Journal of Environmental Chemical Engineering 5 (2017) 1048–1059

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Journal of Environmental Chemical Engineering

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

An environmentally friendly configuration for reduction of toxic

products in a thermally coupled reactor of styrene and tri-reformer of
methane
A. Mirvakilia , H. Khalilpourmeymandib , M. Heravib , M.R. Rahimpourb,*
a
Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Persian Gulf University, Bushehr 75169, Iran
b
Department of Chemical Engineering,, Shiraz University, Shiraz 71345, Iran

A R T I C L E I N F O A B S T R A C T

Article history:
Received 15 August 2016 The aim of this work is a comparison of different hydrogen permeation membranes in a thermally
Received in revised form 27 December 2016 coupled membrane reactor in producing two precious chemicals, hydrogen and styrene. A thermally
Accepted 17 January 2017 coupled membrane reactor is designed as a double pipe reactor where methane tri-reforming for
Available online 20 January 2017 hydrogen production is considered in exothermic side of reactor and styrene production reaction takes
place in endothermic side. The walls of the shell side are coated by the layers of hydrogen perm-selective
Keywords: membrane. The produced hydrogen in the endothermic side is transferred to the permeation side, while
Toxic materials the generated heat in the exothermic side is transferred to the endothermic section. The reactor
Coupling concept
performance is theoretically investigated in the presence of six types of hydrogen perm-selective
Membrane reactors
membranes which are stable at operating conditions. Results are compared with each other and it is
Hydrogen perm-selective membranes
Modeling concluded that the highest hydrogen permeation rate (maximum 0.6 mol/s) is achieved in VCr4Ti4
Differential evolution optimization membrane named as TCMR5. Therefore, it leads to the highest ethylbenzene conversion (98%) and
styrene production yield (95%) in the endothermic side as well as methane conversion (98.5%) in the
exothermic side. Furthermore, toxic materials such as benzene and toluene decrease to about 66% and
46% in TCMR5 rather than the conventional reactor. Consequently, the fifth thermally coupled membrane
reactor encoded TCMR5 is an environmentally friendly configuration than others.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction membranes in membrane reactors in the last decades [8–11]. A

Membranes have been utilized widely in the theoretical
investigations in order to improve the product’s yield/selectivity,
decrease the by-product formation and thermodynamically shift
the reactions towards products [1–4]. Highly energy efficient
separations could be achieved using perm-selective membranes
because of no phase change and low maintenance operation. Using
hydrogen selective membranes for hydrogen recovery is currently
state of the art [5,6]. The separation process is mostly based on
inorganic membrane applications such as Pd and ceramic
membranes [7]. Many efforts have been made for application of
Abbreviations: BZ, benzene; CR, conventional reactor; DE, differential evolution
method; EB, ethylbenzene; Eth, ethylene; MET, methane; NP, number of population;
ST, styrene; TCMR, thermally coupled membrane reactor; TCR, thermally coupled
reactor; TOL, toluene.
* Corresponding author.
E-mail addresses: rahimpor@shirazu.ac.ir, Rahimpor230000@gmail.com
(M.R. Rahimpour).
membrane reactor is a novel structure in which both membrane-
based separations and chemical reactions are being carried out
simultaneously [12]. The type of membrane applied in the
membrane reactors is selected according to some factors such
as selectivity, productivity and some other parameters at the
operating conditions [13]. Detailed descriptions on membrane
reactors are available in the literatures [14,15]
1.1. Thermally coupled membrane reactor
These days, chemicals and related industries are faced up to big
challenges of developing more products at minimum energy and
material consumption as well as decreasing environmental
impacts [16]. For this goal, process intensification is a young area
receiving great attention in the research world. In this way, using
an innovative configuration in the technology of catalytic reactor is
more preferred. For example, coupling of exothermic reaction with
an appropriate endothermic one in a multifunctional reactor is an
interesting method that makes the process more efficient and

http://dx.doi.org/10.1016/j.jece.2017.01.020
2213-3437/© 2017 Elsevier Ltd. All rights reserved.
 A. Mirvakili et al. / Journal of Environmental Chemical Engineering 5 (2017) 1048–1059 1049

