Article

Cite This: Ind. Eng. Chem. Res. 2018, 57, 639−652 pubs.acs.org/IECR

Assessment on CO2 Utilization through Rigorous Simulation:

Converting CO2 to Dimethyl Carbonate
Bor-Yih Yu, Meng-Kai Chen, and I-Lung Chien*
Department of Chemical Engineering, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 10617, Taiwan
*
S Supporting Information

ABSTRACT: This paper intends to discuss the economical

performances and CO2 reduction potential of two CO2-based
dimethyl carbonate (DMC) production processes through rigorous
process simulation. One of them is the direct production process
with addition of butylene oxide (BO) as dehydrating agent (DIR-
BO porocess), while the other is the indirect production process
through ethylene carbonate (EC) as an intermediate (IND-EC
process). Both processes are systematically optimized and heat-
integrated. From economical evaluation, the IND-EC process
exhibits economical attractiveness, while the DIR-BO process
does not. We suggest that once the reaction rate of the DIR-BO
process can be improved, the overall economic performance of the
direct process can be much better. From the aspect of CO2
reduction, the net CO2 emissions throughout both processes are calculated. We found that DIR-EO process is largely carbon
positive, with CO2 emission of 2.242 (kg CO2/kg DMC), yet for the IND-EC process, it is near carbon neutral, with CO2
emission of 0.049 (kg CO2/kg DMC). Thus, from the aspect of achieving CO2 reduction, converting it into DMC provides
limited benefits.

1. INTRODUCTION of phosgene. Therefore, other nonphosgene routes of DMC

To alleviate the great environmental threat caused by CO2
accumulation, the utilization of it as an environmentally benign
feed stock to produce valuable chemicals has been regarded as a
possible way to make a contribution. In the process systems
engineering (PSE) point of view, extensive studies can be done,
as suggested in a recent review paper by Roh et al.1 First, CO2
is an important building block in the C1 industry; thus, the
potential products can be obtained through a screening step.
However, due to the thermodynamically stable structure of
CO2, its conversion toward other chemicals is not easy. Hence,
detailed studies about process route, process design, and
optimization is needed to enhance the production performance.
Moreover, the sustainability and feasibility of the designed
process should also be investigated to find out whether the
current design is economically attractive or not. Last but not
the least, processes for CO2 conversion are now at a relative
early stage; thus, there are still many uncertainties and
bottlenecks need to be overcome.
Among the candidate chemicals, methanol and syngas are
most widely studied currently,1−7 while dimethyl carbonate
(DMC) follows. DMC can be used as the important building
block for different organic synthesis with major production of
polycarbonates, as methylation agent, as solvent for lithium ion
batteries, and as fuel additive. It also has low toxicity and fast
biodegradability. Conventionally, DMC is produced through
methanol phosgenation. Although the reactivity is high, the
application of this method is still limited since the toxic nature
synthesis, majorly through oxidative carbonylation of methanol
(i.e., Bayer process, Enichem process, and UBE process), have
long been regarded as the replacement. In Bayer process,8
methanol, oxygen, and carbon monoxide are reacted in liquid
phase, with CuCl and KCl serving as catalyst. The major
drawback of this process lies in the low productivity, catalyst
deterioration, and the reactor corrosion. In Enichem process,
CO, methanol, and oxygen are reacted directly in vapor phase
to become DMC.9 In this process, the catalyst deterioration is
also the major issue that limits the per-pass conversion to be
within 50%. In UBE process, alkyl nitrite is used as an oxidant
to convert CO into DMC with the aid of palladium catalyst,
and dimethyl oxalate is produced as side product.10 The major
concern of this process is that nitric oxide is formed through
the reaction, and its emission should be carefully regulated.
The production of DMC from CO2 and methanol is also
considered promising because it consumed the undesired
chemical into another useful one. Many researchers have spent
effort in developing catalyst and kinetic expressions,11,12 and in
investigating the thermodynamic behavior for this direct
synthesis route.13−15 However, the direct conversion of CO2
into DMC is severely limited by its thermodynamically stable
Received: July 16, 2017
Revised: October 13, 2017
Accepted: December 15, 2017
Published: December 15, 2017

