Synthesis of Dimethyl Carbonate from Urea and Methanol over Heterogeneous

Catalysts
Mouhua wang Tong Wei Wei Wei Jinhai Yang, Xiuzhi Wang, Yuhan Sun
(State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese
Academy of Sciences, Taiyuan, China, 030001)

Introduction
In recent years, much attention has been paid to dimethyl carbonate (DMC) as an
environmentally benign building block [1]. DMC has a versatile chemical property and has
been used mainly to be a methylating and methoxycarbonylating agent as a safe substitute
for dimethyl sulfate or methyl halides that are toxic or corrosive, it can also be used as a
solvent to replace halogenated solvents such as chlorobenzene [2]. In addition, DMC is
believed to be a good additive of gasoline in the future due to its high octane number of
gasoline and good volatile. Dimethyl carbonate was usually produced from methanol and
phosgene in a concentrated sodium hydroxide solution [3]. Because of the use of phosgene
for its production, DMC has been limited in industrial use. Then, a non-phosgene process
for preparing DMC by oxidation carbonlating of methanol in liquid phase was put on
stream in the EniChem-Ravenna factory using CuCl catalysts [4]. However, the
shortcomings of this process were low production rate, high cost of the separation of
products and reactants, high recycles requirements and the need for corrosion resistant
reactor and process lines. Another non-phosgene process was the synthesis of DMC via
transesterification method [5]. While the method had its advantages, the reaction rate of
epoxides with carbon dioxide was slow and required high pressure, and the exchange
reaction of the cyclic carbonate with methanol was limited by equilibrium. Moreover, the
reactant in the process (such as epoxides) was expensive, and then affected its economic.
In our laboratory, a novel method to synthesize DMC from urea and methanol over solid
base catalysts was explored. At the first, products were carbamate and ammonia, and then
carbamate and methanol were further converted into DMC and ammonia. Ammonia could
be recycled to produce urea with CO2. Obviously, this was an economically benign process.
However, the related detail study for the process hasn’t been seen until now. Only two U.S.
patents [6] were published for producing DMC from urea and methanol in homogenous
catalyst in 2000. Homogenous catalysts were usually some complexes of organotin with a
high boiling electron donor compound acting as solvent, which included bidentate ligands,
and its preparation was very difficult and very expensive. In addition, the separation of the
products was also very complex. Thus, homogeneous catalysts should be disadvantageous
to industrialization. Therefore, considering the reaction thermodynamic and the reaction
mechanism over homogenous catalysts, solid-base catalysts (such as CaO and MgO and
ZnO-K2O and CaO loaded carbon) were studied for synthesis of dimethyl carbonate from
urea and methanol here.
 Results and discussion
The preparation of the solid-base catalysts was as same as the previous work [7]. The
reaction was carried out in a 250mL flask equipped with reflux condenser, water bath and
magnetic stirring. The products were analyzed by Gas Chromatograph after centrifugal
separation of solid catalyst from liquid.
Table1 showed the performance of these catalysts for the synthesis of DMC with urea and
methanol. The catalysts preformed very well. The conversions of urea were above 70%, and
the selectivity of DMC, especially for ZnO-K2O and CaO/Carbon, exceeded 30%, which
were much better than the homogenous catalysts. The by-product was only methyl
carbamate. This indicated that the first step was easier than the second step. In addition, the
catalysts showed the following different reaction performance for methyl carbamate to
DMC: CaO<MgO<Zn-K2O<CaO/carbon. The characterization by XRD, BET, and
CO2-TPD indicated that the base strength and base density as well as pore structure of the
catalysts might be very important. The results preliminarily demonstrated that the methanol
and urea were respectively activated to CH3O- and (NH2)2-C+(O-) over the catalysts, and
then CH3O- attacked the C+ of (NH2)2-C+(O-), and formed carbamate, and the CH3O-
sequentially attacked the C+ of the activated carbamate, and finally led to dimethyl
carbonate. Because of the activation of carbamate was more difficult than that of urea, the
selectivity of carbamate was higher than that of DMC.
In conclusion, the solid-base catalysts demonstrated the high performance for the synthesis
of DMC with urea and methanol. The heterogeneous catalysts would put forward to the
industrial of this process.
Table 1. The reaction performance of the solid-base catalysts

Catalyst CH3OH/Urea Urea conversion DMC selectivity methyl carbamate

Catalyst
(g) (mol ratio) % ％ Selectivity, %
CaO 4 4:1 80 25.65 74.35
MgO 1 4:1 88 28.55 71.45
ZnO-K2O 1 3:1 82 38.77 61.23
CaO-C 2 4:1 85 33.47 66.53
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