circumstances, in situ product removal by insertion of membranes

Nomenclature
in thermally coupled reactor (TCR) can shift the reaction to higher
production rate. In particular, it is a promising technique which has
av Specific surface area of catalyst pellet (m2 m3)
achieved so much interest in a vast variety of industrialized
Ac Cross section area of each tube (m2)
applications [21]. In this study, dehydrogenation of ethylbenzene
Ai Frequency factor for elementary reaction step i
(EB) and tri-reforming reactions is coupled in a reactor.
(kmol kgcat1 h1)
c Total concentration (mol m3)
1.2. Tri-reforming concept
Cp Specific heat of gas at constant pressure (J mol1 K1)
dp Particle diameter (m)
Tri-reforming reactions are synergetic combinations of endo-
Di Inside diameter (m)
thermic carbon dioxide and steam reforming and exothermic
Ei Activation energy for elementary reaction step i (kJ
oxidation of methane. CO2, H2O, and O2 in the flue gas, which are
kmol1)
coming out of fossil-fuel-based power plants, can be applied as co-
F Total molar flow rate (mol s1)
reactants for tri-reforming of natural gas with the purpose of
Fo,1,Fo,2 Inlet flow rates as decision variables in the endo-
producing syn gas (one of the main sources for hydrogen
thermic side and exothermic side
production).
hf Gas-solid heat transfer coefficient (W m2 K1)
J Hydrogen permeation rate (mol s1 m1)
1.3. Styrene
kg Mass transfer coefficient for component i (m s1)
ki Reaction rate coefficient (kmol kg cat1 h1)
One of the significant monomers for polystyrene manufacture
K Conductivity of gas phase (W m1 K1)
is styrene, used in latex and polystyrene resins. There are two
KEB Equilibrium constant of EB dehydrogenation
industrial processes which produce styrene: dehydrogenation of
L Reactor length (m)
ethylbenzene and as a by-product in the oxidation of propane with
P Total pressure (for exothermic side: bar; for endo-
ethylbenzene hydroperoxide and Mo complex-based catalyst [11].
thermic side: Pa)
Catalytic dehydrogenation of ethylbenzene has played a significant
Pi Partial pressure of component i (Pa)
role in producing styrene. In fact, approximately 90% of total
Ri Reaction rate of component i (mol kg1 s1)
styrene is produced by this process at operating temperature of
T Temperature (K)
550–650
C and atmospheric or sub-atmospheric pressure in the
Ts Solid phase temperature (K)
presence of Fe2O3 catalyst [22].
ug Linear velocity of fluid phase (m s1)
The potential of styrene production enhancement by catalyst
Ushell Overall heat transfer coefficient between shell and
improvement appears to be limited owing to drawbacks of
tube sides (W m2 K1)
thermodynamic equilibrium. Consequently, desperate attempts
yi Mole fraction of component i
are needed in order to improve the process performance [22].
ys Solid phase mole fraction of component
Performance of a membrane catalytic reactor was investigated
yj,og Fluid phase mole fraction of component i at the
by Moustafa and Elnashaie [23]. A hybrid fixed bed reactor was
entrance of j side of the reactor
modeled, leading to a remarkable enhancement in both ethylben-
z Axial reactor coordinate (m)
zene conversion and yield of styrene in comparison with an
industrial catalytic reactor. About 51% conversion of ethylbenzene
Greek letters
and 45% yield of styrene were reported.
rb Bulk density of reactor (Kg m3)
e Void fraction of catalytic bed
1.4. Objective
DHf,i Enthalpy of formation of component i (J mol1)
h Effectiveness factor
The purpose of this work is to model a novel thermally coupled
m Viscosity of fluid phase (Pa s)
membrane reactor for integration of endothermic dehydrogena-
tion of ethylbenzene reaction and methane tri-reforming selected
Superscripts and subscripts
as an exothermic reaction. The operating conditions of this reactor
i Component numerator
are optimized via a differential evolution method in order to
j Reaction numerator
maximize ethylbenzene and methane conversions. Furthermore,
o Inlet
different hydrogen perm-selective membranes are employed in
s Solid
the model. The new optimized configuration is modeled for one
g Gas
membrane each time and the results are compared with the
conventional reactor.

2. Process description

A detailed description of conventional ethylbenzene dehydro-

decreases the operational and capital costs [17,18]. The pioneers in
coupling endothermic and exothermic reactions were Hunter and
McGuire [19]. In general, the coupled reactors exist into these three
important classes: direct coupling, recuperative coupling and
finally regenerative coupling. At present, recuperative coupling has
considerably attracted the attention of countless scholars [20]. The
simultaneous production of dimethyl ether and hydrogen via
dehydrogenation of decalin is the example of recuperative
coupling. These two reactions are affected by thermodynamic
restraints which limit the reactant conversions. Under these
genation reactor (CR) and conventional tri-reformer reactor (CR)
are accessible in the literature [24]. The proposed configuration in
this work is called thermally coupled membrane reactor (TCMR)
which is as follows. The coupled configurations are fabricated as a
fixed-bed thermally coupled membrane reactor. The internal
design of this reactor is such that the exothermic side in the tube of
the reactor, the endothermic side in the shell of the reactor, and the
permeation side outside of the shell are fabricated in a tubular
reactor. Methane with steam, CO2 and O2 flow through the
exothermic section and synthesis gas is produced during the tri-
1050 A. Mirvakili et al. / Journal of Environmental Chemical Engineering 5 (2017) 1048–1059

reformer reactions. The EB dehydrogenation reaction takes place in

the endothermic section where the heat is released and transferred
to the exothermic side when getting cooler. Styrene is produced C 6 H5 CH2 CH3 ! C 6 H6 þ C 2 H4 DH 0 298 K ¼ 105:4 kJ=mol ð4Þ
during the dehydrogenation of EB reaction as a main product.
Other products of this reaction network are H2, MET (methane), BZ
(benzene), TOL (toluene), Eth (ethylene), CO and CO2. The wall of C 6 H5 CH2 CH3 þ H2 ! C 6 H5 CH3 þ CH4 DH 0 298 K ¼ 54:6 kJ=mol
the endothermic side in the coupled reactor is coated with ð5Þ
hydrogen perm-selective membrane layers so as to permeate
hydrogen through the membrane layers to the permeation side.
Nitrogen flows as a sweeping gas in the permeation side and 2H2 O þ C 2 H4 ! 2CO þ 4H2 DH0 298K ¼ 210:2kJ=mol ð6Þ
carries the permeated hydrogen. The schematic diagram of TCR
and TCMR are depicted in Figs. 1 and 2.
The characteristics and input data for different sides of the
TCMR are presented in Table 1.
CH4 þ H2 O ! CO þ 3H2 DH 0 298 K ¼ 206:1 kJ=mol ð7Þ

