Ceria-catalyzed conversion of carbon dioxide into dimethyl carbonate with 2-cyanopyridine

Article abstract of DOI:10.1002/cssc.201300229

DMC run: Carbon dioxide can be converted into dimethyl carbonate in a reaction system involving 2-cyanopyridine as a dehydration agent, catalyzed by CeO₂. Regeneration of the coproduct 2-picolinamide can be achieved over a Na₂O/SiO₂ catalyst. As a whole, the system servest to react carbon dioxide with methanol to produce dimethyl carbonate. Copyright

Full text of DOI:10.1002/cssc.201300229

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DOI: 10.1002/cssc.201300229
Ceria-Catalyzed Conversion of Carbon Dioxide into
Dimethyl Carbonate with 2-Cyanopyridine
[a]
[a]
[a]
[a]
Masayoshi Honda, Masazumi Tamura, Yoshinao Nakagawa,* Satoru Sonehara,
[b]
[b]
[a]
Kimihito Suzuki, Ken-ichiro Fujimoto, and Keiichi Tomishige*
[
8h]
Technology for the conversion of carbon dioxide into useful
compounds is part of a future sustainable society without anxi-
diimide (Cu I , 5 MPa, 338 K),
and butylene oxide
2
2
[11]
(ZrO -KCl-Mg, 9.5 MPa, 423 K), reporting DMC yields of 40%,
2
[
1]
eties about global warming. Approaches to the conversion of
0.8%, and 7.2%, respectively, based on methanol. We reported
[
2]
carbon dioxide can be divided into two strategies: reductive
and nonreductive ones. The energy level of carbon dioxide is
very low, and its reductive conversion into target compounds
the use of an excess amount of acetonitrile (CeO , 0.5 MPa,
2
[12b]
[12d]
423 K)
or benzonitrile (CeO , 1 MPa, 423 K),
using rela-
2
tively low CO2 pressures and achieving DMC yields of 9%
(48 h) and 47% (86 h), respectively. On the other hand, the
[
3]
[4]
such as formic acid or methanol requires large energy
inputs, using highly reactive reducing agents such as molecular
hydrogen. Target compounds for its nonreductive conversion
[13]
separation of methanol from DMC is another critical issue.
DMC forms an azeotrope with methanol at atmospheric pres-
sure, with an approximate methanol/DMC composition of
70%:30%. Based on these findings, numerous separation tech-
niques including extractive distillation, liquid–liquid extraction,
[
5]
include organic carbonates. The most useful organic carbon-
ate is dimethyl carbonate (DMC), which has been used as elec-
trolyte in lithium-ion batteries and as starting material for poly-
[
6]
[13]
carbonate resins. A promising, future large-volume use is as
evaporation, and selective adsorption were developed. From
[
7]
additive to gasoline and diesel fuels. DMC is synthesized
from carbon dioxide according to:
the viewpoints of industrial process requirements and atom
economy, the development of a reaction system for the com-
plete conversion of methanol to DMC is desired.
2
CH OH þ CO ! ðCH OÞ CO þ H O
ð1Þ
3
2
3
2
2
This Communication reports that a system comprising a het-
erogeneous CeO catalyst and 2-cyanopyridine is effective for
2
[
8]
[9–11]
Both homogeneous and heterogeneous catalysts
can
the direct synthesis of DMC from carbon dioxide and methanol
under mild reaction conditions (393 K). 2-Cyanopyridine acts as
dehydration agent, leading to improvements of the methanol
conversion and DMC yield. In addition, the recyclability of the
dehydrating agent is confirmed by the dehydration of 2-picoli-
namide to 2-cyanopyridine catalyzed by Na O/SiO . As a whole,
catalyze this reaction, and our group has reported that cerium
[
12]
oxide is an effective heterogeneous catalyst. However, the
yield of DMC based on methanol is far from satisfactory be-
cause of equilibrium limitations. The reaction is slightly exo-
ꢀ
1 [6]
thermic, with a heat of reaction of only 23 kJmol . A higher
reaction rate is desirable to achieve higher DMC yields by low-
ering the reaction temperature as well as by removing copro-
2
2
the reaction system produces DMC from methanol and carbon
dioxide, cycling between the hydration of 2-cyanopyridine and
the dehydration of 2-picolinamide.
duced H O. However, conventional dehydration agents are less
2
efficient at high temperature (e.g., molecular sieves) or too re-
active to be conveniently handled (e.g., P O ). On the other
At first, the synthesis of DMC from carbon dioxide and meth-
anol was carried out in an autoclave reactor containing metha-
nol (100 mmol), a stoichiometric amount of 2-cyanopyridine
(50 mmol), 5 MPa CO , and 0.34 g of CeO calcined at 873 K.
