotic
polar solvents, precursors for the synthesis of polycarbonates
and polyurethanes, electrolytes in lithium batteries, production of
drugs, among others.[9-11] Synthesis of cyclic carbonates can be
accomplished by coupling carbon dioxide with epoxides,
polyalcohols and oxidative carboxylation of olefins. [9,12-15]
The process of obtaining cyclic carbonates via the direct
reaction between glycols and CO2 is more sustainable and
ecological than the reaction with epoxides or use of phosgene
(COCl2).[16-18] However, this route has thermodynamic limitations
and the yields are usually low if water suppressor agents are not
used to shift equilibrium.[19]
We have shown that NaY zeolite impregnated with Ag, Zn and
Sn oxides are good catalysts for the direct carbonation of
glycerol to glycerol carbonate.[20] The parent NaY zeolite showed
no conversion at 180 °C, 3 hours and 100 Bar, but when
impregnated with the metal oxides the yield of glycerol
carbonate was up to 5.8%, near the thermodynamic equilibrium
at the reaction conditions.
Due to the adsorption of CO2 on the surface of metallic oxides, it
is possible to use these materials as catalysts in the conversion
of the gas.[20-26]
La2O3 impregnated with different Cu contents were evaluated in
the reaction between glycerol and CO2 in the presence of
CH3CN as dehydrating agent. The catalyst with 2.3% of Cu over
La2O3 showed glycerol conversion of 33.4% and 45.4%
selectivity to glycerol carbonate. Monoacetin was also observed
with a selectivity of 52.9%, at 150 °C, 12 hours and 70 Bar.
Authors stated that the size of the Cu particles and the Cu/
La2O3 basic sites have a significant effect on the conversion to
glycerol carbonate.[24]
Liu et al. synthesized CeO2 with different morphologies using
three methods: traditional precipitation, hydrothermal synthesis
and sol-gel citrate. These materials were tested in the synthesis
of glycerol carbonate. Authors observed that CeO2 exhibits high
activity at 150 °C, 40 Bar and 5 hours. The influence of different
dehydrating agents and solvents was also evaluated. 2-
Cyanopyridine and DMF were used as dehydrating agent and
solvent, respectively, yielding 78.9% of glycerol carbonate. The
catalyst could be reused in five consecutive runs upon
regeneration at 400 °C for 5 h.[26]
o
is washed and calcined at 450 C between the runs. FTIR and TGA
results indicated the formation of ZnCO3 as the main cause of
catalyst deactivation, which may be decomposed upon calcination of
the material. No appreciable leaching of Zn was observed, indicating
a truly heterogeneous catalysis.
Introduction
Carbon dioxide is a major greenhouse gas. Its concentration in
the atmosphere has reached alarming levels in recent decades,
leading to climate changes due to the elevation of the
temperature of the planet.[1] In the last United Nations
Conference on Climate Changes (COP-15), countries have
agreed to reduce their CO2 emissions to keep the increase of
temperature within 1.5 oC until the end of the century. Therefore,
the studies on environmental issues and carbon dioxide
mitigation are increasing in importance.[2-4]
Much of the CO2 released into the atmosphere is due to the
burning of fossil fuels, which are currently the main source of
energy. One of the options for reducing the level of this gas in
the atmosphere is its capture and conversion in products of
industrial interest and high added-value.[5]
Carbon dioxide has been used as coolant fluid in conditioned air
systems, in fire extinguishers, in food preservation and beverage
manufacturing. However, its use as raw material in the chemical
industry is still limited to few processes, especially the
manufacture of urea and salicylic acid.[6,7] CO2 has a high
thermodynamic stability and low chemical reactivity; thus, any
[a]
Prof. Dr. Claudio José de Araújo Mota, Leonardo Peçanha Ozorio
Universidade Federal do Rio de Janeiro
Escola de Química
Av Athos da Silveira Ramos 149, Bloco E, Rio de Janeiro 21941-
909, Brazil
E-mail: cmota@iq.ufrj.br
Zhou et al. studied[27] the use of terminal propargylic alcohols, in
reactions between vicinal alcohols and CO2 in the presence of
silver catalysts. The authors stated that they were able to
produce glycerol carbonate in 82% of yield with 3-Hydroxy-3-
methylbutan-2-one as by-product in 83% of yield, being both
products with high added value compared to glycerol and CO2.
[b]
[c]
Prof. Dr. Claudio José de Araújo Mota
Instituto de Química
Universidade Federal do Rio de Janeiro
Av Athos da Silveira Ramos 149, Bloco A, Rio de Janeiro 21941-
909, Brazil
Prof. Dr. Claudio José de Araújo Mota
INCT, Energia e Ambiente, UFRJ, 21941-909, Rio de Janeiro,
Brazil.
