Chemical Engineering and Processing 75 (2014) 126–133

Contents lists available at ScienceDirect

Chemical Engineering and Processing:

Process Intensification
journal homepage: www.elsevier.com/locate/cep

Optimal conditions of isobutane dehydrogenation in radial flow

moving bed hydrogen-permselective membrane reactors to enhance
isobutene and hydrogen production
M. Farsi, A. Jahanmiri ∗ , M.R. Rahimpour
Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz, Iran

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

Article history: In the isobutane dehydrogenation process, coupling reaction and separation and optimization of the
Received 26 August 2013 intensified process can improve the isobutane conversion and selectivity, reduce operational costs and
Received in revised form lets to produce pure hydrogen. In this research, the radial flow moving bed reactors in the Olefex tech-
11 November 2013
nology have been supported by Pd–Ag membrane plate to remove hydrogen from the reaction zone. The
Accepted 12 November 2013
Available online 22 November 2013
reactions occur in the tube side and the hydrogen is permeated from the reaction zone to the sweep gas
stream. The proposed configuration has been modeled heterogeneously based on the mass and energy
conservation laws considering reaction networks. To prove the accuracy of the considered model, the sim-
Keywords:
Isobutane dehydrogenation ulation results of the conventional process have been compared against available plant data. The Genetic
Radial flow moving bed reactor algorithm as an effective method in the global optimization has been considered to optimize the oper-
Pd/Ag membrane ating condition of membrane reactors to enhance isobutene productivity. In this optimal configuration,
Heterogeneous model the isobutene production has been enhanced about 3.7%.
Genetic algorithm Crown Copyright © 2013 Published by Elsevier B.V. All rights reserved.

1. Introduction continuously from bottom of the reactor to top of the regenerator

Isobutene as one of the unsaturated hydrocarbons is a colorless
and extremely flammable gas at standard pressure and temper-
ature. It is used as a feedstock to produce a variety of chemical
components and additives such as methyl tert-butyl ether (MTBE)
and ethyl tertiary butyl ether (ETBE) to increase the octane number
of gasoline. Also, isobutene is used as a monomer or copolymer
to produce synthetic rubber and various plastics. Alkylation of
isobutene with butane produces isooctane as another fuel additive.
In the past, the isobutene was separated from products of
naphtha steam cracking or fluidized catalytic cracking as a sec-
ondary product. Currently, because of increasing demand for
olefins, some of commercial technologies have been developed
for dehydrogenation of light alkanes such as isobutane, which dif-
fer in catalyst, reactor type and the utilized regeneration system.
The Catofin isobutane dehydrogenation technology commercial-
ized by ABB Lummus, is a cyclic process to produce isobutene
over chromia–alumina catalyst in the adiabatic fixed-bed reac-
tors [1,2]. The FBD technology, commercialized by Snamprogetti,
uses fluidized bed reactors followed by a continuous regenerator
for isobutane dehydrogenation so deactivated catalyst is circulated
∗ Corresponding author. Tel.: +98 711 2303071; fax: +98 711 6287294.
E-mail address: jahanmir@shirazu.ac.ir (A. Jahanmiri).
[3]. In the Olefex process commercialized by UOP, the dehydrogena-
tion reaction occurs in the several adiabatic radial flow moving-bed
reactors over modified Pt–alumina catalyst considering continuous
catalyst regeneration [4].
There are few articles in the literature about modeling of isobu-
tane dehydrogenation process. Cortright et al. presented a rate
equation for isobutane dehydrogenation over Pt–Sn catalysts over
a wide range of temperatures [5]. Bakhshi et al. modeled a bench
scale fixed bed reactor for selective dehydrogenation of isobutane
at steady state condition, homogeneously [6]. Sahebdelfar et al.
modeled the dehydrogenation of isobutane to isobutene in adi-
abatic radial-flow moving bed reactors without considering side
reactions [7]. Farsi et al. modeled the Olefex process for isobu-
tane dehydrogenation considering reaction network at steady state
condition [8]. Isobutane conversion and isobutene selectivity were
obtained at about 38.53% and 90.76%, respectively, which had good
agreement with the plant data.
The integration of membrane separation and reaction in a vessel
has attracted much attention in the recent years [9]. A mem-
brane reactor is a piece of chemical equipment that couples a
reactor with membrane layer to add reactants or remove prod-
ucts from the reaction zone. Removing product from reaction
zone in a membrane reactor increases residence time in the reac-
tor and shifts thermodynamic equilibrium limitations toward the
higher conversion. Also, simultaneous occurrence of reaction and

