Computers and Chemical Engineering 119 (2018) 85–100

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Computers and Chemical Engineering

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

Development of a plant-wide Dimethyl Oxalate (DMO) synthesis

process from syngas: Rigorous design and optimization
Bor-Yih Yu, Chuan-Yi Chung, I-Lung Chien∗
Department of Chemical Engineering, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 10617, Taiwan

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

Article history: The rigorous design and optimization of a complex, plant-wide dimethyl oxalate (DMO) synthesis pro-
Received 22 January 2018 cess from syngas is firstly developed in this work. The whole process can be roughly divided into two
Revised 2 June 2018
sections. The first one is to produce DMO through the coupling reaction, in which CO is reacted with
Accepted 17 August 2018
the intermediate, methyl nitrite (MN). This section includes the production, and also the purification of
Available online 23 August 2018
DMO. The second one is the regeneration reaction to get back MN through a packed column reactor,
Keywords: which is simulated as a modified version of reactive distillation column. After the basic design, system-
Process design atic optimization is investigated through minimizing total annual cost, and the potential heat integration
Optimization strategy is also proposed. During optimization, we found that the methanol circulation rate inside the
Dimethyl Oxalate process is the most influential variable, and a higher methanol flow rate (defined as MeOH/NOs) within
Coupling reaction an acceptable region leads to better economic performance.
Regeneration reaction
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction occurs. Because MN is an intermediate in this reaction pathway,

the used MN is regenerated through the second reaction section
Dialkyl oxalates act as an important intermediate for producing by reacting NO with methanol and oxygen. For continuous opera-
ethylene glycol (EG) indirectly from syngas, which has been con- tion, the consumption rate in coupling reaction and the formation
sidered an environmentally benign process. Ethylene glycol (EG), rate of MN in regeneration reaction should be identical. This is a
the simplest di-alcohol, can be widely used as antifreeze, precursor critical consideration in this DMO synthesis process. The reaction
to polymers, as well as heat transfer agent and solvent. The indi- equations of coupling, regeneration, overall reaction, and side re-
rect syngas-to-EG process has received lots of attention because of action are illustrated in Eqs. (1)–(4), respectively (Ji, 2010; Ji et al.,
two advantages comparing with conventional process through hy- 2010; Liu et al., 2010b; Song et al., 2013).
dration of ethylene oxide (EO). Firstly, syngas is a relatively cheaper
coupling-reaction
raw material which can be derived from coal, biomass, or natu- 2CO + 2MN → DMO + 2NO (1)
ral gas. Secondly, the per-pass conversion in syngas-to-EG process
is much higher than that of conventional process. Because of the
above-mentioned reasons, the syngas-to-EG process has received regeneration-reaction
keen interests in the research field recently. Among the dialkyl ox- 2MeOH + 2NO + 0.5O2 → 2MN + H2 O (2)
alates, dimethyl oxalate (DMO) has received the most attention.
This is because one of its reactant, methyl nitrite (MN), is more overall−rxn
thermally stable compared with other nitrites required for produc- 2CO + 2MeOH + 0.5O2 −−−−−−→ DMO + H2 O (3)
ing different corresponding oxalates. (Jiang et al., 2012; Li et al.,
2004; Gao et al., 2011; Zhu et al., 2012; Yue et al., 2012) side−rxn
The DMO production process from syngas consists of two re- CO + 2MN −−−−−→ DMC + 2NO (4)
action sections. The first one is to generate DMO through the cou-
The coupling reaction is a catalytic, vapor-phase reaction. It
pling reaction, in which CO in syngas is reacted with methyl nitrite
is typically aided by the palladium-based catalysts. Several re-
(MN) to form dimethyl oxalate (DMO) along with nitric oxide (NO).
searchers discussed the preparation of the catalyst for this reac-
Besides, a side reaction to produce dimethyl carbonate (DMC) also
tion (Zhao et al., 2004, 2005; Ji et al., 2009; Peng et al., 2014;
Peng et al., 2015; Xu et al., 2013; Wang et al., 2016), and also de-
∗
Corresponding author. veloped the reaction kinetics (Ji, 2010; Ji et al., 2010; Song et al.,
E-mail address: ilungchien@ntu.edu.tw (I.-L. Chien). 20 07; Tan et al., 20 08). Generally, the proposed kinetic expressions

https://doi.org/10.1016/j.compchemeng.2018.08.025
0098-1354/© 2018 Elsevier Ltd. All rights reserved.
86 B.-Y. Yu et al. / Computers and Chemical Engineering 119 (2018) 85–100

addressed some novel ideas to improve the process performance,

Nomenclature such as the application of different reactor units, possible different
configurations of the process, the related reaction conditions and
Acronyms so on can also be found (Tahara et al., 1984; Crandall et al., 1987;
ASU Air Separation Unit Liu et al., 2013; Zhu et al., 2015; Wang et al., 2015).
CO/MN CO to MN mole ratio in the feed (mol/mol) However, to the best of our knowledge, the complete, rigor-
Ci Distillation column for separation (i = 1–2) ous model and optimization of this process has not been estab-
DMC Dimethyl Carbonate lished yet. Yao provided the conceptual design of the integrated
DMO Dimethyl Oxalate coupling-regeneration process, but with only limited details pro-
EG Ethylene Glycol vided (Yao, 2013). Recently, Pujing Chemical Industry (SHA) Ltd.
FRACCO+MNCO and MN mole concentration in combined established a pilot scale syngas-to-EG plant through the produc-
feed into R-CP (mol%) tion of DMO as the intermediate, and the further research to ex-
HETP Height equivalent to a theoretical plate pand production has been undergoing (Luo et al., 2012). However,
MeOH Methanol most of the information for the real plant remained confidential.
MeOH/NOs Molar Ratio of methanol and NO + NO2 into PCR Therefore, a rigorous, complete process model for this process is in
(mol/mol) need, as it could provide guidance for future research (i.e. scale up,
MN Methyl Nitrite control structure establishment, proposal of energy saving strate-
MSC Methanol Scrubbing Column gies…etc).
NTi Total number of trays (i = 1 or 2) The major contribution of this work is to propose a rigorous
NFi Feed location into the column (i = 1 or 2) steady state model for the plant-wide DMO synthesis process. The
PCR Packed column reactor research contents in this work include design, optimization, and
POLYGEN Poly-generation the potential heat integration strategies. All the details of this work
PSA Pressure swing adsorption are carefully addressed in the following sections. With this rig-
R-CP Coupling Reactor orous simulation study, a flowsheet with better economic perfor-
SA Specific area mance is proposed.
TAC Total Annual Cost (kUSD)
2. Overview of the process
Capital letters
Di Diffusivity of species (i = NO, NO2 ) The overview of the studied syngas-to-DMO process is illus-
Hi Henry’s constant of species (i = NO, NO2 ) trated in this section. All the simulation work is performed in
Ki Adsorption equilibrium constants in coupling reac- ASPEN Plus V8.8, and NRTL-RK is selected as the thermody-
tion (i = 1 to 4) namic model throughout this work. The components included in
Pi Partial pressure for different species (i = CO, MN,NO, this work are dimethyl oxalate (DMO), water, methanol (MeOH),
O2 , NO2 ) dimethyl carbonate (DMC), methyl nitrite (MN), nitric oxide (NO),
Tc-C2 Condenser temperature at C2 nitric dioxide (NO2 ), Argon (Ar), hydrogen (H2 ), carbon dioxide
RMeOH Methanol recovery from PCR overhead vapor into (CO2 ), oxygen (O2 ), nitrogen (N2 ) and carbon monoxide (CO). All
flash liquid the required binary interaction parameters are included in Table 1.
Lower case letters For the binary pairs not mentioned, ideal behaviors were assumed.
h Reactor bed height Besides, Henry’s law is used to express the dissolution of non-
k1 Pre-exponential factor of coupling reaction condensed gas into liquid. As addressed previously, one critical
ri Rate of reactions (i = MN, NO, REG) point for continuous operation of this process is to make sure that
࢞p Pressure drop inside the reactor (pascal) the consumption rate of MN in coupling reaction section and its
formation rate in regeneration section are identical. From the view
Greek symbols point of process simulation, this is taken into consideration by con-
ρs density of solid particle (kg/m3 ) necting the recycle streams. The detailed design and operation of
ρg density of gas (kg/m3 ) these two sections are illustrated in later part of this paper.
ε Void fraction inside reactor After the steady state simulation is completed, optimization
work is performed to find a set of optimal design and operating
were in Langmuir-Hinshelwood type. However, the proposed kinet- variables based on minimization of total annual cost (TAC). Items
ics varied in forms, which shows that there has still been no agree- to calculate TAC include capital cost and operating cost. For evalu-
ment in the reaction mechanism. ating the TAC, the calculation bases suggested by Luyben are used
On the other hand, MN regeneration is a non-catalytic reaction (Luyben, 2011). The equation to calculate TAC can thus be illus-
that occurs at the interface of gas and liquid. There were also con- trated as following Eq. (5), in which the payback period is assumed
tributions in literature which investigated the appropriate reaction to be three years.
condition and kinetics of regeneration reaction. In a recent study, Capital Cost
Liu et al. developed the kinetic expression from their experiment TAC(kUSD/yr ) = + Operating Cost (5)
Payback Period
in a double-stirred cell reactor (Liu et al., 2010b). Their kinetics was
based on the two-film theory with the feeding rates of NO and O2 3. Process development
at stoichiometric ratio. The interested reaction temperature was in
the range of 278–298 (K). In another recent study, Li et al. devel- 3.1. Background and settings in CO coupling reaction
oped another kinetic expression based on the two-film theory at
the temperature between 298 and 318 (K) (Li et al., 2013). Then In CO coupling reaction, CO and MN is reacted to form DMO
they simulated the reaction performance in a numerical packed and the side product DMC. In a recent work by Ji, the reaction
bubble column reactor model, and validated their simulation re- mechanism and operating conditions were carefully investigated,
sults by sets of experiments in a semi-continuous packed bub- and the kinetic parameters were obtained (Ji, 2010). Therefore, this
ble column reactor. Apart from these two papers, patents which work is selected as the basis of our study.
 B.-Y. Yu et al. / Computers and Chemical Engineering 119 (2018) 85–100 87

