Fuel Processing Technology 115 (2013) 233–237

Contents lists available at SciVerse ScienceDirect

Fuel Processing Technology

journal homepage: www.elsevier.com/locate/fuproc

A functionalized basic ionic liquid for synthesis of dimethyl carbonate

from methanol and CO2
Jia Sun, Bin Lu, Xin Wang, Xin Li, Jingxiang Zhao, Qinghai Cai ⁎
Key Lab for Photonic and Electronic Bandgap Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Harbin Normal University,
No. 1 Shida Road Limin development Zone, Harbin 150025, P. R. China

a r t i c l e i n f o a b s t r a c t

Article history: A series of hydroxyl-functionalized basic ionic liquids were synthesized and used as catalysts and reaction
Received 21 February 2013 medium for direct synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide. The
Received in revised form 15 June 2013 hydroxyl-functionalized basic ionic liquid, namely choline hydroxide (CH) is an effective catalyst with high
Accepted 30 June 2013
selectivity (95.2%) to DMC under mild conditions as compared with other similar ionic liquids. The ionic liq-
Available online 21 July 2013
uid can be reused three times without a significant change in its catalytic activity. Furthermore, the relation-
Keywords:
ship between the catalytic reactivity and OH-functional group was discussed and the mechanism of this
Functionalized ionic liquid synthetic reaction was proposed according to the experimental results and previously reported literatures.
Dimethyl carbonate © 2013 Elsevier B.V. All rights reserved.
Carbon dioxide

1. Introduction Zr\Ti\O composite oxides, H3PO4/ZrO2 and Co1.5PW12O40 as cata-

Dimethyl carbonate (DMC) has attracted much attention as an impor-
tant intermediate for polycarbonate resins and environmentally benign
substitute for highly toxic phosgene and dimethyl sulfate in carbonyla-
tion and methylation reactions [1] due to its versatile reactivity. It has
been proposed that DMC can be used as a promising octane enhancer be-
cause of its high oxygen content, reducing particulate emission from en-
gines. Presently, synthesis routes of DMC mainly include phosgene and
non-phosgene ones. Phosgene route is limited for the use of toxic phos-
gene. In the non-phosgene route, DMC is mainly produced by oxidative
carbonylation of methanol and two-step transesterification from epox-
ide, carbon dioxide and methanol [2,3]. The former suffers from the low
production rate, the need for corrosion resistant reactors, and the toxicity
and potential explosion of carbon monoxide while the latter is from high
energy consumption, high investment and production costs due to the
requirement of the intermediate separation. The direct synthesis of
DMC from carbon dioxide and methanol is one of the promising methods
in the development of an environmentally benign process due to CO2
being the most abundant, inexpensive, nontoxic and environmentally ac-
ceptable starting material. Typically, the direct synthesis of DMC in an
autoclave has been reported by several researchers using organotin
[4,5], Ti(IV) alkoxides [6], alkaline metal carbonate [7], ZrO2–CeO2 or
lysts [8,9]. Although the selectivity to DMC over these catalysts is very
high, the conversion of methanol was low due to the inertness of CO2
and deactivation of the catalyst.
Room temperature ionic liquids are being more and more regarded
as relatively clean catalysts and solvents [10] due to their characteristics
of wide liquid range, nonvolatility, and adjustability of chemicophysical
properties. Recently, many organic reactions such as Friedel–Crafts al-
kylation [11], olefin dimerization [12] and Diels–Alder reaction [13]
have been reported to proceed in room temperature ionic liquids with
excellent yield and selectivity. Very recently, Eta et al. have reported
an effect of alkoxide ionic liquid on the synthesis of DMC from CO2
and methanol over ZrO2–MgO [14], the role of the methoxy anion
needs to be further investigated in that case. Our group had also report-
ed the synthesis of DMC catalyzed or promoted by ionic liquids [15,16].
As our continuous research work for activation and conversion of CO2
into DMC catalyzed by ionic liquids, the effective synthesis of DMC
from CO2 and methanol catalyzed by functionalized ionic liquid, choline
hydroxide, is realized. The DMC selectivity is more than 95% under mild
conditions. This report on direct synthesis of DMC from CO2 and meth-
anol using functionalized ionic liquid as catalyst that has not been found
in the reported literatures up to now.
2. Experimental

