chemical engineering research and design 1 2 1 ( 2 0 1 7 ) 173190

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Chemical Engineering Research and Design

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

Design and optimization of dimethyl oxalate (DMO)

hydrogenation process to produce ethylene glycol
(EG)

Bor-Yih Yu, I-Lung Chien

Department of Chemical Engineering, National Taiwan University, Taipei 106, Taiwan

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

Article history: In this work, the steady state design of ethylene glycol (EG) production process by the
Received 18 September 2016 dimethyl oxalate (DMO) hydrogenation is investigated. In comparison with the conventional
Received in revised form 11 March ethylene oxide hydration process for EG production, this novel process provides better con-
2017 version and selectivity. The DMO hydrogenation process is comprised of a reaction section
Accepted 13 March 2017 and a sequence of distillation columns as separation section. In reaction section, DMO is
Available online 21 March 2017 dissolved in methanol, and this DMO solution is then reacted with hydrogen to become EG
and side products. Then, the raw product stream is fed into the sequence of distillation
Keywords: columns to obtain the EG product stream at the specied purity. After the initial process
Process design design is completed, the DMO hydrogenation process is optimized to obtain the optimal
Optimization design with the minimum total annual cost (TAC). During process optimization, it is found
Dimethyl oxalate that the mole ratio of hydrogen to DMO (HDMR) has global inuences on TAC, and thus it is
Ethylene glycol the last variable to be optimized. In this paper, the optimal case with HDMR = 40 is obtained
Hydrogenation through optimization.
2017 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction thesized from syngas directly or indirectly. In the direct synthesis, H2

Ethylene glycol (EG), the simplest diol, is one of the very important com-
pounds in chemical industry. It is widely used as antifreeze, precursor
to polymers, as well as heat transfer agent and solvent. Conventionally,
EG has long been produced from the hydration of ethylene oxide. How-
ever, the ethylene oxide hydration process is highly energy-intensive.
The primary reason is that its per-pass reaction conversion is low.
Therefore, several recycle streams is required in the process in order
to achieve adequate reaction conversion. Furthermore, the main raw
material for ethylene oxide production, ethylene, is produced by pyrol-
ysis of oil. Because of the limited amount of crude oil reserve, large
uctuation of oil price and the increasing EG demand, a more economi-
cal and sustainable EG production process is needed (Yue et al., 2012a,b;
Song et al., 2013).
The syngas-to-EG process has been considered as an alternative
route for EG production. Syngas, mainly comprised of H2 and CO, can
be produced from various sources, such as coal, biomass and natural
gas. Its price is also relatively cheaper than crude oil. EG can be syn-
and CO is directly reacted to form EG in a one step. This way is efcient
in production but is nearly thermodynamically infeasible. Therefore,
the indirect synthesis has drawn more attention. This method synthe-
sizes EG through the formation of some intermediate such as oxalates.
Although the indirect method requires two-stage reaction, the reaction
condition is much more favorable (Yue et al., 2012a,b; Song et al., 2013).
The reaction route of the indirect syngas-to-EG process via oxalates
is described as follows. First, CO undergoes coupling reaction to form
oxalate. Then, the oxalate is further hydrogenated to form EG (Yue
et al., 2012a,b; Song et al., 2013). In CO coupling reaction, CO is reacted
with methyl nitrite (MN) or ethyl nitrite (EN) to form dimethyl oxalate
(DMO) or diethyl oxalate (DEO). Both of these oxalates are candidates
to act as intermediate in hydrogenation. However, MN is more ther-
mally stable than EN, which leads to more safety in reaction. Also,
DMO is solid state under room temperature, and it is easier to trans-
port and store comparing with DEO. These two reasons lead to the
fact that DMO hydrogenation draws more attention in investigating
the oxalate-based, indirect syngas-to-EG process (Li et al., 2004; Zhou
et al., 2009).

Corresponding author. Fax: +886 2 3366 3040.
E-mail address: ilungchien@ntu.edu.tw (I.-L. Chien).
http://dx.doi.org/10.1016/j.cherd.2017.03.012
0263-8762/ 2017 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
174 chemical engineering research and design 1 2 1 ( 2 0 1 7 ) 173190

to thermodynamic analysis (Li et al., 2004; Yin et al., 2008), reactor con-
guration (Gao et al., 2011; Zhu et al., 2012, 2014; Han et al., 2016), the
Nomenclature
derivation of kinetic expressions (Xu et al., 1995; Zhang et al., 2007; Zhu
Acronyms et al., 2013; Li et al., 2015), and conceptual design of the process in open
COL-i Distillation column for separation, i = 13 literature (Yao, 2013).
DEO Diethyl oxalate However, most of the above-mentioned previous contributions did
DMC Dimethyl carbonate not provide a complete design owsheet, also there is no optimization
or further study. Thus the major contribution of this paper is to provide
DMO Dimethyl oxalate
detail information of the rigorous steady state design and optimization.
EG Ethylene glycol
In optimization, a set of optimal design and operating conditions are
EN Ethyl nitrile
obtained with minimized total annual cost (TAC) by sequential itera-
EtOH Ethanol
tive method. Due to the recycle streams, there are some interaction
FEHE Feed-efuent-heat-exchanger behaviors during optimization, thus the optimization algorithm needs
HDMR Hydrogen to DMO mole ratio (mol/mol) to be carefully established and appropriately simplied. With rigorous
MeOH Methanol simulation study, a owsheet with better economic performance is pro-
MN Methyl nitrite posed, and the studies included in this work can provide solid basis for
MG Methyl glycolate further process study.
MG-Conv MG conversion (%)
MDMR MG to DMO mole ratio (mol/mol) 2. Overview of the process
NT Total number of trays
NF Feed location into the column
In this section, overview of the studied DMO hydrogenation
REACT Reactor section
process is illustrated, and all the simulations are performed in
TACi Total annual cost, i = REACT, COL-1, COL-2, and
ASPEN Plus V8.8. NRTL-RK is selected as the thermodynamic
COL-3 (kUSD)
model throughout this work. The components including
TAC-SEN The modied TAC calculated in sensitivity test
in this work are dimethyl oxalate (DMO), water, methanol
(kUSD)
(MeOH), ethylene glycol (EG), dimethyl carbonate (DMC),
methyl glycolate (MG), ethanol (EtOH), hydrogen (H2 ) and car-
Capital letters
bon monoxide (CO). All the binary parameters used in this
Ki Adsorption equilibrium constant for different
study are listed in Table A1. For the binary pairs not shown,
species, i = EG, ME (methanol), H (hydrogen),
ideal behavior is assumed. Also there are some gas compo-
MG, and DMO (MPa1 )
nents in this system, thus Henrys law is included to model
Kpi Reaction equilibrium constant, i = 1 and 2
the dissolution of gases into liquids. The process is divided
(MPa1 )
into reaction section and separation section. Detailed design
pi Partial pressure for different species, i = EG, ME
and optimization of these two sections will be discussed in
(methanol), H (hydrogen), MG, and DMO, (MPa)
later Sections 3 and 4.
TR Reaction temperature ( C)
After the initial steady state design of each section is com-
Tcond Condenser temperature in COL-1 ( C)
pleted, optimization is performed to nd a set of optimal
Lower case letters design and operating variables with minimized total annual
h Reactor bed height (m) cost (TAC). TAC is composed of annualized capital cost and
ki Pre-exponential factor for reactions, i = 13 operating cost. The denition of TAC is illustrated in the fol-
(kmol/kgcat-s/MPa) lowing equation:
r Reaction rates (kmol/s/kg-cat)
p Pressure drop inside the reactor (bar) Capital Cost
TAC (kUSD) = + Operating Cost (1)
Payback Period
Greek symbols
s Density of solid particle (kg/m3 ) Capital cost represents the purchase and instillation cost
g Density of gas (kg/m3 ) of all the process units, including reactor, heat exchangers,
Void fraction inside reactor () distillation columns, and so on. Operating cost includes the
cost of utility (like steam, cooling water. . .etc) and catalyst. The
payback period in Eq. (1) is assumed to be 3 years. Cost evalu-
There are quite a few contributions in open literature that studied ation of equipment and utilities is based on Luyben (2011a). In
the DMO hydrogenation reaction. In most of the kinetic experiment the distillation section, two columns are operated under vac-
studies, DMO is dissolved in methanol and then fed into reactor in
uumed condition. Cost calculation of the vacuum system is
order to avoid solidication. DMO hydrogenation reaction is a two-step,
based on Seiders book (Seider et al., 2009).
exothermic, vapor-phase reaction, and the inexpensive copper-based
catalysts are reported to have high activity and selectivity. The reac-
tion mechanisms and the properties of catalysts have been the top 3. Process description
topics in the related area. Also, different carriers for the copper-based
catalysts were studied, and among which Cu/SiO2 catalyst provided
This section is split into four sub-sections. Section 3.1 intro-
the best yield of EG for hydrogenation of oxalates (Li et al., 2004; Chen
duces the detailed pathway of the related reactions. All the
et al., 2008; Zhou et al., 2009; Lin et al., 2012; Yue et al., 2012a,b; Wen
et al., 2013; Zheng et al., 2015). Although the catalyst durability is still
individual reactions included in the indirect, dual-staged
needed to be improved, and the mechanism of the reaction needs to syngas-to-EG process and some important considerations in
be claried, the production of EG from oxalate has been considered to the overall plant are introduced. Section 3.2 discusses kinetics
have potential to take the leading role in the future. Beside the focus on and the basic reaction performances of the DMO hydro-
catalysis, some other related contributions can be found with respect genation reaction. Section 3.3 presents the potential reactor
 chemical engineering research and design 1 2 1 ( 2 0 1 7 ) 173190 175

