1 s2.0 S0263876212004868 Li

Please cite this article in press as: Bayat, M., et al.
, Dynamic mathematical modeling of a novel dual-type industrial ethylene oxide (EO) reactor.
Chem. Eng. Res. Des. (2013), http://dx.doi.org/10.1016/j.cherd.2012.12.003
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CHERD-1137; No. of Pages 10
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Dynamic mathematical modeling of a novel dual-type
industrial ethylene oxide (EO) reactor
M. Bayat
a
, Z. Dehghani
a
, M. Hamidi
a
, M.R. Rahimpour
a,b,
a
Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345, Iran
b
Department of Chemical Engineering and Materials Science, University of California, Davis, One Shields Avenue, Davis, California
95616, United States
a b s t r a c t
In this paper, the dynamic behavior of a novel dual-type industrial ethylene oxide reactor has been proposed with
taking catalyst deactivation into account. The conguration of two catalyst beds instead of one single catalyst bed
is developed for conversion of ethylene to ethylene oxide. In the rst reactor which is an industrial xed-bed water-
cooled reactor, the feed gas is partly converted to ethylene oxide. This reactor functions at very high yield and at a
higher than normal operating temperature. In the second converter, the reaction heat is used to preheat the feed gas
to the rst reactor and a milder temperature prole is observed. The potential possibilities of a two-stage catalyst
bed system are analyzed using a 1D heterogeneous dynamic model to obtain necessary comparative estimates. A
differential evolution(DE) algorithmis appliedas aneffective androbust methodto optimize the reactors lengthratio.
The results obtained fromthe simulation demonstrate that there is a desirable catalyst temperature prole along the
dual-type reactor (DR) compared with the conventional single-type reactor (SR). In this way, the catalysts are exposed
to less extreme temperatures and thus, diminishing the catalyst deactivation via sintering. Results fromthis study
provided benecial information about the effects of reactors conguration on catalyst lifetime and ethylene oxide
production rate simultaneously.
2012 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Ethylene oxide; Dual-type reactor; Dynamic simulation; Catalyst deactivation
1. Introduction
1.1. Ethylene oxide
Ethylene oxide (EO) is the second largest volume industrial
chemical made from ethylene. Currently, the primary use of
EO as an industrial feed stock is in the manufacture of ethyl-
ene glycol, which is mainly used as a basic raw material for
producing polyethylene terephthalate. Ethylene oxide is com-
mercially produced by a direct gas phase oxidation of ethylene
over silver catalysts with adequate activity and selectivity in
xed-bed reactor (FBR) (Stoukides and Pavlou, 1986).
The general reaction schemes for oxidation of ethylene to
EO are expressed as:
C
2
H
4
+0.5O
2
Ag
C
2
H
4
O LH
298
= 105.39 kJ/mol (1)
C
2
H
4
+3O
2
Ag
2CO
2
+2H
2
O LH
298
= 1321.73 kJ/mol (2)
Corresponding author. Tel.: +98 711 2303071; fax: +98 711 6287294.
E-mail address: rahimpor@shirazu.ac.ir (M.R. Rahimpour).
Received17 August 2012; Receivedinrevisedform2 December 2012; Accepted4 December 2012
The principal stage in EO process is ethylene oxidation
reaction (1) which undergoes a rapid oxidation reaction (2).
The mechanism of these reactions has been studied and
reported by Van Santen and Kuipers (1987).
1.2. Process intensication (PI)
Process intensication (PI) is one of the most considerable
trends in the chemical engineering and process technol-
ogy. Nowadays, researchers pay much attention to this trend
(Stankiewicz and Moulijn, 2004; Ferrouillat et al., 2006a, 2006b;
Stankiewicz and Moulijn, 2000). It refers to the strategies for
achieving dramatic reduction of emissions as well as con-
sumption of materials and energy. The leading starting point
which somehow could be the heart of chemical processes is
frequently innovations in the catalytic reactor technologies.
Thus, auto-thermal reactor as a novel concept is presented
in PI. Recently, the two-stage reactor has become a promis-
ing eld of applying the auto-thermal reactors. The novel
0263-8762/$ see front matter 2012 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cherd.2012.12.003
Please cite this article in press as: Bayat, M., et al., Dynamic mathematical modeling of a novel dual-type industrial ethylene oxide (EO) reactor.
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2 chemical engineering research and design x x x ( 2 0 1 3 ) xxxxxx
conguration of DR systempermits high temperatures in the
rst reactor and lowtemperatures in the second one. The rst
reactor, the isothermal water-cooled reactor, is combined in