0255-2701/$ – see front matter. Crown Copyright © 2013 Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cep.2013.11.006
 M. Farsi et al. / Chemical Engineering and Processing 75 (2014) 126–133 127

In this work the adiabatic reactors in the Olefex process have

Nomenclature been supported by Pd/Ag hydrogen permselective membrane plate
at the same catalyst loading. The object of this study is hetero-
A catalyst activity geneous modeling and optimization of radial flow moving bed
av specific surface area of catalyst pellet (m2 m−3 ) hydrogen-permselective membrane reactors to enhance isobutene
Ap permeation area (m2 ) selectivity, isobutane conversion and hydrogen production. The
Ar cross section area in radial direction (m2 ) sum of isobutane conversion and isobutene selectivity has been
Az cross section area in axial direction (m2 ) considered as the objective function that should be maximized
Cp specific heat of the gas at constant pressure (J mol−1 ) using genetic algorithm as a powerful method in the global opti-
Ci molar concentration of component i (mol m−3 ) mization considering feasible decision variables. The performance
Dp particle diameter (m) of the optimized membrane reactors is compared with the con-
Ep activation energy of permeability, (kJ mol−1 ) ventional Olefex process. The clear advantages of this catalytic
F total molar flow rate (mol s−1 ) membrane reactor include: pure hydrogen production, improving
hf gas–solid heat transfer coefficient (W m−2 K−1 ) isobutene productivity and selectivity and lower purification cost
J hydrogen permeation rate (mol m−1 s−1 ) in the next stage.
k reaction rate constant (mol kg−1 s−1 bar−1/2 )
Keq equilibrium constant I (m3 mol−1 )
2. Kinetics model
L reactor length (m)
N molar flux rate (mol m−2 s−1 )
In the non-oxidative dehydrogenation of isobutane, side
P total pressure (Pa)
reactions such as cracking, oligomerization, isomerization, aroma-
Pi partial pressure of component i (Pa)
tization, alkylation and coking occur in the process. In the Olefex
P0 pre-exponential factor of hydrogen permeability
technology to increase dehydrogenation rate and minimize the
(mol m−2 s−1 Pa−1/2 )
effect of complex side reactions, a Pt–Sn/Al2 O3 catalyst is used.
Q volumetric flow rate (m3 s−1 )
The isobutane dehydrogenation is a reversible and an endothermic
r radial coordinate (m)
reaction. Although increasing temperature and decreasing pressure
ri rate of reaction for dehydrogenation (mol kg−1 s−1 )
shift the reaction toward completion, it promotes main side reac-
Re Reynolds number
tions and catalyst deactivation. The isobutane dehydrogenation
S selectivity
over Pt–Sn/Al2 O3 catalysts is as follow:
T temperature (K)
t time (s) i − C4 H10 ↔ i − C4 H8 + H2 (1)
u superficial velocity of fluid phase (m s−1 )
U overall heat transfer coefficient (W m−2 K−1 ) Hydrogenolysis, propane dehydrogenation and coke formation
X conversion reactions are the main side reactions that take place over the
yi mole fraction of component i (mol mol−1 ) catalyst surface. The high temperature and residence time cause
z axial reactor coordinate (m) isobutane cracking (hydrogenolysis reaction) as the main side reac-
tion.
Greek letters i − C4 H10 + H2 ↔ C3 H8 + CH4 (2)
˛H hydrogen permeation rate constant,
(mol m−1 s−1 Pa−1/2 ) Other side reactions (propane dehydrogenation and coke for-
 penalty parameter mation from isobutene reactions) are as follow:
 catalyst effectiveness factor
C3 H8 ↔ H2 +C3 H6 (3)
 viscosity (kg m−1 s−1 )
 density of fluid phase (kg m−3 )
ε bed void fraction i − C4 H8 ↔ 4C + 4H2 (4)
P pressure difference (Pa) In this work, the kinetic models and reaction rate parameters
have been selected from literature [13,14]. The rate equations com-
Superscripts bined with the equilibrium constant provides enough information
g in bulk gas phase about kinetics of isobutene synthesis.
m in the sweep gas side
p particle
3. Process modeling
s at surface catalyst
3.1. Reaction side