Six different membranes are employed in the model, separately,

which their characteristics and the hydrogen permeation rates are
presented in Table 2 [25–29]. Each membrane is numbered and CO þ H2 O ! CO2 þ H2 DH 0 298 K ¼ 41:2 kJ=mol ð8Þ
named as TCMRi in Table 2 where i is the number of corresponding In this network, all of the side reactions are irreversible with the
membrane. The hydrogen permeation is presented by two only reversible reaction being the main reaction that produces
equations as below: styrene. The corresponding rate equations, expressed as functions
E of component partial pressure in bar, are presented below
J ¼ k0 expð ÞðP1 n  P2 n Þ ð1Þ [23,30,31]:
RT
pH2
r1 ¼ k1 ðPEB  PST Þ ð9Þ
KA
J ¼ F ðp1 n  P2 n Þ ð2Þ

3. Reaction scheme and kinetics r2 ¼ k2 PEB ð10Þ

The reaction network for dehydrogenation of ethylbenzene to

styrene is as follows [23,30]: r3 ¼ k3 pEB pH2 ð11Þ

C 6 H5 CH2 CH3 $C 6 H5 CHCH2 þ H2 DH0 298 K ¼ 117:6 kJ=mol ð3Þ

Fig. 1. Schematic diagram of a thermally coupled reactor (TCR) configuration.

 A. Mirvakili et al. / Journal of Environmental Chemical Engineering 5 (2017) 1048–1059 1051

Fig. 2. Schematic diagram of a thermally coupled membrane reactor (TCMR) configuration.

1=2
r4 ¼ k4 pH2 O pC2 H4 ð12Þ P
r6 ¼ k6 ð ÞpH2 O pCO ð14Þ
T3
Ei
The rate constant is defined as: ki ¼expðAi  RT Þ. The numerical
r5 ¼ k5 pH2 O pCH4 ð13Þ values of Ai and Ei are brought in Table 3.

3.1. Methane tri-reforming reactions

Table 1 The reactions occurred in the tri-reforming reactor are as

Characteristics and input data for different sides of TCMR. follows:
Endothermic side (shell side) specification
The steam reforming of methane:

Parameter Value CH4 þ H2 O$CO þ 3H2 DH 0 298 K ¼ 206:3 kJ=mol ð15Þ

Length of reactor (m) 1.70
Cross-sectional area of the shell side (m2) 5.50 The carbon dioxide reforming of methane:
Feed molar flow rate of: (mol/s)
Ethylbenzene 30 CH4 þ CO2 $2CO þ 2H2 DH 0 298 K ¼ 247:3 kJ=mol ð16Þ
Styrene 0.19
Hydrogen 0.00 The partial oxidation of methane:
Benzene 0.03
Ethylene 0.00 CH4 þ 1=2O2 $CO þ 2H2 DH 0 298 K ¼  35:6 kJ=mol ð17Þ
Toluene 0.24
Methane 0.00 Moreover, there are three other reactions beside the above
Carbon monoxide 0.00 reactions:
Carbon dioxide 0.00
Steam 140 CH4 þ 2H2 O$CO2 þ 4H2 DH 0 298 K ¼ 164:9kJ=mol ð18Þ
Inlet temperature (K) 1060
Inlet pressure (Pa) 2.4 105
Exothermic side (tube side) specification
Parameter Value CO þ H2 O$CO2 þ H2 DH 0 298 K ¼  41:1 kJ=mol ð19Þ
Number of tubes 184
Length of reactor (m) 1.70
Total feed gas flow (kmol/h) 28115.40
Methane feed rate (kmol/h) 9264.40 CH4 þ 2O2 $CO2 þ 2H2 O DH 0 298 K ¼  802:7 kJ=mol ð20Þ
Feed pressure (bar a) 20
Feed temperature (K) 1160
1052 A. Mirvakili et al. / Journal of Environmental Chemical Engineering 5 (2017) 1048–1059

Table 2
Characteristics and hydrogen permeation rate of membranes.

NO. Name of configurations Name Permeability (k0) Activation energy (E) Order (n)
1 TCMR1 Bulk Pd 5.65  108 13.41 kJ/mol 0.60
mol m1 s1 Pa0.62
2 TCMR2 Bulk Pd 3.82  107 20.50 kJ/mol 0.50
mol m1 s1 Pa0.5
3 TCMR3 Nb 1.6  106 10.20 kJ/mol 0.50
mol m1 s1 Pa0.5
4 TCMR4 Ta 1.3  107 14.50 kJ/mol 0.50
mol m1 s1 Pa0.5
6 TCMR5 VCr4Ti4 1 105–1.3  108 – 0.50
mol m1 s1 Pa0.5
5 TCMR6 Pd-Ag 1.12  105 29.16 kJ/mol 0.50
mol m1 s1 Pa0.5