series with the second reactor, the gas-cooled reactor, which
accomplishes partial conversion of feed gas to EO.
1.3. Dual-type reactor
Rahimpour et al. (2011) considered a water-cooled industrial
xed-bed reactor which was 8.7m long. In this study, the
above-mentioned reactor was divided into two reactors called
DR. Both rst and industrial xed-bed reactors are of the same
conguration with the exception of being 6.96m long in the
rst one. Besides, a gas-cooled concept is used for the second
catalyst bed. This system is used to determine the reactants
conversionand components productionina hightemperature
EO process. A DR is a shell and tube heat exchanger reactor in
which the rst reactor, water-cooled reactor, is combined in
series with the second reactor, gas-cooled reactor. This design
has the advantage of preheating cold feed gas inside the shells
of second converter.
Afterwards, the preheated gas is fed into the tubes of the
water-cooled reactor which is an isothermal reactor. In this
stage, the chemical reaction is initiated by Ag catalysts and
feed gas is partly converted to EO. The reacting gas leaving
water-cooled reactor is directed into the tubes of the gas-
cooled reactor in counter-current mode with feed gas passing
throughthe shells. Finally, the reactionhas gone tocompletion
in the reaction side of the second catalyst bed.
1.4. Dynamic simulation
From a theoretical point of view, in the eld of modeling
and simulation of catalytic xed-bed reactors under typi-
cal operating conditions, two different policies have been
implemented: (1) conventional steady-state simulationand (2)
dynamic (transient) simulation.
The extreme complexity of the processes involved in eth-
ylene oxide production, justies the computer simulations of
suchprocesses toget further understanding of systemwithout
the need to perform expensive and time-consuming experi-
ments. The dynamic simulation of ethylene oxide processes
has a wide range of applications including: the start-up and
shut-down investigations, system identication, safety, con-
trol, optimization, transient behavior, and operability studies.
In operability studies, it is more favorable to use dynamic sim-
ulation rather than steady-state simulation, since a realistic
descriptionof transient states of the reactor canbe obtainedby
using dynamic simulation. It is due to the fact that the numer-
ical solution strategies used in dynamic models are more
powerful than the solution of a typical steady-state model.
Thus, it allows for safe and reliable studies of control and opti-
mizationof the reactor (Vasco de Toledo et al., 2001; Setinc and
Levecb, 2001).
1.5. Literature review
Many authors and researchers have been investigated this
reaction in various cases. In recent years, they are trying
to modify this process with possible assumptions. Hwang
and Smith (2004) presented results of ethylene oxide reac-
tor simulation with the purpose of nding an optimal
operating temperature for this reactor under steady-state con-
ditions ignoring catalyst deactivation. Zhou and Yuan (2005)
optimized an industrial ethylene epoxidation process with
considering feed composition, feeding rate and operating
pressure as variable parameters using a 1D homogeneous
model in steady-state conditions. In the work of Cornelio
(2006), a dynamic heterogeneous model of an industrial
EO reactor was developed and afterwards simplied into a
pseudo-homogeneous model. Aryana et al. (2009) modeled
and optimized an industrial ethylene oxide oil coolant reac-
tor without taking the mass balance on catalyst for species
into account. Lahiri and Khalfe (2009) used an integrating sup-
port vector regression and genetic algorithm to model and
optimize an industrial ethylene oxide reactor. Recently, the
articial neural network has been applied by Rahimpour et al.
(2011) for modeling and simulation of an industrial EO reac-
tor. Mathematical modeling and simulation of DR are almost
limited to the Rahimpours studies. A two-stage catalyst bed
for conversion of carbon dioxide into methanol was proposed
by Rahimpour (2008). Afterwards, Rahimpour and Lotnejad
(2007) have considered a dynamic model for studying PdAg
membrane in methanol synthesis. They demonstrated that
using a membrane DR will raise methanol production. This
novel dual-stage conguration was applied as a pioneer
work for gasoline enhancement in FischerTropsch synthesis
(Rahimpour et al., 2010).
1.6. Objectives
There is no information available in the literature which pro-
vides the use of dual-stage conguration in an industrial
ethylene oxide reactor. Therefore, it was decided to study this
novel system. The main purposes of this work are improv-
ing EO production and reducing the catalyst deactivation in