separation leads to the lower cost in the separation stages com-
pared to the conventional processes. Casanave et al. studied
isobutane dehydrogenation over Pt–In catalyst in a packed-bed
zeolite membrane reactor [10]. Higher dehydrogenation yield was
observed due to the hydrogen removal from the reaction zone.
Farsi et al. modeled and optimized isobutane production in the
hydrogen-permselective membrane fixed bed reactors [11]. The
simulation results showed that the isobutane production can be
improved about 16% in the optimized membrane configuration.
Liang and Hughes studied isobutene synthesis from isobutane in
a membrane reactor over Pt/Al2 O3 catalyst, experimentally [12].
Also, they modeled the considered palladium/silver membrane
fixed bed reactor under similar operating conditions.
The conventional dehydrogenation process consists of three
moving bed radial flow reactors in series that the feed stream is
heated and entered to the reactors. The reactors are two concen-
tric tubes that feed is entered from inner tube and flows along the
radial direction. The outlet product from the first reactor is fed to the
second reactor. Due to coke formation on the catalyst surface, the
outlet catalyst from third reactor is sent to the regeneration section.
In the regeneration reactor, formed coke is burnt and the regener-
ated catalyst is recycled to the first reactor and flows along the axial
direction of reactors. Since the outlet temperature from each reac-
tor drops due to endothermic reactions, the inter-stage heaters are
placed between rectors to increase temperature. Fig. 1(a) shows the
schematic diagram of the conventional Olefex process.
128 M. Farsi et al. / Chemical Engineering and Processing 75 (2014) 126–133

1  dHj 1  dHj
N N
2UAp s Ar
− Nj − Nj + (T − T ) − av hf (T g − T c )
dz dr dr dz drdz dz
j=1 j=1
 s
2Ap 0 PH2 PH
2
− =0 (6)
drdz s )
JH2 (HH2 − HH s
PH2 PH
2 2

The mole and energy balances in the solid phase are expressed
by:

g

N
av kgi (Ci − Cic ) + ari,j B = 0 (7)
j=1


N
av hf (T g − T c ) + B ari (−Hi ) = 0 (8)
i−1

Since sum of stoichiometric coefficients in right and left sides of

each reaction is not same, thus the total mole changes in the radial
direction. The total mole balances are expressed by:
    
1 d Nj Ar 1 d Nj Az 2Ap +JH2 PH2 PHs
2
− − − =0 (9)
dz dr dr dz drdz −JH2 PH2 PHs
2

The axial temperature and concentration gradients have been

inserted in the model due to axial velocity of catalyst. Since the
Fig. 1. (a) The schematic diagram of the Olefex process (b) elemental view of mem-
catalyst to gas velocity ratio is very low, total and component mole
brane configuration.
balance equations can be simplified to below:
 s
d (Nj Ar ) 2 +JH2 PH2 PH
2
− − =0 (10)
In this study, the conventional reactors in the Olefex tech- dr r −JH2 s
PH2 PH
2
nology have been supported with Pd–Ag hydrogen-permselective
membrane layer. The membrane plates have been inserted  s
1 d 2 +JH2 PH2 PH
in the reactors vertically along the radial direction. The pro- −
g
(Ar ur Cj ) − av kgi (Ci − Czc ) −
2
=0 (11)
duced hydrogen in the reaction zone permeates toward sweep Ar dr r −JH2 s
PH2 PH
2
gas. Fig 1(b) shows an elemental view of proposed membrane
reactors.
In this research, a two-dimensional heterogeneous model, based g