© 2017 American Chemical Society 639 DOI: 10.1021/acs.iecr.7b02923

Ind. Eng. Chem. Res. 2018, 57, 639−652
Industrial & Engineering Chemistry Research
structure. It is reported that the equilibrium conversion of CO2
and methanol to DMC is within 1%, even under extremely high
pressure (>100 bar). Thus, the existing CO2-based DMC
processes are mostly through an indirect route. The indirect
route is basically a trans-esterification reaction, in which a
highly active oxygenated reactant (i.e., epoxides) is reacted with
CO2 to form an intermediate carbonate, and it is further reacted
with methanol to become DMC and the corresponding glycol
as a byproduct. Among the trans-esterification routes, the most
promising one is that via the generation of ethylene carbonate
(EC) as an intermediate. In this method, CO2 is first reacted
with ethylene oxide (EO) to form EC, and EC is further
reacted with methanol (MeOH) to form DMC and ethylene
glycol (EG).16,17 Because of the higher reaction conversion
between EC and MeOH, this process route is more promising
than other routes using different epoxides as the intermediate.
In order to improve the reaction performance in direct
conversion process, some intensification strategies can be
applied. The first one is to utilize a membrane reactor for this
reaction. Inside the reactor, water permeates through the
membrane, while DMC, unreacted methanol, and CO2 remain
as the retentate. Through this strategy, the reaction equilibrium
can shift to the product side by removing the water byproduct.
Kuenen et al. investigates the techno-economic evaluation of
this process, yet they found that the performance is far from
economically attractive due to the low reaction conversion
(about 6.3%) even if a membrane reactor is applied.18
Another strategy for enhancing the direct conversion process
is to add a dehydrating agent inside the reaction system. This
dehydrating agent reacts with water to form a byproduct. Those
possible dehydrating agents include acetonitrile (or other
nitriles), trimethoxymethane, ionic liquids, or butylene
oxide.19−21 Although the conversion can be greatly enhanced,
the low to moderate selectivity toward DMC may make the
separation more difficult. In a recent paper series, it is
discovered that 2-cycaopyridine can be used as a water trap
to form 2-pyrrolidone with very high yield and selectivity.22−26
However, the lack of detailed expression of reaction kinetic
limited the research progress in conceptual design.
In recent contributions, Kongpanna et al. studied the techno-
economic evaluation of different CO2-based DMC production
processes, and they reported that the indirect process through
EC route is the most economical and environmentally friendly
route compared with others.27,28 However, the net carbon
emission from ethylene carbonate route is positive (0.452 kg/
kg DMC), even if CO2 is used as feed stock to generate DMC.
Hence, the process configuration and the operating condition
inside this process still have room for improvement. Thus, in
this work, a more intensified process through reactive
distillation is provided, with a systematic optimization and
heat integration performed to further fortify the process
performance.
This paper intends to focus on the detailed and rigorous
simulation and optimization on two different CO2-based DMC
production processes. One is the direct synthesis process with
addition of butylene oxide (BO) as water trap (called “DIR-BO
process” in the remaining text); the other is an indirect
synthesis process through EC route (called “IND-EC process”
in the remaining text). In both processes, rigorous design and
optimization are investigated. Besides, heat integration is
applied in order to make the energy usage more efficient.
Finally, these two processes are evaluated economically and
environmentally. The performance criteria for economic
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evaluation include return on investment (ROI) and internal
rate of return (IRR), while the amount of CO2 emission is
calculated in environmental evaluation. For a consistent
comparison, the DMC product purity is set at 99.5 mol % in
both processes.
2. OVERVIEW OF THE PAPER
In this work, simulations for both processes are performed in
Aspen Plus V8.8, and UNIQUAC method is selected as the
thermodynamic model throughout this work. Components in
DIR-BO process includes carbon dioxide (CO2), dimethyl
carbonate (DMC), methanol (MeOH), aniline (ANI),
methoxybutane (MB), butylene oxide (BO), butylene glycol
(BG), and water (H2O), while in the IND-EC process, the
components included are CO2, DMC, MeOH, ANI, ethylene
oxide (EO), and ethylene glycol (EG). The binary parameter
sets required to use in this work are listed in Tables S1 and S2.
For the binary pairs not mentioned, the thermodynamic
behavior is simulated as ideal. The Henry’s constants used to
describe the dissolution behavior of CO2 into others are also
listed in Table S3.
After the steady-state design is complete, optimization is
investigated. The objective function for optimization is to
minimize total annual cost (TAC), which can be calculated with
Capital Cost
TAC (kUSD/yr) = + Operating Cost
Payback Period
(1)
where the payback period is assumed to be 8 years, and the
total annual operating time is 8000 h. Correlations provided by
Turton et al. are applied to calculate the capital and utility
costs.29 For evaluating the steam cost, the unit prices are
corrected based on the steam price (21 bar and 215 °C)
provided by Taiwan Institute of Chemical Engineers
(TWIChE). Those steam prices after correction are listed in
Table 1.
Table 1. Utilities Used in This Work
utilities price (USD/GJ) CO2 emission (kg/GJ)
steam (6 bar, 160 °C) 11.80 72.86
steam (11 bar, 184 °C) 13.28 76.60
steam (21 bar, 215 °C) 14.14 82.16
steam (42 bar, 254 °C) 15.73 91.14
cooling water 0.354
electricity 16.9
For evaluating economic performances, CAPCOST, a
calculation package provided by Turton et al., is used. Return
on investment (ROI) and internal rate of return (IRR) are the
major indices to be calculated. For calculating CO2 emission,
the correlation from Gadalla et al. is selected and assumes that
natural gas is the fuel used to produce different grades of
steam.30 The CO2 emission amount per GJ of each grade of
steam is also listed in Table 1.
The details of the processes are illustrated, and the
discussions are included in the following sections. The DIR-
BO process is discussed in sections 3, and the IND-EC process
is discussed in section 4. The economical evaluation and carbon
emission analysis is addressed in section 5. Section 6 gives the
concluding remarks.
DOI: 10.1021/acs.iecr.7b02923
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Figure 1. Optimal flowsheet of the DIR-BO process.

3. DIR-BO PROCESS
3.1. Reaction Pathway and Kinetic Expression. Eta et
al. conducted the experiments for direct DMC production with
butylene oxide (BO) as the dehydrating agent with the aid of
ZrO2−MgO catalyst and developed a kinetic expression in
Eley−Rideal mechanism. This serves as a solid basis for process
development.21
In this reaction system, CO2 is dissolved into liquid methanol
and then reacts with methanol to form the intermediate,
monomethyl carbonate (MC). In contrast, the BO is also added
into the system, and is reacted with methanol to become
another reaction intermediate, methoxybutanol (MB). For
these two reactions, the one between CO2 and MeOH is a
catalytic reaction, and the other one is noncatalytic. For the
intermediates, there are other two reactions accounts for DMC
production. The first one is that MC reacts with MeOH to
form DMC and water, while the other one is that MB reacts
with MC to form DMC and BG. Eta et al. reported that
methanol is adsorbed onto the catalyst, and the catalytic
reaction between activated methanol and CO2 is the rate-
limiting step.21 With this assumption and the quasi-equilibria
for all other elementary steps, the reaction network can be
simplified as the following three individual reactions:
corresponding diol. However, BO does not react with water
directly here. Instead, BO affects the reaction mechanism which
leads to the inhibition of water production and the enhance-
ment of the DMC production. The detailed mechanism could
be found in Scheme 4 in Eta et al.’s work.21
In the kinetic expression provided by Eta et al., only the
production (consumption) rates of DMC, MB, BG, BO, and
MeOH are given. In order to apply this kinetic set, the reaction
rate of CO2 and H2O should first be derived based on atomic
balance. After that, the rate expressions are built into Aspen
Fortran Subroutine for successful description. All the rate
expressions and the parameters included in this study are listed
in the following eq 5−18, which are directly referenced from
the original work by Eta et al.21
dC DMC
= r1ρB
(5)
dt
dCMB
= (r2 − γr1ρB )ω
dt (6)
dC BG
= r2 − (r2 − γr1ρB )ω
dt (7)

2MeOH + CO2 → DMC + H 2O (2) dC BO

= r2
(3) dt (8)
BO + MeOH → MB
MeOH + CO2 + MB → DMC + BG (4) dCMeOH
= −2r1ρB − (r2 − γr1ρB )ω
dt (9)
Equation 2 shows the direct reaction route for DMC formation,
without involvement of BO. On the contrary, eqs 3 and 4 show dCCO2
the altered reaction mechanism with involvement of BO. As a = −r1ρB
dehydrating agent, BO is used to react with water to form the dt (10)