DRs. The benets of this concept will be extensively discussed
regarding temperature and concentration proles as well as
catalyst activity prole along the reactors. Numerical simula-
tion results of the DR are compared with that of conventional
SR at the same process conditions such as temperature, pres-
sure, catalyst mass and feed composition.
2. Reaction kinetics
The kinetics of ethylene oxidation has been widely stud-
ied by many researchers (Borman and Westerterp, 1995;
Gianpiero and Tronconi, 2001; Stegelmann et al., 2004). In
the current work, the corresponding rate expressions have
been selected from Gu et al. (2003) and are represented as
follow:
r
EO
=
exp(10.30 (8358.5,T)) P
ET
P
0.75
O
2
1 +D
n
(3)
r
CO
2
=
exp(12.54 (9835.2,T)) P
ET
P
O
2
1 +D
n
(4)
r
EO
andr
CO
2
are the reactionrates of ethylene oxide andcarbon
dioxide, while P
ET
and P
O
2
are the pressure of ethylene and
oxygen, respectively. D
n
is calculated as follows:
D
n
= 1 = exp
9812.8
T
21.68
P
CO
2
+exp
16129.2
T
34.58
P
0.5
CO
2
P
H
2
O
(5)
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chemical engineering research and design x x x ( 2 0 1 3 ) xxxxxx 3
Steam
Drum
Ethylene oxide
Saturated water
Reaction side
(Fixed-bed)
Ethylene
oxygen
Fig. 1 A schematic diagramof single-type ethylene oxide
reactor.
Table 1 Ethylene oxide reactor feed inlet conditions
(Rahimpour et al., 2011).
Parameter Value
Feed composition (mole fraction)
C
2
H
4
0.25
O
2
0.08
C
2
H
4
O 0.0001
H
2
O 0.0025
CO
2
0.07
N
2
0.1271
CH
4
0.4703
Total molar ow rate (mol s
1
) 0.89
Inlet pressure (bar) 21.7
Inlet temperature (K) 463
Coolant temperature (K) 503
3. The reactor conguration
3.1. Conventional xed-bed single-stage ethylene oxide
reactor (SR)
An industrial SR is often a vertical shell and tube heat
exchanger. The EO reactions are carried out in vertical tubes
containing a packed bed of silver catalysts and surrounding by
boiling water. The heat of exothermic reactions is transferred
to the boiling water and subsequently steam is produced. A
schematic diagramof a single-stage conguration for EO syn-
thesis is illustrated in Fig. 1. The specications of reactor,
catalyst and feed composition are tabulated in Tables 1 and 2.
3.2. Dual-type ethylene oxide reactor (DR)
Fig. 2 depicts the schematic diagram of a two-stage cata-
lyst bed concept for EO production. This system is mainly
based on a cascade reactor systemconsisting of a gas-cooled
and a water-cooled reactor. The feed gas, with the same
Table 2 Catalyst and reactor specications.
Quantity Value
Particle diameter (m) 7.74 10
3
Heat capacity (kJ kg
1
K
1
) 1.0
Specic surface area (m
2
m
3
) 387.59
Bed void fraction 0.5
Number of tubes 5523
Length of reactor (m) 8.7
Second Convertor
(Gas-cooled convertor)
First Convertor
(Water-cooled convertor)
Steam Drum
Shell side
Saturated water
Ethylene oxide
Shell side
Ethylene
oxygen
Fig. 2 A schematic diagramof dual-type ethylene oxide
reactor.
specications as the feed of conventional reactor (as tabulated
in Tables 1 and 2), is fed to the shells of second reactor (gas-
cooled reactor) and it is owing in counter-current mode with
the reacting gas mixture passing through the tubes. In this
way, the feed gas is preheated by the reaction heat produced
in the tube side of second reactor.
The preheated outlet gas fromthe second reactor is fed to
the tubes of rst reactor (water cooled) and subsequently the
chemical reaction is initiated over Ag catalyst. In this stage,
the feed gas is partly converted to EO in an industrial xed-
bed water-cooled reactor. The heat of reaction produced in
the tubes of rst reactor is transferred to the boiling water
inside its shells. This reactor functions at very high yield and
at a higher than normal operating temperature. These factors
allow higher pressure steam to be produced which improves
the energy efciency of the system.
The mixture of unreacted gas and EO leaving the rst reac-
tor is routed to the second stage reactor without any previous
cooling. In this reactor, cold feed gas for the rst reactor is
passed through the shells in a counter-current mode with
the reacting gas mixture and thus, the reaction tempera-
ture is continuously lowered over the reaction pathway. As
fresh feed gas is only fed to the rst reactor, no catalyst poi-
sons reach the second reactor. The poison-free operation and
the low operating temperature result in a practically unlim-
ited catalyst lifetime for the gas-cooled reactor. Generally, the
industrial single water-cooled reactor requires a large inlet gas
pre-heater for synthesis that replacing a relatively small trim
pre-heater will meet this need. In this investigation, all spec-
ications of the rst and second reactors are the same as the
industrial xed-bed EOreactor and tabulated inTables 1 and 2.