Table 3
Arrhenius equation and equilibrium constants for ethylbenzene reactions. p pCO2
k3 1
R3 ¼ ðp p  H2 Þ 2 ð23Þ
Reaction no. Frequency factor Activation energy (kJ/mol) pH2 CO H2 O K III f
9 0.85 90.90
10 14.00 208.10
11 0.56 91.50
k4a pCH4 pO2 k4b pCH4 pO2
12 0.12 104.00 R4 ¼ þ Þ ð24Þ
13 3.21 65.70 ð1 þ K CCH4 pCH4 þ K CO2 pO2 Þ 1 þ K C CH4 pCH4 þ K CO2 pO2
14 21.24 73.60

pH2 O
f ¼ 1 þ K CO pCO þ K H2 pH2 þ K CH4 pCH4 þ K H2 O ð25Þ
The reactions of methane steam reforming (Eqs. (15), (18)), and pH2
the water–gas shift reaction (19), are carried out in the steam
reformer. Moreover, reactions of (15) and (18)–(20) are utilized to The reaction equilibrium constants and the kinetic parameters
describe the tri-reforming process [32]. Reactions (15)–(17) are a of Arrhenius are tabulated in Table 4, and Van’t Hoff parameters for
set of independent reactions. For instance, reaction (15) minus species adsorption are available in Table 5.
reaction (19) results in reaction (16). However, it is suggested to
utilize Eqs. (15) and (18)–(20) since the kinetic rate expressions 4. Mathematical model
have been validated in the literature.
Xu and Froment [33] proposed a general kinetic model for A one-dimensional model has been considered to obtain the
reactions (15), (18), and (19) over Ni-based catalyst. This model mass and energy balance equations. In development of this model
was extensively experienced under lab scale conditions [33,34]. the following assumptions are used:
The kinetic model of methane combustion reaction (Eq. (20)) was
suggested by Trimm and Lam [35]. However, the adsorption model  The gas mixture is ideal in the both catalytic reactor sides.
parameters were modified for Ni-based catalyst because the  Each side of the reactor is operated under steady-state
mentioned model was obtained over Pt-based catalyst [36]. The conditions.
rate expressions of four reactions ((15), (18)–(20)) represented as  One-dimensional plug flow is considered in each section.
R1, R2, R3 and R4 are as follows:  Axial diffusion of mass and heat are ignored in both sides.
 Heat loss of tri-reformer to surrounding is neglected.
k1 p3 p 1  Bed porosity in axial and radial directions is supposed constant.
R1 ¼ ðpCH 4 pH2O  H2 CO Þ  2 ð21Þ
p2:5
H2
4 KI f  The chemical reactions are assumed to take place on the external
surface of the catalyst particles and homogenous reactions are
neglected.
k2 p4 pCO2 1  Wall temperature drops linearly along steam methane reforming
R2 ¼ ðp 4 p2 H2O  H2
3:5 CH4
Þ 2 ð22Þ process.
pH2 K II f  Pressure is constant along tri-reformer reaction side.
 All membranes are stable in the operating conditions.

Table 5
Table 4
Van’t Hoff parameters for species adsorption.
Reaction equilibrium constants and Arrhenius kinetic parameters.
K0i (bar1) DHi (J/mol) K0ic (bar1) DHic (J/mol)
Reaction no. (j) Equilibrium constant, Kj K0j (mol/kg cat.s) Ej (J/mol)
CH4 6:65  104 38280
15 K 1 ¼ expð26830 þ 30:114Þbar2 1:17  1015 bar0:5 240100
Ts CO 8:23  105 70650
18 K 2 ¼ K 1  K 3 bar 2
2:83  10 14
bar0:5 243900
H2 6:12  109 82900
19 K 3 ¼ expð4400
T s  4:036Þ 5:43  105 bar1 67130

 H2O 1:77  105 88680
20 E 86000
kj ¼ k0j  exp RTj 8:11  105 bar2 27300
CH4 (combustion) 1:26  101
6:82  105 bar2 86000 O2 (combustion) 7:78  107 92800
 A. Mirvakili et al. / Journal of Environmental Chemical Engineering 5 (2017) 1048–1059 1053

Table 6
The equations used in mathematical model.

Mass and energy balance equations for the solid phase dy

AFc dz þ av ckg ðys  yÞ ¼ 0
þ av hf ðT s  TÞ þ pADc i UShell ðT Shell  TÞ ¼ 0
dT
AFc C p dz
Mass and energy balance equations for the fluid phase g

F dy J
Ac;jj dzi;j þ av cj kgi;j ysi;j  ygi;j  b AHc;j2 ¼ 0
ZT 4
dT gj
þ av hf ðT sj  T gj Þ  pADc i UðT g3  T g2 Þ  bAc;j2
F JH
Acj C gpj dz
C p dT ¼ 0
Pressure drop T3
ð1eÞ2 mug ð1eÞu2 r
dP
¼ 150 þ 1:75 e3 dp g
dz e3 d2p
Boundary conditions for the fluid phase
z ¼ 0;ygi;j ¼ ygi0;j ;T gj ¼ T gj0 ;Pgj ¼ Pgj0