N

av kgi (Ci − Cic ) + ari,j B = 0 (12)

on mass and energy conservation laws, has been developed to sim-
j=1
ulate Pd–Ag based hydrogen-permselective membrane reactors
at steady state condition. In the heterogeneous model, tempera- The energy balance equations can be simplified to below:
ture and concentration gradient between solid and fluid phases is
considered. In the considered mathematical model, the following 
N
dHj 2U s
assumptions are adopted: − Nj + (T − T ) − av hf (T g − T c )
dr r
j=1
 s
• The gas mixture is in ideal condition (low pressure and high tem- 2 0 PH2 PH
2
− =0 (13)
perature condition). r s )
JH2 (HH2 − HH s
PH2 PH
• Radial diffusion of mass and energy is negligible. 2 2

• Temperature gradient in the solid phase is negligible (Biot num-

ber is less that 0.1). 
N

• The feed flows uniformly in the radial direction of reactors. av hf (T g − T s ) + b ari (−Hf,i ) = 0 (14)
• The system is well isolated. i−1
• The membrane is completely selective.
Due to axial velocity of catalyst, the coke mass balance should
be written in axial direction. In this equation, w is mass fraction of
coke to the catalyst.
Subject to these assumptions, gas phase mole and energy bal-
ances are expressed by: dw
−up − rc = 0 (15)
dz
1 d (Nj Ar ) 1 d (Nj Az ) g Ar The pressure drop through the radial direction of the catalytic
− − − av kgi (Ci − Cic )
dz dr dr dz dz beds is calculated based on Tallmadge equation that is usable in
 s laminar and turbulent regimes [15].
2Ap +JH2 PH2 PH
2
− =0 (5) 150 (1 − ε)2 4.2 (1 − ε)1.166
drdz −JH2 s
PH2 PH f = + (16)
Re 3 ε3
2 ε Re1/6
 M. Farsi et al. / Chemical Engineering and Processing 75 (2014) 126–133 129

Table 1 Table 2
Feed and product specifications of the commercial dehydrogenation reactors. The used correlations for physical properties, mass and heat transfer coefficient.

Reactor 1 Reactor 2 Reactor 3 Parameter Equation

Feed Gas conductivity Lindsay and Bromley [19]

Temperature (◦ C) 634 639 637 Mixture heat capacity [20]
Flow rate (ton h−1 ) 106 106 106 Viscosity of reaction mixtures Lucas [20]
Pressure (barg) 1.4 0.9 0.4 Mass transfer coefficient Cusler [21]
Binary diffusion coefficient Hirschfelder et al. [22]
Reactor
Effective diffusion coefficient in pellet [23]
Catalyst loading (ton) 11.2 12 13.8
Permeation – exothermic side heat transfer [24]
Length (m) 12.5 13.5 15.5
coefficient
Bed void fraction 0.5 0.5 0.5
Gas – catalyst heat transfer coefficient [25]
Catalyst density (kg m−3 ) 800
Catalyst diameter (m) 6 × 10−4
3.3. Auxiliary equations