4. Dynamic reactor model
4.1. Mathematical model
The mathematical model for simulation of single and two-
stage catalyst bed reactor has been developed based on the
following assumptions:
1D heterogeneous model (reactions take place over catalyst
particles)
Plug ow pattern is considered in reaction side
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Axial diffusion of heat and mass are neglected compared
with the convection
No radial heat and mass diffusion in catalyst pellet
Bed porosity in both axial and radial directions is constant
Gas mixtures are assumed to be ideal
Heat loss is negligible
4.1.1. Water-cooled reactor (rst reactor)
The following mass and energy balance equations are devel-
oped for the bulk gas phase:
B
c
t
y
i
t
=
1
A
c
F
i
z
+u
v
c
t
k
gi
(y
is
y
i
) i = 1. 2. . . . . N 1 (6)
B
c
t
c
pg
T
t
=
1
A
c
c
pg
(F
t
T)
z
+u
v
n
(T
s
T) +
D
i
A
c
U
shell
(T
shell
T)
(7)
where y
i
and T are the gas-phase mole fraction and tempera-
ture, respectively and i represents C
2
H
4
, O
2
, CO
2
, C
2
H
4
O, H
2
O.
Nitrogen and methane are inert components.
The mass and energy balances for the catalyst pellets are
obtained as follow:
s
c
t
dy
is
dt
= k
gi
u
v
c
t
(y
i
y
is
) +jr
i
,
B
u i = 1. 2. . . . . N 1 (8)
,
B
c
ps
s
dT
s
dt
= u
v
n
(T T
s
) +,
B
u
N
i=1
jr
i
(LH
.i
) (9)
where y
is
and T
s
are the mole fractions on the catalyst surface
and solid-phase temperature, respectively.
The boundary conditions are as follow:
z = 0; F
t
= F
in
. y
i
= y
i.in
. T = T
in
(10)
4.1.2. Gas-cooled reactor (second reactor)
4.1.2.1. Tube side (reaction side). The mass and energy bal-
ance for solid phase in the gas-cooled reactor is the same as
that in the water-cooled reactor. The following equations are
presented for uid phase:
B
c
t
y
i
t
=
1
A
c
F
t
i
z
+u
v
c
t
k
gi
(y
is
y
i
) i = 1. 2. . . . . N 1 (11)
B
c
t
c
pg
T
t
=
1
A
c
C
pg
(F
t
T)
z
+u
v
n
(T
s
T) (12)
where y
i
and T are the mole fraction of component i and gas-
phase temperature, respectively.
4.1.2.2. Shell side. The mass and energy balance equations for
uid phase can be formulated as follows:
c
t
y
i
t
=
1
A
shell
F
i
sn
z
i = 1. 2. . . . . N 1 (13)
c
t
c
pg
T
sn
t
=
1
A
shell
C
pg
(F
sn
T
sn
)
z
+
D
i
A
c
U(T T
sn
) (14)
The boundary conditions are as follow:
z = L; y
sn
i
= y
i
. T
sn
= T
. F
t
= F
(15)
while, the initial conditions are:
t = 0; y
t
i
= y
ss
i
; T
t
= T
ss
. T
t
tube
= T
ss
tube
. u = 1 (16)
4.2. Pressure drop
The Ergun momentum balance equation is used to give the
pressure drop along the reactor:
dP
dz
= 150
(1 )
2
ju
g
3
d
2
p
+1.75
(1 )u
g
2
,
3
d
p
(17)
where the pressure drop is in Pascal.
In order to complete the simulation of the reactors, heat
and mass transfer between two phases as well as overall heat
transfer coefcient between two sides should be taken into
account. On the other hand, estimation of physical properties
is another important issue in calculations. Therefore, auxil-
iary correlations are added to the set of differential equations.
These correlations are summarized in Table 3. The heat trans-
fer coefcient betweengas phase andreactor wall is applicable
for heat transfer between gas phase and solid catalyst phase.
In recent reactor studies, a constant total molar ow
rate has been considered during modeling. This assumption
reduces the accuracy of predictionfor reactor outlet mole frac-
tions.
In the industrial xed-bed EO reactor, a continuous
decrease of total molar ow rate exists along the reactor
length. Therefore, the total molar owrate is considered to be
variable along the reaction pathway in this study. Moreover,
the molecular weights, heat capacities, viscosity, density and
other properties are assumed to be variable for mathematical
modeling.
4.3. Catalyst deactivation
Catalyst deactivation is one of the most challenging issues in
catalytic reactors. The three main factors affecting catalytic
activity are sintering, poisoning and wearing, while sintering
is the principal reason of Ag catalyst deactivation (Hound
andMinahan, 1996; Montrasi et al., 1983). This process reduces
the catalyst active sites. Reduction of catalyst active sites is
usually expressed by the generalized power lawexpression as
follows (Bartholomew, 2001):
du
dt
= k
d
(u u
)
2
(18)
where k
d
is the sintering rate constant and is a function of
temperature:
k
d
= k
d
0
exp
E
d
RT
(19)
The numerical value of u
is 0.3, E
d
is 40kJ/mol and k
d
0
is 210
3
(month
1
) (Rahimpour et al., 2011; Zhou and Yuan,
2005). On the -Al
2
O
3
support, silver crystallites have sizes of
about a few 100nmand act as bulk silver (Kestenbaumet al.,
2002).
5. Numerical solution
The fundamental structure of the model includes partial dif-
ferential equations of mass and energy conservation rules