Table 1
Thermodynamic parameters in this work (NRTL-RK model).

Comp i DMO DMC MEOH MEOH MEOH DMO

Comp j H2O H2O H2O DMC DMO DMC
Temperature units C C C C C C
Source APV84 LLE-ASPEN NISTV84 NIST-RK APV84 VLE-RK NISTV84 NIST-RK NISTV84 NIST-RK NISTV84 NIST-RK

AIJ −232.3835 5.55738 −2.626 −0.0263 0.986219 −0.1798

AJI −456.4741 −3.3834 4.8241 −1.12624 0.0394066 3.8737
BIJ 12859.6514 −795.715 828.3871 37.9427 0 −195.022
BJI 22864.8848 1513.89 −1329.5435 809.727 0 −737.516
CIJ 0.2 0.337368 0.3 0.1 0.5 0.5

Table 2
Information of reaction and kinetics.

Kinetic parameters

Pre exponential factor (kmol/kgcat-s/atm2 ) Activation energy (kJ/kmol)

k1 6.5983 × 1013 119305

Equilibrium Constant

Pre exponential factor (atm−1 ) Adsorption energy (kJ/kmol)

K1 9.69 × 10−1 11308

K2 4.90 × 10−3 28944
K3 6.44 × 10−2 12290
K4 6.07 × 10−16 125300

ri = [kmol/kgcat-s].

In Ji’s work, a series of sensitivity test on the reaction condi-
tions (temperature, CO to MN feed ratio and residence time) were
performed, and two critical points in designing the coupling reac-
tion to form DMO were pointed out. Firstly, MN undergoes self-
dissociation at the temperature higher than 140 ( °C). The prod-
ucts from self-dissociation are methanol, acetaldehyde, and NO.
Because higher temperature benefits the reaction rate, the upper
limit of temperature implies that temperature control should be
very important. Secondly, MN undergoes catalytic dissociation to
form methyl formate, methanol, water and NO. MN competes with
CO for the active sites on the catalyst, thus MN should not be in
excess in order to inhibit the catalytic dissociation reaction. How-
ever, if CO is in too much excess, it overly occupies the active site,
and causes reaction rate to become lower. Thus, Ji suggested that
the optimal range of CO to MN molar ratio in the feed (CO/MN)
should be in between 1 and 2. With proper selections on reaction
conditions, the undesired MN self-dissociation and catalytic disso-
ciation can be effectively inhibited.
Comparing with the side products from MN dissociation, DMC
is much greater in amount. However, the yield of DMC revealed
slight change with varying temperature, CO/MN, and space velocity
in the reasonable ranges. Although the existence of DMC cannot
be ignored, the selectivity of DMO and DMC was generally very
high (larger than 40). Thus, the coupling reaction still favors the
production of DMO.
Besides, because of the explosive nature of MN, its composition
inside the reactor should also be carefully considered. According to
literature, nitrogen or carbon dioxide can be fed into reactor with
the reactants to serve as diluent. Considering both the safety of
the reactor and the fact that too much inert components lower
C H3 OH + N2 O4 ↔ C H3 ON O(MN ) + HN O3
the reaction rate and increase the system loading, the combined
composition of CO and MN (FRACCO+MN ) should be better in the
range between 30 and 40 mol% (Chen, 1995; Tahara et al., 1984; C H3 OH + O2 ↔ 2HCH O + H2 O
Meng et al., 2004; Yao, 2013). The kinetic expression of coupling
reaction to form DMO provided by Ji et al is illustrated as Eq. (6) in
the following. C H3 OH + N O2 ↔ HCH O + NO + H2 O
The unit of reaction rate is originally in mol/m3 -cat/s, and it is
transferred to be kmol/kg-cat/s in this work in order to be used
in Aspen Plus. In order to fit the original experimental data better,
some of the parameters in Eq. (6) are re-regressed in MATLAB. All
the parameters for this expression are recorded in Table 2. Besides,
the formation rate of DMC was not provided in this expression,
and it is reasonably assumed to be one-forty fifth of the DMO pro-
duction rate throughout the reactor. Also, the self-dissociation and
catalytic dissociation of MN is ignored in this reaction system due
to the low quantity.
3.2. Background and settings in regeneration reaction
The regeneration reaction is to react NO with the added
methanol and oxygen to form MN. However, according to litera-
ture, the reactions involved are quite complicated, including many
sequential and parallel reactions (Li et al., 2013; Liu et al., 2013),
as the following:
2NO + O2 ↔ 2N O2 (7a)
N O2 + NO ↔ N2 O3 (7b)
2C H3 OH + N2 O3 ↔ 2C H3 ON O(MN ) + H2 O (7c)
2N O2 ↔ N2 O4 (7d)
(7e)
(7f)
(7g)

In the reaction network, Eqs. (7a)–(7c) are the desired reactions

k1 PMN PCO to form MN, while Eqs. (7d)–(7g) are the undesired side reactions
rMN = 2
(6)
(1 + K1 PCO + K2 PCO 3 MN + K4 PNO )
2 +K P to form the caustic nitric acid (formula: HNO3 ) and formaldehyde
88 B.-Y. Yu et al. / Computers and Chemical Engineering 119 (2018) 85–100