P u2  To complete the considered mathematical model of the pro-

=f (17)
r Dp cess, auxiliary correlations should be inserted to the model. In the
heterogeneous model, heat and mass transfer coefficients between
Temperature gradient and axial velocity of catalyst result an gas and solid phases, physical properties of chemical species and
activity profile in radial and axial direction of reactors. The catalyst overall heat transfer coefficient should be estimated from proper
activity has been calculated from [16]: correlations. The source of used correlations to calculate physical
properties, mass and heat transfer coefficient are summarized in
C1 = Cmax (1 − e−k1 (L/u) ) (18)
Table 2.
 L k2
C2 = Cmax k2 − Cmax (1 − e−k2 (L/u) ) (19) 4. Optimization problem
u k1
4.1. Genetic algorithm
ln(a) = −(˛1 C1 + ˛2 C2 ) (20)
Genetic algorithm (GA) is an adaptive heuristic search algorithm
Feed specifications, reactor and catalyst characteristics of the
premised on the evolutionary ideas of natural selection and genetic
commercial dehydrogenation reactors have been presented in
[26]. It is a programming technique that mimics biological evo-
Table 1 [17].
lution as a problem-solving strategy such as inherence, mutation,
selection and crossover. GA proceeds first by randomly generat-
3.2. Membrane side ing an initial population of individuals. At every generation, the
individuals in the population are tested according to some qual-
Recently, hydrogen energy has attracted much attention due to ity criterion that called fitness function. To form a new population
its potential to reduce environmental burdens and the viewpoint in the next generation, individuals are selected according to their
of energy security. Hydrogen gas is highly flammable and burns in fitness. Selection alone cannot introduce new individuals into the
air at a very wide concentration range. The selection of processes population. New individuals in the search space are generated by
which generate high purity and cost efficient hydrogen is a major crossover and mutation. Crossover concerns two selected individu-
challenge in energy supplier systems. One of the highly efficient als (parents) that exchange parts of their genomes to form two new
systems to produce hydrogen is dehydrogenation of hydrocarbons individuals (children). Mutation consists in flipping bits of individ-
in the membrane reactors. Generally, the Pd based membranes are ual’s strings at random. In practice, over successive generations,
completely selective and hydrogen can permeate through the layer. the population moves toward an optimal solution in the feasible
In this research, the isobutane dehydrogenation reactor has been domain. The main steps of the GA are given below:
supported by membrane plates to remove hydrogen from the reac-
tion zone. Hydrogen mole flow rate increases in the sweep gas side • Initialization and randomly initialize population
due to hydrogen permeation from the reaction zone to the sweep ◦ Evaluate the objective and fitness function
gas stream. Also, heat transfer between the endothermic reaction ◦ Apply genetic operators
and sweep gas stream results decreasing temperature of the sweep ◦ Selection
gas along the reactors. Mass and energy balance equations are writ- ◦ Crossover
ten for sweep gas side as follows: ◦ Mutation
 s
• Until stopping criteria, repeat
d (NH Ar ) 2 +JH2 PH2 PH
2
− + =0 (21)
dr r −JH2 s
PH2 PH In this paper, GA has been employed to obtain the global opti-
2
mal condition of considered membrane reactors to enhance the
 isobutene production.

N
dHj 2U s 2 0 s
PH2 PH
2
− Nj + (T − T ) + =0
dr r r s )
JH2 (HH2 − HH s
PH2 PH 4.2. Objective function and constraints
j=1 2 2
(22)
In this study, the sum of isobutane conversion and isobutene
where the hydrogen permeation constant is [18]: selectivity is considered as the operational objective function that
should be maximized. Due to severe effect of temperature on
2L P̄0 exp(−Ep /RT ) reaction synthesis kinetics, optimal temperature policy is a key
˛H2 = (23)
ln(Do /Di ) to optimal operation of reactors. Nine decision variables namely,
feed temperature of reactors (T01 , T02 and T03 ), inlet sweep gas
130 M. Farsi et al. / Chemical Engineering and Processing 75 (2014) 126–133

Table 3
Comparison of simulation results and plant data for industrial reactor.
6
Plant data Model R.E. (%)

Concentration (mol m )
-3
Total conversion 38.85 38.53 0.8 5.5
Selectivity 90.65 90.75 0.1
5
temperature (T04 , T05 and T06 ) and inlet flow rate of permeation
4.5
side (F01 , F02 and F03 ) are considered in the optimization problem.
Because of thermodynamic equilibrium limitations, dehydrogena-
4
tion of light alkanes such as propane and butane is conducted
at temperature around 600 ◦ C to achieve reasonable commercial
3.5
yields, hence an upper bound of 700 ◦ C is chosen for feed temper- 0
0
ature [27,28]. The environment temperature (30 ◦ C) is selected as 0.5 0.5
the lower bound for inlet temperature of the permeation side and Dimensional length 1 1
Dimensionless Radius
reactor feed. The bounds of decision variables are:

25◦ C < T01−03 < 700◦ C
Also, three constraints are considered for optimization due to
catalyst deactivation that should be satisfied along the reactors:
Ti < 700◦ C i = 1, 2, 3
These constraints are incorporated into the objective function
using penalty function. Penalty method is a class of optimiza-
tion algorithms for solving constrained problems. The penalty
method replaces a constrained problem by an unconstrained prob-
lem whose solution ideally converges to the solution of the original
constrained problem. The considered objective function for mini-
mization, finally, is thus:
(24) Fig. 2. Isobutene concentration along the radial and axial directions of the 3rd
reactor.
the reactors, catalyst activity reduction in the axial direction due to
(25) coke formation on the catalyst surface and axial velocity of catalyst
result an axial profile for isobutane concentration. Thus, in the pre-
sented results, the axial average of temperature and mole fractions
along the radial direction is presented. The average component
mole fraction in the radial direction is as follows:
sum of F i in axial nodes at a specified radial node
yi =
sum of F t in axial nodes at a specified radial node
(27)


3

P = −(SC4 H8 + XC4 H10 ) +  (max(0, Ti − 700))2 (26) In this section, the optimal operating condition of membrane
i=1 reactors is analyzed and the predicted mole flow rate, selectivity,
conversion and temperature profiles are presented. Genetic algo-
rithm is applied to determine the optimal operating conditions of
5. Numerical solution
the process. The goal of optimization approach is to maximize the
sum of isobutane conversion and isobutene selectivity. The calcu-
The mass and energy governing equations combined with the
lated optimal value for decision variables and obtained conversion
kinetic expressions and auxiliary correlations are comprised non-
and selectivity have been summarized and compared in Table 4.
linear algebraic, ordinary differential equations. The formulated
This table shows that the isobutane conversion and selectivity
model consists of some ordinary differential equations as an initial
in the optimized process is increased about 3.1% and 0.5% com-
value problem, which is not solved analytically. This set of differ-
pared to the conventional process. Simultaneous improvement in
ential equations is solved numerically with 4th order Runge–Kutta
the conversion and selectivity means higher isobutene and lower
method. At the end of this procedure, it is possible to plot the con-
by-products production in the optimized condition.
centration of components and temperature versus reactor length.

6. Results and discussion 200

The mathematical model of the process that is a set of nonlinear

C4H8 molar flow rate (kmol hr )

ordinary differential equations is solved numerically at steady state

-1

160
condition. To demonstrate the accuracy of the considered model
and assumptions, the model of isobutene synthesis side is validated
against the conventional Olefex process in the Imam Khomeini
Petrochemical Complex (I.R. Iran) [28]. The comparison between
120
simulation results and available plant data for the industrial case
is presented in Table 3. It is observed that the simulation results of
the conventional process have a good agreement with the observed 80
plant data.
The produced coke in the heterogeneous catalytic processes
involving hydrocarbon is deposited on the catalyst active sites and 40
Optimized Condition
reduces catalyst activity. Coke deposition deactivates the catalyst
Conventional Condition
by covering the active sites and pore blocking. Conventionally,
to the reduce coke formation and increasing catalyst activity, the 0
hydrogen rich feed is fed to the hydrocarbon process. Fig. 2 shows 0 0.5 1 1.5 2 2.5 3
the isobutane concentration along the radial and axial direction of Dimensionless Radius
the third radial flow reactor in the Olefex process. In this reactor, as
well as decreasing isobutane concentration in the radial direction of Fig. 3. Isobutene mole flow rate along the membrane and conventional reactors.
 M. Farsi et al. / Chemical Engineering and Processing 75 (2014) 126–133 131

Table 4
The simulation results of conventional and optimized membrane processes.

1st reactor 2nd reactor 3rd reactor

Sweep Reaction Sweep Reaction Sweep Reaction

Feed temperature
Optimized membrane 679 593.2 655.4 614.6 652 601.03
Conventional membrane 600 600 610 604 604 604
Olefex – 600 – 610 – 604
Sweep gas flow rate to feed
Optimized membrane 0.12 0.16 0.13

Optimal mem. Conventional mem. Olefex

Results
Conversion 39.74 39.32 38.53
Selectivity 91.22 90.86 90.75
Isobutene production 189.1 186.2 182.4