 Membrane is H2 full perm-selective with respect to other gases. objective function is defined as follows:
F ¼ C EB þ C CH4 ð26Þ
Besides, mass and energy balance equations, kinetic rate of
reactions, auxiliary equations consisting of physical property and Four decision variables consisting of inlet flow rate, F0,1, and
mass and heat transfer coefficient between gas and solid phases as inlet temperature, T0,1 in the endothermic side as well as inlet flow
well as Ergun equation for pressure drop calculation are important rate, F0,2, and inlet temperature, T0,2 in the exothermic side are
parameters which should be used in mathematical model. These considered for the optimization procedure.
equations are tabulated in Table 6 [1,24,30]. As a result, inlet flow rates and temperatures are selected for
decision variables. Range of these variables is as follows:
5. Optimization
80 < F0,1 < 200 mol/s (27)
The aim of the optimization consists of maximizing or
minimizing a real function by systematically choosing input values
from within an allowed set and computing the value of the 922 < T0,1 <1150 K (28)
function. Therefore, it plays a crucial and vital role in manufactur-
ing and engineering activities. In this work, differential evolution
(DE) method as a reliable optimization tool is applied in order to 2500 < F0,2 < 8500 mol/s (29)
maximize ethylbenzene conversion in the endothermic side as
well as methane conversion in the exothermic section.
900 < T0,2 < 1700 K (30)
5.1. Differential evolution (DE) method To avoid the catalyst deactivation, maximum temperature must
not exceed 1700 K in the exothermic side.
Details of DE algorithm and pseudo code are presented in These constraints should be inserted to the objective function
literature [37]. The operating conditions of TCR have been by considering penalty functions. By this technique, the penalty
optimized via DE method. The strategy used in this optimization function automatically discards unacceptable results. In the
process was “DE/best/1/bin” and the number of population was current study, penalty parameter is considered to be 105.
NP = 100. The best DE step size was F = 1. Moreover, the crossover Eventually, the objective function that should be minimized can
probability constant was CR = 0.8. be expressed as follows:
X 2
5.2. Objective function and constraints OF ¼ F þ 105  G i ð31Þ
i¼1
Here, maximizing of ethylbenzene conversion in the endother-
mic side as well as methane conversion in the exothermic side in
TCMR configuration are considered in the objective function. The G1 ¼ maxð0; ð80  F 0;1 ÞÞ ð32Þ

Table 7
Model validation of dehydrogenation of ethylbenzene in TCR.

Industrial reactor Model reactor Error (%)

item Molar flow rate (mol/s) Conversion (%) Molar flow rate (mol/s) Conversion (%)
EB 5.40 47.25 5.37 47.16 0.62
Molar flow rate (mol/s) Yield (%) Molar flow rate (mol/s) Yield (%)
ST 4.33 40.41 4.30 40.37 0.55
BZ 0.42 3.77 0.42 3.83 1.58
TOL 0.56 3.12 0.56 3.11 0.49
Temperature (K) 850 854.26 0.50
Pressure (bar) 2.32 2.28 1.70
1054 A. Mirvakili et al. / Journal of Environmental Chemical Engineering 5 (2017) 1048–1059

Table 9
The optimized parameters in thermally coupled reactor.
G2 ¼ maxð0; ðF 0;1  200ÞÞ ð33Þ
parameter Value
Inlet temperature of exothermic side (K) 1060
Inlet temperature of endothermic side (K) 1160
G3 ¼ maxð0; ð2500  F 0;2 ÞÞ ð34Þ Inlet molar flow rate of exothermic side (mol/s) 136.63
Inlet molar flow rate of endothermic side (mol/s) 5500

G4 ¼ maxð0; ðF 0;2  8500ÞÞ ð35Þ

G5 ¼ maxð0; ðT 0;1  1150ÞÞ
G6 ¼ maxð0; ð922  T 0;1 ÞÞ
G7 ¼ maxð0; ðT 0;2  1700ÞÞ
G8 ¼ maxð0; ð900  T 0;2 ÞÞ
A set of above mentioned differential-algebraic equations is
developed for TCMR modeling. The developed mathematical
model is a set of non-linear initial-value ordinary differential
equations (ODE) contain mass and energy balances in endothermic
and exothermic sides coupled with boundary conditions, algebraic
equations of heat and mass transfer, and algebraic equations of
thermophysical properties. In order to solve these equations, the
backward finite difference approximation is applied, which
transforms the set of differential equations to a set of algebraic
equations.
ð36Þ Ethylbenzene and steam enter the endothermic side as
feedstock. Important products of this side are ST and H2.
Fig. 3(a) and (b) shows mole percentage of EB, ST and H2 in
ð37Þ endothermic side of reactor in the absence of membrane (TCR), in
turn. According to these figures, the production percentage in TCR
increases. Therefore, coupling of endothermic and exothermic
ð38Þ reactions is appropriate for higher production of ST and H2.
In situ removal of hydrogen during EB dehydrogenation leads to
higher production, easily understood by Le Chatelier’s principle.
ð39Þ Therefore, the wall of shell side is coated by a hydrogen perm-
selective membrane and hydrogen is removed through this
membrane. As explained before, the TCMR is modeled six times
with various membranes. Therefore, the reactor is named with

6. Model validation

The model validation for styrene production via steady-state CR

is performed between the industrial data reported by Elnashaie
et al. [30]. The modeling results of CR styrene production and the
corresponding observed data of the industry are accessible in
Table 7. A good agreement is observed between the modeling
results and the industrial data. As a result, this mathematical
model performs well under the industrial conditions. Furthermore,
simulation with HYSYS software is applied for the model validation
of tri-reformer which had been done by Rahimpour et al. [1] and
results are shown in Table 8. A good agreement is observed
between the modeling results and HYSYS data.

