Journal of Cleaner Production 275 (2020) 122773

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Journal of Cleaner Production

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

Recycle optimization of an ethylene oxide production process based

on the integration of heat exchanger network and reactor
Di Zhang , Peng Hang , Guilian Liu *
School of Chemical Engineering and Technology, Xi’an Jiaotong University, Xi’an, Shaanxi Province, 710049, China

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

Article history: Ethylene oxide is an essential product with increasing demand and its production consumes a large
Received 12 January 2020 amount of energy. For a practical ethylene oxide production process, the recycle of the reaction block is
Received in revised form studied as it influences the reactor, the Heat Exchanger Network (HEN) and the profit of the process, and
2 June 2020
could be adjusted easily and efficiently. The recycle optimization of a practical EO production process is
Accepted 10 June 2020
studied based on the integration of HEN and reactor. On the basis of the kinetic and thermodynamic
Available online 17 July 2020
equilibrium, relations among the recycle ratio, outlet temperature and the removed heat of the reactor
Handling Editor: Bin Chen are deduced. With both HEN and the reactor considered, the integration model is built, and an economic
analysis diagram is developed to illustrate the variation of revenue and cost along the recycle ratio; the
Keywords: optimal recycle ratio is identified to be 1.7, the maximum annual profit is 8.4% more than the current
Ethylene oxide value, the recovered energy increases by 29.8% and no other equipment or process changes required.
Recycle ratio © 2020 Elsevier Ltd. All rights reserved.
Optimization
Heat exchange network
Reactor

1. Introduction to its serious environmental pollution and equipment corrosion.

Ethylene oxide (EO) is the third largest organic chemical raw
material in ethylene derivatives and can be applied to produce
various intermediates and fine chemical products. In recent years,
the global production of ethylene oxide keeps growing. From 2007
to 2018, it increased from 19.25 Mt year
1 to 30.95 Mt year
1 and
was estimated to reach 41.28 Mt year
1 in 2020 (Dutia, 2010; Li
et al., 2015). According to a study published by US Energy Infor-
mation Administration (International Energy Outlook, 2019),
ethylene oxide production is the one of the main five industrial
processes with a high total energy consumption and exergy loss.
Although numerous energy-saving strategies have been carried out
for this production process, the optimization measures are too
complicated to implement in the practical processes (Qian et al.,
2016).
In industry, there are three methods for producing ethylene
oxide, including chlorohydrin method, direct oxidation method and
CEBC-EO method. The chlorohydrin method is the first one used in
ethylene oxide production (Spitz, 1971) and is no longer in use due
* Corresponding author. School of Chemical Engineering and Technology, Xi’an
Jiaotong University, Xi’an, 710049, China.
E-mail address: guilianliui@mail.xjtu.edu.cn (G. Liu).
The direct oxidation method was first put forward by Lefort in 1937,
and gradually developed into the most widely used production
process (Roberts, 2000). Compared with the chlorohydrin method,
this method has higher energy efficiency and less equipment
corrosion. CEBC-EO method (Lu, 2016) produces EO from the oxi-
dization of ethylene in the aqueous hydrogen peroxide solution,
with water as a by-product. Compared with the direct oxidation
method, this method has safer operation and higher efficiency. It is
still in the development stage and is expected to be used in in-
dustrial scale shortly. In the widely used direct oxidation process, a
large amount of energy is consumed by heat exchangers, reactors
and distillation columns. It is necessary to retrofit the process to
achieve better energy efficiency and economic performance.
At present, the optimization of EO production process is mainly
concentrated on catalyst improvement, reactor design and process
retrofit. For the direct oxidation method, the silver-based catalyst
was studied (Murray, 1950) to increase the selectivity of EO and
prevent catalyst deactivation (Spath, 1974). For the ethylene epox-
idation in the presence of carbon monoxide and hydrogen, a silver
catalyst was tried out by Yong and Cant (1990) with the selectivity
of EO increased. Thereafter, a more efficient YS silver catalyst was
developed (Li et al., 2012) and applied widely in industry because of
its high selectivity and controllable reaction conditions (Harris