Fig. 3 shows the isobutene molar flow rate along the optimized
membrane and conventional reactors at steady state condition.
According to this figure, isobutane mole flow rate at the outlet of the
first, second and third optimized configuration is calculated about
80.2, 149.2 and 189.1 kmol h−1 . In the optimized process, the isobu-
tane production has been increased about 3.7% compared to the
conventional process. This configuration leads to delay in thermo-
dynamic equilibrium, while conventional reactors approach to the
equilibrium in the second half of reactors, particularly in the second
reactor. According to Le Châtelier’s principle, when an independent
variable of an equilibrium system changes the equilibrium shifts in
the direction that tends to reduce the effect of the change. Hydrogen
transfer from the tube side to the sweep gas decreases hydro-
gen concentration in the reaction zone, which shifts isobutane
dehydrogenation reaction to the right side and higher isobutane
is converted to isobutene. While, there is a difference between
hydrogen partial pressure in the reaction and permeation sides,
hydrogen can continuously pass through the membrane layer into
the sweep gas side. Although lower feed temperature in the first
reactor results lower isobutene production in this stage compared
to the conventional reactor, productivity has been compensated
and improved in the second stage due to higher feed temperature
and hydrogen permeation.
Fig. 4 shows the isobutane conversion along the optimized
membrane and conventional reactors at steady state condition.
Total isobutane conversion is the net of isobutane dehydrogenation
0.4
0.3
C4H10 Conversion
and cracking reactions. According to this figure, isobutane conver-
sion at the outlet of the first, second and third optimized configura-
tion is calculated about 16.1%, 30.87% and 39.73%. Hydrogen perme-
ation has a positive effect on the isobutane dehydrogenation and a
negative effect on the isobutane cracking (dissociation). Hydrogen
permeation from the reaction zone to the sweep gas through the
membrane layer results decreasing hydrogen mole fraction in the
reaction zone and shifts dehydrogenation reaction to the right side
and increases isobutane conversion. Also, it shifts the dissociation
reaction to the left side and decreases isobutane conversion to the
methane and propane and increases isobutene selectivity.
Fig. 5(a) and (b) shows the rate of isobutane dehydrogenation
and cracking reactions along the optimized membrane and con-
ventional processes at steady state condition. Near the reactor
entrance, the rate of isobutane dehydrogenation reaction is fast due
to high temperature and reactant composition in the feed stream.
According to this figure, methane mole flow rate as a undesired
by-product is decreased about 2.25% in the optimized membrane
reactors compared to the conventional process. This figure shows
that a reduction in the rate of isobutane cracking is significantly
higher compared to the isobutane dehydrogenation rate reduction
in the first reactor. The isobutene selectivity in the membrane pro-
cess has approached to 91.22% and it has been enhanced about 0.5%
compared to the conventional process at the same catalyst loading
(Table 5).
Fig. 6 shows the axial temperature profiles in the optimized
and conventional reactors, respectively. In the isobutene produc-
tion process, temperature decreases along the reactors due to the
endothermic dehydrogenation reaction. In the optimized mem-
brane configuration, the reaction side is surrounded with hydrogen
permselective tube and sweep gas supplies part of heat in the
reaction zone. The hydrogen permeation and heat transfer effect
on the process selectivity and conversion, respectively. The sweep
gas temperature has approached toward the reactor temperature

due to heat transfer. The low temperature in the first reactor has
improved process selectivity and high temperature in the sec-
0.2 ond reactor has enhanced the isobutane conversion. The difference
between temperature profile in the third conventional and mem-
brane reactors is negligible.
The hydrogen mole flow rate in the reaction side of membrane
0.1 and conventional reactors is shown in Fig. 7. Hydrogen permeation

Optimized Condition
Conventional Condition Table 5
The comparison between isobutane conversion and selectivity in the membrane and
0 conventional processes.
0 0.5 1 1.5 2 2.5 3
Conventional process Membrane process Improvement (%)
Dimensionless Radius
Conversion 38.53 39.74 3.1
Productivity 182.4 189.1 3.7
Fig. 4. Isobutane conversion along the membrane and conventional reactors.
132 M. Farsi et al. / Chemical Engineering and Processing 75 (2014) 126–133

a 0.8
680

Optimized Condition
Conventional Condition 650
Reaction rate (kmol kgCat s )
-1 -1