conguration of hydrogenation. Finally, Section 3.4 discusses design variables in this reaction, namely, DMO solution
the detailed owsheet and the related design concepts. concentration (in wt%), hydrogen to DMO mole ratio (HDMR),
residence time, reaction temperature (TR ) and pressure.
3.1. Reaction pathway Based on previous studies, DMO is rst dissolved in methanol
with 1530 wt% DMO concentration, and then reacted with
The detailed reaction route of the indirect, two-staged syngas- hydrogen with high HDMR. According to literature, DMO solu-
to-EG process is introduced as follows. In the rst stage, tion concentration has little inuences on DMO conversion,
CO in syngas is reacted with methyl nitrite (MN) to form but EG selectivity rises more with increasing DMO solution
dimethyl oxalate (DMO) and nitric oxide (NO). Simultaneously, concentration (Li et al., 2004; Yin et al., 2008).
side reaction which produces dimethyl carbonate (DMC) also HDMR plays an important role in this reaction. Under a low-
occurs. The used MN is then regenerated by reacting NO with HDMR, the hydrogenation rate will be too low, thus a longer
methanol and oxygen. The reaction equations of coupling residence time is required to achieve certain EG yield. This
reaction, side reaction, regeneration, and overall reaction are may lead to the formation of other side products. According
shown in Eqs. (2)(5), respectively (Ji et al., 2010; Liu et al., 2010; to literature (Tahara et al., 1984), the residence time should be
Li et al., 2013). less than 5 s. Moreover, the slow reaction rate leads to a low
conversion of MG to EG, and the accumulation of MG in the
coupling reaction reactor is likely to cause plugging of catalyst pores and lead
2CO + 2MN DMO + 2NO (2)
to catalyst deactivation. On the other hand, if the HDMR is
reg. reaction too high, the product EG has greater trends to undergo further
2MeOH + 2NO + 0.5O2 2MN + 2H2 O (3)
hydrogenation to form ethanol through the side reaction (Eq.
overall-S1
(8)). Thus, several studies suggest that the operating range of
2CO + 2MeOH + 0.5O2 DMO + 2H2 O (4) HDMR should be in between 40 and 80.
In addition, the temperature, pressure, and the residence
side-S1
CO + MN DMC + 2NO (5) time should not be too high to avoid excessive side reaction.
Literatures suggest the optimal range of reaction temperature
In the second stage, DMO is further reacted with H2 to pro- should be in between 190 and 220 C, and the optimal range of
duce EG and methanol. This is a two-step reaction, in which reaction pressure should be in between 15 to 30 bar. The opti-
DMO is rst hydrogenated to form methyl glycolate (MG) as an mal residence time suggested by the literatures varies based
intermediate. Then, MG is further hydrogenated to form EG. on different kinds of catalyst (Zhang et al., 2007; Zhu et al.,
Along with the main reaction, side reaction of further hydro- 2013; Li et al., 2015).
genation of EG to form ethanol is likely to occur. The reaction In literature, there are various discussions in reaction
equations are shown in Eqs. (6)(9) (Zhang et al., 2007; Zhu mechanisms, and thus the proposed kinetic expressions from
et al., 2013; Li et al., 2015). different research groups vary. Li et al. conducted a series of
experiment with the reaction temperature varies from 453 to
hydro-1 493 K, pressure from 10 to 30 (bar), HDMR from 20 to 70 and
DMO + H2 MG + MeOH (6)
the weight liquid hourly space velocity from 1.5 to 11 h1 (Li
hydro-2 et al., 2015). The ranges of investigated variables are consis-
MG + H2 EG + MeOH (7)
tent with discussion in other literature. Thus it is chosen as
overall-S2 the reference of reaction kinetics in this work. However, the
DMO + 4H2 EG + 2MeOH (8) parameters proposed by Li et al. do not t their experimental
data well. Thus the kinetic parameters are re-regressed based
side-S2
EG + H2 EtOH + H2 O (9) on experimental data. Also, in the original work, the author
stated that the side reaction can be inhibited via selecting
The overall reaction to produce EG from syngas can be better reaction condition, and thus neglected the occurrence
derived: of side reaction in their kinetic study. Based on Xu et al., the
side reaction may have same reaction mechanism as the main
2CO + 4H2 + 0.5O2 EG + H2 O (10) reaction, and it is almost irreversible (Xu et al., 1995). Thus in
this work, the kinetic expression of side reaction is obtained by
Another feature of this reaction pathway is that the exis- re-regression in order to have better completeness of the work.
tence of H2 in the CO coupling stage poisons the coupling The kinetic expressions for the two-step DMO to EG reactions
catalyst. Also, the presence of CO in DMO hydrogenation stage (Eqs. (6) and (7)) and side reaction (Eq. (9)) are shown in Eqs.
deactivates the hydrogenation catalyst. Thus, CO and H2 in (11)(13), respectively, with the required kinetic parameters in
raw syngas from gasier or natural gas reforming reactors Table 1.
should be separated to high purities before entering these
two stages. The separation of pure CO and H2 can be done PMG PME
k1 (PDMO )
KP1 P2H
by pressure swing adsorption process. r1 = KDMO PMG PME KMG PEG PME
1 + KEG PEG + KME PME + + + KH PH
KP1 P2H KP2 P2H
3.2. Reaction kinetics (11)

Several studies investigate the mechanism of DMO

hydrogenation, and propose kinetic expressions in PEG PME
k2 (PMG )
KP2 P2H
LangmuirHinshelwood (LHHW) form. From thermody- r2 = KDMO PMG PME KMG PEG PME
namic point of view, both of the reactions are exothermic, and 1 + KEG PEG + KME PME + + + KH PH
KP1 P2H KP2 P2H
are thermodynamically favorable. There are ve important (12)
176 chemical engineering research and design 1 2 1 ( 2 0 1 7 ) 173190

P=25.5 (bar)
MeOH Recycle (F=1267.04 kmol/hr)