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Table 2. Information of Important Streams in the DIR-BO Process

MeOH BO CO2 CF LIQ-R VAP-R LIQR-2 Flash-V Flash-L COL1-VD
total flow (kmol/h) 41.30 17.84 20.62 1070.55 595.55 436.62 595.55 14.19 581.36 10.41
T (°C) 150.0 150.0 150.0 123.2 150.0 150.0 92.7 47.0 82.8 67.0
P (bar) 45.0 45.0 45.0 45.0 45.0 45.0 45.0 1.5 2.0 1.5
Mole Frac
methanol 1.0000 0.0000 0.0000 0.6492 0.8950 0.2765 0.8950 0.2965 0.9096 0.7130
CO2 0.0000 0.0000 1.0000 0.3223 0.0215 0.7136 0.0215 0.6814 0.0054 0.2410
BO 0.0000 1.0000 0.0000 0.0199 0.0046 0.0018 0.0046 0.0045 0.0046 0.0095
DMC 0.0000 0.0000 0.0000 0.0035 0.0358 0.0070 0.0358 0.0170 0.0363 0.0365
BG 0.0000 0.0000 0.0000 0.0000 0.0298 0.0001 0.0298 0.0000 0.0305 0.0000
MB 0.0000 0.0000 0.0000 0.0046 0.0083 0.0001 0.0083 0.0000 0.0085 0.0000
water 0.0000 0.0000 0.0000 0.0004 0.0049 0.0010 0.0049 0.0006 0.0050 0.0000
aniline 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
COL1-LD COL1-B COL2-D BG COL3-D COL3-B COL4-D water MKP ENT EDC-D DMC
total flow (kmol/h) 544.83 26.13 8.38 17.75 3.45 4.93 0.54 2.90 0.00 490.34 524.10 20.67
T (°C) 67.0 167.5 116.1 211.0 84.5 156.3 64.2 98.9 47.0 47.0 54.5 89.4
P (bar) 1.5 1.8 1.0 1.1 1.0 1.1 1.0 1.0 1.5 1.5 1.0 1.0
Mole Frac
methanol 0.9560 0.0211 0.0657 0.0000 0.1593 0.0000 0.9950 0.0033 0.0000 0.0000 0.9937 0.0010
CO2 0.0012 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0012 0.0000
BO 0.0047 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0048 0.0040
DMC 0.0380 0.0000 0.0001 0.0000 0.0002 0.0000 0.0013 0.0000 0.0000 0.0001 0.0002 0.9950
BG 0.0000 0.6797 0.0021 0.9990 0.0000 0.0031 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
MB 0.0000 0.1884 0.5864 0.0009 0.0014 0.9964 0.0000 0.0017 0.0000 0.0000 0.0000 0.0000
water 0.0001 0.1106 0.3454 0.0000 0.8390 0.0001 0.0037 0.9950 0.0000 0.0000 0.0001 0.0000
aniline 0.0000 0.0002 0.0003 0.0001 0.0000 0.0004 0.0000 0.0000 1.0000 0.9999 0.0000 0.0000