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10.1002/cphc.201700579
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The authors suggested that this reaction pathway may be a
viable alternative to overcome the thermodynamic limitations.
The use of dehydrating agents and solvents shifts the
equilibrium, increasing the yield of glycerol carbonate. However,
they lead to many undesired by-products which make the
purification process expensive. Therefore, the search for more
sustainable dehydrating agents is necessary.[28]
In this study we have synthesized Zn, Sn, Fe, Ce and La oxides
by the sol-gel method to test them as catalysts in the direct
carbonation of glycerol with CO2 (Scheme 1). As the main
objective is the study of the catalytic activity of the materials, no
dehydrating agent was added. Therefore, the reactions were
limited by the thermodynamic equilibrium.
4
3
2
1
50
75
100
125
150
The sol-gel method is successfully used in the production of
metal oxide material for uses in ceramics, glass, films and
fibers.[29,30] In this work, we used this methodology to prepare
different metal oxides through the use of polyvinyl alcohol (PVAl)
as template.[31-33]
Pressure (Bar)
Figure 2. Yield of glycerol carbonate over Fe2O3 as a function of the pressure
at 180 oC and 3 h.
Figure 3 shows the yield of glycerol carbonate with varying
o
reaction time, at 180 C and 150 bar of pressure over Fe2O3. It
can be seen that after 12 h the yield is almost constant, around
6.8%. This is associated with the equilibrium conditions, which
has been calculated to be near this value at non-supercritical
conditions.[19]
The remaining catalysts were tested at 180 oC, 150 bar and 12 h
of reaction time. The results are shown in figure 4.
Scheme 1. Reaction of CO2 with glycerol to produce glycerol carbonate.
Results and Discussion
The prepared metal oxide catalysts were analyzed by XRD.
Figure 1 shows the diffraction patterns, which correspond to the
desired oxide by comparison to the Joint Commitee on Powder
Diffraction Standards (JCPDS) files contained in the
International Center for Diffraction Data (ICDD) database.[34]
8
7
6
5
4
3
2
1
0
A
B
C
D
E
0
5
10
15
20
25
Time (h)
Figure 3. Yield of glycerol carbonate over Fe2O3 as a function of time at 180
oC and 3 h.
10
20
30
40
50
60
70
80
2 (degree)
Figure 1. XRD of the prepared metal oxides: (A) ZnO, (B) SnO2, (C) La2O3,
(D) Fe2O3 and (E) CeO2.
Initial tests were carried out with Fe2O3 to screen the best
reaction conditions. Figure 2 shows the effect of the pressure on
the yields of glycerol carbonate at 180 °C and 3 h of reaction
time. As would be expected, the increase in pressure leads to
higher yield of product.
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10.1002/cphc.201700579
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5B).
8
6
4
2
0
Figure 4. Yield of glycerol carbonate over different metal oxide catalysts at
180 oC, 150 bar and 12 h.
The reaction without catalyst, just pressurizing the glycerol with
CO2 at the reaction conditions, yielded 3% of glycerol carbonate.
A similar yield was observed with SnO2, indicating that the
material has negligible activity at the reaction conditions. The
best performance was observed with ZnO, which showed 8.1%
yield of glycerol carbonate. La2O3 and Fe2O3 gave approximately
the same yield of glycerol carbonate, near 7%, whereas CeO2
presented 6% of glycerol carbonate at the reaction conditions.
The results clearly shows that all the synthesized oxides are
active in the direct carbonation of glycerol. No other organic
product was observed at the conditions used. It is worth to
mention that the liquid fraction, collected after the reaction using
ZnO, was analyzed by ICP to test for leaching. The value of 3.7
g of zinc per gram of sample is somewhat higher than the value
of 0.6 g of zinc per gram of the pure glycerol used in the
experiments. However, it shows that leaching of the catalyst to
the liquid phase is not expressive and the catalysis is truly
heterogeneous.
To better understand the nature of the active sites and reactivity
of the catalysts, we have chosen the ZnO system. A sample of
zinc oxide synthesized without the addition of the polyvinyl
alcohol was also tested in the reaction and showed 5.3% yield of
glycerol carbonate at the same reaction conditions. This value is
lower than the yield observed with the same oxide synthesized
in the presence of PVAl. The difference in activity may be
related with the textural properties of the materials. Whereas the
ZnO synthesized without the addition of PVAl showed 0.9 m²/g
of surface area, the catalyst prepared in the presence of PVAl
showed a significantly higher area of 14 m²/g. The larger surface
area can provide more active sites, explaining the higher yield of
glycerol carbonate. The presence of the polyvinyl alcohol during
the synthesis kept the ZnO crystals more spaced from each
other. After calcination, unfilled gaps between the crystals may
be formed, leading to a porous material with higher surface area.