P= 25.5 bar COMP-2

COL-1 Vapor
Q=265.2 kw F=66.75 (kmol/h)
Purge COMP-1 P=1 (bar)
F=35.65 (kmol/h) Q=249.6 kw Flash vapor T=52.0 ( C)
P=25.5 (bar) F=5053.59 (kmol/h) MeOH 60.51 mol% Pump-2
DMO T=96.7 ( C) P=24.27 (bar) H2 39.46 mol% Q=0.7 (kw)
F=126.55 (kmol/h) T=90.0 ( C) CO 0.02mol%
P=2.02 (bar)
R-out
MeOH 11.04 mol% EtOH 0.01 mol%
T=164.711 ( C) H2 88.91 mol%
DMO 99.99 mol% R-in CO 0.01 mol%
P=25.5 bar
DMC 0.01 mol% Combined T=160 ( C)
Feed MeOH Prod.
FEHE Reactor Cond-1
F=7059.97 (kmol/h) F=241.28(kmol/h)
Feed T=210 ( C) Qc=-16020 (kw) P=25.6 (bar)
P=25.50 (bar)
pump TCF-in=91.1 ( C) Tcond=52 ( C) T=52.0 ( C)
DMO 1.79 mol% MeOH 99.95 mol%
Heater Pump-1 EG 0.02 mol%
H2 MeOH 26.42 mol%
Reactor Q=-6649.6 kw Q=66.2 (kw) H2O 0.01 mol%
F=537.89 (kmol/h) MG 0.05 mol% Flash
P=25.50 (bar) H2 71.69 mol% Outlet Q=0 EtOH 0.02 mol%
CO 0.01 mol% F=9335.38 (kmol/h) P=0
T=20 ( C) TFC
P=24.27 (bar)
H2 99.999 mol% =90.0 ( C) COL-1
TR-out=106.1 ( C)
CO 0.001 mol% NT=20
MeOH 31.12 mol% Cond-2
MG 0.06 mol%
NF=9 Fuel Prod.
Flash liquid D=2.83 (m) Qc=-214.1 (kw) F=8.47 (kmol/h)
H2 66.92 mol% F=1713.48 (kmol/h)
EG 1.87 mol% P=0.17 (bar)
P=24.27 (bar) T=26.1 ( C) MG Recycle
EtOH 0.01 mol% T=90.0 ( C) F=3.81 (kmol/h)
H2O 0.01 mol% MeOH 91.69 mol%
MeOH 90.79 mol% MG 0.23 mol% P=0.12 (bar)
CO 0.01 mol% MG 0.23 mol% Cond-3 T=84.4 ( C)
EtOH 3.72 mol%
H2 1.54 mol% Reb-1 COL-2 H2O 4.12 mol% Qr=-1254.6 (kw) MeOH 0.41 mol%
EG 7.36 mol% NT=9 MG 96.26 mol%
QR=16007.1 (kw) DMC 0.13 mol%
EtOH 0.04 mol% NF=5 EG 0.33 mol%
H2O 0.04 mol% COL-1-bot D=0.53 (m) H2O 2.95 mol%
F=138.39 (kmol/h) DMC 0.05 mol%
P=1.13 (bar)
T=148.2 ( C) COL-3
MeOH 5.62 mol% NT=21
MG 2.79 mol% NF=8
Reb-2 COL-2-bot
EG 91.02 mol% D=1.50 (m)
EtOH 0.23 mol% QR=173.3 (kw) F=129.92 (kmol/h)
H2O 0.34 mol% P=0.21 (bar)
T=148.7 ( C)
DMC 0.01mol%
MeOH 0.01 mol%
MG 2.95 mol%
EG 96.95 mol% Reb-3 EG
H2O 0.09 mol% Qr=1259.3 (kw) F=126.12
(kmol/h)
P=0.20 (bar)
T=149.95( C)
MG 0.14 mol%
EG 99.86 mol%
(EG=99.8 wt%)

Fig. 1 Optimized owsheet of DMO hydrogenation process.

be performed in a single distillation column equipped with a

Table 1 Information of reaction and kinetics.
partial-vapor-liquid condenser, with light gases as vapor dis-
Kinetic parameters
tillate, DMC and MeOH mixture as liquid distillate, and DMO as
Pre exponential Activation bottom product. Because the large difference in boiling point
factor energy (kJ/kmol) between DMO and others, the DMO product can be separated
(kmol/kgcat- to very high purity with a high recovery with ease. Thus, in
s/MPa)
this work, the authors assume that the feed to hydrogenation
k1 3.87 107 44,284 process is at the purity of 99.99 mol% DMO and the remainder
k2 1.75 106 37,710 to be DMC (Crandall et al., 1987; Xu et al., 2010; Jiang et al.,
k3 8.78 1013 137,380 2012; Yao, 2013). The detailed design and operation of DMO
synthesis part is beyond the scope of this paper.
Equilibrium constant
The authors would also like to mention that, just as in
Pre exponential Activation the conventional route, the formation of some heavier by-
factor (MPa1 ) energy (kJ/kmol) products like diethylene glycol (DEG), 1,2-propane-diol, and
KME 5.49 1012 66,356 1,2-butane-diol, poly-glycol and so on are likely to form in
KEG 1.85 104 18,883 this novel route. But due to the lack of kinetic and experimen-
KMG 2.65 102 19,242 tal data and the slight amount in production, these heavier
KDMO 7.92 105 118,170 by-products are not taken into consideration in this work.
KH2 1.20 103 8348 There are also some studies pointed out that during hydro-
KP1 163.4161 17,759
genation reactions, methanol is likely to decompose to form
KP2 0.2873 15,921
CO, which may cause deactivation of catalyst. They suggested
ri = [kmol/kgcat-s]. that designing a catalyst with higher performance or stability,
or to avoid using methanol as solvent could benet the reac-
tion for further studies and industrial applications (Lin et al.,
2012; Wen et al., 2013; Zheng et al., 2015). However, most of
k3 PEG the kinetic experiments so far have used methanol as solvent
r3 = KDMO PMG PME KMG PEG PME
1 + KEG PEG + KME PME + + + KH PH in the experiment. Therefore, this feature is retained in our
KP1 P2H KP2 P2H
work.
(13)

In this work, the DMO feed to hydrogenation reaction is 3.3. Reactor conguration in hydrogenation reaction
assumed to be from its synthesis process as the rst stage (CO
coupling), in which the DMO product is separated from a mix- DMO hydrogenation reaction is highly exothermic in nature.
ture of DMO, DMC, MeOH, and light gases. The separation can Typically for exothermic reactions, there are three kinds
 chemical engineering research and design 1 2 1 ( 2 0 1 7 ) 173190
of reactor congurations. One is to apply several adiabatic
xed-bed reactors in series with inter-stage coolers to reach
the targeted conversion. This reactor conguration is widely
adopted in many chemical plants, like ammonia plant, syn-
thetic natural gas (SNG) plant, and methanol plant (Araujo
and Skogestad, 2008; Luyben, 2010; Zhang et al., 2010; Yu and
Chien, 2015a,b; Meyer et al., 2016). However, this type of reac-
tor conguration is often limited by the operable temperature
range, such as the upper temperature limit for catalyst, or
the temperature that side reaction starts to form. In DMO
hydrogenation reaction, the product EG undergoes further
hydrogenation to form EtOH once the temperature is larger
than 220 C, thus the temperature range for reaction is too
narrow to apply this conguration. Another one is to apply
a xed-bed reactor with numbers of tubes to provide cooling
(Robinson and Luyben, 2011; Milani et al., 2015). However; this
reactor conguration is not suitable to handle a large amount
of heat emitted during reaction and to maintain the reac-
tor temperature in such a narrow range. The third one is to
apply a uidized-bed reactor. According to literature, a u-
idized bed reactor can be able to reach high conversion, to
effectively remove heat, and to provide a near-uniform tem-
perature prole inside (Zhu et al., 2013; Alwahabi and Froment,
2004; Soundarajan et al., 2001; Chang et al., 2013). Thus, the
uidized-bed reactor is the most suitable one to be applied,
and it is selected in our work.
In order to simplify the simulation of reactor without losing
the capability of qualitatively illustrating the reaction perfor-
mance, an isothermal plug ow reactor (RPLUG module) is
assumed here. Under this mode in Aspen Plus, the heat duty
needed to be removed to maintain the reactor at the targeted
temperature will be calculated. For the pressure drop of this
tubular reactor, Eq. (14) is used based on the fact that the
uidized-bed reactor is operated in the uidized or bubbling
region in which the gravity force of solid equals to the drag
force.
p = g(s g )(1 )h (14) uid stream, the reduction in downstream loading dominates
where p is the pressure drop in pascal, g is gravitational
acceleration in m2 /s, s is the density of solid particle in kg/m3 ,
g is the density of gas in kg/m3 , is the void fraction inside the
bed (), and h is the bed height in m. In designing, the catalyst
density is assumed as 980 (kg/m3 ), and the bed voidage inside
the reactor is 0.5. Note that in order to reduce the compression
cost, a reactor with less pressure drop is desired. Hence, the
aspect ratio (length/diameter) of reactor is assumed to be 3.
3.4. Flowsheet of the process
The process owsheet with the optimized results is illustrated
in Fig. 1. In reaction section, the DMO feed owrate is assumed
to be 126.55 (kmol/h), with 99.99 mol% DMO and the remainder
to be DMC as mentioned previously. This DMO feed is mixed
with recycled methanol from later column 1 (COL-1) to become
a solution. In this work, the DMO solution in 20 wt% is adopted
in order to be consistent with the reaction condition in the
original literature (Li et al., 2015). The DMO solution is then
mixed with fresh hydrogen and other four recycled streams
to form the combined feed. The fresh hydrogen is assumed to
be one of the products from a pressure swing adsorption unit,
with the H2 purity to be 5N in mol% (Peking University Pioneer
Co., 2016), and the remainder to be CO. The recycle streams
include the hydrogen-rich vapor from the later ash unit, the
177
non-condensed gas stream from vapor distillate of COL-1, the
pure methanol separated as liquid distillate of COL-1, and the
un-reacted MG separated from column 3 (COL-3). As men-
tioned previously, the reactions take place in an environment
with high HDMR, and the optimal value will be d0etermined
by optimization in later Section 4.
The combined feed is heated in a feed-efuent-heat-
exchanger (FEHE) by exchanging heat with reactor outlet
before fed into the uidized-bed reactor, which is modeled as
described in Section 3.3. The target temperature of the heated
combined feed is set at 50 C less than the reactor outlet tem-
perature, in order to let the pinch temperature between hot
stream and cold stream at FEHE to be larger than 5 C for a rea-
sonable operation. According to the literature cited, reaction
conversion and selectivity toward EG is enhanced at a higher
reactor pressure. However, if the pressure is too high, the
unwanted side reaction is greatly enhanced. Thus the reactor
is reasonably assumed to operate at pressure of 25 bar (Li et al.,
2015). As for the reactor temperature, it is also determined
based on optimization, which is discussed in later Section 4.
In the reactor, DMO is rst converted to MG, and then MG
is converted to EG. Note that based on LeChatliers principle,
DMO will almost deplete at a high EG yield. Thus the reactor
outlet mainly contains EG, EtOH, the unreacted MG, methanol
and hydrogen. The reactor outlet is rst cooled in FEHE, further
cooled by using cooling water, and then sent to a ash unit to
perform vaporliquid separation. The vapor contains mostly
hydrogen, and is then compressed and recycled to reactor
inlet, while the liquid contains methanol, EG, MG and oth-
ers, and is then sent to the downstream distillation sequence
for separation. Among this part, the outlet temperature of
the further cooler (TFC ) is important. A higher TFC makes the
ash unit operate under a higher temperature. This leads to
less methanol condensed in liquid and reduces the loading
of downstream COL-1. But in the meantime, it increases the
owrate in vapor stream and the required compressor work.
Due to the large amount of methanol in existence in the liq-
in the above-mentioned two-way inuence, which makes a
higher TFC favorable. However, if without further cooling, it will
lead to an invalid case that the temperature of combined feed
inlet (TCF-in ) becomes higher than the reactor outlet stream
that leaves FEHE (TR-OUT ). Thus, further cooling is required,
and TFC is set to let the temperature difference between TR-OUT
and TCF-in to be 15 C.
To avoid the accumulation of the impurities (CO, Ar. . .etc), a
small purge stream is needed in the ash vapor recycle stream.
Also because the presence of CO leads to the deactivation of
the hydrogenation catalyst, thus the purge ratio is set so that
the CO content in the combined feed is less than 100 ppm
(mole basis) in our study. The authors would like to mention
that in this work, it is assumed that hydrogen feed comes
from pressure swing adsorption unit with very high purity.
Sometimes, argon, methane, or even water could present in
hydrogen feed, depending on the source of hydrogen. If the
purity of hydrogen is not so high, the purge ratio should also
be higher to prevent the inert species from accumulating.
A three-column distillation sequence is designed to purify
the liquid stream from the ash unit. In column 1 (COL-1),
methanol and the remaining dissolved gas are separated from
the others. It is operated under atmospheric pressure. Due to
the existence of the gas, a partial vaporliquid condenser is
used at the column top. The vapor product from the condenser
is rich in hydrogen, and is then compressed and also recycled
178 chemical engineering research and design 1 2 1 ( 2 0 1 7 ) 173190

