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Applied Energy 88 (2011) 12111223

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Direct dimethyl ether (DME) synthesis through a thermally coupled heat


exchanger reactor
R. Vakili, E. Pourazadi, P. Setoodeh, R. Eslamloueyan, M.R. Rahimpour
Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345, Iran

a r t i c l e

i n f o

Article history:
Received 12 July 2010
Received in revised form 24 September
2010
Accepted 12 October 2010
Available online 12 November 2010
Keywords:
Direct DME synthesis
Coupling exothermic and endothermic
reaction
Cyclohexane dehydrogenation
Auto-thermal reactor

a b s t r a c t
Compared to some of the alternative fuel candidates such as methane, methanol and FischerTropsch
fuels, dimethyl ether (DME) seems to be a superior candidate for high-quality diesel fuel in near future.
The direct synthesis of DME from syngas would be more economical and benecial in comparison with
the indirect process via methanol synthesis. Multifunctional auto-thermal reactors are novel concepts in
process intensication. A promising eld of applications for these concepts could be the coupling of endothermic and exothermic reactions in heat exchanger reactors. Consequently, in this study, a double integrated reactor for DME synthesis (by direct synthesis from syngas) and hydrogen production (by the
cyclohexane dehydrogenation) is modelled based on the heat exchanger reactors concept and a
steady-state heterogeneous one-dimensional mathematical model is developed. The corresponding
results are compared with the available data for a pipe-shell xed bed reactor for direct DME synthesis
which is operating at the same feed conditions. In this novel conguration, DME production increases
about 600 Ton/year. Also, the effects of some operational parameters such as feed ow rates and the inlet
temperatures of exothermic and endothermic sections on reactor behaviour are investigated. The performance of the reactor needs to be proven experimentally and tested over a range of parameters under
practical operating conditions.
2010 Elsevier Ltd. All rights reserved.

1. Introduction
1.1. Dimethyl ether (DME)
Synthesis of new liquid fuels from coal or natural gas has been
under much attention in many countries in recent years. Among
these alternatives, dimethyl ether appears to have the largest
potential impact on society and is one of the superior candidates
for high-quality diesel fuel in near future [13]. Combustion of
DME does not produce pollutants such as hydrocarbons, carbon
monoxide, nitrogen oxides, and particulates. Also, DME has a suitable cetane number about 5560. The physical properties of DME
are similar to liqueed petroleum gas (LPG). Moreover, there exists
no serious problem for the storage, transportation and usage of
DME due to its higher boiling point compared with the LPG. Thus,
DME could replace LPG and be considered as an alternative fuel to
decrease the dependency on petroleum [410].
DME is traditionally produced through dehydration of methanol
which is synthesized from syngas. This process is called two-step
or indirect method of DME production. Indirect method is carried
out in an adiabatic packed bed reactor using acidic porous
Corresponding author. Tel.: +98 711 2303071; fax: +98 711 6287294.
E-mail address: rahimpor@shirazu.ac.ir (M.R. Rahimpour).
0306-2619/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apenergy.2010.10.023

catalysts. Moreover, DME can be produced directly from syngas


in a single-step (direct method). Hybrid catalysts are used for this
aim. Hybrid catalysts are made by pressing the powders of commercial methanol synthesis catalyst and methanol dehydration
catalyst [10,11]. Compared to the indirect process via methanol
synthesis, the direct method is more economical because of the following two reasons:
 The limitations associated with thermodynamic equilibrium of
CO conversion to methanol could be exceeded by the synergy
effect of hybrid catalyst for methanol synthesis and methanol
dehydration.
 Because methanol and DME are produced in one reactor simultaneously, the cost of methanol purication could be eliminated
[10,12].
A lot of work on modelling and simulation of direct and indirect
synthesis of DME in different reactor congurations have been conducted as well as experimental studies. Nasehi et al. [13] modelled
and simulated indirect synthesis of DME in an adiabatic xed bed
reactor and investigated the effects of changes in inlet conditions
on the reactor operation. An experimental study and simulation
of an adiabatic xed bed reactor for dehydration of methanol
to DME was performed by Raoof et al. [14]. Their results