2
5
hand, catalytic hydration of organic compounds is a promising
method of H O removal because a large change in free energy
2
2
2
can be exploited, and both the reactant and the hydrated
The preparation of the catalyst was optimized on the basis of
the results of the calcination temperature (Figure S1). The hy-
[
12b–d]
product can be easily handled.
Previous works used a vari-
ety of dehydration agents, such as acetal (Bu SnO and
dration of 2-cyanopyridine to 2-picolinamide is also catalyzed
2
[
8c]
[14]
Ph NH OTf catalysts, CO 30 MPa, 453 K), dicyclohexylcarbo-
by CeO [Eq. (2)].
2
2
2
2
[a] Dr. M. Honda, Dr. M. Tamura, Dr. Y. Nakagawa, S. Sonehara,
Prof. Dr. K. Tomishige
Graduate School of Engineering
Tohoku University
Aoba 6-6-07, Aramaki, Aoba-ku, Sendai, 980-8579 (Japan)
Fax: (+81)22-795-7215
E-mail: yoshinao@erec.che.tohoku.ac.jp
tomi@erec.che.tohoku.ac.jp
The time course of the reaction is shown in Figure 1. Metha-
nol and 2-cyanopyridine were consumed in a ratio of 2:1, and
equimolar amounts of DMC and 2-picolinamide were formed
following the reaction stoichiometry with increasing reaction
time. The methanol-based yield of DMC and 2-cyanopyridine-
based yield of 2-picolinamide were 94 and 95% at 12 h, re-
spectively. At the same time, only small amounts of methyl car-
bamate (1.0 mmol) and methyl picolinate (1.2 mmol) were ob-
[
b] Dr. K. Suzuki, Dr. K.-i. Fujimoto
Advanced Technology Research Laboratories
Nippon Steel & Sumitomo Metal
2
0-1, Shintomi, Futtsu, Chiba, 293-8511 (Japan)
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/cssc.201300229.
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Table 1. DMC yield in the presence of various nitriles.
[
a]
Entry
Nitrile
Yield of products [%]
DMC
methyl carbamate
0.99
amide
94.6
ester
1.18
1
2
3
94.0
[
[
b]
[b]
[b]
[b]
[b]
91.2
38.6
0.18
86.9
44.1
0.26
0.69
b]
[b]
[b]
0.41
4
5
6
2.06
4.10
2.94
n.d.
n.d.
n.d.
3.06
<0.1
2.72
4.74
0.20
n.d.
3 2
Figure 1. Time course of products of the reaction of CH OH+CO +2-cyano-
7
8
n.d.
n.d.
<0.1
<0.1
pyridine. Reaction conditions: CeO
2 3
0.34 g, CH OH/2-cyanopyridine/
H
3
CꢀCN
0.38
<0.1
0.48
0.74
–
<0.1
<0.1
–
2
CO =100 mmol:50 mmol:5 MPa, 393 K.
9
0.76
0.32
<0.1
1
0
none
–
served as byproducts. The formation of methyl picolinate is at-
tributed to the reaction of 2-picolinamide with methanol
Reaction conditions: [a] CeO
50 mmol:5 MPa, 393 K, 12 h. [b] 373 K.
2
3 2
0.34 g, CH OH/nitrile/CO =100 mmol:
[
Eq. (3)], which co-produces NH . The reaction of DMC with
3
NH gives methyl carbamate [Eq. (4)].
3
these nitriles have the same structure as described above,
which indicates that the presence of a 6-membered nitrogen
heteroaromatic ring is also important. The addition of acetoni-
trile and benzonitrile hardly improved the DMC yield under
these reaction conditions using stoichiometric amounts (en-
tries 8, 9), although these nitriles were effective when using
[12b–d]
excess amounts.
Obviously, 2-cyanopyridine is an efficient dehydration agent.
The previous report ascribed a low yield of DMC in the case of
benzonitrile addition to strong adsorption of benzamide on
[12d]
To the best of our knowledge, this is the first report of
the CeO surface.