of both catalyst and uid phase. The partial differential
ARTICLE IN PRESS
Table 3 Physical properties, mass and heat transfer correlations.
Parameter Equation Reference
Component heat capacity C
p
= u +bT +cT
2
+dT
2
Mixture heat capacity C
p.mix
=
n
i=1
y
i
C
p.i
Viscosity j =
C
1
T
C
2
1+(C
3
,T)+(C
4
,T
2
)
Perry and Green (2008)
Viscosity of reaction mixtures j
m
=
y
i
j
i
M
0.5
u.i
y
i
M
0.5
u.i
Mass transfer coefcient
between gas and solid phases k
gi
= 1.17 Re
0.42
Sc
0.67
i
u
g
10
3
Cussler (1984)
Re =
2Rpug
j
Sc
i
=
j
,D
im
10
4
D
im
=
1y
i
i=j
y
i
,D
ij
Wilke (1949)
D
ij
=
1.4310
7
T
3,2
1,M
i
+1,M
j
2 P
v
1,3
ci
+v
1,3
cj
2
Reid et al. (1977)
Overall heat transfer coefcient
1
U
=
1
n
i
+
A
i
ln(Do,D
i
)
2LKu
+
A
i
Ao
1
no
Heat transfer coefcient between gas phase and reactor wall
n
Cp,j
Cpj
K
2,3
=
0.458
,udp
j
0.407
Smith (1980)
equations, ordinary differential equation of the deactivation
model, non-linear algebraic equations of the kinetic model,
and auxiliary correlations must be solved simultaneously. A
two-stage approach consisting of a steady-state simulation
followed by a dynamic simulation is the solution procedure of
these equations. For this purpose, a steady-state simulation
was used before dynamic simulation to compute the initial
values for dynamic mode.
5.1. Steady-state simulation
For steady-state simulation of dual-type EO reactor, it is con-
sidered to set all the time-variation of the states to zero.
Besides, a fresh catalytic bulk with an activity of unity is
assumed for this purpose. In this way, the initial temperature
and concentration can be specied for the dynamic simula-
tion. The solving procedure is explained below.
After rewriting the model equations, a set of differential
algebraic equations is obtained. Backward nite difference
approximation is utilized to solve these equations and a
non-linear algebraic set of equations is achieved. The set of
non-linear equations are a boundary value problem and can
be solved with the shooting method. The temperature of the
water-cooled reactor (T
in
) is unknown, while the temperature
of feed gas stream (T
f
) is known. By the means of shooting
method, the boundary value problem converts to the initial
value problem. The solution can be achieved by guessing an
approximate value for T
in
of heated feed gas to the water
cooled reactor. These reactors are divided into 100 sections
and the Gauss-Newton method is used to solve the non-linear
algebraic equations in each section. Finally, the calculated
value for the temperature of fresh feed gas stream(T
f
) is com-
pared with the real values. This procedure is repeated until
the specied terminal values are obtained within a small con-
vergence criterion.
5.2. Solution of dynamic model
The simulation results of the steady-state conditions are
considered as initial values for the time-integration of the
dynamic state equations in each node through the reac-
tor. The set of dynamic equations consists of simultaneous
ordinary and partial differential equations due to the deacti-
vation model and conservation rules, respectively, as well as
the algebraic equations due to auxiliary correlations, kinetics
of the reaction system. A discretization has been performed
for the set of equations with respect to axial and time coor-
dinate of the nodes. Globally convergent multi-dimensional
Newtons method is used in MATLAB environment to solve
these equations. Durationof 1100 operating days is considered
for this process. The shooting method procedure in dynamic
simulations is the same as steady-state simulations.
5.3. Model validation
In order to verify the accuracy of the model, simulation results
are compared with the historical process data during 1100
operating days under the design specications (Rahimpour
et al., 2011). The most important characteristic parameter of
the ethylene oxidationreactor is the productionrate of EO. The
calculated results of production rate and the corresponding
observed data of the plant are presented in Table 4. The plant
data used for evaluation is taken from a typical Petrochemi-
cal Complex in Iran. It is noticed that, the model performed
satisfactorily well under industrial conditions and there was
Table 4 Comparison between predicted ethylene oxide
production rates by heterogeneous model with plant
data (Rahimpour et al., 2011).
Time (day) Plant (t/day) Heterogeneous model
Predicted (t/day) Deviation
0 370.00 372.86 0.77
100 370.60 370 0.16
200 372.10 366.5 1.5
300 369.12 363.1 1.633
400 368.50 359.78 2.36
500 361.69 356.56 1.41
600 360.58 353.43 1.98
700 347.61 350.38 0.8
800 354.74 347.41 2.06
900 352.39 344.52 2.23
1000 345.43 341.7 1.07
1100 347.20 338.41 2.52
ARTICLE IN PRESS
0 1 2 3 4 5 6 7 8 9
475
480
485
490
495
500
505
510
515
(a)
(b)
Length (m)
G
a
s