7. Results and discussion

As it is mentioned before, the inlet conditions of TCMR

configuration are optimized via DE method. The results of
optimization are presented in Table 9. Performance of both CR
and optimized TCMR is compared with each other in the preceding
figures.

Table 8
Model validation of tri-reforming reaction in TCR.

Item HYSYS Model Error (%)

Temperature (K) 1158 1161.20 0.28
Compositions (%)
CO2 21.23 20.95 1.32
CO 14.92 15.20 1.87
H2 23.39 23.24 0.64
CH4 0.48 0.43 10.83
N2 0.45 0.18 62.88
H2O 39.53 40.02 1.22
Fig. 3. Comparison of (a) ethylbenzene and styrene (b) hydrogen mole fraction
between endothermic side of TCR and CR.
 A. Mirvakili et al. / Journal of Environmental Chemical Engineering 5 (2017) 1048–1059 1055

Therefore, the performance of these membranes is not suitable for

8
3.6 TCMR configuration. However, the consumption of EB increases
7 TCMR1 dramatically in TCMR3, TCMR5, and TCMR6 configurations. This is
3.4
an obvious claim, especially for TCMR5 in which the total amount
EB mole percent (%)

6 CR of EB is consumed just at the beginning of the reactor length. In

TCMR4 TCMR5, the rate of H2 removal is high through the membrane
5 TCMR2 3.2
1.58 1.61.621.641.661.68 which leads to higher production and consumption of ST and EB,
4 TCR respectively. Pd-Ag as a widely-underutilized membrane causes an
increase in EB conversion; however, less than VCr4Ti4. It is worth
3 mentioning that final selection of each membrane should be
TCMR6 conducted according to the economic viewpoints.
2 The mole percentage of important products of EB dehydroge-
TCMR3
nation is illustrated in Fig. 5(a) and (b). The mole percentage of ST
1
TCMR5 in TCMR5 configuration is higher than other configurations.
0 Generally, membrane application can lead to an increase in the
0 0.5 1 1.5 2 production of ST because in situ hydrogen removal causes a shift in
Length (m) the reversible reaction towards higher ST production. However,
different membranes have different characteristics in the H2
Fig. 4. Comparison of ethylbenzene mole fraction in different types of configura-
tions. permeation rate. The membrane with higher capability of H2
removal leads to higher ST production. It is depicted in Fig. 5(b)
that the trend of H2 mole percentage in TCMR5 differs from other
configurations. At the entrance of reactor, the percentage of H2
TCMR1 to TCMR6. The mole percentage of EB in these six production through TCMR5 model is the highest one owing to an
configurations is compared in Fig. 4. Utilization of TCMR1, TCMR2 increase in the rate of EB dehydrogenation reversible reaction.
and TCMR4 do not show a noticeable difference in comparison TCMR5 is a membrane configuration with a high-performance
with TCR configuration (the configuration without membrane). hydrogen permeability. Therefore, hydrogen permeates well at the
beginning of the membrane and the partial pressure of hydrogen in
the permeation side is high. Since the driving force is the pressure
difference in the permeation and retentate side, hydrogen
permeation rate decreases gradually along 0.2 m from the
a6 beginning of the reactor because of a decline in the hydrogen
TCMR5
pressure difference. Thus, a higher proportion of H2 is produced.
5 Although a bit of H2 is removed from the endothermic side, H2
production rate is more than its removal rate owing to the progress
ST mole percent (%)

TCMR3 TCMR6
4 of reaction towards desired products (H2 and ST). By reduction of
EB mole fraction along the reactor as a reactant, the reaction rate
TCR decreases and H2 removal rate increases. In addition, H2 is
3
consumed for TOL production. Therefore, there is a decline in
3.8 detrimental environmental impacts of production of toxic
2 materials.
3.6 TCMR1

TCMR4
The profile of EB conversion and ST yield are presented in Fig. 6
CR 3.4
1 in the form of percentage. As shown in Fig. 6, in the configuration of
TCMR2 3.2
TCMR5 almost all of EB is converted into ST because EB conversion
1.3 1.4 1.5 percentage is 100% and ST yield percentage is near to 100%.
0 0.5 1 1.5 2
Length (m)
b 7
TCMR5
TCMR3
6

TCMR6
H2 mole percent (%)

4
TCR

3
TCMR1
2 4.1
4
CR 3.9 TCMR2 TCMR4
1
3.8
1.561.581.61.621.641.66
0
0 0.5 1 1.5 2
Length (m)

Fig. 5. Comparison of (a) Styrene (b) Hydrogen mole fraction in different types of
configurations. Fig. 6. Comparison of styrene yield and EB conversion in TCMR5.
1056 A. Mirvakili et al. / Journal of Environmental Chemical Engineering 5 (2017) 1048–1059