https://doi.org/10.1016/j.jclepro.2020.122773
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
2 D. Zhang et al. / Journal of Cleaner Production 275 (2020) 122773
Nomenclature
AE101 Heat transfer area of E
101, m2
Ccapital Annual capital cost of E
101, USD$year
1
Ccomp Annual electricity consumption of compressor K-101,
USD$year
1
CCW Annual cost of cooling utility, USD$year
1
CP Heat capacity flow rate, kW$K
1
Cpi Heat capacity of component i, J$mol
1$K
1
Cpj Average heat capacity of stream j, J$mol
1$K
1
DCp Heat capacity difference between the product and
reactants of the primary reaction, J$mol
1$K
1
Fi Total mole flow rate of stream i, kmol$h
1
Fji Molar flow rate of component i contained in stream j,
kmol$h
1
DHE Energy difference between outlet and outlet streams
of reactor, kW
DHE1 Energy difference for hypothetical stream H1, kW
DHE1 Energy difference for hypothetical stream H5, kW
DHE101 Heat duty of heat exchanger E
101, kW
DHR Reaction heat, kW
DHRQ Standard reaction heat at 1.76 MPa, kJ$mol
1
i Species i
j Stream j
et al., 2019).
Ethylene epoxidation reactor is the critical equipment in the
production of ethylene oxide, and a lot of research has been carried
out on its design and optimization. Pcschel et al. (2011) compared
the reactors with different sizes by numerical calculations and
identified a fixed-bed reactor with higher selectivity. For the fixed-
bed reactor, Liang et al. (2014) established a two-dimensional
mathematical model to examine the influence of operating pa-
rameters and identify the sensitive ones. Abou Shama and Xu
(2018) optimized the operating temperature and pressure of
oxidation reaction in terms of reducing the manufacturing cost.
Based on thermodynamic analysis at adiabatic and isothermal
conditions, Gianmaria and Ernesto (2019) proposed a reactor
operation diagram, and identified the optimal operation parame-
ters in terms of safety and selectivity.
For an established chemical process, the modification of catalyst
and reactor costs a lot; sometimes, even the subsequent process
needs to be changed accordingly. While the retrofit of the unrea-
sonably matched heat exchangers is limited by the investment and
practical space. These factors increase the complexity of process
optimization. Moreover, the optimization may affect the stability of
subsequent process, even the product quality. In terms of
increasing the profit and feasibility of retrofit, convenient and
straightforward modification is more promising. In EO production
process, reactors with external recycle are used in order to improve
the conversion of raw material and recover the high-temperature
energy. The recycle is part of the reactor’s effluent and is sent
back to the reactor. Its parameters, such as recycle ratio, tempera-
ture and pressure, are easy to control.
Shelokar et al. (2003) developed a multiobjective ant algorithm
for a tubular reactor-regenerator system considering the deactiva-
tion of the catalyst, and optimized the recycle ratio of reactor to
achieve maximum process profit, selectivity, and conversion. Ward
et al. (2005) predicted the change of recycle rate along the reactor
temperature, and discussed the implications for control structure.
Liao et al. (2013) introduced a two-dimensional heterogeneous
k Reaction rate constant, mol$kg catalyst
1$h
1$MPa
2
KE101 Heat transfer coefficient of the cold stream of E
101,
kW$K
1$m
2
K1 Reaction rate constant, mol$kg catalyst
1$h
1$MPa
1
PC Power consumed by compressor K-101, kW
Ptotal Reaction pressure, MPa
Pj Partial pressure of component j in reactor, MPa
QC Cooling utility consumed by E
103, kW
QC0 Cooling utility consumption of E
103 when the
recycle ratio is b0 ,kW
QR Heat removed from reactor, MW
QS Duty of E
102, kW
QS0 Duty of E
102 when the recycle ratio is b0 , kW
rET Reaction rate of ethylene, mol$kg catalyst
1$h
1
Rsteam Annual revenue in steam generating, RMB$year
1
Rtotal Annual total revenue, RMB$year
1
Ti Temperature of stream i when the recycle ratio is b, K
T i0 Temperature of stream i when the recycle ratio is b0 , K
TR Reference temperature, K
W Catalyst weight, ton
yij Mole fraction of component i in stream j
X Total conversion of ethylene
XS One-way conversion of ethylene
b, b0 Recycle ratio
fixed-bed reactor model with recycle, and investigated the effects
of concentration and temperature distributions in the reactor.
Huang et al. (2017) employed a heterogeneous fixed-bed model to
simulate the reactors and identify the reactor configuration and the
recycle flow rates of the olefins. Kumar and Kaistha (2018) devel-
oped a steady state real time model of a reactor-separator-recycle
process, and identified the economically dominant component by
analyzing the recycle of unreacted component and improved eco-
nomic benefit by up to 10%. Although reactors with recycle were
widely applied in EO production process, no previous work studied
the optimization of the recycle systematically.
For the established chemical process with given catalysts and
reactors, process retrofit is significantly vital for energy conserva-
tion. The retrofit scheme of Heat Exchanger Network (HEN) can be
developed based on the Pinch Analysis (PA) method. Sun and Luo
(2017) modified the Composite Curves and algorithm table to
determine the minimum temperature approach with energy con-
sumption and capital cost considered simultaneously. Gadalla et al.
(2015) proposed a new diagram to analysis HEN and directly
identify the cross-pinch match of heat exchangers. Based on this, Li
and Chang (2017) removed the unreasonable match to target the
optimal energy consumption. Later, they (Li et al., 2019) extended
this approach to a larger scale HEN to deal with the phase transition
and multi-pinches problems. Yee et al. (2019) proposed a graphic
screening tool for retrofiting the HEN. Diban and Foo (2019) took
the inlet and outlet temperatures of the heating medium as vari-
ables and optimized them for the maximum annual revenue. With
the integration of reactor and HEN considered, Zhang et al. (2018a)
proposed a graphic pinch-based diagram to identify the optimal
operating parameters.
For the EO production process, there is a limited researches on
the pinch based retrofit. Based on the Composite Curves, Du et al.
(2003) identified the energy bottleneck and investigated the po-
tential energy utilization in a ethylene oxide/ethylene glycol unit. A
simulation model of EO production was developed by Galatro and
Verruschi (2010) using Pro II for identifying the optimal
 D. Zhang et al. / Journal of Cleaner Production 275 (2020) 122773
conditions of the separation block. Rahimpour (2011) introduced a
thermally coupled reactor with the endothermic dehydrogenation
of cyclohexane and the exothermic ethylene oxide synthesis pro-
cess integrated. This reactor can save energy and generate
hydrogen simultaneously. Based on the visualized energetic pro-
cess flowsheet, Ghannadzadeh and Sadeqzadeh (2017) improved
part of EO production process and evaluated the overall energy
consumption and exergy loss in different units. Later,
Ghannadzadeh and Meymivand (2019) assessed the environmental
sustainability of the ethylene oxide production process according to
energy and exergy demand. Barecka et al. (2016) proposed a pro-
