Article

Cite This: Ind. Eng. Chem. Res. 2019, 58, 17898−17905 pubs.acs.org/IECR

Optimization of a Reactive Distillation Process for the Synthesis of

Dialkyl Carbonate Considering Side Reactions
Jongchan Hur, Jinwoo Park, Robert Stephen Landon, and Il Moon*
Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 03722, Republic of
Korea
*
S Supporting Information

ABSTRACT: Dimethyl carbonate (DMC) is an environment-friendly

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chemical, widely used as a solvent, reagent, and fuel additive. It is

produced commercially via transesterification, an equilibrium reaction
in which ethylene carbonate (EC) and methanol (MeOH) react to
produce DMC and a useful coproduct, monoethylene glycol (MEG).
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However, side reactions occur, such as the reaction of EC with MEG to

produce diethylene glycol and CO2. These reactions must be
considered to simulate the DMC process accurately. Reported
theoretical results without considering the side reactions differed by
1.7% from industrial results. Here, side reactions were considered to
improve the simulation accuracy; a relative error of only 0.1% was
obtained. The optimal EC:MeOH feed ratio was changed (from 8.1 to 8.5) to increase the profit to 0.2 USD per kmol of EC.
Thus, herein we show how to increase the profit by process modification, which will be useful for studies involving commercial
plant simulation.

■ INTRODUCTION
Dimethyl carbonate (DMC) is a safe, environmentally friendly,
and biodegradable organic carbonate.1 It is often used for
methylation and alkoxycarbonylation.2 Also, the market
demand of DMC is more than 90 000 ton/year.3 There are
three processes for the commercial manufacturing of DMC, as
shown in Figure 1.4 The oldest process is the phosgene
process. However, this process is undesirable given the toxicity
of phosgene. The second process is oxidative carbonylation,
which is the most prevalent commercial process.3 The
conversion of this process is high (nearly 100%), but it
requires the separation of the methanol/DMC/water ternary
system, which is challenging. The final process is the
transesterification of a cyclic carbonate with methanol
(MeOH). It was operated at a commercial scale beginning in
the early 2000s. This route produces an equimolar amount of a
useful monoethylene glycol (MEG) as a coproduct. This has
the advantage that glycols are produced at a commercial scale
and also avoids the use of highly toxic chemicals.3
Several studies have been conducted on the transester-
ification process. These studies have been centered on three
directions: MeOH/DMC separation, catalyst selection, and
process optimization. It is challenging to separate MeOH and
DMC because they form an azeotropic mixture. Hsu et al.5
proposed an extractive distillation process in which aniline was
used as the entrainer to recover DMC with high purity. Wei et
al.6 and Zhang et al.7 reduced the energy used for DMC
separation by using pressure swing distillation. Wang et al.8
effectively recovered DMC using poly(acrylic acid)/poly(vinyl
alcohol) blend membranes.
There are various types of catalysts used for DMC synthesis;
for example, alkali metals,9 metal oxides,10 mixed metal
oxides,11−14 hydrotalcites,15 and ionic liquids16 are all used
as catalysts. The use of heterogeneous catalysts, such as metal
oxides, mixed metal oxides, and hydrotalcites, results in very
low (<60%) yields and selectivities.13 Alkali metals are
homogeneous catalysts used for transesterification. They are
commercially available catalysts, have high (>90%) yields and
selectivities, and are reasonably priced.
Various optimization methods have been applied to
transesterification. Holtbruegge et al.17−19 studied the
preparation of DMC and propylene glycol by reacting
propylene carbonate with MeOH. They studied an efficient
reactive distillation column and proposed an optimization
algorithm. Huang et al.20 minimized the energy use through
heat integration. In addition, a dynamic/simulated temper-
ature/flow rate cascade control method was proposed.21 Lin et
al.22 reduced the energy use by 20.8% using a heat-exchanger
network. Fang et al.23,24 developed a new setup for providing
the experimental data and mathematical model and found the
optimal operating conditions.
However, previous studies have not considered the side
reactions. Side reactions may result in reduced yields and
purities of products.25 Fang’s results show that the ethylene
carbonate (EC) conversion rate is 100%.24 However, the EC
Received: May 12, 2019
Revised: August 26, 2019
Accepted: August 29, 2019
Published: August 29, 2019