⁎ Corresponding author at: Key Lab for Photonic and Electronic Bandgap Materials,
Ministry of Education, Colleges of Heilongjiang Province, School of Chemistry and
Chemical Engineering, Harbin Normal University, No. 1 Shida Road, Limin Development
Zone, Harbin 150025, PR China. Tel./fax: +86 451 88060580.
E-mail address: caiqinghai@yahoo.com (Q. Cai).
2.1. Materials
Chemicals used in this study contain methanol (A. R.) and potassium
hydroxide (A. R.), which were purchased from Tianjin Fuchen Chemical

0378-3820/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fuproc.2013.06.009
234 J. Sun et al. / Fuel Processing Technology 115 (2013) 233–237

Reagent Company. Carbon dioxide (purity = 99.99%) was supplied by
Dawn Gas Company. Choline chloride and DMC standard sample
(≥99.0%) were purchased from Sinopharm Chemical Reagent Co., Ltd.
of China.
2.2. Preparation of catalyst
Basic ionic liquid choline hydroxide (CH) was synthesized by the fol-
lowing procedure: 20 mL of methanol (0.5 mol), 7.0 g of choline chloride
(CC, 0.05 mol) and 2.8 g of potassium hydroxide (0.05 mol) were
charged into a three-neck flask. The mixture was stirred at 60 °C for
12 h in a water bath. After cooling to room temperature, the mixture
solution was filtered to remove solid KCl. The filtrate was evaporated
under reduced pressure and the CH was obtained. Other ionic liquids
such as EtmimOH (1-ethoxyl-3-methylimidazolium hydroxide),
EtmimBr (1-ethoxyl-3-methylimidazolium bromide), EmimOH
(1-ethyl-3-methylimidazolium hydroxide), and BmimOH (1-butyl-3-
methylimidazolium hydroxide) were synthesized according to previous
reported literatures [17,18].
2.3. Procedures of the reaction
The catalytic reaction was carried out in a stainless steel autoclave
(0.25 L) with an electric heater and a mechanical stirrer. 25 mL of meth-
anol (0.625 mol) and 8 g of CH (0.066 mol) were charged into the reac-
tor. After being purged three times with carbon dioxide, the reactor was
pressured to an initial pressure of 3 MPa CO2 and heated to 140 °C under
stirring. The reaction was carried out at this temperature for 6 h. When
the reaction was finished, the mixture solution was distilled to separate
medium may stabilize the charged intermediately [12], making the reac-
tion easier to proceed. However, inorganic base KOH was completely in-
active (entry 5) in comparison with basic ionic liquid EmimOH and
BmimOH. Interestingly, when ethyl linked to nitrogen atom on imidazole
ring was substituted by ethoxyl radical, the functionalized ionic liquid
with alcohol hydroxyl EtmimOH indicated more activity than EmimOH
did (entry 6), while EtmimBr also displayed no activity (entry 7). This
suggested that the synergic effect of alcohol hydroxyl with strong basic
anion OH− played a very important role for fixation and activation of
CO2 and methanol, further converted into DMC. In order to make the re-
action equilibrium shifting to the production of DMC, CaO was added to
the catalytic reaction system for adsorbing water produced in the reaction
process. No any promotion action was achieved with CaO used (entry 8).
It was well known that the direct carbonylation of methanol proceeds
through its bifunctional activation by acidic and basic sites of the catalysts
[9]. The base-promoted activation generates alkoxo moiety of CH3O−,
which attacks carbon atom with positive charge in CO2 molecule to afford
an anionic monomethyl derivative of carbonic acid CH3OCOO−. Con-
versely, the acid-catalyzed activation of methanol via acting on O atom
of CH3OH molecule produces methyl cation CH+ 3 that may further react
with CH3OCOO− to form DMC. According to the above principle, the
stronger basicity of this catalytic system accelerates the absorption of
CO2 into the solution and generation of CH3O− by the base-promoted
activation. On the other hand, the alcohol hydroxyl or the OH− of CH co-
ordinately attacked the different parts of methanol molecule. The coordi-
nation of the O atom to the H atom between hydroxyls of methanol and
100
Amount of DMC (mmol)/Selectivity (%)