cess intensification approach to debottleneck the process based on
pinch analysis and select the most promising process intensifica-
tion technology (Barecka et al., 2017). In addition, the equipment
improvements, such as adding a new stripper (Age et al., 2006) or
setting a side reactor in distillation column (Ding et al., 2019), were
applied in the retrofit of ethylene oxide production.
According to the study introduced above, both the optimization
of recycle and HEN are proved to be effective for reducing the en-
ergy consumption. However, the variation of recycle streams affect
reactors and the source/sink streams of HEN. The relations between
recycle and the energy consumptions of HEN are various for
different processes. To improve the energy efficiency and economic
performance of EO process, it is necessary to optimize the recycle
with the integration of HEN and reactor considered. Based on the
literature review and the best of the authors’ knowledge, there is no
corresponding research reported.
This work aims to study the recycle optimization of an practical
EO production process based on the integration of HEN and reactor.
On the basis of reaction kinetics and thermodynamics, relations
among the recycle ratio, outlet temperature and the removed heat
of reactor are deduced first. The variations of heating and cooling
utilities are analyzed, and the integration model is then built with
both HEN and reactor integrated. Based on this, economic perfor-
mance diagram is plotted to evaluate the effect of the recycle ratio,
as well as the variation of revenue and cost, and the optimal recycle
ratio corresponding to the maximum total profit is identified.
2. Process and methodology
The EO production process based on the ethylene (ET) epoxi-
dation consists of four functional blocks, ethylene reaction, EO
absorption and reabsorption, CO2 removal and EO refining, as
shown by Fig. 1. The recycle of the reaction block influences the
Fig. 1. Simplified flowchart of ethylene oxide production process.
3
kinetic equilibrium and thermodynamic equilibrium of the reactor,
as well as the HEN integration. To improve the energy efficiency, its
flow rate can be optimized with all these factors considered. Its
adjustment can be achieved easily, even without any investment.
2.1. Flowsheet data of the process
The process with the annual production of 38,521.5 tons of EO is
depicted by the flowsheet shown in Fig. 2 (without EO refining
block). In this process, the fresh feeds, C2H2 and O2, are mixed with
the recycling gas in M-101, and are converted into EO in reactor R-
101 at 543 K and 1.76 MPa. R-101 is loaded with YS-7 silver-based
catalyst (Liang et al., 2007), which can be operated in pressure in-
terval [1.5 MPa, 1.9 MPa] and temperature interval [503 K, 573 K].
The main reactions processed in this reactor are shown below:
1 1
Primary reaction ET þ O2 /EO
2
2
Secondary reaction ET þ 3O2 /2CO2 þ 2H2 O
where, ET stands for ethylene.
The effluent of R-101 contains EO, ET, CO2, O2 and CH4, and is
cooled down and sent to absorber column C-203. In this column,
light components (CO2, CH4 and O2) are separated from the top and
sent to the CO2 removal block. Some trace components (such as
aldehydes and acids) absorbed by the alkalescent quencher (dilute
solution of KHCO3) are extracted from the bottom of C-203 together
with EO, which is further recovered from the top of column C-205.
In the middle of C-203, recycled water absorbs ET and the rich
aqueous solution flows into stripper C-204, which separates EO
from water. In the CO2 removal block, CO2 is removed in absorber C-
202 by K2CO3 solution, and the latter is regenerated in C-201. The
remaining components, CH4 and O2, are recycled back to M-101. EO
obtained at the top of C-204 is sent to the EO refining block, while
the regenerated recycle water is extracted in the middle of this
column. Besides, due to the hydration of EO, a small amount of
byproduct, ethylene glycol (MEG), is obtained at the bottom of C-
204.
To simulate the process presented above by Aspen plus 8.8, the
following two key issues are addressed:
1) The desired product, EO, is produced by the primary reaction,
while the secondary reaction is the complete oxidation of ET.
4 D. Zhang et al. / Journal of Cleaner Production 275 (2020) 122773
Fig. 2. Flowchart of the ethylene oxidation process.
Based on the literature research (Chen et al., 2018), the selec-
tivity of primary reaction with this catalyst is up to 91%~94%, and
thus the secondary reaction can be ignored. However, there is
CO2 in the actual reactor effluent. To achieve reasonable results
and simplify the analysis, the secondary reaction is ignored and
a hypothetical stream of CO2 is inlet into the reactor, as depicted
by the dotted line in Fig. 2. Besides, a CO2 removal block is used
in the downstream.
2) The reactant and product of the ethylene oxidation reaction,
ethylene and ethylene oxide, are both flammable and explosive;
their explosive limits in the air are [4%, 28%] and [3%, 100%]
(volume fraction), respectively (Fabiano et al., 2015). As the
primary reaction and secondary reaction are highly exothermic,
the recycle gas that consists of O2, ET and EO has a great risk of
explosion. Therefore, CH4 is introduced into the system as a
stabilizer to dilute the ET and EO (Liu et al., 2016). Most of CH4
circulates into reactor R-101 after CO2 is removed, and a small
amount is to be replenished due to the loss in CO2 removal
block. Besides, the recycle of CH4 can remove part of the reaction
heat to prevent the catalyst from deactivation.
Based on the data of a real industrial process, the simulation
model is built in Aspen Plus to obtain more detailed data for sup-
plementing the industrial data and verifying the feasibility and
accuracy of the optimization results. In the simulation, RK-SWS
model is used to calculate the thermodynamic equilibrium data,
as it is suitable for the system of polar/nonpolar gas mixture at
higher temperature and pressure.
2.2. Methodology
The reaction system is the core of the ethylene oxide production
process, and its effluent is processed in the downstream sub-
systems. In this section, the effects of the recycle ratio on reactor
temperature and energy consumption are investigated, and the
resulted variations of heating and cooling utility consumptions are
analyzed according to the Composite Curves. On the basis of this,
the economic analysis is performed to present the variation of
profit and cost along with the recycle ratio.
2.2.1. Parameter relations of reaction block
The reaction block contains reactor (R-101), a heat exchanger
(E
101), steam generator (E
102), a recycle stream compressor (K-
101) and a product cooler (E
103), and its flow sheet is enlarged in
Fig. 3. The streams are marked by letters (C and H denote cold and
hot streams, respectively) and numbers.
In this block, the effluent of R-101 flows through E
102 and
E
101 to recover its energy and then is split into two sub-streams.
One sub-stream is compressed by K-101 and circulated into the
reactor; the other is sent to the downstream block after further
cooled down through E
103. In E
101, the fresh feed (effluent of
M-101 in Fig. 2) is preheated, and the boiler water is heated in
 D. Zhang et al. / Journal of Cleaner Production 275 (2020) 122773 5