Figure 5A shows the SEM image of the ZnO prepared with the
addition of PVAl. The sponge-like morphology is consistent with
the SEM results of other oxide materials synthesized in the
presence of PVAl.[35] ZnO prepared without the addition of PVAl
Figure 5. SEM Images: (A) ZnO synthesized with PVAl, (B) ZnO synthesized
without PVAl.
The reuse of the ZnO catalysts synthesized in the presence of
PVAl was carried out considering two different post-treatments.
In the first case, the ZnO was washed with 30 ml of methanol
o
and dried at 160 C between the reactions. A gradual loss of
activity occurred and after 3 consecutive runs the yield of
glycerol carbonate was 4.8 %. The second procedure consisted
in washing the material with 30 ml of methanol followed by
calcination at 450 oC. No significant loss of activity was observed
after four consecutive runs (Fig. 6). A thermogravimetric analysis
(TGA) of the ZnO subjected to washing and drying after the
three runs showed 42% of mass loss up to 477 °C, indicating the
desorption or decomposition of species on the surface. On the
other hand, the TGA analysis of the calcined catalyst after four
runs showed no appreciable mass loss in the same temperature
range, indicating that calcination has completely regenerated the
catalyts (figure 7).
The comparative FTIR analysis between the ZnO before and
after pressurization with CO2 under the reaction conditions is
shown in figure 8. One can see the intense bands at 1526 and
1387 cm-1, in addition to bands of lower intensity in the region
from 1050 to 700 cm-1, all of which refer to the formation of
polydentate carbonate species.[36-40] The FTIR spectrum of ZnO
pressurized with CO2 is similar to the spectrum reported for
ZnCO3 nanoparticles,[41] suggesting that some phase of zinc
carbonate may be formed upon pressurization with CO2 at the
reaction conditions.
The XPS analysis of the ZnO catalyst before and after reaction
did not indicate any major change in the oxidation state of the
zinc atom. The spectra (not shown) presented two peak
components with binding energy of 1021 eV and 1044 eV, which
have being referred to the Zn 2p3/2 and Zn 2p1/2, respectively,
characteristic of Zn-O bond. In the spectrum of the regenerated
catalyst (after calcination) it was also noticed that the width of
the peak at half height had changed, with the FWHM of Zn 2p3/2
of 1.932 eV, whereas for the fresh catalyst the value was 1.524
eV. These data may indicated that after calcination there should
in the synthesis medium presents
a bulkier morphology,
consistent with a more compact aggregation of the crystal (figure
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10.1002/cphc.201700579
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be some agglomeration leading to slightly larger particle
size.[42,43]
A
B
8
A
6
4
2
0
0
1
2
3
4
Use
8
6
4
2
0
B
4000
3500
3000
2500
2000
1500
1000
500
Wavenumbers (cm-1)
Figure 8. FTIR spectra: (A) ZnO after pressurization with CO2, (B) ZnO.
0
1
2
3
Use
Figure 6. Yield of glycerol carbonate upon the reuse of ZnO: (A) calcination at
450 oC between the runs; (B) drying at 160 oC between the runs.
0
100
200
300
400
500
600
100
90
A
0
100
200
300
400
500
600
100
90
80
70
60
A
80
70
100
B
50
90
80
70
100
90
80
70
60
50
B
0
100
200
300
400
500
600
Temp (OC)
Figure 9. TGA profiles: (A) ZnO after pressurization with CO2, (B) ZnCO3.
0
100
200
300
400
500
600
Temp. (O C)
Catalytic test with commercial zinc carbonate was carried out
and showed the same yield of glycerol carbonate of the blank
reaction, without any catalyst. In addition the reaction of glycerol
and ZnCO3 at the same conditions, with N2 as pressurizing gas,
did not yield any glycerol carbonate. Therefore, we should
Figure 7. TGA profiles: (A) ZnO upon washing with methanol and drying at
160 oC; (B) ZnO upon washing with methanol and calcination at 450 oC.