(formula: HCHO). Essentially, among the desired and undesired re- Table 3
Parameters required in regeneration reaction.
actions, the key components are N2 O3 and N2 O4 , respectively. Thus
in operation, it is designed to enhance the reaction (7b), and in the Henry’s constant (bar) In form of: ln(Hi ) = A + B/T
meantime to inhibit reaction (7d). The undesired reactions can be A B
effectively inhibited by selecting the suitable operating conditions.
HNO 8.55 −918.76
Firstly, moderate temperature (30–45 °C) and pressure (around nor- HNO2 10.90 −1275.80
mal pressure) are required for this reaction network. This is be- HMN 9.92 -2133.90
cause low temperature and high pressure favor the equilibrium of
Diffusivity (cm2 /s) In form of: ln(Di ) = A + B/T
reaction (7b). Secondly, the methanol to NO feed ratio should be in
excess to suppress the formation of N2 O4 . Generally, the methanol A B
concentration should be kept at above 70 wt% for this purpose. NO −5.1955 1428.1
Note that the formation of MN always accompanies with forma- NO2 −5.0138 1428.1
tion of water, which dilutes the methanol concentration in the re-
actor. However, the unreacted methanol is separated with water in
a following distillation column. Hence, methanol should not be in
too much excess in order to avoid wasting energy. Also, an overly-
into Aspen Plus in unit of pressure. Besides, the henry’s constant
high methanol concentration accelerates the side reactions. A suit-
between MN and methanol is also needed for describing the sep-
able range of methanol to NO feed ratio is in between 1.5 and 2.2,
aration performance, and it was referenced from Liu et al. in this
as suggested in literature (Liu et al., 2013). The feed molar ratio
work (Liu et al., 2010a). Because the solubility of MN into methanol
between NO and O2 (NO/O2 ) is also important. From the view-
is very small, it is possible to separate these two components by
point of inhibiting the formation of undesired N2 O4 and reaction
condensing the methanol.
to form formaldehyde, and to maximize the reaction conversion,
Based on the above-mentioned characteristics of the regener-
NO/O2 should be large. However, if the remaining NO is sent back
ation reaction, it is not suitable to simulate the regeneration re-
with MN into coupling reactor (R-CP), it will cause the coupling
actor into a plug-flow reactor (module “RPLUG”) in Aspen Plus.
reaction to become slower. Thus, the optimal NO/O2 is at around
Instead, a packed column reactor with packing inside to provide
stoichiometric ratio (=4) from the process understanding. In addi-
large amount of gas-liquid interface and a counter-current flow
tion, due to the explosive nature of MN, nitrogen is often used as
type is more suitable. Thus, this can also be viewed as a modified
inert in the reactor for safety concerns.
version of reactive distillation process, which is a conventionally,
By combining Eqs. (7b) and (7c), we can get the following
widely-used process intensification technique to reach high con-
Eq. (8) to express the reactions which produces MN and water
version for those liquid-phase, equilibrium-limited reactions. The
from methanol, NO, and NO2 :
design, control, optimization, and different reaction configuration
2C H3 OH + N O2 + NO ↔ 2C H3 ONO + H2 O (8) of various reactive distillation process can be extensively found
Note that the overall regeneration reaction mentioned in in literature (Cao et al., 2017; Chua et al., 2017; Harvianto et al.,
Eq. (2) can then be obtained by further combining Eqs. (7a) and 2017; Kaewwisetkul et al., 2017; Shi et al., 2017; Zang et al., 2017;
(8). Norkobilov et al., 2017). In most of those studies, the built-in mod-
In this work, the rate expression of NO oxidation reaction is ule RADFRAC in Aspen Plus can successfully describe the perfor-
cited from Pradhan et al. (1997), which is listed as in Eq. (9). On mance of a reactive distillation column. So here in this work, RAD-
the other hand, the rate expression of regeneration reaction is cited FRAC unit is also selected to express the packed bed reactor for
from Li et al. (2013), and is listed as in Eq. (10). Because the re- simulation purpose. Note that there is a distinct difference of this
generation reaction occurs on the interface of gas–liquid, this set packed column reactor from the conventional reactive distillation
of reaction kinetic was derived from their experimental data in a column. In this process, the regeneration reaction occurs at the
packed bubble column reactor using two-film theory. These com- gas-liquid interface, in which the reaction holdup should be spec-
plicated rate expressions were established with the aid of Fortran ified based on the area of the interface. The simulation study of
subroutine in this study. this kind of reactive distillation process has also been scarce in the