p
h
a
s
e

t
e
m
p
e
r
a
t
u
r
e

(
K
)
First Reactor
Second Reactor
7 7.2 7.4 7.6 7.8 8 8.2 8.4 8.6
462
464
466
468
470
472
474
476
478
480
Length (m)
T
e
m
p
e
r
a
t
u
r
e

o
f

c
o
o
l
a
n
t

(
K
)
Fig. 3 Temperature proles of gas phase (a) and coolant (b)
along the dual-catalyst bed system.
an acceptable agreement between observed plant data and
simulation data.
6. Results and discussions
A parametric analysis is performed to address the essential
parameters, such as temperature, catalyst activity and EOpro-
duction rate proles along the reactors.
0 1 2 3 4 5 6 7 8
460
470
480
490
500
510
520
Length (m)
G
a
s

p
h
a
s
e

t
e
m
p
e
r
a
t
u
r
e

(
K
)
SR
DR
Fig. 4 Comparison between gas phase temperature
proles along single-type and dual-type reactor.
6.1. Reactors length ratio effect
Differential evolution method is used to determine the opti-
mal reactors length ratio for ethylene oxide production
process. The target of this work is to maximize the EO pro-
duction during 1100 operating days.
The variation range of this variable is as follows:
0 - L
Ratio
L
1
L
- 1
513K is considered as a constraint for the temperature of
catalytic bed along the reactor due to the catalyst deactivation
at higher temperatures.
A penalty function method is applied to automatically
eliminate the unacceptable results. In this study, 10
7
is con-
sidered as the penalty parameter, however, this parameter
depends on the order of magnitude of the decision variables.
The objective function that should be minimized is:
OF = (Product rateof EO) +10
7
N
i=1
C
2
i
(20)
where
C = max (0. T 513)
The optimumvalue for maximization of objective function
is achieved as L
ratio
= 0.8 (using DE Algorithm and MATLAB
programming). Therefore, the length of rst reactor is chosen
to be 6.69m. A brief description of the DE method is given in
Appendix A.
6.2. Results of steady-state simulation
Fig. 3 demonstrates gas temperature prole along the two-
stage catalyst bed system. As it can be seen in Fig. 3(b), the
feed gas is fed to the shells of the second bed at 463K and is
pre-heatedusing the heat of catalytic reactionwhichproduced
in tube side of this bed. The outlet synthesis gas is at 478Kand
its temperature is high enough to initiate the reaction in the
rst reactor. In this way, the need for a large heat exchanger
to preheat the feed gas with outlet product stream (as in
the industrial xed-bed single-stage reactor) is eliminated. A
continuous reduction of the reacting gas temperature in the
second bed canbe seeninFig. 3(a). Consequently, the catalysts
0 1 2 3 4 5 6 7 8
0
50
100
150
200
250
300
350
400
Length (m)
E
t
h
y
l
e
n
e

o
x
i
d
e

p
r
o
d
u
c
t
i
o
n

r
a
t
e

(
t
o
n
/
d
a
y
)
SR
DR
Fig. 5 Comparison of ethylene oxide production rate
prole for DR and SR systems for fresh catalyst.
ARTICLE IN PRESS
are exposed to less extreme temperatures and thus, catalyst
deactivation via sintering is circumvented as it is presented in
the following gures. This system results in important tech-
nical features owing to the extremely favorable temperature
proles over the catalyst beds. As perceived by Fig. 3(b), if we
go in the opposite direction of the curve (from8.7mto 6.96m)
the coolant gas temperature continuously increases along the
reactor lengthas a consequence of heat transfer fromthe reac-
tion side to the shell side.
Fig. 4 compares temperature proles of gas phase along the
conventional SR with DR system. As this gure shows, the rst
reactor of the dual-type operates at higher temperatures than
single-type. The higher temperature prole in two-stage cata-
lyst bed systemimproves the reaction rate and consequently
leads to more EO production in this system.
The comparisonof simulationresults of EOproductionrate
for SR and DR at rst day is depicted in Fig. 5. As it can be
seen, the highest EO production rate is achieved in DR. The
difference betweenDRand SRperformance is attributed to the
positive effects of higher temperature prole at rst section
of the reactor and improvement of the reaction rate in the
water-cooled reactor.
0 1 2 3 4 5 6 7 8
460
470
480
490
500
510
520
Length (m)
T
e
m
p
e
r
a
t
u
r
e

(
K
)
100th day
(a) (b)
(c) (d)
(e) (f)
SR
DR
0 1 2 3 4 5 6 7 8
0.99
0.991
0.992
0.993
0.994
0.995
0.996
0.997
0.998
0.999
1
Length (m)
A
c
t
i
v
i
t
y
100th day

SR
DR
0 1 2 3 4 5 6 7 8
0
50
100
150
200
250
300
350
400
Length (m)
E
t
h
y
l
e
n
e

o
x
i
d
e

p
r
o
d
u
c
t
i
o
n

r
a
t
e

(
t
o
n
/
d
a
y
)
100th day
SR
DR
0 1 2 3 4 5 6 7 8
460
470
480
490
500
510
520
Length (m)
T
e
m
p
e
r
a
t
u
r
e

(
K
)
800th day
SR
DR
0 1 2 3 4 5 6 7 8
0.92
0.93
0.94
0.95
0.96
0.97
0.98
0.99
1
Length (m)
A
c
t
i
v
i
t
y
800
th
day
SR
DR
0 1 2 3 4 5 6 7 8
0
50
100
150
200
250
300
350
400
Length (m)
E
t
h
y
l
e
n
e

o
x
i
d
e

p
r
o
d
u
c
t
i
o
n

r
a
t
e

(
t
o
n
/
d
a
y
)
800th day
SR
DR
Fig. 6 Comparison between temperature proles (a) and (d), activity proles (b) and (e) and ethylene oxide production rate
proles (c) and (f) in two types of systems at 100th day and 800th day of operation.
ARTICLE IN PRESS
0
500
1000
1500
0
2
4
6
8
10
470
480
490
500
510
520
(a)
(b)
Time (day)
Length (m)
T
e
m
p
e
r
a
t
u
r
e