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10.1002/cphc.201700579
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conclude that ZnCO3 is neither a catalyst nor is involved in the
mechanistic pathway of the glycerol reaction with CO2 in the
presence of ZnO. In fact, the formation of zinc carbonate
phases on the catalyst surface may be the cause of
deactivation, when no calcination is performed. Figure 9 shows
the TGA profiles of ZnO pressurized with CO2 and ZnCO3. Both
present a similar profile, with the maximum temperature of
of ZnCO3 phase. On the other hand, calcination of the ZnO
catalyst at 450 C completely recover the catalytic activity, due
to the decomposition of the carbonate phase and regeneration
of the catalyst.
o
Experimental Section
o
weight loss aroung 350 C. These data support the FTIR results
and point out to the formation of ZnCO3 as the most probable
cause of catalyst deactivation. Upon calcination, the carbonate
is decomposed and the catalytic activity restored, indicative of
the regeneration of the catalyst.
The proposed mechanism may involves the reaction of glycerol
with the zinc oxide surface to form an adsorbed alkoxide, which
Preparation of the catalysts
Two aqueous solutions were prepared: one saturated solution with the
metal salts (SnCl2, Fe(NO3)3, Zn(NO3)2, Ce(NO3)3, La(NO3)3) and other
with polyvinyl alcohol (10 wt%). The solutions were mixed, maintaining
the metal ion:monomeric unit ratio equal to 1:3, magnetically stirred for 3
hours at 60 ºC and then heated to completely evaporate the water. The
resulting material was heated, with the aid of a silicone oil bath, to 250 °C
and kept at this temperature for 30 min to decompose the polymer, and
obtaining the precursor powder of the catalysts. The metal oxides are
obtained after calcination of this precursor powder at 450 °C (1 °C / min)
for 4 h, except for the lanthanum oxide precursor which was calcined at
850 °C. This procedure is similar to that described by Fernandes to
obtain other metal oxide nanoparticles.[31-33]
then attacks the CO2 molecule to form
a carboxylate
intermediate. In the sequence, the secondary hydroxyl of the
glycerol may attack the carboxyl group to produce the cyclic
carbonate (figure 10).
The materials were characterized by BET Surface Area, using nitrogen
adsorption isotherm, X-ray Diffraction (XRD), thermogravimetric analysis
(TGA), Fourier Transform Infrared (FTIR),
X ray photoelectron
spectroscopy (XPS), Inductively Coupled Plasma Mass Spectrometry
(ICP-MS) and Scanning Electron Microscopy (SEM).
Catalytic Test
The catalytic tests were carried out in a 100 ml Parr reactor with 25.2 g
glycerol (analytical grade) and the metal oxide (mass referring to 2 mmol
of the metal), which was previously dried at 160 °C for 30 min. In all tests,
the system was initially cooled to 0 oC, pressurized with 55 bar of CO2
(99.999%) and heated to 180 °C. Upon heating, the pressure in the
system increased and were controlled to the desired value at the desired
temperature by releasing the excess of CO2. At the end, the system was
cooled down, pressured was released and the catalysts was vacuum
filtered on a glass membrane. About 0.5 g of the liquid fraction was
diluted in methanol in a 5 mL volumetric flask. Tetraethyleneglycol
(internal standard) was added to the samples, which were then analyzed
by gas chromatography coupled to a mass spectrometer (Agilent 5975).
The yield of glycerol carbonate was obtained using a calibration curve.
Figure 10. Possible mechanistic scheme for the formation of glycerol
carbonate over zinc oxide catalyst.
- Reuse test
Two procedures were employed: in the first, the ZnO material was
washed with 30 mL of methanol and dried at 160 °C for 30 min between
the runs. The second procedure involves washing the material with 30
mL of methanol followed by calcination at 450 °C for 60 min, before using
in a subsequent run.
Conclusions
Five different metal oxides (Fe, Zn, La, Ce and Sn) were
prepared by the sol-gel method in the presence of polyvinyl
alcohol. All were active to the formation of glycerol carbonate in
o
the reaction of CO2 with glycerol at 180 C and 150 bar. Zinc
Acknowledgements
oxide showed the best performance with a yield of glycerol
carbonate of 8.1% after 12 h of reaction time. This value is close
to the thermodynamic equilibrium calculated at non-supercritical
conditions.
Loss of catalytic activity was observed upon drying the catalyst
at 160 oC between the runs and was associated to the formation
Authors acknowledge financial support from CNPq, CAPES and
FAPERJ. They also acknowledge the Laboratório Multiusuários
de Espectroscopia from IQ/UFRJ for the XPS analysis.
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Keywords: Glycerol • CO2 • Cyclic carbonates • Metal oxide •
Zinc Oxide
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Glycerol carbonate can be
prepared from the reaction
of CO2 with glycerol in the
presence of metal oxide
catalysts
Leonardo P. Ozorio, Claudio
J. A. Mota*
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Title
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Author(s), Corresponding Author(s)*
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