the ionic liquid from the reaction mixture and the distillate was analyzed
80
by GC (Agilent 7820) and GC–MS (Agilent 7890-5975).
60
3. Results and discussion
40 Selectivity
3.1. Catalytic performance of various catalysts Amount of DMC
20
The direct reaction of methanol with carbon dioxide for producing
DMC using various catalysts such as CH, CC, EtmimOH, EtmimBr, 1.5
EmimOH, BmimOH, CH/CaO, CH/CH3I and KOH was tested and the results
were shown in Table 1. As can be seen, CH was found to have a higher ac- 1.0
tivity with 95.2% selectivity to DMC (entry 1), while CC was completely
0.5
inactive (entry 2). This finding indicated that the Brönsted basicity of
the catalyst plays a key role for fixing and activating CO2 and methanol.
0.0
However, similar experiments were carried out with respect to other 110 120 130 140 150 160 170
two basic ionic liquids, EmimOH and BmimOH. EmimOH exhibited a Temperature (deg)
very low activity for the synthetic reaction (entry 3), while just trace of
DMC was found when using BmimOH as the catalyst for the reaction 100
(entry 4). These findings implied that the ionic liquid with shorter cation
Amount of DMC (mmol)/Selectivity (%)

carbon chain length exhibited relatively higher activity for the reaction of 80
methanol with CO2 since it possesses higher polarity. The polarity and
electrostatic field of the ionic liquids used as catalyst and reaction 60

Table 1 40 Selectivity
Catalytic performances using various ILs. Amount of DMC
20
Entry ILs P/mmol (conv/%) S/%

1 CH 1.63 (0.6) 95.2 1.5

2 CC – –
3 EmimOH 0.31 (0.1) 87.0
1.0
4 BmimOH Trace –
5 KOH – –
6 EtmimOH 0.62 (0.2) 77.6 0.5
7 EtmimBr – –
8 CH/CaO 1.56 (0.5) 93.0 0.0
9 CH/CH3I 8.19 (2.7) 98.8 110 120 130 140 150 160 170
Conv—conversion; S—selectivity; ILs—ionic liquids; P—amount of DMC produced. Temperature (deg)
Reaction conditions: reaction temperature = 140 °C, time = 6 h, initial pressure of
CO2 = 3.0 MPa (0.3 mol), and catalyst = 0.066 mol. Fig. 1. Effect of reaction temperature on the synthesis of DMC.
 J. Sun et al. / Fuel Processing Technology 115 (2013) 233–237 235