Fig. 3. Reaction block of ethylene oxidation process.

E
102 to generate steam. Table 2

For reactor R-101, the recycle influences its conversion and Reactor R-101’s feed composition.

temperature. As the reaction is highly exothermic, part of the re- Component mol % Component mol %
action heat needs to be removed to prevent its temperature CH4 0.58 CO2 0.03
runaway. The recycle can take away part of the reaction heat to ET 0.305 EO 0
facilitate the reaction and energy recovery. Since the recycle dilutes O2 0.085
the reactant and affects the reactor’s product, and the reactor’s feed
and product are part of the HEN, the recycle affects the integration
between the reactor and HEN.

The recycle ratio, b, is the ratio between the molar flow rates of 5241:7
k ¼ exp 12:39
(3)
stream H5 and H4. It indicates the amount of recycle, and can be TH1
calculated by Eq. (1).


2203:5
F KO2 ¼ exp
2:83 (4)
b ¼ H5 (1) TH1
FH4
with ET taken as the key component, its conversion can be repre-
where, F is the total molar flow rate of the stream (H5 or H4)
sented by total conversion (X) and one-way conversion (XS),
indicated by the subscript.
respectively. The former works for the whole reaction block and can
Detailed parameters of R-101 and the feed at the operating
be calculated by Eq. (5). The latter is calculated with only the inlet
condition are listed in Table 1 and Table 2. In Table 1, T represents
and outlet of reactor R-101 considered and can be represented by
the temperature of the stream indicated by the subscript.
the total conversion, as shown by Eq. (6).

ET
F ET
FC0 H6
2.2.1.1. Kenitic equilibrium. Since the secondary reaction producing X¼ ET
(5)
FC0
CO2 is ignored, the effect of CO2’s partial pressure can be taken out
of consideration. Based on this, the reaction rate in terms of ET (rET,
mol$kg catalyst
1$h
1) is expressed by Eq. (2) (Zhang et al., 2018b). XS ¼
X
(6)
1 þ bð1
XÞ
kP O2 P ET

rET ¼ (2) where, Fji stands for the molar flow rate of component i in stream j.
1 þ KO2 P O2
Eq. (6) shows that the total conversion of ET does not equal to
where, Pi denotes the partial pressure of component i in reactor. k is the one-way conversion, and the latter changes along the recycle
the reaction rate constant of primary reaction while KO2 is the ratio. In the design, the reaction system cannot be taken as a black-
adsorption equilibrium constant of O2; they can be calculated ac- box; the reactor should be analyzed separately and its design
cording to Eq. (3) and Eq. (4), respectively. equation is represented by Eq. (7).

ðS
X
Table 1 W 1 þ K1 P O2
ET þ F ET
¼ dX (7)
Reactor R-101’s operating parameters. FC1 H5
kP O2 P ET
0
Parameter Value Parameter Value

TC0 358 K Total inlet feed 7850 kmol h
1 To guarantee the stability of the downstream blocks, the total
TH1 543 K Catalyst weight (W) 8.3 t conversion of the reaction block is kept unchanged. In the kinetic
TH2 483 K Conversion of ET 0.157 equilibrium equation of the reactor, the total conversion is used
TC1 473 K Recycle ratio (b) 1 instead of the one-way conversion to reduce the number of vari-
TH6 328 K Reaction pressure 1.76 MPa
ables. With Eq. (6) substituted into Eq. (7), Eq. (8) is derived to show
6 D. Zhang et al. / Journal of Cleaner Production 275 (2020) 122773

the design equation with total conversion. same composition with the reactor’s effluent (stream H1). To
simplify the energy equilibrium of the reactor, it is assumed that
X
ð
1þbð1
XÞ the recycle is not mixed with the fresh feed, but only passing
W 1 þ K1 P O2 through the reactor with its temperature increased from TH5 to TH1;
ET ½1 þ bð1
XÞ
¼ dX (8)
FC0 kP O2 P ET while the fresh feed (stream C1) flows through the reactor directly
0
with the total conversion (X). Based on this, the reaction heat (DHR)
According to the experimental data [48], the partial pressure for can be calculated by Eq. (15).
each component in the reactor (Pi) is proportional to its mole 
fraction when the pressure is lower than 2.0 MPa, and can be DHR ¼ FC0
ET
X DHRQ þ DCpðTH1
TR Þ (15)
described by Eq. (9).
where, DHRQ is the standard reaction heat at 1.76 MPa and equals
P i ¼ P total ,yiH1 (9) to
106.9 kJ mol
1; the reference temperature, TR, is taken as
298 K; DCp denotes the difference of heat capacity (mole) between
where, Ptotal is the pressure of reactor R-101 and equals 1.76 MPa the product and reactants of the primary reaction.
yiH1 stands for the mole fraction of component i in the reactor
effluent (H1). 2.2.1.4. Heat removed from the reactor (QR). Since the oxidization of
In the effluent of R-101 (H1), the mole fractions of ET and O2 are ET releases a large amount of heat, the reactor’s temperature should
related to the total conversion and the inlet feed, as shown by Eq. be controlled to prevent the temperature runaway and catalyst
(10) and Eq. (11), respectively. deactivation. The energy (QR) is removed by the cooling water
(CW), which flows through the jacket outside the reactor, and its
2yET
C0 ð1
XÞ value satisfies the energy equilibrium equation.
yET
H1 ¼ (10)
2
yET
C0 X
2.2.1.5. Energy difference (DHE). To calculate the energy difference
between the outlet and inlet streams of reactor R-101, both streams
2yO2