1 652.1
 literature.
rNO = − 4.747 PO2 PNO 2 (9) The simulation of packed column is described in detail here.
RT T Firstly, it is modelled as a column with equilibrium stages, and
then we assume a reasonable height equivalent to a theoretical
PNO2
rREG = plate (HETP) to a single stage. After that, pressure drop and col-
HNO2
  23725  P 
umn diameter can be estimated by the built-in “packing sizing”
  NO DNO2 PNO2 and “packing rating” functions. In this work, the authors assume
DNO2 3.7×107 exp − − CMeOH (10) that the column is packed with 1-mm Raschig ring randomly. The
RT HNO 3DNO HNO2
surface area for packing is 220 (m2 /m3 ), the void fraction of this
The unit of rNO is kmol/m3 /s, and the unit of rREG is in
packed column is 0.92, and the HETP is 2 ft. Because the unit of
mmol/cm2 /s. Pi is the partial pressure of components (i = O2 , NO,
reaction is in an area-based unit, thus the reaction holdup should
and NO2 ), while Hi and Di are the henry’s constant and diffusivity
be the actual gas-liquid contacting surface area that the packing
of the species (i = NO and NO2 ). For the remaining notations, CMeOH
provided. The reaction holdup can be calculated by the following
is the methanol concentration, R is the ideal gas constant, and T is
Eq. (11):
temperature in unit of K.
In Li et al.’s work, henry’s constant and diffusivity were listed
in temperature range of 298–318 (K), thus the expressions can be Holdup(area2 ) = π /4 (DIAM )2 (HEP T )(SA )(1 − V OID ) (11)
obtained by simple regression (Li et al., 2013). All the parame-
ters required in Eqs. (9) and (10) are listed in Table 3. Note that
in the original work by Li et al, the Henry’s constants were re- Where DIAM is column diameter in meter, SA is specific surface
ported in unit of kPa-cm3 /mmol. Therefore some necessary conver- area of the packing in m2 /m3 , and VOID is the dimensionless void
sion should be made, as the Henry’s constants can only be input fraction inside the packed column.
 B.-Y. Yu et al. / Computers and Chemical Engineering 119 (2018) 85–100
Fig. 1. Optimized flowsheet of DMO synthesis process.
4. Steady state process design
The process flowsheet with the optimized result is illustrated
in Fig. 1. The optimization of this process is discussed in later
Section 5. The fresh feed is assumed based on our previous poly-
generation work, with 10% of total amount of syngas sent to the
EG production process (Yu and Chien, 2015). The Syngas-to-EG pro-
cess is a dual-staged process, with formation of DMO as in the first
stage, and hydrogenation of DMO to EG in the section stage. Note
that hydrogen causes the deactivation of coupling catalyst in the
first stage, and CO causes the deactivation of hydrogenation cata-
lyst in the second stage. Thus, the raw syngas is separated by a
pressure swing adsorption (PSA) process to become three streams.
One is the 99.99 mol% CO stream (remaining: H2), another one is
the 99.99 mol% H2 stream (remaining: CO), and the other one is
the tail gas stream. The recovery of each component in this PSA
unit is set to be 90%. (Peking University Pioneer Co., 2016) After
that, the CO stream is assumed to undergo selective oxidation to
become hydrogen-free, and is sent to DMO synthesis process. From
calculation, the fresh CO feed is 256.3 (kmol/h), with 99.88 mol%
purity and the remainder to be water.
The fresh CO feed is first mixed with fresh nitrogen and the
MN-rich gas recycled from regeneration section to become a com-
bined feed, then is preheated and sent to the coupling reactor (R-
CP). As discussed in Section 3.1, the CO to MN feed ratio (CO/MN)
is set at 1.5, and the total composition of CO and MN (FRACCO+MN )
is set at 0.4 in the combined feed. Considering the exothermic
89
nature of coupling reaction and the narrow range of feasible op-
erating temperature as discussed previously, fluidized-bed reac-
tor is better to be adopted. A fluidized-bed reactor has proper-
ties such as being able to reach high conversion, having good
heat removal ability, and providing a near-uniform temperature
inside (Soundararajan et al., 2001; Alwahabi and Froment, 2004;
Turton et al., 2008; Yu and Chien, 2016; Chang et al., 2013). Hence,
it is especially suitable for the coupling reaction.
In order to simplify the simulation of reactor without losing the
capability of qualitatively illustrating the reaction performance, an
isothermal plug flow reactor (RPLUG module) is assumed here in
this work. Under this mode in Aspen Plus, the heat duty which
should be removed to operate the reactor at the targeted temper-
ature will be calculated. For the pressure drop of this tubular re-
actor, Eq. (12) was used based on the fact that the fluidized-bed
reactor is operated in the fluidized or bubbling region in which
the gravity force of solid equals to the drag force.
p = g(ρs − ρg )(1 − ε )h (12)
Where ࢞p is the pressure drop in pascal, g is gravitational ac-
celeration in m/s2 , ρ s is the density of solid particle in kg/m3 , ρ g
is the density of gas in kg/m3 , ε is the void fraction inside the bed
(-), and h is the bed height in meter.
In designing the fluidized-bed reactor, the catalyst density is as-
sumed as 880 (kg/m3 ), and the bed voidage inside the reactor is
0.6. The pressure of reactor is set at 2.5 bar. Considering that high
temperature enhances the reaction rate, thus the reactor tempera-
ture is set at 135 °C, at which self-dissociation and catalytic disso-
90 B.-Y. Yu et al. / Computers and Chemical Engineering 119 (2018) 85–100
1.0
0.9 DMC
DMO
0.8
Recovery
0.7
0.6
0.5
0.4
0.3
0 20 40 60 80 100 120 140
MeOH inlet flowrate (kmol/hr)
Fig. 2. Sensitivity analysis on DMO and DMC recovery with varying MeOH flow
rate.
ciation of MN can be ignored. Beside, due to the exothermic nature
of coupling reaction, large amount of waste heat can be generated
from the reactor. The steam at pressure of 15 psig (2 bar, 121 °C)
is assumed to be generated from the waste heat, and then applied
in downstream C2 as heat source in reboiler (Douglas, 1988). This
heat management can also be graphically found in Fig. 1.
The reactor outlet is then heat-exchanged with the combined
feed to become partial vapor-liquid, and then further cooled to
47 °C by using cooling water in an auxiliary cooler. This cooled re-
actor outlet stream is then separated in an adiabatic flash unit to
condense most of the product DMO in liquid stream. Apart from
DMO, part of the side product DMC is also condensed in liquid
stream. As illustrated in Fig. 1, about 97% DMO and 51% DMC in
the cooled reactor outlet is condensed by flash unit. Because there
is still small amount of DMO left in vapor stream, this stream is
then sent to a methanol scrubbing column (MSC) which methanol
is used to scrub the remaining DMO. The reason for adopting MSC
is because DMO solidifies under room temperature, and may de-
posit on the wall, finally leads to plugging.
Scrubbing DMO using methanol may also recover DMC at the
same time. In literature, it was suggested that DMC should also
be almost totally scrubbed by methanol with DMO. Then the
methanol-DMO-DMC mixture is further separated in a downstream
column, in which DMO comes out as the bottom product, the
DMC and methanol comes out as the liquid distillate, and the non-
condensed light gases comes out as vapor distillate. The liquid dis-
tillate is sent to a further purification process to separate methanol
and DMC. Because methanol and DMC forms a minimal boiling
azeotrope, thus some advanced separation techniques, like pres-
sure swing distillation or extractive distillation, should be applied
(Hsu et al., 2010; Wang et al., 2010; Zhang et al., 2017).
However, scrubbing DMO is much easier than scrubbing DMC.
A simple sensitivity test is illustrated in Fig. 2. In this test, the
condenser temperature for MSC is set at 15 °C, which is the low-
est temperature allowed for using chilled water as cooling source.
From this figure, it is clear that a far large amount of methanol
flowrate is needed to completely scrub DMC, and it will be un-
economical to separate these components. Note that when inlet
methanol flowrate is at zero, the DMO recovery is already close to
perfect, while DMC recovery is at about 33%. This is because there
is fair amount of methanol in the reactor outlet. This methanol
content is condensed in the MSC condenser, and is served as scrub-
bing agent. From the sensitivity test, it shows that the circulated
methanol is adequate for scrubbing almost all DMO in MSC un-
der a certain condenser temperature. It also illustrates that the
methanol amount circulated in the process has critical influence
throughout the system, which affects the required total number of
trays, and also the condenser temperature in MSC under a given
DMO recovery. Because of very little DMC amount in this system,
it is assumed that no extra methanol enters MSC for enhancing
scrubbing performance on DMC. In this part, the condenser tem-
perature of MSC was adjusted to let DMO recovery to reach 99.99%,
and with no additional specification on DMC recovery.
The bottom stream from MSC is combined with the liquid out-
let stream in flash unit, and is sent to a downstream column (C1)
for further separation. C1 is a regular distillation column equipped
with a partial-vapor condenser, with two degrees-of-freedoms to
be determined. There are two product streams in this column. The
bottom stream is the DMO product, and is send to second stage
(hydrogenation) of this syngas-to-EG process. The vapor distillate
160 contains methanol, DMC, and some light gases. For the degrees-of-
freedoms, reflux ratio and reboiler duty are adjusted to let DMO
product purity to be 99.99 mol% and recovery to be 99.99% at the
bottom. According to two US patents, to recover DMC from this
stream may be uneconomical. Instead, it can be sent to a hydroly-
sis reactor, which converts DMC to methanol (Tahara et al., 1984;
Crandall et al., 1987). Methanol from the hydrolysis reactor can be
recycled back into the DMO production process. This further treat-
ment part is beyond the scope and is not discussed in this paper.
The vapor stream from MSC, majorly contains NO, MeOH, un-
reacted MN, CO, and inert species, is sent to regeneration reaction
section. Before entering, a slight amount of this stream is purged
in order to avoid the accumulation of inert. Because this purge
stream contains NO, a large purge flowrate leads to greater amount
of NO makeup flowrate in order for continuous operation. Thus,
this purge ratio is reasonably set at 1%. After that, the major por-
tion of the vapor stream is then mixed with oxygen and makeup
NO stream, and is sent to the packed-column reactor (PCR).
The purity of the fresh oxygen stream feeding into the PCR is
assumed to be 99 mol% O2 and the remaining to be Argon (Yu and
Chien, 2015). The amount of oxygen is added so that NO to O2
mole ratio in the mixture is 4.0. The NO makeup stream mentioned
in the previous paragraph is also fed into the PCR. According to lit-
erature, this NO stream can be obtained by the oxidation of liquid
ammonia under normal pressure and high temperature (typically
80 0–90 0 °C) (Hickman and Schmidt, 1991; Schmidt et al., 1994).
The reaction is aided by gauze catalyst in an environment with ex-
cess oxygen. The NO production process is beyond the scope of this
work and is not further investigated.
As mentioned in the previous section, PCR is modeled using
the built-in RADFRAC module, and the kinetic expression of re-
generation reaction is described by the Aspen Fortran Subroutine.
The combined vapor stream is fed to PCR from the bottom, while
methanol is fed from top. Originally, the reaction environment in
PCR is characterized by the molar ratio of methanol (including
fresh feed and recycle stream) to NO. However, NO2 forms dur-
ing regeneration reaction by the oxidation of NO, and there is
some NO2 not reacted in PCR and exists throughout the process.
Thus, the reaction environment in PCR should be determined as
the molar ratio of total methanol to the summation of NO and
NO2 . This variable was named MeOH/NOs. In the optimized flow-
sheet in Fig. 1, MeOH/NOs is at 2.1. In this study, PCR is operated
under pressure of 1.5 (bar), and the reactions are assumed to oc-
cur throughout the column. The generated MN comes out from the
overhead vapor along with other gaseous components and some
amount of methanol. This stream is then condensed, and flashed
to achieve vapor-liquid separation. The vapor stream from the flash
unit is compressed and recycled to R-CP, while the liquid stream is
sent back to PCR as a reflux. In PCR condenser, the outlet tem-
perature is an important variable because it determines how much
portion of methanol not condensed from the overhead vapor, and
is recycled back into R-CP. The amount of methanol recycled is im-
 B.-Y. Yu et al. / Computers and Chemical Engineering 119 (2018) 85–100 91

(a) (b) (c)

46.0
100 Conversion Temperature MeOH
0.95
45.8
90
45.6 0.90
80

Methanol (wt. frac.)