Etmim+ formed a hydrogen bond resulting in polarization of C\O bonds,
and the anion OH− made a nucleophilic attack on the positively charged
carbon atom of methanol at the same time. As a result, methyl cation CH+
3 produced amount and selectivity of DMC. The data indicated that the
was easily produced by these kinds of interaction. Obviously, the produc-
−
tion rate of CH+
3 was certainly much lower than that of CH3O in stronger
basic medium, suggesting that the latter is rate determined step. This
conclusion was completely confirmed by the successive runs. When
methyl iodide that easily provides CH+ 3 in basic medium was added to
this system, the amount of DMC was greatly increased (entry 9). This is
remarkably due to the rate determined step being enhanced.
3.2. Influence of various reaction conditions
3.2.1. Reaction temperature
Fig. 1 showed the catalytic reaction results with CH as catalyst at dif-
ferent temperatures. As the temperature was increased from 110 to
140 °C, the produced amount and selectivity of DMC were increased,
and then both of them were decreased when the temperature exceeded
140 °C. The decrease in amount of DMC at elevated temperature was
likely attributed to the nature of the reaction thermodynamics because
this reaction is an exothermic (ΔH = −15.51 kJ/mol) [19], raising
temperature may not be propitious to the formation of DMC in view
of thermodynamics. Besides, the decline of the selectivity to DMC was
due to high generating rate of the byproduct dimethoxyl methane at
higher temperature. Therefore, the reaction should be conducted
under suitable temperature. 140 °C was found to be an appropriate
temperature for the reaction.
3.2.2. Amount of the catalyst used
Fig. 2 illustrated the effect of catalyst (EtmimOH) amount upon the
produced amount of DMC was increased from 1.0 to 1.63 mmol with
the increase of the amount of the catalyst from 33 mmol to 66 mmol.
And then, the amount declined smoothly as the amount of the catalyst
continuously increased. The selectivity to DMC was almost unchange-
able in all range of catalyst amount, indicating that the amount of the
ionic liquid used in this system was irrespective of the selectivity to
DMC. The reaction was evidently retarded with excess catalyst, proba-
bly because the stronger basicity of this medium inevitably reduced
the acidic or electrophilic sites of the catalyst, causing the rate deter-
mined step generating CH+ 3 to be slowed down. In addition, the reduced
production of dimethoxyl methane showed that the step producing
CH+3 also played an important role for the side-reaction.
3.2.3. Reaction pressure
The influence of the reaction pressure on the synthesis of DMC was
investigated and the results were shown in Fig. 3. As initial pressure
increased from 1.5 to 3 MPa, the produced amount of DMC smoothly
increased from 0.7 to 1.63 mmol. Thereafter, the amount of DMC pro-
duced was constant when the pressure remained increasing. The
pressure almost did not affect the reaction activity over 3 MPa and the
selectivity to DMC retained constant all over the range of the pressure.
That is, high CO2 pressure or excess CO2 is advantageous to the synthe-
sis of DMC.

100
100
Amount of DMC (mmol)/Selectivity (%)
Amount of DMC (mmol)/Selectivity (%)

80
80
60
60
40 Amount of DMC
40 Selectivity
Amount of DMC 20
20 Selectivity
1.5
1.5

1.0 1.0

0.5 0.5

0.0 0.0
4 5 6 7 8 9 10 1.5 2.0 2.5 3.0 3.5
Amount of Ionic Liquid (g) Pressure (MPa)

100
100
Amount of DMC (mmol)/Selectivity (%)

Amount of DMC (mmol)/Selectivity (%)

80
80
60
60

40 40 Amount of DMC
Selectivity Selectivity
20 Amount of DMC 20

1.5 1.5

1.0 1.0

0.5 0.5

0.0 0.0
4 5 6 7 8 9 10 1.5 2.0 2.5 3.0 3.5
Amount of Catalyst (g) Pressure (MPa)

Fig. 2. Effect of the amount of ionic liquid on the synthesis of DMC. Fig. 3. Effect of reaction pressure on the synthesis of DMC.
236 J. Sun et al. / Fuel Processing Technology 115 (2013) 233–237

100 reaction proceeded, implying that longer reaction was disadvantageous

Amount of DMC (mmol)/Selectivity (%)

to the synthesis of DMC. Moreover, the selectivity to DMC was retained

80
constant all over the time range. This phenomenon suggested that ex-
cess reaction time likely led to hydrolysis of DMC formed in this situa-
60
tion [20].
40 Amount of DMC
Selectivity 3.3. Proposed reaction mechanism
20
According to the previously reported literatures, as well as the exper-
1.5 imental results obtained in this case, a reaction mechanism of DMC syn-
thesis from CO2 and methanol catalyzed by hydroxyl-functionalized
1.0 basic ionic liquid was proposed and shown in Scheme 1. This reactive
procedure involves the activation of methanol by basic ionic liquid to
0.5 generate methoxide anion CH3O−. Then, the methoxide anion CH3O− at-
tacks the carbonyl carbon charged positively in the molecule of CO2 that
0.0
has also been activated by functionalized ionic liquid CH to form the
2 4 6 8 10
intermediate CH3OCOO−. At the same time, the alcohol hydroxyl of CH
Reaction Time (h) coordinately interacts with oxygen and/or hydrogen atoms of CH3OH
molecules to generate hydrogen bond network, which results in weaken-
100 ing C\O bonds, and the OH− anions make a nucleophilic attack on the
positively charged carbon atom of methanol. As a result, methyl cation
Amount of DMC (mmol)/Selectivity (%)