Table 2 Status of all variables in the process.

Fixed variables

Sections Variable name Values

REACT Reactor pressure 25 bar

FEHE Tout =TR 50 ( C)

COL-1 COL-1-P 1 bar at column top

Adjusted variables

Sections Variable name Specications

REACT Purge ratio Let CO < 100 ppm at reactor inlet

TFC Let the temperature difference between hot stream
outlet and old stream inlet from FEHE to be 15 ( C)
Diameter By reaching the target MG-Conv
Length Setting L/D = 3

COL-1 COL-1-RR Methanol recovery = 99.5% at top

COL-1-QR Methanol purity = 99.95 mol% at top

COL-2 COL-2-RR MG recovery = 99.5% at bottom

COL-2-QR EG + MG purity = 99.9 mol% at bottom

COL-3 COL-3-RR EG recovery = 99.99% at bottom

COL-3-QR EG purity = 99.8 wt% at bottom

Optimization variables

Sections Variable name Interested range Limitations

REACT HDMR 4070 ()

TR 200220 ( C) ()
MG-Conv 9599% Pre-determined through sensitivity analysis

COL-1 COL-1-NT 1626 Tbot < 150 ( C) for using LPS

COL-1-NF 513 Tcond > 47 ( C) for using cooling water
Tcond 4757 ( C)

COL-2 COL-2-P 0.150.19 (bar) Tbot < 150 ( C) for using LPS
COL-2-NT 79 Tcond > 15 ( C) for using chilled water
COL-2-NF 36

COL-3 COL-3-P 0.10.14 (bar) Tbot < 150 ( C) for using LPS
COL-3-NT 1525 Tcond > 47 ( C) for using cooling water
COL-3-NF 79

(): No specic limitations in optimization. Just vary to let TAC minimized.

back to the reactor inlet. The recycle of this vapor product is
optional, depending on the amount of inert species. In this
work, the source of hydrogen is assumed to be very pure, thus
this vapor stream is recycled to decrease the loss of hydro-
gen. The liquid distillate stream will be methanol, and is also
pumped back to the reactor inlet. Note that methanol is in
net production in DMO hydrogenation reaction, thus a part of
the methanol is split and treated as a product. This methanol
stream can be used in previous CO coupling reaction, which is
not studied in this work.
There are three degree-of-freedoms in COL-1 needed to be
specied. The reux ratio is used to maintain the methanol
purity at 99.95 mol%, while the reboiler duty is adjusted to let
the methanol recovery at 99.5% at column top. The other one
is the condenser temperature, which is determined through
optimization. If the methanol recovery is set beyond 99.5%,
it will lead to an overly increase in reboiler temperature, as
methanol continues to be distilled and the concentration of
EG and MG rises a lot. This will lead to a large increase in
both operating cost and TAC. Thus the methanol recovery is
reasonably set at this value.
The bottom product from COL-1 is sent to column 2 (COL-2)
to separate the remaining methanol and by-product ethanol
from the top, and others at bottom. The top product of COL-
2 is assumed to be used as fuel, and is not further puried.
Two degree-of-freedoms are needed to be specied. The rst
one is that the recovery of MG is set at 99.5% at the bottom,
and the second one is that the purity of combined EG and MG
are set to be 99.9 mol% at the bottom. Reux ratio and reboiler
duty of COL-2 is adjusted to reach these two specications.
The bottom of COL-2 is sent to column 3 (COL-3) to separate
MG from the top, and EG from the bottom. The collected MG
is sent back to the DMO reactor inlet. At column bottom the
target purity of EG is set at 99.8 wt%, and the recovery of EG
is set at 99.99%. These two specications are also achieved by
adjusting reboiler duty and reux ratio of COL-3.
Besides, the rectication of EG is often operated under vac-
uumed condition in real plant. The main reason is to reduce
the reboiler temperature so that to reduce the formations of
other heavier byproducts like di-ethylene glycol, tri-ethylene
glycol, as well as poly-glycols. Although those heavier com-
ponents are not considered in this study, the EG rectication,
including both COL-2 and COL-3 is assumed to be operated
under vacuumed condition in order to reveal this important
feature of the real process (Meirelles et al., 1992; Thakore
and Bhatt, 2007; Rasuli et al., 2016). The design consideration
 chemical engineering research and design 1 2 1 ( 2 0 1 7 ) 173190 179

Start of optimization

Select a value of H2/DMO

Select a value of reactor temperature (TR)

Select a value of MG conversion (MG-Conv)* Select a value of P-COL-2 Select a value of P-COL-3

Select a value for condenser temperature in Select a value of NT-COL-2 Select a value of NT-COL-3
COL-1 (Tcond)

Select a value of NF-COL-2 Select a value of NF-COL-3

Select a value of NT-COL-1

TACCOL-2 minimized with fixed NT- TACCOL-3 minimized with fixed NT-
Select a value of NF-COL-1
COL-2 and NT-COL-2? No COL-3 and NT-COL-3? No
Yes Yes
TACREACT+COL-1 minimized with fixed NT-COL-1
and NF-COL-1? TACCOL-2 minimized with P-COL-2 TACCOL-3 minimized with P-COL-3
Yes No fixed NT-COL-2 and NT-COL-2? fixed NT-COL-3 and NT-COL-3?
No No
Yes
Yes Yes
TACREACT+COL-1 minimized with fixed Tcond, NT- Get the optimal COL-2 under given Get the optimal COL-3 under given
COL-1 and NF-COL-1? No H2/DMO H2/DMO
Yes