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R. Vakili et al. / Applied Energy 88 (2011) 12111223

Nomenclature
av
AC
Ai
Ao
c
Cp
dp
Di
Dij
Dim
Do
fi
F
G
hf
hi
ho

DHf,i
ki
kg
K
KB
K
Ki
Kp
Kpi

specic surface area of catalyst pellet (m2 m3)


cross section area of each tube (m2)
inside area of inner tube (m2)
outside area of inner tube (m2)
total concentration (mol m3)
specic heat of the gas at constant pressure (J mol1)
particle diameter (m)
tube inside diameter (m)
binary diffusion coefcient of component i in j (m2 s1)
diffusion coefcient of component i in the mixture
(m2 s1)
tube outside diameter (m)
partial fugacity of component i (bar)
total molar ow rate (mol s1)
mass velocity (kg m2 s1)
gassolid heat transfer coefcient (W m2 K1)
heat transfer coefcient between uid phase and reactor wall in exothermic side (W m2 K1)
heat transfer coefcient between uid phase and reactor wall in endothermic side (W m2 K1)
enthalpy of formation of component i (J mol1)
reaction rate constants
mass transfer coefcient for component i (m s1)
conductivity of uid phase (W m1 K1)
adsorption equilibrium constant for benzene (Pa1)
equilibrium constant of reaction i in DME synthesis
adsorption equilibrium constant for component i in
DME synthesis reaction
equilibrium constant for dehydrogenation reaction (Pa3)
equilibrium constant based on partial pressure for component i in methanol synthesis reaction

demonstrated that using pure methanol as the feed of the process


contributes to much slower catalyst deactivation. Song et al. [15]
studied direct process for DME production from syngas in a
pilot-scale xed bed reactor. They applied one-dimensional heterogeneous model to their reactor and found good agreement between their model-based simulation and experimental results.
Liu et al. [16] modelled and designed a three-phase bubble column
reactor for direct synthesis of DME from syngas considering the
inuence of inert carrier back mixing on transfer and the inuence
of catalyst grain sedimentation on reaction. Slurry reactors are able
to provide an efcient heat management because of a liquid phase
existence but there would be a very high mass transfer resistance
in this kind of reactors [17,18]. Lu et al. [19] simulated a uidized
bed reactor for DME synthesis from syngas by using plug ow
model. The experimental results showed considerable differences
in CO conversion and DME productivity in comparison to xed
bed and slurry reactors. Omata et al. [20] studied DME production
from syngas in a temperature gradient reactor to overcome both
the equilibrium limitations at high temperatures and low catalyst
activity related to low temperatures. Then, they optimized the
operating conditions of the reactor for higher CO conversion by
combining genetic algorithms and articial neural networks. The
mathematical model of the pipe-shell xed bed reactor was built
based on the global kinetics of the direct synthesis of DME from
syngas on hybrid catalyst by Hu et al. [21]. Furthermore, the optimum structure and optimum operating conditions of the pipeshell xed bed reactor were specied in their study. Farsi et al.
[22] modelled a shell and tube xed bed reactor for indirect DME
production. Also, the DME production in the isothermal reactor is
maximized by adjusting the optimal temperature distribution
along the reactor using genetic algorithm.

Kw
L
Mi
N
P
Pi
rCO
rCO2
rDME
rC
ri
R
Rp
Re
Sci
T
u
ug
U

vi
yi
z

thermal conductivity of reactor wall (W m1 K1)


reactor length (m)
molecular weight of component i (g mol1)
number of components (N = 8 for methanol synthesis
reaction, N = 4 for dehydrogenation reaction)
total pressure (for exothermic side: bar; for endothermic side: Pa)
partial pressure of component i (Pa)
rate of reaction for hydrogenation of CO (mol kg1 s1)
rate of reaction for hydrogenation of CO2 (mol kg1 s1)
rate of reaction for dehydration of methanol(mol kg1 s1)
rate of reaction for dehydrogenation of cyclohexane
(mol m3 s1)
reaction rate of component i (for exothermic reaction:
mol kg1 s1; for endothermic reaction: mol m3 s1)
universal gas constant (J mol1 K1)
particle radius (m)
Reynolds number
Schmidt number of component i
temperature (K)
supercial velocity of uid phase (m s1)
linear velocity of uid phase (m s1)
overall heat transfer coefcient between exothermic
and endothermic sides (W m2 K1)
atomic diffusion volumes
mole fraction of component i (mol mol1)
axial reactor coordinate (m)