(
K
)
0
200
400
600
800
1000
1200 0
5
10
0.88
0.9
0.92
0.94
0.96
0.98
1
Length (m)
Time (day)
A
c
t
i
v
i
t
y
Fig. 7 The proles of (a) reactor temperature and (b)
catalyst activity along a DR system.
6.3. Results of dynamic simulation
We have carried out simulations with position dependent
catalytic activity proles to investigate the effect of catalyst
activity on the production rate by using simulation results
and showing the reasons for better performance of DR in com-
parison with SR. Fig. 6 shows gas-phase temperature, activity
and EO production rate proles along the DR and SR at 100th
day and 800th day of operation. The local change of activity
along the reactor is due to the local variation of temperature,
which consequently affects the catalytic activity of bed. As it
can be seen from Fig. 6(b) and (e), the activity level sharply
reduces in the rst reactor because the catalysts are exposed
to higher temperatures at any time. Since temperature prole
declines along the gas-cooled reactor of DR (see Fig. 6(a) and
(d)), the catalyst activity is increased in this stage. The lower
temperature prole along the gas-cooled reactor of DR system
leads to a lower rate of catalyst deactivation along the reactor.
Therefore, DRcongurationprovides a more favorable catalyst
activity, in comparison with SR, as shown in Fig. 6(b) and (e).
As a consequence, the EO production rate in DR is higher than
that in the SR that can be seen in Fig. 6(c) and (f).
Fig. 7 illustrates the reactor temperature proles as well as
the catalyst activity versus time and length for a DR. In the
rst reactor (fromthe reactor entrance to 6.96m), the temper-
ature of the reacting gas mixture on rst days is higher due
to fresh catalyst and higher conversion. The rate of reaction
heat decreases during further operationas the catalyst is deac-
tivated. Since the heat of reaction is continuously removed by
the cooling water, the temperature of the reacting gas mixture
is reduced with time in the rst reactor. In the second bed
0
200
400
600
800
1000
1200
0
2
4
6
8
10
0
0.005
0.01
0.015
0.02
0.025
Time (day)
Length (m)
E
t
h
y
l
e
n
e

o
x
i
d
e

m
o
l
e

f
r
a
c
t
i
o
n
Fig. 8 The prole of ethylene oxide mole fraction versus
length and time for a DR.
(from 6.96m to 8.7m), the catalyst activity increases which
leads to an enhancement of EO concentration gradient along
the reactor and thus, heat of reaction rises with time. Since
the ability of the coolant gas for removing the heat of reaction
is less thanthat of coolant water, temperature decreases along
the reactor in course of time, as showed in Fig. 7(a).
The minimum activity level is observed near the inlet of
the rst reactor that is exposed to higher temperatures at dif-
ferent times. The catalyst in the gas-cooled reactor tends to
0 100 200 300 400 500 600 700 800 900 1000 1100
504.5
505
505.5
506
506.5
507
507.5
(a)
(b)
Time (day)
A
v
e
r
a
g
e

o
f

t
e
m
p
e
r
a
t
u
r
e

(
K
)

SR
DR
0 100 200 300 400 500 600 700 800 900 1000 1100
0.9
0.91
0.92
0.93
0.94
0.95
0.96
0.97
0.98
0.99
1
Time (day)
A
v
e
r
a
g
e

o
f

a
c
t
i
v
i
t
y
SR
DR
Fig. 9 Comparison of (a) average temperature and (b)
average activity in the reactor at a period of 1100 operating
days for two types of reactor systems.
ARTICLE IN PRESS
0 100 200 300 400 500 600 700 800 900 1000 1100
330
340
350
360
370
380
390
Time (day)
E
O