On the other hand, the very high DMC
2
almost complete conversion of methanol to DMC using CO as
yields in the present case indicate that the desorption of 2-pi-
2
carbonyl source.
colinamide from the surface of CeO is much easier than that
2
The selection of a suitable nitrile is very important to obtain
of benzamide. This may be because the three amides derived
from effective nitriles form intermolecular hydrogen-bonds be-
tween the H atoms in the amide groups and the N atoms of
good yields, although CeO can catalyze the hydration of vari-
2
[
14]
ous nitriles. Table 1 shows the additive effect of various ni-
[15]
triles to the reaction system of methanol+CO2 over CeO2.
the pyridine rings neighboring the amide groups,
and
“
Yield of products” shows the results of the reactions conduct-
weaken the interaction between the ꢀNH2 groups and Ce
atoms on the catalyst surface to suppress the poisoning. The
weaker adsorption of 2-picolinamide compared to benzamide
was confirmed by TG-DTA (Figure S2). Furthermore, the addi-
ed after 12 h when the DMC yield was almost saturated. With-
out addition of any nitriles, the yield of DMC was saturated at
0
.3% by the equilibrium limitation of Equation (1) (entry 10).
Among various nitrogen-containing nitriles, 2-cyanopyridine
entry 1) and pyrazine-2-carbonitrile (entry 2) were effective
and the yields of DMC were 94% and 91%, respectively.
-Cyanopyrimidine (entry 3) was also effective and gave a DMC
tion of 2-picolinamide in the reaction of methanol+CO +
2
(
2-cyanopyridine did not bring any effects either for DMC for-
mation rate and yield (Figure S3).
2
From a practical point of view, the CeO catalyst should be
2
yield of 39%; however, a much higher amount of 2-cyanopyr-
imidine was consumed due to side reactions such as decom-
position and dimerization of 2-cyanopyrimidine (see Table S1).
In contrast, 3- and 4-cyanopyridines (entries 4, 5) gave only
recyclable. The recyclability of CeO2 was verified by activity
tests of the used catalyst (Table S2). The physical properties of
CeO2 did not change, not even after three repeated tests
through catalyst regeneration by calcination at 823 K. Further-
more, inductively coupled plasma (ICP) results confirmed that
the Ce content in the solution was below the detection limit
(<0.1 ppm). This result demonstrates that catalytically active
2.1% and 4.1% of DMC, respectively, which suggests that
a cyano group at the 2-position relative to the nitrogen atom
is important. However, pyrrole-2-carbonitrile (entry 6) and
methyl aminoacetonitrile (entry 7) were not effective although
species are not eluted from the CeO under the reaction condi-
2
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tions, and that the observed catalysis is truly heterogeneous in
nature.
Experimental Section
See the Supporting Information for details, including reuse experi-
ments and characterization methods.
Finally, the regeneration of 2-cyanopyridine was also investi-
gated. Regarding the dehydration of primary amides to nitriles,
classical dehydrating agents such as acidic (e.g., P O , POCl ,
2
5
3
SOCl ) and basic reagents (e.g., NaBH ) are known to be effec- Acknowledgements
2
4
[
16]
[17]
tive,
and many catalysts have been reported.
However,
only a few papers have been reported as for the dehydration
of 2-picolinamide to 2-cyanopyridine [the reverse reaction of
Eq. (2)], and excess amount of expensive dehydrating agents
have been used, such as N-methyl-N-(trimethylsilyl)trifluoroace-
Part of this research was funded by the Cabinet Office, Govern-
ment of Japan through its “Funding Program for Next Generation
World-leading Researchers”.
[
18a,b]
[18c]
tamide,
sulfonic acid anhydride and triethylamine.
metal-supported SiO was developed for the dehydration of
ethyl dichlorophosphate,
and trifluoromethane
Keywords: carbonates
·
carbon dioxide
·
cerium
·
[
18d]
In contrast, alkali-
heterogeneous catalysis · metal oxides
2
2
-picolinamide to 2-cyanopyridine as a heterogeneous catalyst
Table S3). The reaction was conducted by using Soxhlet reac-
tor, and mesitylene as a solvent (438 K). The time course of
-picolinamide dehydration over Na O/SiO2 is shown in
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Received: March 13, 2013
Published online on June 25, 2013
1
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