1.2. Coupling
Process intensication (PI) is currently one of the most signicant trends in chemical engineering and process technology. It
has been paid much attention in the research world [23]. It is related to strategies for reduction of emissions as well as consumption of energy and materials. Innovations in catalytic reactor
technologies, which somehow could be the heart of chemical processes, are often the preferred starting point. In this way multifunctional auto-thermal reactor is a novel concept in process
intensication. At present, coupling of endothermic and exothermic reactions would be a promising eld of using multifunctional
auto-thermal reactors. In this type of reactors, an exothermic reaction is considered as the heat producing source to drive the endothermic reaction(s) [24,25]. In recent years, auto-thermal reactors
have been regarded to an important topic of so many articles in
the literature. In addition, an extension of their applications for
coupling of endothermic and exothermic reactions has been attempted. Bhat and Sadhukhan [26] reviewed the process intensication for methane steam reforming by coupling and using the
membrane separation technologies to overcome mass transfer,
heat transfer and thermodynamic equilibrium associated limitations. Hunter and McGuire [27] were among the rst ones who
suggested and did the experimental coupling of endothermic and
exothermic reactions by means of indirect heat transfer. They considered heat exchangers in which catalytic combustion or another
highly exothermic reaction was utilized (or applied) as a heat
source for preparation of the necessary heat for an endothermic
reaction. Altimari and Bildea [28] discussed about design and control of plant wide systems including coupling of exothermic and
endothermic reactions (a rst-order reaction for endothermic side

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R. Vakili et al. / Applied Energy 88 (2011) 12111223

and a second order for exothermic one) at steady-state condition.


Annaland and Nijssen [29] studied a new reactor concept for highly
endothermic, heterogeneously catalyzed gas phase reactions, at
high temperature with rapidity and reversible catalyst deactivation to provide necessary heat for endothermic side. Patel and
Sunol [30] developed a distributed mathematical model for a thermally coupled membrane reactor in order to couple the methane
steam reforming with the exothermic methane combustion. Kirillov et al. [31] studied a mathematical model and applied a numerical method to analyze the operation of coupled methane steam
reforming by fuel oxidation. They used a two dimensional mathematical models to describe the processes in exothermic and endothermic compartments of the reformer. Glockler et al. [32]
presented a short-cut theory to design and analyze an optimal
system for coupling exothermic and endothermic reactions in an
adiabatic xed-bed reactor with reverse ow mode. Elnashaie
et al. [33] considered a specic system which contains simultaneous catalytic dehydrogenation of ethyl benzene and hydrogenation of benzene coupled through hydrogen selective membranes.
Also, rigorous models were developed and used to explore the
basic characteristics of a number of congurations for a number
of catalysts and membranes. Abo-Ghander et al. [34] investigated
co-current and counter-current operation modes for the above
conguration and compared the simulation results with achieved
corresponding results from an industrial adiabatic xed bed reactor at the same feed conditions. Khademi et al. [35] considered
co-current mode of a membrane heat exchanger reactor conguration with three sides in which methanol synthesis and dehydrogenation of cyclohexane to benzene took place in the exothermic and
endothermic sides respectively and hydrogen which was produced
in the endothermic side permeated from surface membrane to the
third side. Farsi et al. [36] simulated the methanol dehydration to
dimethyl ether (indirect DME synthesis) with cyclohexane dehydrogenation in an integrated reactor which formed of two xed
beds as a heat exchanger reactor.
Considering great advantages of direct synthesis of DME from
syngas through indirect method and also large savings in opera-