yET
C0 X
yO C0 C1 and H5 should be considered. In this section, DHE1 is used to
H1 ¼ (11)
2

2
yET
C0 X denote the energy difference between streams C1 and H1, while
DHE2, is used to represent that between streams H1 and H5.
where, yiC0 stands for the mole fraction of component i at the inlet In order to recover more energy with a smaller heat exchanger,
feed of reaction block (C0). the minimum temperature difference between streams H2 and C1
With Eqs. (9)~(11) substituted into Eq. (8), Eq. (12) is obtained to is set as 10 K (TH2-TC1 ¼ 10 K), and that between stream H1 and H2 is
show the kinetic equilibrium of reactor R-101. With the data in 60 K (TH1-TH2 ¼ 60 K). It can be deduced that the difference between
Tables 1 and 2 substituted into Eq. (12), Eq. (13) is acquired. It in- TH1 and TC1 is 70 K (TH1-TC1 ¼ 70 K). DHE1, can be calculated by Eq.
dicates the relationship between recycle ratio (b) and the outlet (16).
temperature of the reactor (TH1) when the total operating conver-
sion (X) is fixed at 0.157. On the basis of this equation, the outlet DHE1 ¼ FC0 , CpH1 , TH1
FC0 , CpC0 ,TC1 (16)
temperature of reactor R-101 at different recycle ratios can be
identified. In this equation, CpC0 and CpH1 are the average heat capacity of
stream C0 and H1, respectively, and can be calculated by Eq. (17).
W b  2 Since the total conversion is kept unchanged, the compositions of
, , k , P total
FC0 1 þ b
ET C0 and H1 do not change, CpC0 and CpH1 are constant and DCp ¼
 h   i CpH1
CpC0 .
2
yET 2
yET total 2yO2
yET X
C0 X C0 X þ K1 P C0
¼ 
C0
 (12) X
2yET ð1
XÞ 2y O2

y ET X Cpj ¼ qij Cpi (17)
C0 C0 C0

 where, Cpj stands for the average heat capacity of stream j, and Cpi
10:78b 5241:7
, exp 12:39
¼ 45:75 is the heat capacity of component i; qij denotes the mole fraction of
1þb TH1

 component i in stream j.
2203:5
þ 6:67 exp
2:83 (13) Similarly, the recycle (H5) flow through R-101 and its temper-
TH1
ature increases from TH5 to TH1. The increment of its energy (DHE2)
is shown by Eq. (18).

DHE2 ¼ bFH5 CpH1 ðTH1
TH5 Þ

2.2.1.2. Thermodynamic equilibrium. Besides kinetics, the thermo-

1 ET
dynamic equilibrium of the reactor should be satisfied and is shown ¼ bCpH1 FC0
FC0 X ðTH1
TH5 Þ (18)
by Eq. (14). In this equation, the heat removed from the reactor (QR, 2
absolute value), the energy difference between the inlet and outlet Eq. (19) shows the energy balance of E
101, and is rearranged
stream of reactor (DHE), and the reaction heat (DHR) are considered. into Eq. (20) to identify TH3.

QR þ DHE þ DHR ¼ 0 (14)
DHE101 ¼ FH1 CpH1 ðTH2
TH3 Þ ¼ FC0 CpC0 ðTC1
TC0 Þ (19)

2:1ðTH1
70
TC0 Þ
TH3 ¼ TH1
60
  (20)
2.2.1.3. Reaction heat (DHR). In the reaction block shown in Fig. 3, ð1 þ bÞ 2
yET
C0 X
the preheated feed (stream C1) is mixed with the recycle (stream
H5), and the mixture flows into the reactor. The recycle has the where, DHE101 is the duty of E
101.
 D. Zhang et al. / Journal of Cleaner Production 275 (2020) 122773 7

Compressor K-101 is a single-stage compressor, and its inlet

pressure is 1.6 MPa. When its outlet pressure is 1.9 MPa and the
variable factor (n) is taken as 1.3, the relationship between TH5 and
TH3 is shown by Eq. (21) (Balmer, 2010).

n
1
1:9 n
TH5 ¼ TH3 ¼ 1:04TH3 (21)
1:6
Substituting Eq. (20) and Eq. (21) into Eq. (18), the energy dif-
ference of stream H5 is obtained and shown by Eq. (23).
 " #
bFC0 CpH1 2
yET
C0 X 2:18ðTH1
70
TC0 Þ
DHE2 ¼ 62:4þ  
0:04TC0
2 ð1þ bÞ 2
yET
C0 X
(22)

with Eq. (15), Eq. (16) and Eq. (22) combined, Eq. (23) is obtained to
indicate the energy equilibrium of reactor R-101.