TACREACT+COL-1 minimized with fixed MG-Conv,

Tcond, NT-COL-1 and NF-COL-1? No ( TACREACT+COL-1+TACCOL-2+TACCOL-3)
Yes minimized under given H2/DMO? No

TACREACT+COL-1 minimized with fixed TR, MG- Yes

Conv, Tcond, NT-COL-1 and NF-COL-1? No Optimization Completed
Yes

Get the optimal case of REACT+COL-1 under

specified H2/DMO

Fig. 2 Algorithm of sequential iterative optimization algorithms for the whole process.
*MG-Conv is determined based on the parings with HDMR and TR , as listed in Table 4.
Compressor
P= 25.5 bar
Purge (1%)
MG
T=93 ( C)

MeOH
T=52 ( C)
TCF-Out=TR-50
DMO
F=126.55 (kmol/h) Combined Feed
Flash
P=25.5 (bar) TCF-in FEHE Reactor (TR)
vapor
T=164.711 ( C)
DMO 99.99 mol% H2
DMC 0.01 mol% Further Cooler
Flash
Q=0
**Vary: Reactor Outlet TFC P=0
(1) H2/DMO mole ratio (HDMR)
(2) MG/DMO mole ratio (MDMR)
TR-Out=TCF-in-15
(3) TR
Flash liquid

Fig. 3 Flowsheet for sensitivity analysis.

should include to let the bottom temperature not greater than
150 C so as to use industrial low-pressure steam (at 6 bar,
160 C) (Luyben, 2011a,b). Note that in vacuum system, the
pressure drop inside the column should be kept small. Hence,
a 1-inch weir height is specied in the calculation of pressure
drop by the Aspen built-in tray rating function.
As mentioned in previously, some heavier by-products are
not included in this work. Thus in real situation, there might
be several more distillation columns to purify the products
after COL-3. But the further separation is beyond the scope of
this work.
4. Optimization of process
This section is split into six sub-sections. Section 4.1 discusses
the overview of optimization, in which the method, proce-
dure, and other required information is introduced. Section 4.2
investigates the basic understandings of the related inuences
on the system by the selected optimization variables. Section
4.3 illustrates the preliminary studies to simplify the optimiza-
tion. Section 4.4 records the optimization results of section
REACT+COL1, while Section 4.5 discusses the optimization of
COL-2 and COL-3. Section 4.6 is the summary of the optimiza-
180 chemical engineering research and design 1 2 1 ( 2 0 1 7 ) 173190
Table 3 Relationship between MDMR, FMGin , FMGout and the corresponding MG-Conv in sensitivity analysis.
MDMR (%) FMG in (kmol/h) FMG in combined feed (kmol/h)
1 1.265 1.279
2 2.531 2.559
3 3.796 3.838
4 5.061 5.126
5 6.327 6.407
MGConv = 1 MGout /(MGin + DMOin ).
tion. Due to the size of the text, only the major results are
included in the paper.
4.1. Overview of optimization
Before optimization starts, it is important to identify and to
categorize the variables. Table 2 is a summary of all the vari-
ables and their status inside this process. According to this
table, some variables are xed at given values based on over-
all process understandings, and is labeled as Fixed variable.
There are also some other variables that can be adjusted to
reach some specications, which act as constraints as the opti-
mization proceeds. Those variables are labeled as Adjusted
variables in Table 2. In this work, the specications related
to separation performance can be reached with the aid of
the Aspen built-in function Design specication/vary in the
RADFRAC model, which is used to rigorously simulate the
downstream distillation columns. Other specications can
be achieved by the Flowsheeting design/spec function. The
remaining variables, labeled as Optimization variables in
Table 2, are the design and operating variables in the process.
The reason to optimize those variables is two-fold. Firstly, they
cannot be neither determined only by overall process under-
standings, nor be limited by given constraints. Secondly, the
changing of those variables causes more obvious TAC changes.
Note that all the constraints (specications) mentioned in
Table 2 needs to be satised as the design and operating vari-
ables vary throughout the procedure of optimization.
Sequential iterative method is selected as the method for
optimization in this work. In this method, the decision vari-
ables are varied one at a time, which is considered more
time-consuming in performing optimization. There are sev-
eral other methods of simultaneous optimization through
solvers which is more efcient in calculation. However,
convergence problems may cause difculties in performing
the calculation in simultaneous optimization, especially for
a complicated process with reaction section and recycled
streams. Hence, the authors selected the sequential itera-
tive method for optimization. Through this method, a better
understanding of the process can also be obtained despite the
need of more simulation time.
The whole process can be divided into four sections from
upstream to downstream in the following order, reaction sec-
tion (REACT), COL-1, COL-2 and COL-3. Because the process
contains reaction section and separation section, the order of
optimization is desired to be from upstream to downstream.
However, there are interactions between different sections in
the process, thus the algorithm of the sequential iterative opti-
mization needs to be modied. The rst interaction is between
REACT and COL-1 as the operating temperature of ash unit
affects the loading of COL-1, and the condenser temperature in
COL-1 inuences the heat exchanging performance in REACT
due to the recycling of both vapor and liquid distillate. Thus
FMG out (kmol/h) MG-Conv (%)
1.356 99.00
2.713 98.02
4.113 97.05
5.433 96.11
6.791 95.18
these two sections are combined to become REACT+COL-1 in
optimization. The second interaction is between COL-3 and
REACT, as the unreacted MG is separated from COL-3 and
recycled back to REACT. The recycled MG owrate reects the
reaction performance, as it is the portion that unreacted in
the reactor. This interaction is included in the optimization
algorithm by a series of sensitivity test which acts as the pre-
liminary tasks of the optimization. The detailed information
of this sensitivity analysis is disclosed in later sub-Section 4.3.
4.2. Selection of variables to be optimized
In REACT, reactor temperature (TR ), H2 -to-DMO molar ratio
in the combined feed (HDMR), and targeted MG conversion
(MG-Conv) are considered the most inuential variables. Their
characteristics and how they affect the system performances
are described in detail in the following paragraphs. In short, an
optimal operating condition should give a decent MG conver-
sion, without the occurrence of overly further hydrogenation.
The inuence of temperature is direct, as higher temper-
ature always leads to greater reaction rates. However, the
selectivity toward EG drops under high temperature due to
the existence of side reaction. HDMR has more complicated
inuences on the system, with its effects to be three-fold.
First, it inuences reaction rate and selectivity directly, as
both of them become higher under a larger HDMR. Second,
the compression cost of the recycled ash vapor rises as the
HDMR increases. Third, HDMR reects the system loading
in REACT and it affects the performance of feed-efuent-
heat-exchanger (FEHE) as well as the determination of further
cooler outlet temperature (TFC ). Aside from COL-1, HDMR
also inuences the performance of COL-2 and COL-3, because
these two columns are used to separate the product and the
unreacted species, which has close relationships with HDMR.
As for reaction conversion, the targeted MG conversion should
be specied in this hydrogenation reaction instead of DMO
conversion. This is because DMO is almost completely con-
sumed at a high EG yield. The targeted MG conversion can
be specied by varying the reactor size under a set of given
reaction condition.
In COL-1, the condenser temperature (Tcond ), total number
of trays (NT) and feed location (NF) are variables to be opti-
mized. Among these three variables, Tcond is more important
as it not only affect the performance in COL-1 but also inu-
ence the heat exchange performance in REACT. The operation
of COL-2 and COL-3 is operated under vacuumed condition,
with the optimization variables to be column pressure, NT,
and also NF. The determination of the optimization variables
should also be limited by the temperature constraints men-
tioned as in Table 2, which are based on the grade of utility
used as heating and cooling sources.
As mentioned in Section 4.1, the optimization can be
performed in the order of REACT+COL-1, COL-2, and COL-3.
 chemical engineering research and design 1 2 1 ( 2 0 1 7 ) 173190 181

(a) HDMR=40 (b) HDMR=50

TR=205 TR=210 TR=205 TR=210
900 TR=215 TR=220 800 TR=215 TR=220

850 780
TAC-SEN (kUSD)

TAC-SEN (kUSD)
800 760

750 740

700 720

0.02 0.03 0.04 0.05 0.02 0.03 0.04 0.05

MDMR (mol/mol) MDMR (mol/mol)
(c) HDMR=60 (d) HDMR=70
960
1100 TR=200 TR=205 TR=200 TR=205
TR=210 TR=215 940 TR=210 TR=215
1050
920
1000
900
TAC-SEN (kUSD)

TAC-SEN (kUSD)

950
880
900
860
850
840

800
820

750 800

0.01 0.02 0.03 0.04 0.05 0.01 0.02 0.03 0.04 0.05
MDMR (mol/mol) MDMR (mol/mol)

Fig. 4 Sensitivity test results.