0.6

Temperature (C)
620

0.4 590

560 Reaction side

0.2
Sweep gas
Conventional Reactor
530
0 0.5 1 1.5 2 2.5 3
0 Dimensionless Radial
0 0.5 1 1.5 2 2.5 3
Dimensionless Radius Fig. 6. The axial temperature profiles in the reaction side, sweep gas and conven-
tional reactors.
b
700
Optimized Condition
Conventional Condition
Reaction rate (kmol kgCat s )
-1 -1

0.04 H2 molar flow rate (kmol hr )

-1

650

0.03
600
0.02

550
0.01
Optimized Mem.Reactor
Conventional Reactor
500
0 0 0.5 1 1.5 2 2.5 3
0 0.5 1 1.5 2 2.5 3
Dimensionless Radial
Dimensionless Radius
Fig. 7. Hydrogen mole flow rate along the membrane and conventional reactors.
Fig. 5. (a) Isobutene dehydrogenation (b) cracking reaction rate along the mem-
brane and conventional reactors.

0.03
from reaction zone decreases hydrogen content in the reaction side.
Although in the conventional process hydrogen content increases
Coke fraction (kg coke/kg cat.)

along the reactors, hydrogen mole flow rate decreases and its slope
changes at the last part of membrane reactors due to increasing
hydrogen permeation from reaction side toward sweep gas and 0.02
lower rate of hydrogen production. At the initial part of membrane
reactors, the lower hydrogen permeation rate and higher hydrogen
production through the dehydrogenation reaction result increasing
hydrogen content along the reactors. This figure shows that because
of hydrogen transfer from the second reactor and hydrogen produc-
0.01
tion, the rate of permeated hydrogen in the third reactor is more
significant compared to other reactors. The lower permeation can
be seen in the first reactor due to the low conversion and hydro-
gen content. According to this figure, permeated hydrogen in the Optimized Condition
optimized membrane configuration is about 70 kmol h−1 . Conventional Condition
Fig. 8 shows the coke content profile along the axial direction of 0
0 0.5 1 1.5 2 2.5 3
the membrane and conventional reactors. The axial velocity of cat-
alyst results a coke profile along the reactors. Produced coke in the Dimensionless Radius
catalytic hydrocarbon processes is deposited on the catalyst active
Fig. 8. Coke content along the membrane reactors.
sites and reduces the reaction rate. Coke deposition deactivates the
 M. Farsi et al. / Chemical Engineering and Processing 75 (2014) 126–133
catalyst by covering the active sites and pore blocking. The higher
temperature at the reactors entrance causes the lower catalyst
active sites and decreasing temperature along the radius direction
results the higher catalyst activity. Therefore, the catalyst activity
changes in the radial and axial directions due to reactant and cat-
alyst movement, respectively. To reduce the coke formation and
increasing catalyst activity, the hydrogen reach feed is always fed
to thermal hydrocarbon processes. The predicted coke to catalyst
mass fraction at the outlet of the third reactor is about 1.84%.
7. Conclusion
In this study, the dehydrogenation of isobutane to isobutene in
the Pd/Ag based hydrogen permselective membrane reactors was
modeled and optimized at steady state condition. Genetic algo-
rithm was employed to determine the optimal operating conditions
of the membrane reactors considering the sum of isobutane conver-
sion and isobutene selectivity as the objective function. Also, feed
temperature of reactors (T01 , T02 and T03 ), inlet sweep gas tem-
perature (T04 , T05 and T06 ) and inlet flow rate of permeation sides
(F01 , F02 and F03 ) are considered as decision variables in the opti-
mization problem. The results of mathematical simulation of an
industrial case were compared with the plant data and the accu-
racy of the proposed model was proved. Then, it was shown that
the isobutane conversion is enhanced about 3.1% in the optimized
membrane process compared to the conventional process. Also,
as well as 70 kmol h−1 hydrogen production, isobutene productiv-
ity in the optimized membrane process was increased about 3.7%.
This optimized configuration represents some important improve-
ments compared to the conventional process as follows: higher
isobutene production rate and its selectivity, lower purification cost
and hydrogen production.
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