80
CH+ +
3 is easily produced in this situation. Finally, the activated CH3 reacts
−
60 with the intermediate CH3OCOO to produce the target product DMC
and release the base OH−, realizing the catalytic cycle. In this process, it
40 Amount of DMC is worthy of note that the generating rate of activated particle CH3O− is
Selectivity very high due to the strong basicity of the ionic liquid. On the contrary,
20 formation rate of activated CH+3 is relatively low in this medium. The lat-
ter is considered to be the rate determined step. Therefore, addition of
1.5 methyl iodide that provides methyl cation to the system accelerates the
direct reaction rate of methanol with CO2, which has verified the above
1.0 conclusion. Besides, the byproduct dimethoxyl methane was produced
during the reaction, which also validates the formation of methyl cation
0.5 −
CH+3 and CH3O , followed by the reaction between them for producing
the by product CH3OCH2OCH3.
0.0
2 4 6 8 10
3.4. The catalyst recycles
Reaction Time (h)

Fig. 4. Effect of reaction time on the synthesis of DMC.

3.2.4. Reaction time
The catalytic performance-time profile of the direct reaction of
methanol with CO2 at 140 °C was shown in Fig. 4. As seen in the figure,
the DMC amount was rapidly increased with reaction time, achieving
1.63 mmol after 6 h. Beyond 6 h, the amount fell down when the
In order to further evaluate the performance of the catalyst, reuse
experiments of the catalyst were carried out. At the end of the reaction,
the catalyst was separated by distillation under reduced pressure and
then reused for the next run under the same conditions. Fig. 5 indicated
that the activity of catalyst was almost no obvious change even at the
third run with the reused CH. The results implied that CH can be
recycled efficiently, even though the selectivity to DMC was also inde-
pendent of reused runs at first three times.

Scheme 1. Proposed mechanism.