The permeation rate of hydrogen removal from endothermic
side of all configurations is depicted in Fig. 7(a) and (b). The
permeation rate of H2 is illustrated in Fig. 7(a) for TCMR1, 2, and 4.
The trend of hydrogen permeation rate is similar in all config-
urations. The proportion of hydrogen permeation increases
dramatically at the beginning of the reactor length until it reaches
a maximum value and then it falls down gradually. It occurs due to
fast production rate of H2 at the entrance of the reactor length.
Consequently, its mole fraction, partial pressure, and rate of
permeation through the membrane increase. Furthermore, as H2
production decreases, its partial pressure reduces; thus, the rate of
permeation to the reaction media declines. A reduction in the
partial pressure difference between reaction and sweeping media
is another reason for fall of hydrogen permeation rate. In fact,
because of the presence of hydrogen in the sweeping media at the
inlet of the reactor, its partial pressure increases.
Fig. 7(b) represents H2 permeation rate in TCMR3, 5, and 6
configurations. H2 permeation rate for TCMR3 and TCMR6 is
approximately 10 times more than previous configurations
(TCMR1, 2 and 4) and H2 permeation rate for TCMR5 is almost
100 times higher than previous configurations. Pd-Ag membrane is
used for TCMR6 configuration which has a relatively good
permeation rate. However, the highest permeation rate is related
to TCMR5. In these three configurations, the trend of H2
permeation rate is the same. There is a dramatic increase in the
permeation rate of H2 at the entrance of the reactor and
subsequently it continues the trend gradually and slowly.
Indeed, H2 permeates in to the permeation side of these three
configurations. High rate of permeation at the entrance of the
reactor is due to ST production reversible reaction which produces
high proportion of H2. Hydrogen partial pressure rises in the
endothermic reaction abruptly owing to the fact that it is not
observed in the reaction media at first and it is produced through
the reaction. Furthermore, because of the absence of H2 in the
sweeping side at the entrance of the reactor, both partial pressure
difference between the reaction media and the sweeping side and
the permeation rate are high. As time passes, the rate of reversible
reaction decreases because of feed consumption. Moreover, other
reactions do not occur.
H2 is produced during the side reactions. However, its
production via these reactions is very slight. At the initial parts
of reactor length, where the permeation rate is high, a significant
amount of H2 drives out into the sweeping side. Therefore, H2
partial pressure increases in the mentioned side which finally leads
to a decrease in the partial pressure difference in both reaction side
and sweeping side along the reactor. Accordingly, the permeation
rate drops. However, the pressure difference is seen even at the end
of the reactor length, and hydrogen drives out slowly from the
reaction media.
A figure for reaction temperature is presented in Fig. 8.
The profile of temperature of the endothermic and exothermic
sides in both TCR and CR is illustrated in Fig. 8(a). As known,

1600
a Conventional exothermic
Conventional endothermic
1400 Exothermic in TCR
-3 Endothermic in TCR 772
x 10
Temperature (K)

2
a TCMR1 1200
771

1.698 1.7
H 2 permeation rate (mol/s)

TCMR2
1.5 TCMR4
1000

1 800

0.5 600
0 0.5 1 1.5 2
Length (m)

1100
0
0 0.5 1 1.5 2 b TCR
Length (m) 1050
TCMR 1
0.7 TCMR 2
b 1000
TCMR 3
0.6
Temperature (K)
H 2 permeation rate (mol/s)

TCMR 4
950
TCMR3 TCMR 5
0.5 TCMR 6
TCMR5 900
0.4 TCMR6
850
0.3
0.05 800
0.2
0 750
0.1 0 0.1 0.2
700
0 0.5 1 1.5
0
0 0.5 1 1.5 2 Length (m)
Length (m)
Fig. 8. Temperature profile in (a) exothermic and endothermic sides of TCR and CR
Fig. 7. Comparison of H2 permeation rate in (a) TCMR1, 2, 4 (b) TCMR3, 5, 6. (b) endothermic side of TCR, TCMR1-6.
 A. Mirvakili et al. / Journal of Environmental Chemical Engineering 5 (2017) 1048–1059 1057