Temperature (C)
45.4
Conversion (%)

70 0.85
45.2
60 0.80
45.0

50 44.8
0.75
40 44.6

30 44.4 0.70

0 2 4 6 8 10 0 2 4 6 8 10 0 2 4 6 8 10
Height (m) Height (m) Height (m)
Fig. 3. Conversion, temperature and methanol concentration profile inside PCR.

portant for the performance in MSC, as mentioned previously. Thus other degree-of-freedom to be specified, and this value is deter-
this temperature should be determined by optimization, and is fur- mined based on optimization. Note that as the methanol purity is
ther discussed in Section 5. not specified to be ultra-high, as the energy consumption increases
From the previous section, the design of PCR has to meet some with higher targeted purity. It is suggested by open literature that
requirements. The design results are collected from Fig. 3(a) to 95–98 mol% is suitable in this situation, and 95 mol% is selected in
(c). Fig. 3(a) illustrates the conversion profile in PCR, with the this work (Tahara et al., 1984).
height of PCR calculated from bottom to top. Because PCR is mod-
eled by specifying the number of equilibrium stages and HETP, the
5. Process optimization
height is calculated by the multiplication of them. Those points in
Fig. 3(a) represent the average values within a given stage. As the
5.1. Overview of optimization
result reveals, the conversion increases quickly as height goes up
initially, and the increment become less as the height increases.
The first step of optimization is to identify and to categorize
This is because the amount of NO and NO2 become less in the
the variables. Table 4 lists all the variables which need to be deter-
higher portion of the PCR. However, in order to react NO more
mined in the process. In this table, the variables are categorized
efficiently and to avoid NO and O2 recycle back to R-CP, 15 equi-
into three types, Fixed Variables (FVs), Adjusted Variables (AVs)
librium stages (equivalent to 9.14 m of packing) are used to make
and Optimization Variables (OVs). FVs are those variables fixed
the conversion of NO reach 97%. Fig. 3(b) illustrates the temper-
at given values based on overall process understandings. AVs are
ature profile inside PCR. From the result, the temperature of the
those variables adjusted to reach some specifications, and the ba-
whole column is in the range between 44.4 and 45.8 °C. This is
sis for setting AVs are mostly related to separation performances
consistent with the suggestion that the maximum operating tem-
like purity and recovery. OVs are remaining variables that cannot
perature should be around 45 °C in order not to enhance the un-
be categorized to be FVs or AVs, and are treated as design and op-
desired side reactions. Besides, the variation of temperature is not
erating variables in this system. OVs have distinct features com-
large, which may be concluded from the fact that the regeneration
pared with FVs and AVs. Firstly, they cannot be determined only by
is just slight exothermic in nature. The result in Fig. 3(b) also sup-
overall process understandings, nor can they be limited by given
ports the simplification in the work that modeled the regeneration
constraints. Secondly, the changing of those variables lead to ob-
reactor as a CSTR module. Fig. 3(c) illustrates the composition pro-
vious influences on the process performances, typically in energy
file of methanol inside PCR. Due to the large amount of reaction at
consumption or cost. Thus, they have to be determined through
the bottom part of PCR, there is large amount of water generated,
optimization.
which dilutes the methanol concentration. From this sub-figure, it
Before optimization starts, the calculation of capital and oper-
reveals that methanol concentration is above 70 wt% throughout
ating costs should be clarified. As mentioned previously, the cal-
the column. This is consistent with the assumption that side re-
culation of costs for the major equipment and the required util-
actions (Eq. (7f) to (7 h)) are effectively inhibited and thus are ig-
ity is based on the correlation provided by Luyben (2011). Besides,
nored in this work.
the heat source of C2 reboiler is 15-psig steam generated from
The bottom stream from PCR contains mostly methanol and
the waste heat in R-CP. There is no cost data of steam with this
water, and slight amount of DMC is further separated in another
quality in Luyben’s book. According to Douglas, the cost of steam
downstream distillation column (C2). This column is equipped with
with this quality is at 2.284 (USD/GJ) (Douglas, 1988). Because Luy-
a partial vapor-liquid condenser with three outlet streams, thus it
ben’s correlation is adopted throughout this work, thus this price
has three degrees-of-freedoms to be specified. The vapor distillate
is prorated with high pressure steam cost (at 42 bar and 254 °C)
contains the non-condensed light gases, the liquid distillate is the
provided by Luyben, and with 10% penalty from generating steam.
pure methanol that is recycled to PCR, and the bottom is the aque-
Thus the cost for the 15-psig steam is set at 3.6 (USD/GJ) in this
ous waste. In order to save energy, the specification of liquid distil-
work. If the amount of steam generated exceeds the requirement
late is set at 95 mol% methanol, and the bottom is set at 99 mol%
in C2 reboiler, the remainder is viewed as a bonus from the process
water. Reflux ratio and reboiler duty are adjusted to reach these
with the same price. On the contrary, the industrial low-pressure
two specifications. Condenser temperature of C2 is selected as the
steam (6 bar, 154 °C, unit price = 7.78 USD/GJ) is used to make up
92 B.-Y. Yu et al. / Computers and Chemical Engineering 119 (2018) 85–100

Table 4
Status of variables in this process.

Fixed Variables (FVs)

Sections Variable name Values

R-CP Reactor pressure 2.5 bar

Temperature 135 °C
FEHE Tout =TR - 10 (°C)
CO/MN 1.5
CO + MN 40 mol%
MSC Pressure 2 bar
PCR NT 15
Pressure 1.5 bar
C1 Pressure 1 bar
C2 Pressure 1 bar

Adjusted Variables (AVs)

Sections Variable name Specifications

C1 C1-RR DMO recovery = 99.99% at bottom

C1-Qr DMO purity = 99.99 mol% at bottom.
C2 C2-RR Methanol = 95 mol% at liquid distillate
C2-Qr Water = 99 mol% at bottom

Optimization Variables (OVs)

Sections Variable name Interested range Related limitation

MSC NT-MSC 3–6 (-)

C1 NT1 11–17 (-)
NF1 3–7 (-)
C2 Tc-C2 47–62 (°C) ≥ 47 (°C)
NT2 16–22 (-)
NF2 10–17 (-)
PCR MeOH/NOs 1.5–2.2 1.5∼2.2
RMeOH 0.73–0.85 MeOH > 70 wt% in PCR bottom