(a) TAC-SEN under varying TR and MG/DMO at HDMR = 40.
(b) TAC-SEN under varying TR and MG/DMO at HDMR = 50.
(c) TAC-SEN under varying TR and MG/DMO at HDMR = 60.
(d)TAC-SEN under varying TR and MG/DMO at HDMR = 70.

Because HDMR has global inuences on the system, thus it is
the last one to be optimized. In the rst part (REACT+COL-1),
the optimal cases with respect to different HDMR are obtained.
The optimization algorithm for section REACT+COL-1 is illus-
trated in the left half of Fig. 2. Other variables listed within the
network include TR , MG-Conv, Tcond (condenser temperature
of COL-1), COL-1-NF (feed location), and COL-1-NT (total num-
ber of trays in COL-1). These several local optimal cases for
section REACT+COL-1 under different given HDMR are then
used for further optimization of COL-2 and COL-3.
The optimization of COL-2 and COL-3 are performed
sequentially with the algorithms to be generally the same,
with the procedure shown in the right half of Fig. 2. After the
optimization under different HDMR in each section is com-
pleted, they are combined to nd out the optimal HDMR for
this process. Then the nal optimal case can be obtained.
4.3. Preliminary studies prior to optimization
Some preliminary studies can be performed to simplify the
optimization procedure before starting. In REACT, the selected
variables (HDMR, TR and MG-Conv) inuence the reaction
performance in similar ways, so their inuences can be inte-
grated. Hence, REACT is rst investigated separately through
a series of sensitivity test as the preliminary studies. The pur-
pose of this sensitivity test is to nd the optimal MG-Conv
under different given HDMR and TR so that the determination
MG-Conv can be coupled with those other two variables.
The detailed information for this sensitivity test is
described below. A simple owsheet is used to represent the
REACT section, which is illustrated in Fig. 3. The process con-
guration and the related specications of this owsheet are
the same as that in Fig. 1. Because the inuence of MG-Conv
on the process is majorly through affecting reaction perfor-
mance, thus a modied TAC, named TAC-SEN, is dened to
only include the items related to reaction performance. The
items included are capital cost for reactor and compressor,
operating cost for catalyst, electricity and EG stream cost.
It is not desired to reach complete MG conversion because
the side reaction to produce EtOH from EG may occur under
a large residence time. Hence, the optimal MG conversion is
likely to be within 9599%, depending on the given HDMR and
TR . The unreacted MG is then separated in the downstream
distillation column sequence, and recycled back to the reactor
inlet. Based on the separation specications in the plant-wide
process mentioned in Table 2, about 6% of MG will be lost in
182 chemical engineering research and design 1 2 1 ( 2 0 1 7 ) 173190

Table 4 Pairings between given HDMR, reactor temperature, and the optimal MG conversion determined from
sensitivity analysis.
Conditions HDMR (mol/mol) and TR ( C) Optimal MG-Conv (%) Conditions HDMR (mol/mol) and TR ( C) Optimal MG-conv (%)

40, 205 97 50, 215 97

40, 210 97 50, 220 97
40, 215 97 60, 200 98
40, 220 96 60, 205 98
50, 205 97 60, 210 98
50, 210 97 60, 215 97

(a) (b)
HDMR=40 HDMR=50 TAC (REACT+COL-1)
6400 HDMR=60 6400
TAC (REACT+COL-1) (kUSD)

TAC (REACT+COL-1) (kUSD)

6300 6300

6200 6200

6100 6100

6000 6000

5900 5900

5800 5800
200 205 210 215 40 45 50 55 60
TR (C) HDMR (mol/mol)

(c) (d)
HDMR=40 740 HDMR=40
136 HDMR=50 HDMR=50
HDMR=60 HDMR=60
720

700
TAC (COL-2) (kUSD)

TAC (COL-3) (kUSD)

134
680

660

132 640

620

600
130
0.16 0.17 0.18 0.10 0.11 0.12 0.13 0.14
P-COL-2 (bar) P-COL-3 (bar)

Fig. 5 Optimization results.

(a) TAC for REACT and COL-1 under varying HDMR and TR .
(b) Minimized TAC for REACT and COL-1 under varying HDMR.
(c) Minimized TAC for COL-2 under varying P-COL-2.
(d) Minimized TAC for COL-2 under varying P-COL-3.

other streams and is not recycled. This means that in order to In addition, there are still some other assumptions here:
connect the recycle stream, the MG at reactor outlet should be
about 6% more than that at the reactor inlet. This feature is
(1) Assume no EG and ethanol in the inlet stream in sensitivity
considered to qualitatively represent the performance of the
test.
plant-wide process in the sensitivity test. For convenience in
(2) The price of catalyst is 10 USD/kg with its life to be half
analysis, another variable, MG to DMO mole ratio (MDMR) is
year (total of 20 USD/kg on a yearly basis) (Luyben, 2010,
introduced here. It is used to represent the relative amount of
2011b; Luo et al., 2012).
MG to that of DMO in the inlet ow. Generally, a larger MDMR
(3) The price of EG is set at 1220 USD/kg, which is referenced
value means lower MG conversion. Table 3 listed the relation-
from the contract price from ICIS.com (ICIS pricing, 2014).
ship in MDMR, MG inlet owrate (FMG,in ), MG outlet owrate
(4) The cost for fuel stream is neglect because its purication
(FMG,out ), and the corresponding MG conversion (MG-Conv).
is not considered in this work.
 chemical engineering research and design 1 2 1 ( 2 0 1 7 ) 173190 183

Table 5 Optimal design and operating conditions based on different HDMR.

HDMR 40 50 60

REACT+COL-1
TR ( C) 210 210 205
MG Conv (%) 97 97 98
Tcond ( C) 52 52 52
NT-COL-1 20 18 18
NF-COL-1 9 7 8

COL-2 P-COL-2 (bar) 0.17 0.17 0.17

NT-COL-2 9 9 9
NF-COL-2 5 5 5

COL-3 P-COL-3 (bar) 0.12 0.12 0.12

NT-COL-3 21 20 19
NF-COL-3 8 8 8

TAC (kUSD) REACT Capital 1959 2053 2309

Operating 240 312 500
TAC 893 996 1269
COL-1 Capital 3461 3351 3320
Operating 3785 3888 3944
TAC 4938 5005 5051
COL-2 Capital 146 145 145
Operating 86 86 83
TAC 134 134 131
COL-3 Capital 561 557 525
Operating 450 457 428
TAC 637 642 603
Total TAC 6602 (optimal) 6779 7054