styrene is produced during the endothermic reaction in the

conventional reactor and it gets warm by steam. An approximately
50 K reduction in temperature along the reactor length is shown by
this figure. However, the exothermic tri-reforming reactions are
cooled by a coolant in the shell side of the conventional reactor.
Under such circumstances, there is a temperature peak at the
initial part of the reactor length. Actually, a great source of heat is
generated immediately by the exothermic reactions in this part of
the reactor owing to the high reaction rate; therefore, a
temperature rise is inevitable. Nevertheless, eventually the
temperature falls due to a gradual reduction in the reaction rate
and cooling of reaction media.
In the TCR model, the temperature of exothermic side is always
higher than the one in endothermic side, even at the end parts of
the reactor length.
Due to the simultaneous occurrence of exothermic and
endothermic reactions, the produced heat in the exothermic side
is transferred to the endothermic section along the reactor.
Consequently, the exothermic side temperature does not increase.
Likewise, the rate of endothermic reaction rises in this configura-
tion in comparison with the conventional reactor. Heat transfer
from the exothermic section to the endothermic one continues to
the end of the reactor and the temperature of both sides decrease.
To clarify the fact, the temperature of exothermic side reduces
owing to the heat transfer. Moreover, the temperature of
endothermic side diminishes because the endothermic reaction
accompanies with a temperature decline.
The effect of different types of membranes on the temperature
of endothermic side is illustrated in Fig. 8(b). According to this
figure, it can be concluded that implementing a hydrogen perm-
selective membrane causes a decrease in the temperature of
endothermic side. This phenomenon occurs because of two
reasons: (1) the rate of endothermic reaction increases by removal
of hydrogen through the membrane (dehydrogenation of EB); thus,
a temperature reduction more than the previous configurations
can be seen (TCR, CR). (2) By hydrogen removal from the reaction
media, some proportion of heat is driven out and the temperature
decreases. However, in TCMR1, 2, and 4 which their membrane
layers are not capable enough for highly removal of H2, there is no
significant temperature difference compared to TCR. On the other
hand, the temperature has an intensive decrease in TCMR3, 5, and 6
which their membrane layers have a high potential of H2 removal.
To explain it more, it can be said that in these three configurations,
the rate of the reversible reaction increases dramatically. As a
result, the temperature extremely decreases. Afterwards, a slight
increasing trend of temperature is observed in these three
configurations. It occurs because the exothermic reaction rate
decreases to the point that a temperature reduction is not
considerable and heat is transferred to the endothermic section
leading to an increase in the temperature of the endothermic
reaction zone.
Molar flow rate of products in CR, TCR and TCMR configurations
in the endothermic side is compared in Fig. 9. Fig. 9(a) presents the
molar flow rate of EB, ST, H2, BZ, and ETH. The least amount of EB at
the outlet of the reactor is related to TCMR5 configuration. This
statement proves that situating of VCr4Ti4 membrane causes a high
Fig. 9. Molar flow rate of (a) EB, ST, H2, BZ and ETH in the endothermic side of CR,
increase in EB dehydrogenation reversible reaction and almost all TCR, TCMR1-6, (b) TOL, MET, CO and CO2 in the endothermic side of CR, TCR, TCMR1-
of EB is consumed in this configuration. Furthermore, the efficiency 6 (c) MET, CO, CO2, H2O and H2 in the exothermic side of CR, TCR, and TCMR5.
in TCMR5 is higher than TCMR6. The highest amount of ST is
produced in TCMR5 configuration. In addition, the least amount of
H2 is related to TCMR5 owing to the high efficiency of the
membrane applied in TCMR5. The highest H2 permeation rate is reversible due to H2 removal and also the side reactions should
allocated to this membrane. BZ and ETH, as the side products of this compete with ST production reversible reaction. Hydrogen
section, are produced much less than ST and H2. Totally, the removal helps the reversible reaction and the possibility of side
proportion of BZ and ETH in TCMR is less than the one in CR and reactions occurrence reduces. Therefore, the production of toxic
TCR. Because in these membranes, the reaction is strongly materials such as BZ and TOL decreases which is a positive point
1058 A. Mirvakili et al. / Journal of Environmental Chemical Engineering 5 (2017) 1048–1059
0.5
0.4
H 2 Recovery
0.3
0.2
0.1
0 with a high level of purity is produced by applying this
1050
1000
1.8
950
1.2
Endo temperature (K) 0.6
900 0 Length (m)
Fig. 10. Effect of endothermic side temperature on H2 recovery in TCMR5.
and applying TCMR5 reduces environmental pollutions which
considerably affect climate and environment.
Molar flow rate of other side products such as TOL, MET, CO and
CO2 which is illustrated in Fig. 9(b), decreases in membrane
reactors and a severe reduction of these side products is seen in the
profile corresponds to TCMR5. In this configuration, the purest ST is
produced and toxic materials such as BZ and TOL reach their least
amounts. This assertion confirms the superiority of applying
TCMR5 rather than the other configurations. Therefore, this
process is an environmentally friendly process.
The highest amount of output materials is related to H2O
leaving the endothermic side of the reactor. H2O enters 4.6 times
more than EB at the inlet of the reactor and it is consumed much
less than EB.
In Fig. 9(c), the profile of outlet products is observed in TCMR5,
TCR and CR configurations for the exothermic side. The amount of
output MET is negligible in TCMR5 and TCR. Output molar flow rate
from the exothermic side in TCR and TCMR5 is more than the one in
CR. The amount of product increases slightly in TCMR5 in
comparison with the one in TCR.
Fig. 10 gives information about the impact of exothermic side
temperature on H2 recovery for TCMR5. When the temperature is
low, the value of H2 recovery is high. However, the temperature
does not have considerable influence on H2 recovery generally.
8. Conclusion
The main goal of this study is a theoretical comparison about
the performance of six hydrogen perm-selective membranes
implemented in a thermally coupled reactor. The thermally
coupled reactor has been proposed for producing styrene and
synthesis gas in parallel. In the configuration of this reactor,
exothermic reactions provide the required heat for endothermic
reactions. As expected, appropriate and suitable coupling of
exothermic and endothermic reactions in a single configuration
can lead to lower cost and energy consumption as well as a better
temperature distribution and a product concentration distribution
along the reactor length. In the current work, hydrogen is removed
from the endothermic side by applying various hydrogen perm-
selective membranes in the wall of the reactor shell. Dehydroge-
nation of EB as an endothermic reaction and tri-reforming reaction
as an exothermic reaction occur in TCMR. DE method is applied as
an optimization method in order to maximize EB conversion in the
endothermic side as well as MET conversion in the exothermic side.
The obtained results are as follows:
 Theoretical analysis proves an acceptable performance of
TCMR3, 5, and 6 in comparison with other membranes; however,
TCMR5 which is VCr4Ti4 has the best performance among others.
 The superiority of TCMR5 is that it produces the purest styrene
with low level of toxic materials.
 Not only the TCMR5 reduces environmental pollutions which
significantly affect climate and environment, but also styrene
configuration.
 This assertion is proved by the numerical report. The ratio of
styrene mole percentage in TCMR5 to the one in TCR is 1.67, while
it is 1.49 in TCMR3, and 1.25 in TCMR6.
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