© 2019 American Chemical Society 17898 DOI: 10.1021/acs.iecr.9b02629

Ind. Eng. Chem. Res. 2019, 58, 17898−17905
Industrial & Engineering Chemistry Research
Figure 1. DMC synthesis routes: (A) phosgene process, (B) oxidative carbonylation, and (C) transesterification of a cyclic carbonate with
methanol.4
Figure 2. DMC production process.26
conversion rate in a commercial plant is not 100%, mostly due
to the presence of the side product diethylene glycol (DEG),
which in practice then must be removed from the waste in the
MEG purification column. This is especially significant since
MEG must be produced in high purity (>99.9%). Thus, it
seems likely that the calculated preferred operating conditions
of the MEG purification column will vary depending on
whether an idealized 100% EC conversion rate is considered or
the presence of the DEG side product (as observed in practice)
is taken into account.
Thus, to better optimize the process, it was proposed to
develop a model that considers the side reactions, more
accurately simulating plant operations, and use it to optimize
the existing process, balancing the energy required vs the
product yield. It has already been shown that the MeOH/EC
feed ratio is the most important operating parameter affecting
the process.24 Thus, the objective of this study is to find the
optimal feed ratio considering the side reactions.
■
MODELING
Process Description. The manufacture of DMC can be
largely divided into reaction and separation steps. Figure 2
shows a process flowsheet for the transesterification to DMC
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and monoethylene glycol (MEG). It consists of a reactive
distillation column for the initial conversion, and a series of
distillations to separate the DMC and MEG from the waste
heavies, as well recover and recycle unreacted EC and MeOH.
Details concerning the columns and operating condition were
those of Miyaji et al.26 A reactive distillation column (RD
column) with 40 stages was used, with the EC and the
homogeneous catalyst feeds at stage 3 and the methanol feed
at stage 30. The top product of the RD column contains DMC
and MeOH, whereas the bottom product is a mixture of MEG,
diethylene glycol (DEG), MeOH, and the catalyst. The
distillate is then sent to the DMC separating column (DS
column) to produce high-purity DMC (>99.5%) and MeOH
for recycling. Meanwhile, the bottom stream of the RD column
is sent to the MeOH-separating column (MS column) where
methanol is taken overhead to be recycled, and the bottom
stream goes to the MEG-purifying column (MP column).
Here, high-purity MEG (>99.9%) is recovered, while the
bottom stream of this is discarded as waste. The distillate
streams of the DS column and MS column are mixed with
fresh methanol and recycled to the RD column. The boiling
point temperature of all species is listed in Table S1. The
operating conditions are listed in Table S2, and the flow
DOI: 10.1021/acs.iecr.9b02629
Ind. Eng. Chem. Res. 2019, 58, 17898−17905
Industrial & Engineering Chemistry Research
Figure 3. Main reaction kinetics.23
Figure 4. Side reaction kinetics.
Figure 5. Experimental results: (a) plot of DEG yield vs time and (b) plot of lnk vs 1/T to determine the rate constant, MEG/EC = 1/1, catalyst
loading = 0.2 wt %.
summary is described in Table S3.26 Several assumptions were
made: the process is at a steady state, the reactions occur only
in the liquid phase, and the stage-to-stage pressure drop is the
same for each stage in all the columns.
Reaction and Kinetics. The transesterification reaction
between EC and MeOH is a reversible and exothermic
reaction (Figure 3). The main reaction kinetics were reported
by Fang.23 The reaction rate is second order with respect to
the methanol concentration, and the reverse reaction is faster
than the forward reaction. The equilibrium constant (K)
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decreases with increasing temperature. Therefore, an excess of
methanol is generally used to push the reaction in the forward
direction, recover the unreacted methanol, and recycle it.
EC reacts with the product MEG to produce DEG and CO2
(Figure 4). This reaction is nonreversible. Therefore,
minimizing the reaction between EC and MEG is an important
way to increase the yield of DMC and MEG. The reaction rate
constants of the side reactions were obtained through an
experiment. The kinetics were obtained experimentally in a
standard 500 mL laboratory glassware (at 333, 353, and 373
DOI: 10.1021/acs.iecr.9b02629
Ind. Eng. Chem. Res. 2019, 58, 17898−17905
Industrial & Engineering Chemistry Research Article

Figure 6. Relationship between yield, energy, and feed ratio when (a) considering the side reaction and (b) not considering the side reaction.