(5) For calculating variation of EG cost in different cases, a
reference production rate of 125.9 kmol/h is set, which cor-
responds to a total of 99.5% yield from the feed DMO. The
cost resulted from different EG production rate is counted
in the operating cost.
The authors would like to mention that the selection of
reference case in the above mentioned assumption (5) will
only affect the value, but not the relative relationship of TAC-
SEN among cases. Because the purpose of this sensitivity test
is to recognize the effect of temperature and HDMR on MG
conversion, thus this assumption is reasonable.
The results for the sensitivity test are illustrated in Fig. 4,
in which some conclusions can be made. Firstly, TAC-SEN is
higher at larger value of HDMR, thus it is clear that com-
pression cost plays a more important role on TAC-SEN than
the catalyst cost does. Secondly, under given HDMR, there are
trade-offs with respect to TR . This is because higher tempera-
ture increases the reaction rate, and thus the requirement in
catalyst cost decreases. On the other hand, higher tempera-
ture leads to greater trend in side reaction, thus the EG loss
will be more. Thirdly, the optimal MDMR exists under given
HDMR and reactor temperature.
As mentioned previously, an optimal TAC-SEN does not
represent the nal optimization result because this is only a
simplied term of TAC which discusses about the cost related
to reaction performance. However, pairings of optimal MDMR
with given HDMR and TR can be made based on the above
sensitivity analysis and served as the starting point of the
rest of optimization studies. These pairings results are listed
in Table 4. Through the preliminary studies, the optimization
procedure can be somewhat simplied based on better pro-
cess understanding, and it is considered crucial in sequential
iterative optimization.
4.4. Optimization work and results (REACT and
COL-1)
After selecting the pairings of variables as in Table 4, the
optimization continues. Firstly, REACT+COL-1 is optimized to
nd several local optimal cases for section with minimized
TACREACT+COL-1 under given HDMR. The catalyst unit price used
in optimization is the same as that in previous sensitivity anal-
ysis. In some cases, the heat duty of reactor calculated by
Aspen Plus is negative. This means that some amount of heat
should be removed in order to operate the reactor under the
given temperature. This waste heat can be recovered by gen-
erating the industrial medium pressure steam (MPS, at 11 bar
and 184 C), and is viewed as a bonus from the system, with
its income offsets the operating cost term in TAC calculation.
For calculating the income from MPS, a 10% penalty for gen-
eration is considered, and thus the unit price of MPS is at 7.40
USD/GJ. However, if a positive heat duty is calculated in any
other cases, the combined feed after FEHE still needs to be fur-
ther heated in order to operate the reaction under the given
temperature. In these cases, high pressure steam (at 42 bar
and 254 C) with the unit price of 9.88 USD/GJ is used for this
heating purpose (Luyben, 2011a,b).
Table A2 recorded the value of TAC in each of REACT and
COL-1 section (TACREACT and TACCOL-1 ) with respect to differ-
ent HDMR, TR and Tcond . Generally, TACCOL-1 increases along
with HDMR increases. This is because a high HDMR results in
a higher heat loading in REACT, and leads to a lower temper-
ature in ash unit. This leads to a larger amount of methanol
that is condensed in ash liquid and increase the loading in
COL-1. Also from this table, the optimal Tcond is at 52 C. This
is because if Tcond is too low or too high, condenser duty and
reboiler duty increases too much, respectively. Fig. 5(a) illus-
trates the changing of TACREACT+COL-1 under different design
and operating conditions. Due to the size of text, only the
major optimization result with varying of two outer-most vari-
184 chemical engineering research and design 1 2 1 ( 2 0 1 7 ) 173190
ables in the sequential iterative optimization, HDMR ratio and
TR , are collected. From Fig. 5(a), it is clear that under given
HDMR, the optimal operating reactor temperature exists, and
it becomes lower as HDMR decreases. Fig. 5(b) shows the opti-
mal TACREACT+COL-1 under different HDMR, and the TAC with
HDMR = 40 and TR = 210 C is the lowest. Some detailed results
with varying Tcond , NT-COL-1 and NF-COL-1 under the optimal
HDMR and TR are recorded in Fig. A2. For conciseness, only the
optimization results near the optimal condition are presented
in this paper. Besides, cases with HDMR larger than 60 result
in further increase in TAC, and is also not shown in this paper.
The optimal design and operating variables for section
REACT+COL-1 are all listed in the upper part of Table 5.
The detailed, itemized TAC in this combined section are
included in Table A3. From the table, it is concluded that
TACCOL-1 is much larger than TACREACT , because large amount
of methanol is used as medium and is separated in COL-1. In
this work, in order to be consistent with the reaction condi-
tion in the original literature, the DMO solution of 20 wt% is
adopted. If methanol amount can be decreased, the improve-
ment of overall TAC can be apparent. For the data presented in
these tables, the reference case to calculate stream cost from
different EG production rate is already corrected to that from
nal optimal condition (HDMR = 40 and TR = 210 C) with other
corresponding variables listed in Table 5.
The authors would also like to mention that the optimiza-
tion results imply an optimal HDMR at 40, which occurs at a
boundary of our interested region. However, operation under
a low-HDMR leads to slower MG conversion rate which is
unwanted as discussed in Section 3.1. To the best of our efforts,
there is no previous contributions which suggested that DMO
hydrogenation should operate at HDMR lower than 40. Thus,
further decreasing HDMR is no4F7CH5t studied. Also, catalyst
cost is likely to affect the optimization result. If the catalyst
cost is higher, the optimization result will shift to a high HDMR
case, as reacting in a condition with faster kinetics becomes
more favorable. In this work, a moderate 20 USD/kg catalyst
cost (on a yearly basis) is assumed. The further study of how
catalyst cost affects the optimization result is also beyond the
scope of this paper.
4.5. Optimization work and results (COL-2 and COL-3)
The optimal cases of section REACT+COL-1 for HDMR under
40, 50, and 60 are taken out for further study. The optimiza-
tion results of COL-2 is illustrated in Fig. 5(c), and the itemized
TACCOL-2 included in the left part of Table A4. From Fig. 5(c),
it reveals that the optimal pressure is at P = 0.17 bar for all the
selected HDMR. It is also observed that the HDMR = 60 case
has lower TACCOL-2 , and this is because the paired MG-Conv is
98% so that less MG is left inside COL-2. However, the variation
of COL-2 among different HDMRs and pressures are too slight
to affect the overall optimization results. The detailed results
related to different column pressures, NT-COL-2 and NF-COL-
2 under HDMR = 40 are recorded in Fig. A3, and the optimal
variables found are NT-COL-2 = 9, and NF-COL-2 = 5.
The optimization result of COL-3 is illustrated in Fig. 5(d),
with the itemized TACCOL-3 also included in right side of
Table A4. From the results, it reveals that the optimal pressure
is at P = 0.12 (bar) for all three HDMR cases. However, it also
illustrates that the HDMR = 60 case saves about 5% TAC from
the other two cases, and the reason is also due to the differ-
ent MG-Conv as in COL-2. Although the difference in TACCOL-3
related to varying HDMR is more obvious than TACCOL-2 , the
changing is still too slight to affect the overall optimization
results. Fig. A4 illustrates the TACCOL-3 for the HDMR = 40 case
under different pressures, NT-COL-3 and NF-COL-3, and the
optimal variables found are NT-COL-3 = 21, and NF-COL-3 = 8.
4.6. Summary of the optimization
After the optimization of each section is nished, the opti-
mization results are combined. The combined results are
illustrated in Table 5. In Fig. 5(b)(d), the optimization results
for each section with respect to different HDMR are illustrated,
and a minimized TAC existed at HDMR = 40 once all the sec-
tions are combined. Other corresponding optimal design and
operating conditions are also listed in Table 5. Again, it is clear
that HDMR is the most important variable, and we suggest
that it should be the last one to be determined in optimiza-
tion. Also note that about 80% of TAC comes from COL-1, and
this is because of the large amount of methanol in existence
to dissolve DMO. If the methanol amount can be reduced, a
great improvement can be expected on overall economic per-
formance.
5. Conclusion
In this work, the rigorous steady state design and optimiza-
tion work of DMO hydrogenation process are investigated. The
process is divided into four sections, REACT, COL-1, COL-2,
and COL-3. Among all the variables to be optimized, HDMR
has global inuences on the system and leads to some inter-
active behaviors in among sections and should be the last
variable to be determined. Before optimization starts, a series
of sensitivity test is performed to investigate the inuence
of HDMR and TR on MG-Conv. Through sensitivity test, the
pairings among these three variables are established, which
simplies the optimization procedure. After that, the reaction
section (REACT) and column 1 (COL-1) are optimized to get the
optimal cases under different HDMR. Then, COL-2 and COL-3
in the previous obtained optimal cases are then optimized.
After the optimization for all the sections are completed, they
are combined to nd the optimal HDMR. From this work, the
design and operating variables are thoroughly investigated,
and a more economical owsheet of DMO hydrogenation pro-
cess is proposed.
Acknowledgement
The research funding from the Ministry of Science and Tech-
nology of R.O.C. under grant no. MOST 105-2221-E-002-210 is
greatly appreciated.
Appendix A.
Tables A1A4 and Figs. A1A3.
 chemical engineering research and design 1 2 1 ( 2 0 1 7 ) 173190 185

Table A1 Binary parameters used in this work.

Comp-i DMO MeOH MeOH H2O MeOH
Comp-j H2 O H2 O EG EG ETOH
Source APV84 LLE-ASPEN APV84 VLE-RK APV84 VLE-RK APV84 VLE-RK APV84 VLE-RK

AIJ 232.384 2.626 33.519 0.318 3.059

AJI 456.474 4.824 1.033 0.053 1.939
BIJ 12859.651 828.387 10000.000 33.277 1328.872
BJI 22864.885 1329.544 620.696 174.464 877.049
CIJ 0.200 0.300 0.300 0.300 0.300

Comp-i EG H2 O DMO DMO MeOH

Comp-j ETOH ETOH MeOH DMC DMC
Source APV84 VLE-RK APV84 VLE-RK NISTV84 NIST-RK NISTV84 NIST-RK NISTV84 NIST-RK

AIJ 0.302 3.622 0.039 0.180 0.026

AJI 14.174 0.922 0.986 3.874 1.262
BIJ 20.145 636.726 0.000 195.022 37.943
BJI 4440.971 284.286 0.000 737.516 809.727
CIJ 0.470 0.300 0.500 0.500 0.100

Comp-i DMC ETOH DMC DMC DMO

Comp-j H2 O DMC MG EG MG
Source NISTV84 NIST-RK NISTV84 NIST-RK R-PCES R-PCES R-PCES

AIJ 5.557 0.466 0.000 0.000 0.000

AJI 3.383 1.429 0.000 0.000 0.000
BIJ 795.715 183.784 1.783 273.294 225.497
BJI 1513.890 871.375 118.470 351.788 384.705
CIJ 0.337 0.100 0.300 0.300 0.300

Comp-i DMC ETOH DMC DMC DMO MG

Comp-j H2 O DMC MG EG MG ETOH
Source NISTV84 NIST-RK NISTV84 NIST-RK R-PCES R-PCES R-PCES R-PCES

AIJ 5.557 0.466 0.000 0.000 0.000 0.000

AJI 3.383 1.429 0.000 0.000 0.000 0.000
BIJ 795.715 183.784 1.783 273.294 225.497 115.947
BJI 1513.890 871.375 118.470 351.788 384.705 251.695
CIJ 0.337 0.100 0.300 0.300 0.300 0.300

Unit of the parameters: C.