dC H 2 O 3.2. Process Development. The optimized flowsheet of

= r1ρB − r2 + (r2 − γr1ρB )ω DIR-BO process is illustrated in Figure 1, with the information
dt (11)
of important streams listed in Table 2. First, fresh CO2, MeOH,
⎛ C C ⎞ and BO are mixed with several recycled streams and then sent
r1 = k1⎜CMeOH − DMC BG ⎟PCO2 to the reactor. Those recycled streams include the vapor outlet
⎝ KCMB ⎠ (12) from several later units (reactor, flash unit, and later column 1),
r2 = k 2C BOCMeOH (13) the unreacted liquid methanol, and MB.
The optimal operating condition for reactor mainly follows
⎛ −62000 ⎛ 1 1 ⎞⎞ Eta et al.’s work,21 and the reactor is modeled as a continuous
k1 = 1.6 × 10−5 exp⎜ ⎜ − ⎟⎟
stirred-tank reactor (RCSTR module). For the composition of
⎝ R ⎝T 423.15 ⎠⎠ (14)
combined feed sent into reactor, CO2 and MeOH are set at
k 2 = 0.0112 (15) near stoichiometric ratio, and the molar ratio between MeOH
and BO is set at 30. The molar ratio between MeOH and BO
⎛ α(y + 1)C ⎞ ‐1 leads to a trade-off between reaction conversion and selectivity.
ω=⎜ 2
DMC
+ 1⎟ With less BO added, the reaction conversion is barely
⎝ (α + y) CMeOH ⎠ (16) enhanced, while with more BO, it may lead to the generation
of the undesired product, MB, as more reaction intermediate
⎛ y ⎞⎛ ⎛ 2α ⎞ C DMC ⎞ accumulates in the reactor. For operating temperature, 150 °C
γ=⎜ ⎟⎜⎜1 − ⎜ ⎟ ⎟⎟
⎝ α + y ⎠⎝ ⎝ α + y ⎠ CMeOH ⎠ (17) is also selected based on the trade-off between reaction
conversion and selectivity. Another undesired side product,
CMB dimethoxymethane, would be generated easily at temperature
y= higher than 150 °C. For operating pressure, it seems that the
CMeOH (18)
reaction conversion is not sensitive to the operating pressure.
where the concentrations (Ci) are in unit of mol/liter, and PCO2 Thus, the lowest one, 45 bar, mentioned in Eta et al.’s work21
is in bar. For the parameters, the equilibrium constant (K) is was selected for the sake of easier industrial application. The
0.0036 (bar), the bulk catalyst density (ρB) is 33.3 (kg/m3), and reactor holdup is designed to have 90% liquid and the
the value of α in eq 17 is 0.0014. Because the values of K and α remaining vapor. On the basis of the experimental results
are not specified in the original work,21 these two values are provide by Eta et al.,21 the conversion of each species becomes
obtained by re-regression from the experimental data at the much slower after 12 h. Hence, the liquid-phase residence time
temperature of 150 °C, which is the most suitable reaction is reasonably set at this value.
temperature suggested by the authors. Note that k2 is a The liquid reactor outlet is first heat-exchanged with the
constant. This is potentially because Eta et al. focused more at liquid stream from later flash unit, and is further cooled to 47
T = 150 °C and only obtain the kinetic parameter under this °C and decompressed to 1.5 bar. The reason to cool the outlet
temperature. stream to 47 °C is because this temperature is considered as the
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lowest allowable one by using the cheap cooling water. This
operation enables the easier separation for the unreacted CO2
with MeOH and DMC in the flash unit. After that, the liquid
stream from the flash unit is sent to column 1 (COL-1), in
which MeOH and DMC are obtained from liquid distillate,
while H2O, MB, and BG come out at the bottom. Besides, the
adoption of a partial vapor−liquid condenser enables the
noncondensed gas to be separated. This vapor distillate is
compressed and recycled to the reactor inlet.
The bottom stream of COL-1 is then sent to column 2
(COL-2), column 3 (COL-3), and column 4 (COL-4) for
further separation. In COL-2, the side product BG is obtained
at the bottom, while the remaining species comes out as liquid
distillate. In COL-3, the unreacted MB is obtained at the
bottom and is recycled to reactor inlet, while the liquid distillate
contains mostly water. Note that from the boiling point ranking
of this system, water lies in the middle, which makes it difficult
to separate. However, in order not to retard the reaction
equilibrium, the removal of this slight amount of water is
indispensable. In COL-4, the unreacted methanol is separated
from water and sent back to reactor inlet, in order to fulfill
better recovery of it.
The liquid distillate from COL-1 contains 95.6 mol %
MeOH and 3.8 mol % DMC, and the balance is BO. This
stream is sent to the downstream for further separation.
However, MeOH forms an azeotrope with DMC, thus the
mixture cannot be separated using a single column. The T−xy
diagram of MeOH and DMC is shown in Figure 2. There are
Figure 2. T−xy diagram between MeOH and DMC under 1 bar.
many contributions focused on separation of MeOH and DMC
in literature, and it can be concluded that extractive distillation
is better than pressure-swing distillation because the azeotropic
composition of MeOH and DMC does not vary much under
different pressures.17,18,31,32 Hsu et al. reported that aniline is an
effective entrainer to enhance the relative volatility between
MeOH and DMC; thus, it is selected as the entrainer in the
further separation section in this work.17
From the T−xy diagram, it is noted that the composition of
COL-1 liquid distillate lies in the right-hand side of azeotropic
composition. However, due to the narrow vapor−liquid
envelope in this region, purifying to the azeotropic composition
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by a preconcentrator column may not be economical. Thus,
this stream is directly sent to the extractive distillation section.
In a typical extractive distillation process, two columns are
required, including an extractive distillation column (EDC) and
a solvent recovery column (SRC). For the MeOH and DMC
separation system, MeOH is obtained at the top of EDC and
DMC comes out from top of SRC. The MeOH separated from
EDC is pumped and then recycled to the reactor inlet. Note
that there is a 0.01% purge of EDC distillation to avoid the
water accumulation. In this work, three different extractive
distillation configurations are discussed and compared. The
configuration of traditional extractive distillation configuration
is illustrated in Figure 3a. In order to be more energy-saving, a
simple heat-integration can be achieved by adopting a feed−
effluent heat-exchanger (FEHE), as shown in Figure 3b. This
FEHE performs heat exchange between the SRC bottom
stream and the feed stream to EDC. Through this design
configuration, the reboiler duty of EDC can be greatly reduced.
A further heat-integration strategy is to configure it into an
extractive dividing-wall column system, as shown in Figure 3c.
The design of a dividing-wall column was widely discussed in
literature. From previous literature, it is known that it has the
advantage to reduce the remixing effect in a typical distillation
column and can improve the separation efficiency. There are
also different configurations for a dividing-wall column. In this
work, as the products are obtained from the distillate streams in
different columns, a dividing-wall configuration that integrates
two different reboilers is used. Figure 3d shows the
thermodynamically equivalent configuration of an EDWC
configuration. For simulation purpose, the whole column can
be divided into three parts, and each part is designed separately.
In this subfigure, the side rectifier C1 represents the original
EDC, while C2 and C3 performed as the original SRC. In
operation, the vapor traffic of C1 is provided by a portion of the
overhead vapor from C3. Besides, the diameter of the upper
part of EDWC can be determined by the equivalent-diameter
method as in the previous work by Wu et al.32
The brief optimization results for these three configurations
can also be found in Figure 3a,c. When operating at entrainer-
to-feed molar ratio (E/F) equal to 0.9, a 29.8% TAC reduction
is achieved with adoption of FEHE. When EDWC config-
uration is adopted, a further 13.4% reduction in TAC is
obtained.
3.3. Optimization Work. In the whole process, COL-1 and
the extractive distillation section are needed to be optimized.
For COL-2, COL-3, and COL-4, the TAC change with varying
design and operating variables may be too slight to take into
consideration. This is because the throughputs of these two
columns are very small compared with COL-1 and the
extractive distillation section.
In COL-1, there are three variables to be optimized,
including the condenser temperature (Tcond), total number of
stages (NT-COL1), and feed locations (NF-COL1). The
optimization work can be achieved by a simple sequential
iterative method, with the algorithm shown in the left part of
Figure S1. The results are recorded in Figure 4a. From this
figure, it is shown that the optimal point is at Tcond = 67 °C,
NT‑COL1 = 50, and NF‑COL1 = 38. After the optimization of COL-
1, the heat integration between flash liquid and reactor effluent
is adopted to save energy.
Next, the extractive distillation section is optimized, with the
algorithm shown in the right side of Figure S1. In this section,
six variables need to be optimized, including entrainer-to-feed
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Figure 3. Different process configurations for MeOH/DMC separation via extractive distillation
molar ratio (E/F)), rectifying section stages of EDC (NREC),
extractive section stages in EDC (NEXT), stripping section
stages of and EDC (NSTR), total number of stages of SRC
(NT-SRC), and feed location in SRC (NF-SRC). After the
optimal point under each E/F is found, the FEHE is added in
order to save energy. The optimization results without FEHE
are collected as in Figure 4b, while the results with FEHE are
shown in Figure 4c. From these subfigures, it is shown that a
lower E/F leads to lower TAC, but an optimal point at E/F =
0.85 is found in the cases with FEHE.
In EDWC, there are also several variables to be determined,
including E/F, total number of trays of C1, C2, and C3 (NT1,
NT2, and NT3), two feed locations of EDC feed (NF1 and
NF2), and the vapor split ratio (FV). Those symbols are all
mentioned in Figure 3d. Among them, FV is used to make sure
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that BO and methanol left in bottom product from C1 are low
enough to provide DMC from distillate of C2. The remaining
six variables are optimized. The algorithm for sequential
iterative method is shown in Figure S2, and the optimization
results are recorded in Figure 4d. From this figure, it is found
that the optimal E/F is 0.9. It is also found that E/F changing
leads to little variation in TAC. Comparing with the traditional
configuration with FEHE, the optimal E/F found in EDWC
also shifts somehow to a larger value.
4. IND-EC PROCESS
4.1. Reaction Pathway and Kinetic Expression. In the
IND-EC process, the overall reaction is divided into two steps
which occur in different reaction sections. The reaction
equations are
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Figure 4. Optimization results of the DIR-BO process.