K) using sodium methylate as a homogeneous catalyst (at 0.2

and 0.3 wt %). EC of 99.9% purity (Green Chemical Co., Ltd.)
and MEG of 99.9% (Ggreen Chemical Co., Ltd.) were used as
reactants in the experiment. Mixtures of 50 mol % EC and 50
mol % MEG were prepared, heated to reaction temperature,
and the catalyst added while stirring. Samples were taken and
analyzed by a HP 7890 gas chromatograph equipped with
flame ionization detector. Figure 5 shows the results of the
experiment to determine the side reaction kinetics.
Thermodynamic Model. The Soave−Redlich−Kwong
(SRK) equation of state was used. The SRK model equation
is commonly used for estimating the phase equilibrium of
hydrocarbons and is a version of the Redlich−Kwong equation
modified to improve the vapor−liquid equilibria and vapor
pressure calculations for systems that exhibit strong polar
effects. The key equations are shown in eqs 1−4.
RT a(T ) Figure 7. Optimal feed ratio considering and not considering the side
P= − reaction.
V−b V (V + b) (1)

ij RT yz
b = 0.08664jjj c zzz
j Pc z
k {
Table S6 lists a comparison of the industrial and calculated
(2) DMC production results. The data were obtained for variable
feed ratios of 8.1, 8.3, and 8.5 under the process operating
a(T ) = acα(T ) (3) conditions. The previous study, which did not consider the
side reaction, showed a relative error of 1.7% from the
α(T ) = [1 + (0.48 + 1.57ω − 0.176ω 2)(1 − Tr0.5)]2 industrial data. However, considering the side reaction
(4) improves the simulation accuracy, and a relative error of
Here, b is the SRK volume parameter, a(T) is the SRK 0.1% from the industrial data was obtained in this study.
parameter, and ac is the value of a at the critical point. α(T) is When considering the side reaction, the industrial and the
a modified version of the Redlich−Kwong equation that is a calculated results are in a fairly good agreement. Thus, our
function of the acentric factor, allowing the better estimation of model will aid in plant optimization (improve yield and reduce
the vapor pressure of the pure components. The binary energy usage) by allowing more accurate plant simulations.
interaction parameters were obtained from the work of Hsu.5 Optimal Feed Ratio. The relationships between the DMC
The parameter sets are shown in Table S4. and MEG yields, energy, and the MeOH/EC feed ratio are

■
shown in Figure 6a,b. As the feed ratio increases, the methanol
RESULTS AND DISCUSSION concentration in the feed increases, and the DMC and MEG
yields also increase. Since the main reaction is of the second
Simulation Results. The calculated results are compared
order with respect to methanol, the forward reaction rate is
with the industrial data and their relative error by eq 527
faster; therefore, the side reaction decreases and the yield
industrial − calculated increases.
relative error(%) = × 100 However, as the feed ratio increases, so does the amount of
industrial (5)
unreacted methanol. Since unreacted methanol is recovered for
The industrial data were obtained from an actual plant (Green reuse, the energy cost increases as the ratio increases.
Chemical Co., Ltd.) located in Korea. Also, the operating Therefore, it is necessary to find the optimal feed ratio to
conditions are shown in Table S5. balance the increased yields and methanol recovery cost.
17901 DOI: 10.1021/acs.iecr.9b02629
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Figure 8. Location of DEG production: (a) DEG production rate diagram and (b) [EC] × [MEG] diagram.

Figure 9. Effect of the feed ratio on DEG production rate. Figure 11. Effect of the feed ratio on the DMC production rate.

Economic evaluation is important to find the optimal C E = UEHE (8)

point.28,29 To find the optimal feed ratio, a profit index is
proposed. The equations for calculating the profit index (I) are Here, I is the profit index in United States dollars (USD) per
shown in eqs 6−8. kilomole (kmol) of EC. Si represent the sale price of DMC and
MEG. Ui is the unit price of DMC and MEG and Yi is the yield
I= ∑ Si − CE (6) of DMC and MEG. CE is the energy cost in USD per kmol of
EC. UE is the unit price of energy (USD/kJ) and HE is the heat
Si = UY
i i (7) duty (kJ) per kmol of EC. Table S7 shows the economic

Figure 10. Effect of the feed ratio on the concentration of (a) MeOH and (b) EC.