the difference in reboiler duty. Last but not least, the cost of cata-
lyst is assumed to be 25 (USD/kg).
It is also important to consider the costs of the raw material
into TAC calculation. In this work, the raw materials used for re-
actions are CO, methanol, NO and O2 . The amount of CO input to
the process is assumed to be identical to all the optimized cases
studied, so that its cost is then ignored. For methanol, there is
a major input (stream MeOH-MKP on Fig. 1), and some possible
loses (streams PUG-1, PUG-2, and PUG-3 on Fig. 1) in the pro-
cess. The major loss is through PUG-1. However, as mentioned
in Section 3, this stream is used for regeneration of methanol,
which is not studied in this work. Therefore, methanol which goes
out through this stream is actually not lost. On the other hand,
losses through PUG-2 and PUG-3 are slight, which can be inferred
from Fig. 1. Hence, the raw material cost of methanol can also
be neglected from calculation of TAC. For oxygen, the required
amount is not much. In this work, we assume that the syngas-
to-EG process is part of a poly-generation process, so the source
of oxygen is from an air separation unit, which is operated at a
large scale. So the raw material cost of O2 can also be reasonably
ignored.
Hence in this study, only the cost for the makeup NO is consid-
ered in the stream cost when analyzing TAC. Because there is no
cost data from open literature, thus the NO cost was set at 3 times
of the cost of the raw material ammonia, to be 0.93 (kUSD/MT).
The way of calculating this makeup cost is first to set a reference
case, and then the makeup flow rate in each other case is sub-
tracted from that in the reference case and then calculate the cor-
responding cost difference. Finally, this cost difference is included
in the operating cost of TAC. Note that although the value of calcu-
lated TAC may be different as the reference case changes, the rel-
ative relationship among cases do not change. Through this way, a
convenient and reasonable analysis can be provided. In the results
of this work, the final optimal point obtained in later Section 5.3 is
selected as the reference point, with all the data already corrected.
5.2. Selection of optimization variables
The whole process contains five major units (R-CP, MSC, C1, PCR
and C2) with a major recycle stream to provide MN to the coupling
reactor (R-CP). Thus in optimization, all these units should be con-
sidered at the same time to account for the interaction behavior
among units. Through the changing of optimization variables, the
recycle stream should be always remained connected. For the pur-
pose of convenience during optimization, the recycle stream from
top of PCR to coupling reaction (stream REC in Fig. 1) was broken,
but with aspen built-in “Transfer” function applied to make the
flowrates, temperature and compositions of two broken streams
identical. Through this way, the essence of connecting the recycle
stream can be retained.
Due to the large amount of variables to be determined, some
preliminary tests were performed to appropriately simplify the op-
timization problem. In R-CP, CO/MN and FRACCO+MN are two im-
portant variables that affect reaction performance. CO/MN affects
the amount of catalyst required for a given targeted reaction con-
version. In the range between 1.5 and 2.0 suggested by litera-
ture (Ji, 2010), the required catalyst amount dropped as CO/MN
increased, which implied that the reaction rate was higher un-
der lower CO/MN value. Thus in this work, CO/MN is fixed at 1.5
throughout the optimization work. Also, FRACCO+MN was suggested
to be in range of 30–40 mol%. From the preliminary analysis, it
reveals that TAC decreases as FRACCO+MN increases. This is be-
cause of the fact that less inert species (nitrogen in this work) is
 B.-Y. Yu et al. / Computers and Chemical Engineering 119 (2018) 85–100 93

circulated inside the system, which leads to lower system load-

ing. Thus, FRACCO+MN was fixed at 40 mol% in the optimization
work.
After the preliminary work, eight variables remain in the op-
timization algorithm. They are namely the molar ratio of MeOH
to NO and NO2 fed into PCR (MeOH/NOs), condenser temperature
in PCR (Tc-PCR ) and in C2 (Tc-C2 ), total number of stages of MSC
(NT-MSC), C1 (NT1), C2 (NT2), and feed location of C1 (NF1) and
C2 (NF2). Among them, MeOH/NOs is the most important one,
as it affects the overall circulation rate of methanol throughout
the system. A large MeOH/NOs makes the scrubbing of DMO eas-
ier, which leads to less cooling duty in MSC condenser. However,
the reboiler duty required in separation may also be increased.
A low MeOH/NOs affects the process in the opposite way. More-
over, the methanol content in PCR is likely to be less than the re-
quired value (70 wt%) for inhibiting the undesired side reaction.
Thus the trade-off resulted from MeOH/NOs is obvious, and this
variable is listed as the outer-most one in the loop for sequential
iteration.
The following variables from outer to inner layer are Tc-C2 ,
Tc-PCR , and NT-MSC in order. The variation of Tc-C2 causes the
trade-off of operating cost and capital cost in C2, and it also af-
fects the performances in PCR. Tc-PCR is also important as it af-
fects the portion of methanol recycled to R-CP and the remaining
to serve as reflux back to PCR. For easier convergence in perform-
ing optimization, Tc-PCR is replaced with MeOH recovery from PCR
overhead vapor to flash liquid (RMEOH ). Essentially, the meanings
of these two variables are in similar ways, as a higher Tc-PCR leads
to a lower RMeOH . Last but not least, NT-MSC affects the perfor-
mance in MSC, majorly in its condenser duty. This is because a
larger NT-MSC makes the recovery of DMO easier and thus less
amount of condensed methanol is required. In addition, it also in-
fluence slightly on PCR, as methanol amount flowing into PCR may
change.
The inner-most variables are NT1, NT2, NF1 and NF2. However,
because the performances of C1 do not affect the performances of
other units, NT1 and NF1 can be optimized independently. From
the overall process understandings mentioned above, the algorithm
for sequential iterative optimization can be established as in Fig. 4.
Generally, those six variables (MeOH/NOs, Tc-C2 , RMeOH , NT-MSC,
NT2 and NF2) are optimized in the first stage. After they are opti-
mized, NT1 and NF1 are optimized sequentially to find the mini-
mized overall TAC.

5.3. Discussions of optimization results

The optimization starts from simulation of a base case operated

under MeOH/NOs = 2.0, Tc-C2 = 47 °C, RMeOH = 0.85, NT-MSC = 5,
NT2 = 18, NF2 = 12, NT1 = 15, and NF1 = 5, without the proposed
heat integration strategy mentioned in Section 3.3. Under this situ-
ation, the heat source required in C2 is totally low pressure stream Fig. 4. Algorithm for sequential iterative optimization in this work.

(6 bar, 7.78 USD/GJ). On the other hand, all of the 2-psig steam re-
covered from R-CP is viewed as the bonus from this process, and
the earning is subtracted from the TAC. The TAC of this case is
3797.5 USD/y. Then, the heat integration strategy is applied with-
out changing any of the design variables, and it is found that 13.5%
reduction in TAC can be obtained. The calculation results are listed
in the first two columns of Table 5. From this calculation, it is con-
cluded that the process can be largely benefited by this simple
heat integration.
Then, the optimization is performed, with the heat-integrated
base case serving as the starting point. The major optimization re-
sults are illustrated from Figs. 5 to 9, while the other detailed re-
sults are included in the appendix. Fig. 5 describes the variation
of TAC (in kUSD) and methanol content at PCR bottom (in wt%)
under different RMeOH from 0.82 to 0.84, Tc-C2 from 47 to 62 (°C),
and NT-MSC from 3 to 5. For investigating Tc-C2 , a 5 (°C) interval
was firstly adopted to take an overall and quick glance at the im-
pact of this variable on TAC. Generally, as Tc-C2 increases, TAC de-
creases first and then increases. For the cases under a low Tc-C2 ,
the capital cost of condenser in C2 is large, because the tempera-
ture difference of distillate and cooling water is quite small. Also,
a larger reboiler duty is required to reach the specification men-
tioned in Table 4. As Tc-C2 increases, the capital cost of condenser
and the utility cost in reboiler both decreases. However, there are
two negative effects from a high Tc-C2 . The first one is that a high
Tc-C2 increases the cooling duty required in PCR condenser, as the
94 B.-Y. Yu et al. / Computers and Chemical Engineering 119 (2018) 85–100

(a) (b)
3240 0.7025
NT-MSC = 3 NT-MSC = 3
3220 NT-MSC = 4 NT-MSC = 4
0.7020
NT-MSC = 5 NT-MSC = 5
3200
0.7015

MeOH (wt%)
TAC (kUSD)

3180
0.7010
3160
0.7005
3140

3120 0.7000

3100 0.6995
46 48 50 52 54 56 58 60 62 64 46 48 50 52 54 56 58 60 62 64
o o
Tc- C2 ( C) Tc- C2 ( C)

(c) (d)
3260 0.708
NT-MSC = 3 NT-MSC = 3
3240 0.707
NT-MSC = 4 NT-MSC = 4
NT-MSC = 5 0.706 NT-MSC = 5
3220
0.705
3200
MeOH (wt%)
TAC (kUSD)