Figure 5. Optimal flowsheet of the IND-EC process.

EO + CO2 ↔ EC (19) For eq 19, the reaction occurs under high-pressure condition,
with the conversion toward EC favored at lower temperature.
EC + MeOH ↔ DMC + EG (20) Compared with eq 20, the reaction rate of eq 19 is relatively
645 DOI: 10.1021/acs.iecr.7b02923
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Table 3. Information of Important Streams in the IND-EC Process

CO2 EO rout EC EC-in MeOH-F MeOH-R RD-D EG ED-in ANI MKP SRC-B DMC
total flow 22.01 20.01 22.01 20.00 20.00 40.16 91.85 111.93 20.09 111.93 85.07 0.01 85.07 20.09
(kmol/h)
T (°C) 50.0 50.0 80.0 202.5 47.0 45.0 64.3 63.5 201.4 74.4 54.0 54.0 157.1 89.1
P (bar) 50.5 50.5 50.5 0.3 1.3 1.5 1.5 1.0 1.3 1.5 1.1 1.2 1.4 1.0
Mole Frac
EO 0.0000 1.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
CO2 1.0000 0.0000 0.0910 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
EC 0.0000 0.0000 0.9089 1.0000 1.0000 0.0000 0.0000 0.0000 0.0005 0.0000 0.0000 0.0000 0.0000 0.0000
DMC 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.1786 0.0000 0.1786 0.0000 0.0000 0.0000 0.9950
EG 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.9950 0.0000 0.0000 0.0000 0.0000 0.0000
MeOH 0.0000 0.0000 0.0000 0.0000 0.0000 1.0000 0.9999 0.8214 0.0043 0.8214 0.0000 0.0000 0.0000 0.0046
aniline 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.9999 1.0000 0.9999 0.0004