ET
FC0 X DHRQ þ DCPðTH1
TR Þ
QR
FC0 , CpC0 , ðTH1
70Þ
  "
FC0 CpH1 2
yET
C0 X 2:18bðTH1
70
TC0 Þ
¼ 62:4b þ  
2 ð1 þ bÞ 2
yET
C0 X
# temperature (TH4) changes into TH4’, which can be calculated by Eq.

0:04bTC0 þ TH1
with the data of Tables 1 and 2 substituted into Eq. (23), Eq. (24) is
obtained to demonstrate the relationship among the recycle ratio,
removed heat and outlet temperature of the reactor. On the basis of
this equation and Eq. (13), the outlet temperature and removed
heat at different recycle ratios can be calculated.
 0  
0:12ðTH1
431Þ
ð10:95þ0:00057TH1 Þ
QR
b
0:005TH1
0:82
ð1þ bÞ

3:18¼0
2.2.2. Energy analysis
For the reaction block under the current operating condition,
the data of streams are listed in Table 3, and its Composite Curve
diagram is shown by Fig. 4. ABCD stands for the hot composite
curve, while EF is the cold one. QS corresponds to the duty of E
102,
while QC is the cooling utility consumed by E
103. Since the
temperatures of streams change along the recycle ratio, the data of
each stream need to be recalculated when the ratio is adjusted.
The effluent of reactor R-101 corresponds to stream H1; its
supply temperature, TH1, corresponds point A, and can be calculated
based on Eq. (13) and Eq. (24). When the recycle ratio changes from
b to b0 , TH1 changes to TH1’. As TH1-TH2 ¼ 60 K and TH2-TC1 ¼ 10 K,
TH10 -TH20 ¼ 60 K and TH20 -TC10 ¼ 10 K.
Stream H4 corresponds to segment CD, its target temperature
(TH6, point D) and heat capacity flow rate (CPCD) keep unchanged
because of the invariant total conversion. The coordinate of point C
Fig. 4. Composite Curves for the reaction system before and after the recycle ratio is
adjusted.
is (QC, TH4). When the recycle ratio is adjusted to b0 , its supply
(23) (20). The horizontal line corresponding to TH4’ intersects DC or its
extension line at point C0 . DC’ corresponds stream H4 at recycle
ratio b0 . And the duty of E
101 changes to QC’, which can be
calculated based on Eq. (25). Based on this, the horizontal coordi-
nate of point C0 , QC’, can be identified.
 0 
QC0 ¼ CPH4 TH4
TH6
0 1:02 TH1
428
¼ 113:8 TH1
0
388 (25)
ð1 þ b Þ
(24) Stream C1 corresponds to segment EF, and its supply tempera-
ture (TC0) and heat capacity flow rate are not affected by b and stay
unchanged. The coordinates of points E and F are (QC þ QE101, TC1)
and (QC, TC0), respectively. When the recycle ratio is adjusted to b0 ,
its target temperature is TC1’, and the corresponding horizontal line
intersects EF at E0 . When point C shifts to C0 , the horizontal line
corresponding to TC0 intersects the vertical line corresponding to
point C0 at point F0. Shifts FE’ rightward until point F coincides with
F0, point E0 will shift to E00 . F0 E00 corresponds to the cold stream C1 at
b0 . The coordinates of point E00 and F0 are (QC0 þQE101’, TC1’) and (QC’,
TC0’), respectively. The vertical line passing through E00 intersects
the horizontal line corresponding to TH2’ at B0 ; C0 B0 corresponds to
stream H2, whose duty can be calculated by Eq. (19).
As H1 and H2 are the same hot stream flowing through different
heat exchangers, the CP of stream H1 is supposed to be the same
with that of stream H2; thus the slope of segment CB is identical
with that of BA. The extended line of C0 B0 coincides the horizontal
line corresponding to TH1’ at point A0 . A0 B0 represents hot stream H1
when the recycle ratio is b0 ; its heat duty depends on the flow rate
of the recycle and can be calculated by Eq. (26).

Table 3
Stream data of reaction block.

Streams Heat exchanger Temperature, K Enthalpy change, kW CP, kW$K
1

Supply Corresponding point Target Corresponding point

C0 E
101 361 E 473 F 14,021.00 125.19

H1 E
102 543 A 483 B 12,649.80 210.83
H2 E
101 483 B 414 C 14,021.00 203.20
H4 E
103 414 C 328 D 9786.80 113.80
8 D. Zhang et al. / Journal of Cleaner Production 275 (2020) 122773


0
1þb  0  02 0 10
TH1
421
1:03ðT H1
431Þ
QS0 ¼ CPAB TH1 0

TH2 ¼ 4; 324:9b
7; 357b þ 15; 681:9 ðT
TC1 Þ
ðTH3
TC0 Þ ð1þbÞ
2 LMTD¼ H2 ¼ 2 3
ðTH2
TC1 Þ
(26) ln ðTH3
TC0 Þ
6 10 7
ln4 1:03ðTH1
431Þ5
where, QS0 is the heat duty of E
102 when its heat duty is b0 . TH1
421
ð1þbÞ

Based on the previous analysis, it can be identified that, when

the recycle ratio changes to b0 , A0 B0 C’D is the new hot composite (30)
curve, while F0 E00 is the cold one. 2 3
The flow rate of stream H5 changes along the recycle ratio, as
6 10 7
well as the power consumed by compressor K-101 (PC). The latter 129ðT3
431Þln4 1:03ðTH1
431Þ 5
can be determined by Eq. (27) [48] with the gas constant taken as TH1
421
ð1þbÞ
QE101
0.39 kJ mol
1$K
1.