0.704
3180 0.703

3160 0.702
0.701
3140
0.700
3120 0.699
3100 0.698
46 48 50 52 54 56 58 60 62 64 46 48 50 52 54 56 58 60 62 64
o o
Tc- C2 ( C) Tc- C2 ( C)

(e) (f)
3280 0.712
NT-MSC = 3 NT-MSC = 3
3260 NT-MSC = 4 0.711 NT-MSC = 4
NT-MSC = 5 0.710 NT-MSC = 5
3240
0.709
MeOH (wt%)
TAC (kUSD)

3220
0.708
3200 0.707
3180 0.706

3160 0.705
0.704
3140
0.703
46 48 50 52 54 56 58 60 62 64 46 48 50 52 54 56 58 60 62 64
o o
Tc- C2 ( C) Tc- C2 ( C)
Fig. 5. Optimization results at MeOH/NOs = 2.0
(a)(b) TAC and MeOH content under varying Tc-C2 and NT-MSC at RMeOH = 0.82
(c)(d) TAC and MeOH content under varying Tc-C2 and NT-MSC at RMeOH = 0.83
(e)(f) TAC and MeOH content under varying Tc-C2 and NT-MSC at RMeOH = 0.84.
 B.-Y. Yu et al. / Computers and Chemical Engineering 119 (2018) 85–100 95

Table 5
TAC comparison between the base cases (with and without heat integration) and the optimized case.

Capital Cost (unit: kUSD)

Base case (w/o heat integration) Base case (w/ heat integration) Optimized

Reactor 253.0 253.0 252.9

FEHE 125.1 125.1 123.9
MSC 100.9 100.9 84.6
MSC–Cond 142.5 142.5 75.9
C1 100.7 100.7 97.1
C1 Cond 10.7 10.7 14.5
C1 Reb 142.0 142.0 154.6
Cooler 201.3 201.3 214.1
Flash 457.5 457.5 456.3
PCR 318.3 318.3 318.1
Packing 92.4 92.4 92.3
Liq Dist. 9.5 9.5 9.5
PCR Cond 369.5 369.5 265.3
C2 199.1 199.1 186.5
C2 Cond 626.4 626.4 326.9
C2 Reb 300.1 300.1 276.8
Compressor 1818.3 1818.3 1865.0
Operation Cost (unit: kUSD)

Cooling water 61.9 61.9 59.7

Chilled-water 594.2 594.2 613.7
LPS 954.9 0 0
MPS 234.1 234.1 270.8
Electricity 295.4 295.4 304.6
Refrigeration 85.1 85.1 0
Catalyst 362.8 362.8 362.7
NO −17.0 −17.0 0.0
Bonus from steam 529.7 87.9 135.4
Total (unit: kUSD)

Capital 5267.5 5267.5 4814.6

Operating 2041.7 1528.6 1476.1
TAC 3797.5 3284.5 (−13.51%) 3080.9 (−18.87%)

liquid distillate is majorly methanol and is recycled back to the top
of PCR. The second one is that the purge amount in vapor distillate
increases with Tc-C2 . In the purge stream, there is some loss of the
valuable NO which is not reacted in PCR. The penalty of NO loss
from C2 purge cannot be ignored. Those reasons mentioned above
combined to form the trade-off in TAC. And from Fig. 5, it is clear
that the suitable Tc-C2 is likely to be in the range between 52 or 57
(°C). The detailed investigation on TAC in this region is illustrated
later.
Two other trends can also be concluded from Fig. 5. The first
one is that cases of greater RMeOH have higher TAC, and this is
because larger amount of cooling duty is required at PCR con-
denser. However, the requirement of MeOH content higher than
70 wt% cannot be achieved once the RMeOH is too low. Also, a
higher RMeOH implies that less amount of methanol is recycled to
coupling reaction and MSC. Thus, the required condenser temper-
ature in MSC becomes lower under a given DMO recovery, which
increases the cooling duty requirement. The second trend is that
comparing with RMeOH , NT-MSC has a relatively small impact on
TAC.
Fig. 6 describes the variation of TAC (in kUSD) and methanol
content at PCR bottom (in wt%) at different RMeOH from 0.77 to
0.79, Tc-C2 from 47 to 62 (°C), and NT-MSC from 3 to 5 under
MeOH/NOs = 2.1. The major conclusions obtained from Fig. 5 re-
tains in Fig. 6, but with lower optimal RMeOH than that un-
der MeOH/NOs = 2.0. The reason is due to the larger amount of
methanol existed in PCR, which directly reduces the cooling utility
required in MSC under the same DMO recovery, and also relieves
the limitation to maintain the methanol concentration at above
70 wt% in the process. Moreover, both of the optimal RMeOH under
MeOH/NOs = 2.0 and 2.1 occur at the boundary. Once the RMeOH
becomes even lower, the methanol concentration of 70 (wt%) can-
not be satisfied.
Fig. 7 describes the variation of TAC (in kUSD) and methanol
content at PCR bottom (in wt%) at different RMeOH from 0.73 to
0.75, Tc-C2 from 47 to 62 (°C), and NT-MSC from 3 to 5 under
MeOH/NOs = 2.2. The major conclusions are again similar to those
obtained from Fig. 5. However, a distinct difference comparing
with cases under MeOH/NOs = 2.0 and 2.1 is that the optimal point
is no longer at the boundary. This means that under this situ-
ation, the amount of methanol circulated in the process is rela-
tively abundant, which does not tend to let the MeOH concentra-
tion lower than the constrained value during optimization.
For the above-mentioned three cases, the detailed information,
including the TAC and the methanol concentration, is listed from
Table A1 to A3, while the optimization results for NT1, NT2, NF1,
NF2 under each MeOH/NOs are illustrated from Fig. A1 to A6.
As mentioned earlier, it is also found that for the optimal cases
under MeOH/NOS at 2.0, 2.1, and 2.2, the TACs at Tc-C2 = 52 and
57 (°C) are at the relative low points, and are very close. Hence, a
deeper look into this region is necessary. The TAC calculation re-
sults between Tc-C2 = 52 and 57 (°C) under each MeOH/NOS with
the optimal RMeOH are listed in Fig. 8(a)–(c). From these results, it
is found that the optimal Tc-C2 is at 54 °C, although the variation is
still not very large.
For even lower MeOH/NOs value, such as 1.9, it becomes more
difficult to satisfy the constrained 70 wt% of MeOH composition. As
there is now less MeOH inside PCR, the PCR condenser should be
operated under a much lower temperature in order to condense
more MeOH back into PCR. This leads to the need of the higher
96 B.-Y. Yu et al. / Computers and Chemical Engineering 119 (2018) 85–100

(a) (b)
3240 0.7045
NT-MSC = 3 NT-MSC = 3
3220 NT-MSC = 4 0.7040 NT-MSC = 4
NT-MSC = 5 NT-MSC = 5
3200 0.7035

3180 0.7030
TAC (kUSD)

MeOH (wt%)
3160 0.7025

3140 0.7020
0.7015
3120
0.7010
3100
0.7005
3080
46 48 50 52 54 56 58 60 62 64 46 48 50 52 54 56 58 60 62 64
o o
Tc-C2 ( C) Tc-C2 ( C)

(c) (d)
3260 0.712
NT-MSC = 3 NT-MSC = 3
3240 0.711 NT-MSC = 4
NT-MSC = 4
3220 NT-MSC = 5 0.710 NT-MSC = 5

3200 0.709
MeOH (wt%)
TAC (kUSD)

3180 0.708
3160 0.707
3140 0.706
3120 0.705
3100 0.704
3080 0.703
46 48 50 52 54 56 58 60 62 64 46 48 50 52 54 56 58 60 62 64
o o
Tc-C2 ( C) Tc-C2 ( C)

(e) (f)
3280
NT-MSC = 3 0.715 NT-MSC = 3
3260 NT-MSC = 4 NT-MSC = 4
NT-MSC = 5 0.714 NT-MSC = 5
3240
3220 0.713
MeOH (wt%)
TAC (kUSD)