 186
chemical engineering research and design 1 2 1 ( 2 0 1 7 ) 173190
Table A2 Combined TAC of REACT and COL-1.
HDMR = 40, TR = 205 ( C) HDMR = 40, TR = 210 ( C) HDMR = 40, TR = 215 ( C)

Tcond (C) COL-1 REACT SUM Tcond (C) COL-1 REACT SUM Tcond (C) COL-1 REACT SUM

47 4935.837 935.160 5870.997 47 4951.838 886.379 5838.217 47 5069.257 890.543 5959.800

52 4915.466 944.015 5859.481 52 4938.257 893.196 5831.453 52 5007.378 899.420 5906.798
57 5183.544 954.779 6138.323 57 5204.479 905.397 6109.876 57 5247.636 910.551 6158.187

HDMR = 50, TR = 205 ( C) HDMR = 50, TR = 210 ( C) HDMR = 50, TR = 215 ( C)

Tcond (C) COL-1 REACT SUM Tcond (C) COL-1 REACT SUM Tcond (C) COL-1 REACT SUM

47 5026.735 1028.210 6054.945 47 5046.305 989.571 6035.875 47 5073.834 1012.898 6086.733

52 4989.553 1034.763 6024.317 52 5005.495 996.251 6001.746 52 5026.628 1019.552 6046.180
57 5218.241 1046.198 6264.439 57 5229.968 1008.738 6238.705 57 5248.742 1030.850 6279.593

HDMR = 60, TR = 200 ( C) HDMR = 60, TR = 205 ( C) HDMR = 60, TR = 210 ( C)

Tcond (C) COL-1 REACT SUM Tcond (C) COL-1 REACT SUM Tcond (C) COL-1 REACT SUM

47 5090.616 1286.321 6376.938 47 5104.602 1263.342 6367.944 47 5137.875 1246.234 6384.109

52 5038.134 1292.610 6330.744 52 5050.750 1269.313 6320.063 52 5077.688 1252.408 6330.096
57 5234.817 1303.086 6537.903 57 5247.090 1279.997 6527.087 57 5269.278 1262.813 6532.092
 chemical engineering research and design 1 2 1 ( 2 0 1 7 ) 173190 187

Table A3 Optimized results (itemized TAC) for REACT+COL-1.

HDMR 40 50 60

Capital cost (KUSD) REACT Tubes 87.586 11.492 54.856

Reactor 158.382 129.344 139.341
HX1 420.788 434.416 440.833
HX2 241.816 283.749 322.972
Comp 872.348 1017.722 1176.803
Flash 177.822 175.879 174.031
COL-1 COL 440.919 404.900 403.607
COND 980.207 979.256 974.410
REB 1121.935 1142.236 1189.906
COMP 917.773 824.961 751.830

Operating cost REACT Cat 165.253 119.409 134.559

(KUSD) Electricity 121.320 146.408 174.777
CW 67.795 78.919 88.880
MPS 114.086 5.015 138.938
EG 0.000 27.671 37.454
COL-1 Steam 3492.257 3611.969 3681.128
CW 163.320 163.076 161.837
ELEC 129.067 113.331 101.202

TAC (KUSD) REACT Tot Cap 1958.743 2052.602 2308.835

Tot Opt 240.282 312.050 499.701
TAC 893.196 996.251 1269.313
COL-1 Tot Cap 3460.835 3351.353 3319.752
Tot Opt 3784.645 3888.377 3944.166
TAC 4938.257 5005.495 5050.750
Total TAC 5831.453 6001.746 6320.063

Optimal design and TR ( C) 210 210 205

operating conditions MG Conv (%) 97 97 98
Tcond ( C) 52 52 52
NT-COL-1 20 18 18
NF-COL-1 9 7 7

Table A4 Optimization result (itemized TAC) for COL-2 and COL-3.

COL-2 COL-3

HDMR 40 50 60 40 50 60
MG conversion 97% 97% 98% 97% 97% 98%

Optimal design and NT 9 9 9 21 20 19

operating condition NF 5 5 5 8 8 8
Ptop /Pbot (bar) 0.170/0.210 0.170/0.210 0.170/0.210 0.120/0.200 0.120/0.203 0.120/0.200

Important DIAM (m) 0.513 0.518 0.504 1.506 1.519 1.464

parameters QC (kw) 214.130 218.911 207.892 1254.633 1278.626 1213.963
QR (kw) 173.338 175.553 168.344 1259.335 1290.638 1221.540
T-TOP ( C) 26.145 26.058 26.007 84.368 84.436 81.475
T-B ( C) 148.691 148.080 149.117 149.950 149.855 149.487

Capital cost (KUSD) COL 39.258 39.690 38.538 244.115 236.868 218.543
COND 44.407 45.218 43.821 73.074 73.902 74.878
REB 62.131 60.539 62.502 243.474 245.881 231.810

Operating cost Steam 38.839 39.335 37.720 282.172 289.185 273.703

(KUSD) CW 27.320 27.930 26.524 12.791 13.036 12.377
Vac. Steam 19.589 18.675 18.266 154.682 154.568 141.769

TAC (KUSD) CAP 145.795 145.447 144.860 560.663 556.651 525.231

OPT 85.748 85.940 82.509 449.645 456.789 427.849
TAC 134.346 134.422 130.796 636.532 642.340 602.926
188 chemical engineering research and design 1 2 1 ( 2 0 1 7 ) 173190

(a) (b)
5100
NT-COL-1-18 NT-COL-1-18
NT-COL-1-20 NT-COL-1-20
5080
NT-COL-1-22 4960 NT-COL-1-22
TAC(REACT+COL-1) (kUSD)

TAC(REACT+COL-1) (kUSD)
5060

5040

5020 4950

5000

4980
4940
4960

4940
5 6 7 8 9 10 6 7 8 9 10 11
NF-COL-1 NF-COL-1
(c) (d)
5250
5260 NT-COL-1-18 TAC(REACT+COL-1)
NT-COL-1-20
NT-COL-1-22 5200
5250
TAC(REACT+COL-1) (kUSD)

TAC(REACT+COL-1) (kUSD)
5150
5240
5100

5230
5050

5220
5000

5210 4950

5200 4900
5 6 7 8 9 46 48 50 52 54 56 58
NF-COL-1 Tcond (C)

Fig. A1 Optimization results of COL-1 at HDMR = 40, TR = 210 ( C), and different Tcond , NT-COL-1 and NF-COL-1.

165
NT=8
NT=9
160 NT=10
TAC (COL-2) (kUSD)

155

150

145

140

135

3 4 5 6 7
NF-COL-2

Fig. A2 Optimization results of COL-2 at HDMR = 40, TR = 210 ( C) P = 0.17 (bar), with different NT-COL-2 and NF-COL-2.
 chemical engineering research and design 1 2 1 ( 2 0 1 7 ) 173190 189

(a) (b)
662 NT=25 NT=21
NT=23 655 NT=19
NT=21
660

650
658
TAC(COL-3) (kUSD)

TAC(COL-3) (kUSD)
656
645
654

652 640

650
635
648

7 8 9 7 8 9
NF-COL-3 NF-COL-3

(c)
760 NT=15

755

750
TAC(COL-3) (kUSD)

745

740

735

730

725

7 8 9
NF-COL-3

Fig. A3 Optimization results of COL-3 at HDMR = 40, TR = 210 ( C) with different P, NT-COL-3 and NF-COL-3.
*Under P = 0.12 bar, Tbot > 150 C if NT-COL-3 > 21.
**Under P = 0.14 bar, Tbot > 150 C if NT-COL-3 > 15, and TAC increases dramatically as NT-COL-3 < 15.

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