faster. However, to the best of our knowledge, there is no
appropriate kinetic expressions for this reaction provide in
literature. For simulation purposes, Souza et al. used an
imaginary kinetic expression for this reaction which is fast
enough.33 In this work, we did not make such an extra
assumption but modeled eq 19 as an equilibrium reaction
instead. The equilibrium constant of this reaction is predicted
directly in Aspen Plus based on Gibbs energy minimization.
Similar to the results by Souza et al., our simulation setting can
also lead to an almost-complete reaction conversion.
Note that in some recent publications, the concept of one-
pot synthesis was proposed, in which eqs 19 and 20 are
designed to take place in the same reactor,34,35 but considering
the different reaction condition requirement of these two
reactions, the process configuration with two individual
reaction sections seems to be more appropriate.
For eq 20, the kinetic expression is referenced from Fang and
Xiao16 and is illustrated in the following equations:
C EGC DMC
rate = k f C ECCMeOH −kr
CMeOH (21)
⎛ −13060 ⎞
k f = 1.3246 exp⎜ ⎟ case shown in Figure 5, the cheaper 11 bar steam can be used as
⎝ RT ⎠ (22)
⎛ −28600 ⎞
kr = 15022 exp⎜ ⎟ then a higher grade of steam should be used for total required
⎝ RT ⎠ (23)
where the reaction rate is in mol/L·min, concentration is in
mol/L, and activation energies are in J/mol.
4.2. Process Development. The optimized flowsheet of
the IND-EC process is provided in Figure 5, and the
information on streams is collected in Table 3. Streams of
fresh CO2 and EO are mixed and sent to the reactor. The
reactor is operated at 50.5 bar and 80 °C, and EO conversion
reaches over 99.99%. The reactor effluent is decompressed to
1.5 bar, and then sent to a stripper to distill off the remaining
CO2 inside the EC-rich liquid. Almost all the CO2 comes out
from the stripper overhead vapor, and this stream is not
recycled to the reactor in order to avoid the costly compressing
step. In the stripper bottom, the high-purity EC stream is
obtained. Because of the high boiling point of EC, the stripper
is operated at 0.3 bar, in which the 21 bar steam can be utilized.
The EC stream obtained from the previous reaction section
is cooled and fed into the reactive distillation column (RDC) at
the upper section. The fresh and unreacted MeOH stream is
also fed to RDC at the lower section. After reaction, the
mixture of methanol and DMC comes out as the liquid
distillate stream, while EG is obtained at the bottom. In reactive
646
distillation section, the major target is to keep EC conversion
high. Hence, the targeted EC conversion is set at 99.95%, and
the reacting condition with excess in MeOH could be helpful.
The distillate stream from RDC is then sent to the
downstream extractive distillation process to separate DMC
and MeOH. The overall process configuration is the same as
the one mentioned in previous Figure 3a but with two
differences. The first difference is that in this process, the feed
sent to extractive distillation section has composition of 82.13
(mol %) MeOH and 17.87 (mol %) DMC, which contains less
MeOH in this feed stream. For comparison purposes, the
composition of MeOH in the feed stream of Figure 3a is at
95.60 mol %. This difference will reflect on the required E/F
ratio in the EDC to drive MeOH up at this column. As a result,
the optimal E/F ratio is at 0.90 in Figure 3a, while for this case,
E/F is lower at 0.76. The second difference also arises due to
the difference of feed compositions in these two cases. With
much less DMC (only 3.8 mol %) in the feed stream of Figure
3a, this lead to results that the same grade of steam is required
in both EDC and SRC. Thus, further integrate these two
columns into an extractive-dividing-wall column (EDWC) can
greatly improve the economic performance. However, in this
the reboiler heat source in EDC, while the 21 bar steam should
be used in SRC. If it is integrated to an EDWC configuration,
energy. As already concluded in a previous work by Wu et al.,32
this leads to an increase in overall utility cost, even if the total
reboiler duty is reduced. Hence, for indirect synthesis route, the
EDWC configuration is not utilized.
4.3. Optimization. Inside this process, the RDC and the
extractive distillation section are the most important part to be
optimized. Four variables in RDC should be determined,
namely, excess ratio between feed MeOH and EC (ER), total
number of stages (NT-RDC), the rectifying section stages
(NREC) and reaction section stages (NRXN). While the
variables discussion in extractive distillation section is the same
as those mentioned in section 3.3.
ER is the most important parameter in this process, and its
influences can be addressed in two aspects. First, larger ER
enhances the reaction conversion from the thermodynamic
viewpoint. The specified reaction conversion of EC is very high
(99.95%), thus there should be a minimum ER value to reach
the targeted conversion. Second, ER affects the distillate
composition of RDC, which leads to different separation
performance in extractive distillation section. The process
provided by Hsu et al. has ER = 7.8,17 and this made the RDC
distillate composition to be 85.29% MeOH, which is pretty
DOI: 10.1021/acs.iecr.7b02923
Ind. Eng. Chem. Res. 2018, 57, 639−652
Industrial & Engineering Chemistry Research
Figure 6. Optimization results of the IND-EC process.
close to the azeotropic composition (86.5 mol % MeOH) at 1
bar. As ER decreases, the loading of RDC and EDC can be
directly reduced; this may lead to better overall economic
performance.
Note that the process configuration in this work is somewhat
similar to the typical preconcentrator column followed by an
azeotropic separation section (i.e., extractive or heterogeneous
azeotropic distillation system), as the RDC provided a distillate
stream with near azeotropic composition. Luyben discussed the
effect of preconcentrator distillate composition on the perform-
ance of ethanol−water separation based on heterogeneous
azeotropic distillation system.36 The effect in the same
ethanol−water system was also discussed by Kiss and Ignat
based on extractive distillation system. 37 The general
conclusion is that the lower distillate composition saves the
energy requirement in the preconcentrator column yet
increases that in the downstream azeotropic separation section.
Thus, the distillate composition plays an important role in these
processes. As the feed ratio into RDC apparently affects its
distillate composition, it should be carefully determined
through optimization.
The overall optimization is also performed by a sequential
iterative method, with ER as the outermost variable. Other
variables are located inside the network. The overall algorithm
is illustrated in Figure S3.
The optimization results are illustrated in Figure 6, and only
the major results are included. The general results show that
TAC drops obviously as ER decreases in the region we
investigated, and from this we conclude that the trade-off
mentioned above does not exist. The reason for this is because
there is a stringent requirement in reaction conversion
(99.95%) for EC in RDC. Thus, once ER becomes too small,
647
Article
this specification can no more be reached. From our results, the
lower limit for ER is found to be 6.6. This reduction only leads
to a decrease of MeOH content in EDC distillate from the
original 85.29 mol % to 82.13 mol %, and is the major reason
for the nonexistence of the trade-off between RDC and the
downstream extractive distillation section.
As for E/F in extractive distillation section, the optimal point
is at 0.76. E/F is an important design parameter in the
extractive distillation process which affects the separation
efficiencies. Hence, an obvious trade-off in capital cost and
operating cost may be well expected by varying E/F. However,
from Figure 6b, the TAC variation from changing E/F is not
large. The reason is that we start the optimization from the
previous optimal result (E/F = 0.883) obtained by Hsu et al., in
which the process is optimized based on Douglas’ work with
payback period set at 3 years.17,38 During the reinvestigation of
optimization based on different cost correlations and payback
years, we actually take a deeper look on the effect of varying E/
F; thus, the moderate change in TAC is reasonable.
In summary, comparing this process to Hsu et al.’s work, a
16.8% reduction on TAC is observed.17 The detailed
information for this comparison can be found in Table 4.
Note again that the process proposed by Hsu et al. was
optimized based on the Douglas’ work,38 in which the utility
cost is much cheaper than the ones suggested by Turton et al.
Thus, we suggest that optimization based on Turton et al.’s
model leads to an optimal solution with lower utility
requirement, and is more suitable in evaluating CO2 reduction.
DOI: 10.1021/acs.iecr.7b02923
Ind. Eng. Chem. Res. 2018, 57, 639−652
Industrial & Engineering Chemistry Research Article