1:02ðTH1
431Þ
PC ¼ 0:143b TH1

60 (27)
ð1 þ bÞ
2.2.3. Economic analysis
In the previous sections, each equipment of the reaction block is
studied, the duties of heating and cooling utilities, electricity and
recovered energy are identified. To identify the effect of recycle
ratio, the annual cost and energy revenue should be analyzed with
both the energy and capital costs considered, as the recycle ratio
affects the heat transfer area and capital cost of heat exchangers.
2.2.3.1. Cost of cooling utilities. Both heat exchanger E
103 and
reactor R-101 consume the cooling water. With the price of cooling
water and the annual operating time taken as 0.043 USD$ton
1 and
8000 h (Cui et al., 2014), respectively, the total cost of cooling water
can be calculated by Eq. (28) (Note, the temperature of the cooling
water increases by 5 K in these processes, and the energy it takes
away is 21,000 kJ$ton
1).


1:02T3
436:56
CCW ¼ 5; 086:7  T3

388 þ 45:3QR
ð1 þ bÞ
(28)
where, CCW represents the annual cooling utility cost, USD$year
1.
2.2.3.2. Energy recovery revenue in steam generating. In E
102, the
energy of the reactor’s effluent is recovered to generate steam.
Since the difference between the inlet and outlet temperatures of
the reactor’s effluent is 60 K, the energy consumed for steam
generation is only related to the recycle ratio, and can be calculated
by Eq. (26). Producting a ton of steam (1.5 MPa) costs 4,138,000 kJ of
energy. With the price of steam taken as 21.4 USD$ton
1, the rev-
enue of generating steam (Rsteam) can be calculated by Eq. (29).
02 0
Rsteam ¼ 193; 817:3b
329; 698:6b þ 701; 205 (29)
2.2.3.3. Capital cost. Stream H1’s temperature and flow rate vary
with the recycle ratio. This affect its outlet temperature from E
101,
the Logarithmic Mean Temperature Difference (LMTD) and duty of
E
101. Eq. (30) can be used to calculate the LMTD. With this
equation substituted into Eq. (19), Eq. (31) is obtained to calculate
the heat transfer area (AE101) of E
101.
AE101 ¼ ¼
KE101 ,LMTD H1
431Þ
10
TH1
421
1:03ðT
ð1þbÞ
(31)
where, KE101 is the total heat transfer coefficient of E
101 and is
taken as 2.1 kW K
1$m
2.
When the recycle ratio is adjusted, if heat transfer area of E
101
(20 m3) can meet the demand of heat transfer, no capital is needed,
as shown by Eq. (33); otherwise, the heat exchanger E
101 should
be replaced, and its annual capital cost (Ccapital) is estimated by Eq.
(33) (Jiang et al., 2018).
Ccapital ¼ 0Area  20 (32)
Ccapital ¼ 142:8 þ 114:3A1:2
E101 Area > 20 (33)
2.2.3.4. Electricity consumption of compressor. Based on Eq. (27),
the annual operating cost of compressor K-101, denoted as Ccomp,
can be represented by Eq. (34). In the derivation of this equation,
the price of electricity is taken 0.14 USD$(kW$h)
1, which is the
peak industrial tariff of Beijing (Price list of industrial and
commercial electricity in Beijing, 2014).
1:02ðTH1
431Þ
Ccomp ¼ 134:3b TH1