tional and capital costs due to utilizing of multifunctional autothermal reactors, it seems direct synthesis of DME in a multifunctional heat exchanger reactor to be a proper route especially from
the view point of economic considerations. Thus, we decided to
investigate mathematically the direct synthesis of DME and the
dehydrogenation of cyclohexane to benzene simultaneously in an
auto-thermal heat exchanger reactor. Due to the complexity of
the process stem from the interaction between exothermic and
endothermic reactions in heat exchanger reactors, a suitable mathematical model is required to make an appropriate initial sense of
what could be achieved in coupled reactors. Besides, this suitable
mathematical model will then be used for the optimization of
the process conditions and reactor control. The experimental data
for practical operating conditions can be utilized in conjunction
with the mathematical model in order to develop and modify the
model as a future work for new plant setups and revamps of process improvements. The corresponding results of our coupled reactor simulation are compared with the results of a pipe-shell xed
bed reactor which has been proposed by Hu et al. [21].
2. Process description
2.1. Conventional direct DME synthesis reactor (CDR)
Direct synthesis of DME has been proposed in a pipe-shell xed
bed reactor by Hu et al. [21]. Fig. 1 demonstrates a schematic for
direct synthesis of DME from syngas. In this reactor, hybrid catalysts placed in the pipes. Also, the syngas and boiling water entered
in the pipe and shell side, respectively. The heat of DME synthesis
reactions is transferred to the boiling water from the pipe wall. The
related catalyst specications and operational conditions are gathered in Table 1.
2.2. DME coupled reactor
A conceptual schematic for the co-current mode of a two-side
heat exchanger reactor conguration is shown in Fig. 2. In this

Fresh Water

Syngas
Steam Drum

Natural Gas

Steam
Reforming

Steam

Distillation Unit-1

DME

Fig. 1. Schematic diagram of a pipe-shell xed bed reactor for DME synthesis directly from syngas.

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Table 1
Operational conditions and properties of catalyst for conventional DME reactor [21].

3. Reaction scheme and kinetics

Parameter

Value

Unit

3.1. Dimethyl ether synthesis

Feed composition (mole fraction)


CO
CO2
DME
CH3OH
H2O
H2
N2
CH4
Inlet temperature
Inlet pressure
Number of pipes
Diameter of pipes
Volumetric ow rate of raw gas
Length of reactor
Temperature of boiling water
Thermal conductivity of wall

0.1716
0.0409
0.0018
0.003
0.0002
0.4325
0.316
0.044
493
50
4177
/38  2
2.04  105
5.8
513
48









K
bar

mm
Nm3 h1
m
K
W m1 K1

DME synthesis from syngas is an exothermic equilibrium reaction. In the current work, a hybrid catalyst (mass ratio 1:1) of commercial methanol synthesis (CuO/ZnO/Al2O3) and methanol
dehydration (c-Al2O3) is utilized. The synthesis of methanol from
CO as well as CO2 and dehydration of methanol in the system is regarded as the independent reactions.

Typical properties of catalyst


Particle diameter
Density of catalyst bed
Porosity

/5  5
1200
0.455

mm
kg/m3


CO 2H2 $ CH3 OH DH298K  90:55 kJ=mol

CO2 3H2 $ CH3 OH H2 O DH298K 49:43 kJ=mol

2CH3 OH $ CH3 OCH3 H2 O DH298K 21:003 kJ=mol

The rates expressions have been selected from Nie et al. [39]
and are represented as follow:

rCO
novel coupled reactor, the rst side is the exothermic side where
DME synthesis takes place on the hybrid catalyst. The second side
is an endothermic side which is used as a coolant medium, instead
of boiling water, where hydrogenation of cyclohexane to benzene
takes place on Pt/Al2O3 catalyst. Heat is transferred continuously
from the exothermic side to the endothermic one and drive the
endothermic reaction properly in order that hydrogen production
occurs. The associated operational conditions for endothermic side
are reported in Table 2.