p
r
o
d
u
c
t
i
o
n

r
a
t
e

(
t
o
n
/
d
a
y
)
SR
DR
Fig. 10 Comparison of ethylene oxide production rate over
a period of 1100 operating days for DR and SR systems.
have lower temperature which improves catalyst activity in
this reactor, as presented in Fig. 7(b). Furthermore, this gure
shows that during operation time the catalyst deactivation is
mainly due to thermal sintering which is the loss of catalyst
active surface area owing to the crystallite growth of either
support material or active phase.
Fig. 8 demonstrates prole of EO mole fraction along the
reactor in course of time. This prole is similar to steady-
state simulation where the EO mole fraction increases along
the reactor, although the rate of conversion decreases. Cata-
lyst deactivation is the main reason for reduction in EO mole
fraction.
Fig. 9(a) and(b) presents the average temperature andactiv-
ity proles in reactor for two different types of reactor systems
ina periodof 1100 days of operation, respectively. Fig. 9(a) illus-
trates that average temperature in the DR systemis less than
that in the SR system in course of time. Catalysts in the DR
are exposed to less extreme temperatures in comparison with
the SR and catalyst deactivation via sintering is circumvented.
The result of Fig. 9(b) shows that the lowest deactivation rate
of catalyst corresponds to DR.
Fig. 10 depicts a comparison of EOproduction rate between
DRandSRsystems ina periodof 1100 operating days. Since the
lowest average temperature and also the lowest average cata-
lyst deactivation refers to the dual-type EO reactor (see Fig. 9),
the highest conversion and EO production rate corresponds to
DR systemin this operating period.
7. Conclusion
The potential possibilities of the DRsystemare analyzed using
a dynamic 1D heterogeneous model to obtain the necessary
comparative estimates. A comparison of the calculated cat-
alyst temperature prole along the reactor between SR and
DR represents that there is an extremely favorable catalyst
temperature prole in DR system. This favorable temperature
prole leads to a higher catalyst activity along the reactor and
results in a longer catalyst lifetime. An increase in EO produc-
tion rate has also been observed due to a desirable catalyst
temperature prole along DR and a higher level of catalyst
activity in the gas-cooled reactor of dual-type. These features
suggest that the concept of DR system is an attractive candi-
date for application in conversion of ethylene to EO.
Appendix A. DE optimization algorithm
The traditional optimization techniques have limited applica-
tions. The main difculty of these techniques is the possibility
of detecting the local optimum instead of global one owing
to their sensitivity to initial guess. Considering this fact, it
is important to develop more practical optimization meth-
ods based on natural phenomena (evolutionary computation)
such as simulated annealing (SA) (Kirkpatrik et al., 1983),
evolution strategies (ESs) (Schwefe, 1981), genetic algorithms
(GAs) (Goldberg, 1989; Davis, 1991) and DE (Price and Storn,
1997).
DE is an efcient and simple optimization method, which
is remarkably fast and robust innumerical optimizationand is
more likely to nd a functions true global optimum(Babu and
Angira, 2006). According to the type of optimization problem,
different strategies and different values of number of popula-
tion (NP), DE-step size (F), and crossover probability constant
(CPR) should be specied. Variation can exist between these
strategies regarding the vector to be perturbed, number of dif-
ference vectors considered for perturbation and the type of
crossover used. In this investigation, the suitable value chosen
for NP is 100, the range of DE step size is 0.51.0 and crossover
probability constant is within the range of 0.01.0. Generally,
CPR should be as large as possible (Babu and Munawar, 2007).
Babu and Angira (2006) and Babu and Munawar (2007) pre-
sented more details of basic version of DE, its strategies, and
choosing the operating parameters.
Appendix B. Nomenclature
List of symbols
A
c
cross section area of each tube (m
2
)
A
i
inner area of each tube (m
2
)
A
o
outside are of each tube (m
2
)
A
shell
cross section area of shell (m
2
)
a activity of catalyst ()
a
v
specic surface area of catalyst pellet (m
2
m
3
)
c
Pg
specic heat of the gas at constant pressure
(J mol
1
k
1
)
c
Ps
specic heat of the catalyst at constant pressure
(J mol
1
k
1
)
d
p
particle diameter (m)
E
d
activation energy used in the deactivation model
(J mol
1
)
F
t
ow rate of gas in tube side (mol s
1
)
F
sh
total molar ow in shell side (moles
1
)
K
d
deactivation model parameter constant (s
1
)
k
gi
mass transfer coefcient for component i (ms
1
)
L length of reactor (m)
P total pressure (bar)
T bulk gas phase temperature (K)
T
s
temperature of solid phase (K)
T
shell
saturated temperature of boiling water at operating
pressure (K)
t time (s)
U
shell
overall heat transfer coefcient between coolant and
process streams (Wm
2
K
1
)
u
g
linear velocity of uid phase (ms
1
)
y
i.s
mole fraction of component i in the uid phase in
shell (mol mol
1
)
ARTICLE IN PRESS
y
s
is
mole fraction of component i in the solid phase in
shell (mol mol
1
)
y
t
i
mole fraction of component i in the uid phase in
tube side (mol mol
1
)
y
t
is
mole fraction of component i in the solid phase in
tube side (mol mol
1
)
z axial reactor coordinate (m)
Greek letters
LH
f,i
enthalpy of formation of component i (J mol
1
)
LH
298
enthalpy of reaction at 298K (J mol
1
)
B
void fraction of catalytic bed ()
s
void fraction of catalyst ()
j viscosity of uid phase (kgm
1
s
1
)
v stoichiometric coefcient ()
v
ci
critical volume of component i (cm
3
mol
1
)
, density of uid phase (kgm
3
)
,
B
density of catalytic bed (kgm
3
)
,
s
density of catalyst (kgm
3
)
j catalyst effectiveness factor ()
Superscripts
sh shell side
ss initial conditions (i.e., steady-state condition)
t tube side
Subscripts
f feed conditions
in inlet conditions
out outlet conditions
s catalyst surface
limit
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