17902 DOI: 10.1021/acs.iecr.9b02629

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Industrial & Engineering Chemistry Research
Figure 12. Effect of the feed ratio on the liquid temperature.
assumptions for the index of profit. The assumptions are based
on PLATTS price data in 2018.
As can be seen in Figure 6, as the feed ratio increases, the
DMC and MEG yields also increase; the DMC and MEG
production increases at the same EC input, resulting in an
increase in DMC and MEG sales. On the other hand,
unreacted methanol recovery energy usage also increases,
resulting in increased energy costs. Therefore, there is an
optimum point that maximizes the profit index. The same
pattern is observed when side reaction is either considered or
ignored. However, the optimal points differ when the side
reaction is taken into account. When the side reaction is
included, the optimal feed ratio is 8.5 but, when excluded,
drops to 8.1 (Figure 7). Thus, operating at the optimal feed
ratio found in this study should increase the profit by 0.2 USD
per kmol of EC.
Location of Side Reaction. Figure 8a shows the DEG
production rate in the different stages of the RD column. DEG
is mostly produced between the EC and methanol feed stages.
This is because of the high concentrations of EC and MEG
between the EC and methanol feed stages (Figure 8b).
The DEG production for different feed ratios vs stage
number is plotted in Figure 9. As the feed ratio is increased,
the peak DEG production moved to the EC feed stage and the
peak area decreased. This is because, as the feed ratio increases,
Figure 13. Effect of the feed ratio on top and bottom compositions: (a) top diagram and (b) bottom diagram.
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the concentration of MeOH increases, the reaction with
MeOH accelerates, and the concentration of EC rapidly
decreases. When the feed ratio is less than 8.3, DEG is also
generated at the bottom of the RD column.
Effect of Feed Ratio on RD Column. The MeOH
concentration profile, the main reaction rate profile, the
temperature profile, and the composition of the top and
bottom streams were obtained for various feed ratios. As
shown in Figure 10a,b, as the feed ratio increases, the
concentration of MeOH in the liquid increases and the
concentration of EC decreases. Most reactions occur between
the EC and MeOH feed stages, and Figure 11 shows the peak
DMC production rate moving toward the EC feed stage, as the
feed ratio increases, due the increasing concentration of
MeOH in the liquid.
The effect on column temperature is more complicated. As
the feed ratio increases, the temperature first increases and
then decreases (Figure 12). The higher the concentration of
MeOH, the lower the temperature because MeOH has a low
boiling point. However, as the reaction increases, the
temperature increases because the reaction is exothermic.
In addition, when the feed ratio changes, the top and bottom
compositions change (Figure 13a,b). As the feed ratio
increases, the methanol yield increases, while the DMC yield
decreases in the top stream; this is the nonazeotropic point.
Meanwhile, in the bottom stream, the yield of MEG increases,
whereas those of DMC, EC, and DEG decrease. When the feed
ratio is less than 8.3, the yields of EC, DEG, and DMC
increase.
■
CONCLUSIONS
In this study, we have proposed an improved model that
considers the side reactions in the DMC production process. A
previous study, which did not consider the side reaction,
showed a relative error of 1.7% from the industrial data.
However, in our study, we found that including the side
reaction improved the simulation accuracy, and a relative error
of 0.1% vs the industrial data was observed. As a result, we
found that the optimal EC:MeOH feed ratio shifted
significantly (8.1−8.5), with the potential to increase the
profit by 0.2 USD per kmol of EC produced. Furthermore, we
identified the location of the DEG side reaction, it being
produced between the EC and MeOH feed stages in the RD
DOI: 10.1021/acs.iecr.9b02629
Ind. Eng. Chem. Res. 2019, 58, 17898−17905
Industrial & Engineering Chemistry Research Article

column. Thus, the results of this study can potentially be used Abbreviations
to increase profits via a small modification of the process DMC dimethyl carbonate
conditions. In addition, we hope that this study will help to MeOH methanol
guide future studies to improve DMC production. Our next EC ethylene carbonate
step will be to examine how to further reduce the side MEG monoethylene glycol
reactions. DEG diehylene glycol

■
*
ASSOCIATED CONTENT
S Supporting Information
CO2
RD
DS
carbon dioxide
reactive distillation column
DMC separating column
The Supporting Information is available free of charge on the MS MeOH separating column
ACS Publications website at DOI: 10.1021/acs.iecr.9b02629. MP MEG purifying column
Boiling point temperature of all species (Table S1); SRK Soave−Redlich−Kwong

DMC production operating conditions (Table S2); flow
summary of DMC production (Table S3); binary
interaction parameters of the DMC production process
(Table S4); plant operating conditions (Table S5);
comparison of the industrial and calculated results
(Table S6); economic assumptions (Table S7) (PDF)
■
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■ AUTHOR INFORMATION
Corresponding Author
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Ind. Eng. Chem. Res. 2019, 58, 17898−17905