Table 4. TAC Comparison between the Optimal Process and another widely used correlations provided by Sieder et al. also
the Results of Hsu et al.17 assumed in a similar way.39
5.1. DIR-BO Process. In this process, the raw materials are
Hsu et al. this work
CO2, MeOH, and BO, with the unit prices set to be 70 (USD/
ratio 7.8 6.6 MT), 310 (USD/MT), and 1600 (USD/MT). There is no
E/F 0.883 0.760 open market data for BO price. Traditionally, BO is synthesized
as the byproduct of ethylene oxide (EO) and propylene oxide
RD-vessel 156.22 189.41 (PO) through the hypochlorination reaction. Thus, the authors
RD-tray 50.31 69.49 assume that the production cost of BO is similar to the EO
capital
cond 77.11 73.55 price (1510−1700 USD/MT) and PO price (1680−1810
RD REB 117.44 123.03 USD/MT),40,41 and in base case calculations, it is set at 1600
steam 740.71 660.31 (USD/MT). The products are DMC and BG, with the base
operating
CW 18.36 16.00 case prices set at 685 (USD/MT)42 and 2200 (USD/MT).43
RD TAC 809.20 733.25 However, due to the uncertainties and volatilities in unit
ED-vessel 149.79 176.58 prices, the evaluation results may vary greatly as they change.
ED-tray 49.48 79.20
Recent financial news in China stated that the unit price of
ED-cond 72.92 65.99
DMC has dropped from about 900 USD/MT in January to less
ED-REB 89.36 74.61
than 700 USD/MT at the end of April in 2017.44 The reason
SR-vessel 57.13 54.87
capital for this drop was due to the price fluctuation of the upstream
SR-tray 24.36 29.60
propylene oxide and methanol. This phenomenon clearly
SR-cond 50.60 50.31
ED shows the volatility of DMC market. Also, in the marketing
SR-REB 63.15 61.49
report provided by ICIS.com, there is also a fluctuation region
HX1 50.72 52.03
for the prices. Thus, the uncertainties resulted from different
HX2 53.81 51.76
BO and BG unit price should also be taken into consideration.
steam ED 573.13 410.13
In this work, the price uncertainties are investigated through a
operating steam SR 246.10 195.14
series of sensitivity analyses. The interest region for each price
CW 22.13 16.32
is stated as below. DMC unit price is varied from 100−150%
ED TAC 924.02 708.63
base case value, BO price is fluctuated from 95−105% of its
total total TAC 1733.22 1441.89 (−16.81%)
base case value, while the price of BG is studied in between
90−100% base case value. For CO2 and MeOH, the sensitivity
5. ECONOMICAL EVALUATION AND CARBON analysis on their price is not studied, as these two components
EMISSION CALCULATION are very common chemicals around the world.
After design and optimization of the steady-state simulation are In this work, the authors consider an economically attractive
finished, economical evaluation is investigated. The economical case should have ROI > 15% and IRR > 10%. The analysis
evaluation is performed by the software package CAPCOST, result of base case is listed in Table S4, and the sensitivity
which is provided by Turton et al. For the indices to be analysis results are shown in Figure 7. For the base case, it is
evaluated, both the nondiscounted profitability criteria (ROI) clear that it just approaches the break-even point, which is not
and discounted profitability criteria (IRR) are calculated. In considered economical. However, as BO price drops a bit and
calculating IRR, a 10% commercial interest rate is assumed to the DMC price rises a bit, the economic performance is
discount the value of money as time goes on. somewhat improved. Given the DMC price trend and the
The items for economical evaluation can be roughly divided reason for its dropping mentioned above, it is likely that the
into two parts, namely, capital cost and operating cost. In DMC unit price can bounce back in the future. However, in
determination of capital cost, the size, material, and operating order to be economically attractive, the DMC price has to be
condition of each process unit should be known. For evaluating 40−50% higher than the base case value. Thus, in the current
the operating cost, the most important part could be the cost of stage, the economical attractiveness is not obvious.
utilities, operating labor, and raw materials. Also, the analysis Besides, the reactor in this process is very expensive. As listed
results may be highly dependent on the financial model; thus, in Table S4, it accounted for almost 60% of total capital
the parameters inside the model should be carefully set. investment (total grass root cost in the table), which is not the
Turton et al.’s capital cost correlations were regressed from typical case of an industrial plant. In the contribution by Eta et
the actual cost information from vendors. Thus, in each al, the kinetic parameters were obtained under a reactor
correlation, there is a feasible regions and is bounded by the condition with bed void fraction around 97% (assume the
upper and lower limit of the equipment size. However, for catalyst density is 1000 kg/m3). Therefore, the catalyst amount
some units, the feasible size range is relatively narrow (i.e., has some room to be increased. By this operation, the residence
reactor, kettle reboiler, etc.), and some units in this work are time required can be greatly reduced and can save the capital
designed to have their sizes exceed the upper limits under the investment. However, due to the lack of kinetic parameters, the
given category. Therefore, the costs for those units are assumed further improvement on the process is not continued. Instead,
to be calculated based on the correlations of other units with we proposed a hypothetical situation that the reactor size can
similar type. The assumptions are stated as the following. First, be reduced and investigate the influence of it on the overall
the reactor cost is calculated by the correlation used for economic performance of the base case. The analysis result is
horizontal vessel. Second, the reboiler cost are calculated as shown in Table 5. If the reactor size can be reduced, then the
floating type heat exchanger. Lastly, the double-pipe category is enhancement in economic performance can be apparent, as
assumed for all the heat exchangers with exchanging area less about 17% net increment in ROI and 14% increment in IRR
than 10 m2. The authors consider these assumptions valid, as can be obtained as the reactor size is reduced to 10% of its
648 DOI: 10.1021/acs.iecr.7b02923
Ind. Eng. Chem. Res. 2018, 57, 639−652
Industrial & Engineering Chemistry Research Article

Figure 7. Sensitivity analysis results of ROI and IRR on the DIR-BO

process. Figure 8. Sensitivity analysis results of ROI and IRR on the IND-EC
process.
Table 5. ROI and IRR at Different Reduced Reactor Sizesa
reactor ratio ROI (%) IRR (%)
process, which can be viewed as the total capital investment,
100% −0.67 X
and is the basis for calculating ROI and IRR.
20% 11.55 11.22
A common point can be concluded from these two
10% 16.68 14.56
a
processes, that is, the revenue provided by the side-product
Calculated as DMC unit price = 685 USD/MT, and BO unit price = (BG or EG) plays an important role in the economic analysis.
1600 USD/MT and BG unit price = 2200 USD/MT.
Thus, a more conservative ROI and IRR target should be
suggested in the economical evaluation in order to deal with the
price fluctuation.
original size. Thus, the authors consider this process has the 5.3. Carbon Emission. Beside economical evaluation, the
potential in the future, as long as the details in reaction section emission of carbon dioxide is also an important criterion to be
can be further studied and clarified. compared. Being different from the economical evaluation, the
5.2. IND-EC Process. In this process, the raw materials are analysis of CO2 emission is independent to production rate. In
CO2, MeOH and EO, while the products are DMC and EG. this work, the calculation of carbon emission is based on the
The unit prices for CO2, MeOH, and the base case unit price correlation provided by Gadalla et al, and natural gas is
for DMC are set at the same values as in previous section. As assumed to be used as the fuel to produce steam.30 The
referenced from ICIS.com, the base case unit prices of EO and emission amount per GJ of different grades of steam is already
EG are set as 1.56 (USD/kg) and 1.2 (USD/kg), respectively. collected in Table 1, while the analysis results of the two
Again, sensitivity analysis is performed on varying EO (95− processes studied in previous sections are listed in Table 6.
105%), EG (90−100%), and DMC price (95−105%) in order
to investigate the uncertainties.
Table 6. Comparison of CO2 Emission Amounta
The evaluation result of the base case is listed in Table S5,
while the sensitivity analysis results are illustrated as in Figure 8. DIR-BO IND-EC
From the results, it is clear that the base case is pretty emission (COL-1 Reb) 1.387 emission (STR Reb) 0.020
economically attractive with 26.55% ROI and 17.01% IRR. The emission (COL-2 Reb) 0.041 emission (RD Reb) 0.265
results could be well-expected as the reaction conversion is emission (COL-3 Reb) 0.062 emission (EDC Reb) 0.172
much higher as comparing with the DIR-BO process, which emission (COL-4 Reb) 0.017 emission (SRC Reb) 0.079
leads to less system loading. Because of this, the sensitivity emission (DWC-Reb) 1.066
analysis focuses more on lowering the profit from products. emission (Reactor) 0.156
From the sensitivity results, the general trend is the same as consumption −0.487 consumption −0.487
that in the DIR-BO process. However, it is found that ROI and net emission 2.242 net emission 0.049
IRR change dramatically compared with the previous case. This
a
is resulted from the much less total grass roots cost in this Unit: (ton CO2)/(ton DMC generated).