60 (34)
ð1 þ bÞ
with different costs calculated according to Eqs. (28e34), the total
annual profit of modifying this system can be identified according
to Eq. (35).
Rtotal ¼ Rsteam
CCW
Ccapital
Ccomp (35)
This equation can be used to identify the total annual profit at
different recycle ratios, with the variations of outlet temperature
and the removed heat of the reactor considered. Note, in the
calculation of the total annual profit, only the energy and capital
cost affected by the recycle ratio are considered.
3. Results and discussion
3.1. Effect on reactor parameters
At the current operation, the recycle ratio is 1.0, the corre-
sponding outlet temperature (TH1) and removed heat of the reactor
(QR) are 543 K and 4.67 MW. As TH1-TH2 ¼ 60 K and TH2-TC1 ¼ 10 K,
TH2 and TC1 are identified to be 483 K and 473 K, respectively, and
TH3 calculated according to Eq. (20) is 428 K.
The relation among the outlet temperature of the reactor (TH1),
the heat removed from the reactor (QR) and recycle ratio (b) is
plotted in Fig. 5. Considering the limitation of catalyst and
 D. Zhang et al. / Journal of Cleaner Production 275 (2020) 122773
Fig. 5. Variation of temperatures and removed heat of the reactor.
equipment, the recycle ratio varies within interval [0.55, 2.5]. From
this figure, it can be seen that, TH2, TC1 and TH3 vary significantly in
recycle ratio interval [0.55, 1.7] and nearly keeps unchanged in
interval (1.7, 2.5]. The removed heat decreases fast between recycle
ratio 0.55 and 1.7, while nearly keeps unaltered in interval (1.7, 2.5].
As the recycle ratio increases, the recycle flowrate increases, as well
as the heat removed by this stream; the one-way conversion of the
reactor (XS) decreases according to Eq. (7). The increment in recycle
flowrate will dilute the concentration of reactor’s feed and lead to
the decrement in reaction rate and reaction heat. This results in the
decrement of the outlet temperature of reactor (TH1), which can be
calculated according to Eq. (14). Because of this, TC1 and TH2 (the
outlet stream of preheater E
101 and steam generator E
102)
decrease accordingly. Based on thermodynamic equilibrium of the
reactor shown by Eq. (15), the energy supplied to reactor decreases.
TH3 is influenced by both the outlet temperature and recycle ratio as
calculated by Eq. (21). When the recycle ratio increases, the heat
duty of E
101 decreases due to the decrease of TC1; and the tem-
perature difference between stream H3 and H2 decreases. This
causes the increase of TH3.
The cycle ratio represents the backmixing degree of raw mate-
rial in the reactor. When the recycle ratio is greater than 1.7 as
shown in Fig. 5, the operation performance of the Plug Flow Reactor
Fig. 6. Economic analysis diagram for reaction block.
9
(PFR) is nearly equivalent to that of a Continuous Stirred Tank
Reactor (CSTR). In other words, 1.7 is the minimum recycle ratio for
the reactor to achieve the well mixed effect.
3.2. Economic analysis diagram
According to Eqs. (28)~(35), Fig. 6 is constructed to illustrate the
variation of the annual profit and cost along the recycle ratio, and
the following information is obtained:
1) The total annual profit mainly comes from the energy recovery
of steam generating. It together with the energy recovered by
E
102 increase significantly in recycle ratio interval [0.5, 1.7]
and remain stable in (1.7, 2.5]. When the recycle ratio is adjusted
from 1.0 to 1.7, the recovered energy will increase from 4.62 MW
to 6 MW, and the increment accounts for 29.8%.
2) As the recycle ratio increases, the cooling water cost decreases
gradually, and the cost of compressor increases approximate
linearly with the gas flowrate. The cooling utility consumption
(consumed by E
103 and R-101) decreases from 6.76 MW to
6.43 MW, and the decrement accounts for 4.88%.
3) The heat transfer area of E
101 decreases along the recycle
ratio. When the recycle ratio is greater than 1.0, the current area
of E
101 can meet the demand of heat transfer, and this
equipment does not need to be replaced. When the recycle ratio
decreases from 1.0 to 0.5, its capital cost will increase by 6728.6
USD per year.
4) In Fig. 6, the total annual profit at the present condition is
561,400 USD per year. With the recycle ratio adjusted to 1.7, the
maximum total revenue, 608,600 USD$year
1 is obtained, 8.4%
more than the current value, and no any other change on the
process or equipment needed. When the recycle ratio increases
further, the steam revenue almost keeps unchanged, while the
compressor cost increases significantly. This leads to a slightly
decrement in total profit. The optimal recycle ratio is 1.7.
5) At the optimal recycle ratio, it can be identified from Fig. 5 that
the optimal operating temperature of the reactor decreases to
524 K, the removed heat decreases to 4 MW accordingly, and the
outlet temperature of the hot stream of E
101 increases to
432 K.
To verify the results identified by the proposed method, the
system at the optimal recycle ratio is simulated by Aspen Plus 8.8,
and the simulation results are consistent with the data identified by
the proposed method, as shown by Table 4.
The proposed optimization method can be applied to guide
design and operation of chemical process. It could be extended to
optimize the recycle together with the reaction and separate
blocks, in terms of increasing the energy efficiency and profit of the
whole process further. The proposed method can be used in the
systems where the secondary reaction can be ignored and the re-
action kinetics of the primary reaction is known. The results are
accurate when the heat capacity of hot and cold streams related to
the recycle does not change significantly.
4. Conclusions and future work
In this paper, an ethylene to ethylene oxide process is studied
with the recycle ratio optimized based on the integration of HEN
and reactor. Equations deduced based on kinetic and thermody-
namic equilibrium show the variations of the outlet temperature
and removed heat of the reactor along recycle ratio. Energy con-
sumptions are analyzed based on the Composite Curves. The eco-
nomic analysis diagram illustrate the variation of revenue and cost
along recycle ratio clearly. With the equipment and catalyst
10 D. Zhang et al. / Journal of Cleaner Production 275 (2020) 122773

Table 4
Comparstion of the results obtained by the proposed method and simulation.

Data Current data Optimum value identified by the proposed method Results obtained based on simulation Error

Recycle ratio 1.0 1.7 1.7 0

Outlet temperature of reactor, K 543 524 524.7 0.13%
Outlet temperature of the hot stream of E
101, K 428 433 432.04
0.22%
Removed heat, MW 4.67 4 4.04 1.0%
Steam revenue, USD$year
1 668,600 735,700 736,280.8 0.079%
Cooling water cost, USD$year
1 66,571 63,586 63,885.9 0.47%
Compressor cost, USD$year
1 40,629 63,514 63,375.2
0.22%
Total annual profit, USD$year
1 561,400 608,600 609,037.7 0.072%

operating in their feasible region, the optimal recycle ratio is
identified to be 1.7, and the maximum revenue is 608,600 USD per
year, 8.4% more than the current value, the recovered energy in-
creases by 29.8%, and no any other change on the process or
equipment needed.
In the proposed method, only the recycle ratio is adjusted while
the original matches of HEN remains unchanged. For a practical
process, it is convenient and efficient to achieve better economic
performance without retrofit on the process or equipment. The
proposed optimization method can be applied to guide its design
and operation. Furthermore, this method could be extended to
optimize the recycle together with the reaction and separate
blocks, in terms of increasing the energy efficiency and profit of the
whole process further. This will be studied in the future work.
CRediT authorship contribution statement
Di Zhang: Conceptualization, Methodology, Software, Writing -
original draft. Peng Hang: Validation, Writing - review & editing.
Guilian Liu: Investigation, Supervision.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgement
Financial supports provided by the National Natural Science
Foundation of China (21736008 and U1662126) are gratefully
acknowledged.
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