 J. Sun et al. / Fuel Processing Technology 115 (2013) 233–237 237

100 References
80
Amount of DMC (mg)/Selectivity (%)

[1] O. Yoshio, Catalysis in the production and reactions of dimethyl carbonate, an en-
vironmentally benign building block, Applied Catalysis A: General 155 (1997)
60 133–166.
[2] H. Cui, T. Wang, F. Wang, C. Gu, P. Wang, Y. Dai, Transesterification of ethylene
40 carbonate with methanol in supercritical carbon dioxide, Journal of Supercritical
Fluids 30 (2004) 63–69.
20 [3] A.A. Shaikh, S. Sivaram, Organic carbonates, Chemical Reviews 96 (1996) 951–976.
[4] J. Kizlink, I. Pastucha, Preparation of dimethyl carbonate from methanol and carbon
dioxide in the Presence of Sn(IV) and Ti(IV) alkoxides and metal acetates, Collection
of Czechoslovak Chemical Communications 60 (1995) 687–692.
2.0
[5] J. Kizlink, I. Pastucha, Preparation of dimethyl carbonate from methanol and carbon
dioxide in the presence of organotin compounds, Collection of Czechoslovak Chem-
1.5
ical Communications 59 (1994) 2116–2118.
[6] K. Kohno, J.-C. Choi, Y. Ohshima, H. Yasuda, T. Sakakura, Synthesis of dimethyl carbon-
1.0
ate from carbon dioxide catalyzed by titanium alkoxides with polyether-type ligands,
ChemSusChem 1 (2008) 186–188.
0.5
[7] S. Fang, K. Fujimoto, Direct synthesis of dimethyl carbonate from carbon dioxide
and methanol catalyzed by base, Applied Catalysis A: General 142 (1996) L1–L3.
0.0
[8] J. Kizlink, Synthesis of dimethyl carbonate from carbon dioxide and methanol in
1 2 3 4 the presence of organotin compounds, Collection of Czechoslovak Chemical
recycle times Communications 58 (1993) 1399–1401.
[9] Y. Ikeda, M. Asadullah, K. Fujimoto, K. Tomishige, Structure of the active sites on
Fig. 5. The reusability of the catalyst. H3PO4/ZrO2 catalysts for dimethyl carbonate synthesis from methanol and carbon
dioxide, The Journal of Physical Chemistry. B 105 (2001) 10653–10658.
[10] L.A. Blanchard, D. Hancu, E.J. Brenneckle, J.F. Beckman, Green processing using
ionic liquids and CO2, Nature 399 (1999) 28–29.
4. Conclusions [11] C.E. Song, W.H. Shim, E.J. Roh, J.H. Chol, Scandium(III) triflate immobilised in ionic
liquids: a novel and recyclable catalytic system for Friedel–Crafts alkylation of
aromatic compounds with alkenes, Chemical Communications (2000) 1695–1696.
The prepared choline hydroxide was found to be an effective catalyst [12] Q. Cai, J. Li, F. Bao, Y. Shan, Tunable dimerization of α-methylstyrene catalyzed by
for the direct synthesis of DMC from carbon dioxide and methanol acidic ionic liquids, Applied Catalysis A: General 279 (2005) 139–143.
[13] F. Zulfiqar, T. Kitazume, One-pot aza-Diels–Alder reactions in ionic liquids, Green
under milder conditions. The catalyst exhibited good catalytic perfor-
Chemistry 2 (2000) 137–139.
mance with high selectivity to DMC (above 95%) at 3 MPa and 140 °C [14] V. Eta, P. Mäki-Arvela, E. Salminen, T. Salmi, D.Y. Murzin, J.-P. Mikkola, The effect
for 6 h. The hydroxyl-functionalized basic ionic liquid activated metha- of alkoxide ionic liquids on the synthesis of dimethyl carbonate from CO2 and
nol by means of the strong basic sites of OH− and acidic sites of alcohol methanol over ZrO2–MgO, Catalysis Letters 141 (2011) 1254–1261.
[15] Q. Cai, L. Zhang, Y. Shan, M. He, Promotion of ionic liquid to dimethyl carbonate
hydroxyls to form CH3O− and CH+ −
3 . The CH3O successively reacts with synthesis from methanol and carbon dioxide, Chinese Journal of Chemistry 22
CO2 to form CH3OCOO−, and then CH+ −
3 reacts with CH3OCOO to pro- (2004) 422–424.
+ [16] H. Wang, B. Lu, Q. Cai, F. Wu, Y. Shan, Synthesis of dimethyl carbonate from methanol
duce DMC. The experiments showed that the CH3 generation was con-
and carbon dioxide catalyzed by potassium hydroxide under mild conditions, Chinese
sidered to be the rate determined step due to the strong basic medium. Chemical Letters 16 (2005) 1267–1270.
The catalyst was easily recovered and reused. [17] P. Bonhote, A.P. Dias, N. Papagerigiou, K. Kalyanasundaram, M. Grätzel, Hydrophobic,
highly conductive ambient-temperature molten salts, Inorganic Chemistry 35
(1996) 1168–1178.
[18] S. Abelló, F. Medina, X. Rodríguez, Y. Cesteros, P. Salagre, J.E. Sueiras, D. Tichit, B.
Acknowledgments Coq, Supported choline hydroxide (ionic liquid) as heterogeneous catalyst for
aldol condensation reactions, Chemical Communications (2004) 1096–1097.
[19] Q. Cai, C. Jin, B. Lu, H. Tangbo, Y. Shan, Synthesis of dimethyl carbonate from
We make a great acknowledgment for the financial support to this
methanol and carbon dioxide using potassium methoxide as catalyst under
work by the Foundation of Educational Department, the Natural Science mild conditions, Catalysis Letters 103 (2005) 225–228.
Foundation of Heilongjiang Province and the Academic Leader Founda- [20] V. Eta, P. Mäki-Arvela, A.-R. Leino, K. Kordás, T. Salmi, D.Y. Murzin, J.-P. Mikkola, Syn-
thesis of dimethyl carbonate from methanol and carbon dioxide: circumventing
tion of Harbin Science and Technology Bureau, China (Nos. 12511143,
thermodynamic limitations, Industrial and Engineering Chemistry Research 49
B201119 and 2013RFXXJ009). (2010) 9609–9617.