649 DOI: 10.1021/acs.iecr.7b02923

Ind. Eng. Chem. Res. 2018, 57, 639−652
Industrial & Engineering Chemistry Research Article

Table 6 illustrates that CO2 is in net emission in the DIR-BO
process. Given the fact that CO2 is used as feed stock to
produce DMC, 2.18 ton of CO2 is emitted as 1 ton of DMC is
produced. The reason is that the reaction conversion is still low,
with only about 10% of total methanol conversion. Although it
is already improved a lot compared with the direct production
process without BO addition (<1%), the current result is still
not promising. The low conversion leads to a high utility
requirement in COL-1, as almost all the methanol is boiled to
the liquid distillate. From the analysis results, COL-1 accounts
for about half of the total CO2 emission in this process. Hence,
in order to become a real green process, the enhancement in
heat-integrated. Thus, converting it into DMC can barely reach
net CO2 reduction and may not have too much upside for
further improvement.
■ ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.iecr.7b02923.
Detailed information of parameters for thermodynamic
models, term-wise information of economical evaluation,
and algorithm for sequential iterative optimization
(PDF)

■
reaction conversion is of top priority.
As for the IND-EC process, the net CO2 emission is at
0.049(ton/ton DMC produced) and is considered to be much AUTHOR INFORMATION
more environmentally friendly than the DIR-BO process. The Corresponding Author
CO2 emission greatly improved compared with the value *Tel.: +886-3-3366-3063. Fax: +886-2-2362-3040. E-mail:
reported by Kongpanna et al. (0.452 ton/ton DMC ilungchien@ntu.edu.tw.
produced).27 The reason of this difference is that a more ORCID
intensified process is evaluated in this work, as DMC is I-Lung Chien: 0000-0003-2947-8713
produced via reactive distillation. Also, the re-evaluation of Notes
process optimization and the heat integration strategy are also The authors declare no competing financial interest.

■
part of the reasons for this reduction. Note that a near-carbon-
neutral process from this route is obtained here in this work. ACKNOWLEDGMENTS
This reveals the difference between rigorous process simulation
and conceptual design, as this process uses CO2 as feed stock to The research funding from the Ministry of Economic Affairs of
produce DMC especially intended for reducing its emission. R.O.C. under grant no. 106-EC-17-D-11-1466 is greatly
appreciated.

■
In conclusion, we also mention that if reducing CO2
emission is the main purpose then converting CO2 to DMC
may not be an effective way in the current stage. The
NOMENCLATURE
conversion in the DIR-BO process is still low, which leads to Acronyms
large amount of utility required in separating the unreacted BG Butylene glycol
reactants. However, although the conversion in the IND-EC BO Butylene oxide
process can be quite high, the process still slightly emits CO2. DMC Dimethyl carbonate
The major issue is that one of the reactant, methanol, forms a DIR-BO Direct production process with addition of BO
minimum boiling point azeotrope with DMC. Also, the EC Ethylene carbonate
composition of the MeOH/DMC azeotrope has high MeOH EDC Extractive distillation column
composition. Hence, it inevitably requires a large amount of EDWC Extractive dividing-wall column
utility to distill MeOH when separating, which is the major EG Ethylene glycol
source of CO2 emission. For future research, the reaction with EO Ethylene oxide
higher stoichiometry in CO2, and also a product which can be ER Excess ratio (= mole MeOH/mol EC)
easily separated from the unreacted reactants can be considered IND-EC Indirect production process via generating EC as an
more promising. intermediate
IRR Internal rate of return (%)
6. CONCLUSION MB Methoxybutanol
In this work, two CO2-based dimethyl carbonate (DMC) MC Monomethyl carbonate (MC)
production processes, namely, the DIR-BO porocess and the MeOH Methanol
IND-EC process are rigorously studied. After steady-state RDC Reactive distillation column
design, these two processes are optimized and heat-integrated, ROI Return on investment (%)
and the optimal processes are compared directly through SRC Solvent recovery column
complete economic evaluation and the ability to reduce of CO2. TAC Total annual cost (kUSD)
From the economical evaluation result, two conclusions can be Capital Letters
made in this study. One is that the economical performances Ci Molar concentration of components (mol/L)
are greatly influenced by the fluctuation of product prices. The E/F Entrainer to feed ratio [(mol/h)/(mol/h)]
other is that the reactor in DIR-BO process is very costly, and FV Vapor split ratio (−)
the reduction of this cost provides a large improvement to K Equilibrium constant for the direct reaction (bar)
overall economic performance. Thus, the authors consider that NEXT Extractive section stages in EDC
the indirect production process exhibits the attrectiveness for NF Feed location into the column
investment, while the direct production route currently does NREC Rectifying section stages
not but has the potential to become economically favorable. NRXN Reaction section stages
From the results of carbon emission calculation, both processes NSTR stripping section stages of EDC
are in CO2 net emission, despite the fact that CO2 is the raw NT Total number of trays
material to produce DMC and the processes are optimized and P Pressure (bar)
650 DOI: 10.1021/acs.iecr.7b02923
Ind. Eng. Chem. Res. 2018, 57, 639−652
Industrial & Engineering Chemistry Research
R Ideal gas constant (=8.314 J/mol-K)
T Temperature (K)
Lowercase Letters
ki Kinetic constant for reaction (i = 1, 2, f, r) (k1: mol/h-gcat,
k2: L/mol-hr, kf,:L/mol-hr, kr: 1/h)
ri Rate of reactions in DIR-BO process (i = 1, 2) (r1: mol/h-
gcat, r2: mol/L-hr)
y Reaction parameter in DIR-BO process (−)
Greek Symbols
α Kinetic parameter for the direct reaction (−)
ρB Bulk density in the reactor (g/L)
ω Reaction parameter in DIR-BO process (−)
γ Reaction parameter in DIR-BO process (−)
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652 DOI: 10.1021/acs.iecr.7b02923

Ind. Eng. Chem. Res. 2018, 57, 639−652