3200 0.712
3180 0.711
3160 0.710
3140
0.709
3120
0.708
3100
46 48 50 52 54 56 58 60 62 64 46 48 50 52 54 56 58 60 62 64
o o
Tc-C2 ( C) Tc-C2 ( C)
Fig. 6. Optimization results at MeOH/NOs = 2.1
(a)(b) TAC and MeOH content under varying Tc-C2 and NT-MSC at RMeOH = 0.77
(c)(d) TAC and MeOH content under varying Tc-C2 and NT-MSC at RMeOH = 0.78
(e)(f) TAC and MeOH content under varying Tc-C2 and NT-MSC at RMeOH = 0.79.
 B.-Y. Yu et al. / Computers and Chemical Engineering 119 (2018) 85–100 97

(a) (b)
0.7095
3280 NT-MSC = 3 NT-MSC = 3
NT-MSC = 4 NT-MSC = 4
3260 NT-MSC = 5 0.7090 NT-MSC = 5

3240

MeOH (wt%)
TAC (kUSD)

0.7085
3220

3200 0.7080

3180
0.7075
3160

3140 0.7070
46 48 50 52 54 56 58 60 62 64 46 48 50 52 54 56 58 60 62 64
o o
Tc-C2 ( C) Tc-C2 ( C)

(c) (d)
3280 0.7130
NT-MSC = 3 NT-MSC = 3
3260 NT-MSC = 4 NT-MSC = 4
NT-MSC = 5 NT-MSC = 5
3240 0.7125
MeOH (wt%)
TAC (kUSD)

3220
0.7120
3200

3180
0.7115
3160

3140
0.7110
46 48 50 52 54 56 58 60 62 64 46 48 50 52 54 56 58 60 62 64
o o
Tc-C2 ( C) Tc-C2 ( C)

(e) (f)
3280 0.7170
NT-MSC = 3 NT-MSC = 3
3260 NT-MSC = 4 NT-MSC = 4
NT-MSC = 5 NT-MSC = 5
3240 0.7165
MeOH (wt%)
TAC (kUSD)

3220

3200 0.7160

3180

3160 0.7155

3140
46 48 50 52 54 56 58 60 62 64 46 48 50 52 54 56 58 60 62 64
o o
Tc-C2 ( C) Tc-C2 ( C)
Fig. 7. Optimization results at MeOH/NOs = 2.2
(a)(b) TAC and MeOH content under varying Tc-C2 and NT-MSC at RMeOH = 0.73
(c)(d) TAC and MeOH content under varying Tc-C2 and NT-MSC at RMeOH = 0.74
(e)(f) TAC and MeOH content under varying Tc-C2 and NT-MSC at RMeOH = 0.75.
98 B.-Y. Yu et al. / Computers and Chemical Engineering 119 (2018) 85–100

grade cooling medium, the refrigerant. Besides, similar to PCR, the

MSC condenser should also be operated at a lower temperature,
(a) so that enough MeOH can be condensed and sent back to MSC in
3122 order to reach 99.9% DMO recovery. These two adjustments made
Min. TAC the TAC rise up. Under MeOH/NOS = 1.9, fewer converged runs with
3120 satisfied MeOH composition can be obtained. Among them, the op-
timal point under MeOH/NOS = 1.9 was at RMeOH = 0.89, MSC = 5,
3118 Tc- C2 = 62 (°C). Operating at these conditions, the MeOH concen-
Min. TAC (kUSD)

tration at PCR bottom was 70.08 (wt%), and the TAC is 3233.4
3116 (kUSD).
To this point, the optimization is completed. The overall op-
3114 timization results are collected in Fig. 9. The optimal operating
condition is at MeOH/NOS = 2.1, RMeOH = 0.77, Tc- C2 = 54 (°C), NT-
3112 MSC = 4, NT2 = 18, NF2 = 12, NT1 = 13, and NF1 = 5. The calculated
TAC is 3080.9 (kUSD).
3110 The itemized TAC of the optimized case is also listed in
Table 5 in order for direct comparison. We found that 6.2% and
52 53 54 55 56 57
18.87% reduction on TAC can be reached compared with the heat-
Tc-C2 (oC) integrated base case, and the original base case, respectively. Two
(b) comments can be made from this discovering. The first one is that
3110 the reduction of TAC from the heat-integrated base case to the fi-
Min. TAC nal optimized point is not very obvious. This may be because the
3105 suitable operating region for this process as concluded from the
literature has been narrow, which led to another fact that the se-
3100 lected starting point of the optimization is pretty close to the opti-
Min. TAC (kUSD)

mal point. The second one is that larger MeOH/NOs lead to lower
3095 TAC. This conclusion is different from those summarized in open
literatures, which suggested that lower MeOH/NOs is better. This
3090 difference is likely to be arisen from the utility cost in C2 reboiler
and cooling cost of PCR. In this work, the utility used in PCR con-
3085
denser is chilled water, with the unit cost to be 4.43 USD/GJ as
suggested by Luyben. This is close to the steam price used in C2
3080
reboiler (3.60 USD/GJ), which is generated from the waste heat of
3075 R-CP. If the heating source changes, the optimization results are
52 53 54 55 56 57 likely to shift based on the new steam unit cost. In this work, the
Tc-C2 (oC) reason for the lower steam cost is because of the inclusion of a
primary heat integration scheme, which is also a practical strategy
(c) in industry when trying to become more energy-saving. Thus, the
authors consider the optimization work provided in this paper to
3152 Min. TAC be reasonable.

3150 5. Conclusion
Min. TAC (kUSD)

In this work, the rigorous steady state design and optimization

3148 of DMO synthesis process was investigated. The whole process is
made up of coupling reaction and regeneration reaction, and con-
3146 tains five major units (R-CP, MSC, C1, PCR, and C2). The most dis-
tinct difference in this work was not to recover the DMC from the
3144 system. With this design strategy, the amount of methanol added
into MSC can be reduced which can greatly save the energy in
downstream separation. After the steady state design was com-
3142
pleted, optimization was performed by sequential iterative method.
Among the selected design and operating variables, it was found
52 53 54 55 56 57
that the methanol circulation rate inside the process was critical,
Tc-C2 (oC)
which was majorly affected by the methanol NO+NO2 feed ratio
Fig. 8. TAC variation between Tc-C2 = 52 and 57 °C (MeOH/NOs), methanol recovery in PCR condenser (RMeOH ), con-
(a) At MeOH/NO = 2.0 and RMeOH = 0.82 denser temperature in C2 (Tc-c2 ), and total number of stages in
(b) At MeOH/NO = 2.1 and RMeOH = 0.77 MSC (NT-MSC). Through this study, a better understanding of DMO
(c) At MeOH/NO = 2.2 and RMeOH = 0.74.
production process could be achieved and a complete economical
process flowsheet was provided.
 B.-Y. Yu et al. / Computers and Chemical Engineering 119 (2018) 85–100 99

(a) (b)
3150 MeOH/NOs = 2.0 MeOH/NOs = 2.1
3120
Min. TAC (kUSD)

Min. TAC (kUSD)

3140
3110

3130
3100

3120
3090

3110
3080

0.82 0.83 0.84 0.77 0.78 0.79

RMeOH (-) RMeOH (-)
(c) (d)
3160 3240
MeOH/NOs = 2.2 Min. TAC

3155 3200

Min. TAC (kUSD)

Min. TAC (kUSD)

3150 3160

3120
3145

3080
3140
0.73 0.74 0.75 1.9 2.0 2.1 2.2
RMeOH (-)
MeOH/NOs (-)
Fig. 9. Overall optimization results
(a) Minimized TAC under MeOH/NOs = 2.0
(b) Minimized TAC under MeOH/NOs = 2.1
(c) Minimized TAC under MeOH/NOs = 2.2
(d) Total minimized TAC.

Acknowledgment
The research funding from the Ministry of Science and Technol-
ogy of R. O. C. under grant no. MOST 105-2221-E-002-210 is greatly
appreciated.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.compchemeng.2018.
08.025.
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