Natural Gas
Reformer

k1 fCO fH22 1  b1

k2 fCO2 fH32 1  b2

rCO2

k3 fCH3 OH 1  b3
p 2
K CH3 OH fCH3 OH

fCH3 OH
K f 1 fCO fH22

Argon
Tank

Syngas

Cyclohexane Feed Line

Cyclohexane
Argon
Syngas

Endothermic Side
Exothermic Side

1 K CO fCO K CO2 fCO2 K H2 fH2 4

rDME

b1

1 K CO fCO K CO2 fCO2 K H2 fH2 3

Cyclohexane Tank

Hydrogen
Benzene
DME
Hydrogen

Separation Unit-2

Heat Transfer

Benzene

P-48

Product

Separation Unit-1

Fig. 2. Schematic diagram for the co-current mode of a heat exchanger reactor conguration.

DME

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stant, respectively, which are clubbed into Table 4 Pi is the partial


pressure in Pa.

Table 2
Operational conditions and properties of catalyst for benzene synthesis process.

a
b

Parameter

Value

Unit

Feed composition (mole fraction)


C6H12
C6H6
H2
Ar
Total molar ow rate
Inlet temperature
Inlet pressurea
Shell inner diameter
Bed void fraction
Particle diameterb

0.3
0.0
0.0
0.7
0.15
493
1.013  105
0.08
0.39
3.55  103





mol s1
K
Pa
m

m

Obtained from Kusakabe et al. [37].


Obtained from Markatos et al. [38].

b2

fCH3 OH fH2 O
K f 2 fCO2 fH32

b3

fDME fH2 O
2
K f 3 fCH
3 OH

where fi and K are the fugacity of component i and equilibrium


constant of reaction i, respectively [40,41]. The reaction rate constants are tabulated in Table 3.

4. Mathematical model
The mathematical model for simulation of the novel coupled
reactor with co-current ow regime has been developed based
on the following assumptions:
 The gas mixture is considered as an ideal gas in both catalytic
reactor sides.
 One-dimensional heterogeneous model is considered for both
reactor sides.
 The reactor is simulated in the steady-state condition.
 The radial diffusion in the catalyst particles is neglected in each
side.
 Bed porosity in both axial and radial directions is constant.
 Heat loss to surrounding is neglected.
4.1. Solid phase
The mass and energy balance equations for solid phase are represented as follow:

av cj kgi;j ygi;j  ysi;j gri;j qb 0

3.2. Dehydrogenation of cyclohexane


Hydrogen would be a cost-effective fuel which can be produced
in large scale in near future. One method for hydrogen production
is the use of alternative fuels which are easily transformed to
hydrogen and can be stored in liquid form [42]. One of these mentioned fuels is cyclohexane. The reaction scheme for dehydrogenation of cyclohexane to benzene is represented as follows:

C6 H12 $ C6 H6 3H2

DH298K 206:2 kJ=mol

10

The following equation is used for cyclohexane dehydrogenation rate, rC [43]:

rC

kK P PC =P3H2  PB
1

11

K B K P P C =P3H2

where k, KB, and KP are the reaction rate constant, the adsorption
equilibrium constant for benzene, and the reaction equilibrium con-

B
3

k1
k2
k3
KCO
K H2
K H2
K CH3 OH

1.828  10
0.4195  102
1.939  102
8.252  104
2.1  103
0.1035
1.726  104

43,723
30,253
24,984
30,275
31,846
11,139
60,126

N
X

gri;j DHf ;i 0

13

i1

where ysi;j and T sj are the solid-phase ith-component mole fraction


and temperature in jth side of reactor, respectively. gk,j is effectiveness factor of kth reaction in jth side of the reactor which is
obtained from a dusty gas model calculations [44]. Detailed information about such a dusty gas model is given in Appendix A.
4.2. Fluid phase
The following mass and energy balances are written for the
uid phase:

Table 3
Reaction rate constants for DME synthesis.
k = A exp (B/RT)

av hf T gj  T sj qb

12



1 dF i;j
av j cj kgi;j ysi;j  ygi;j 0
AC dz
C gpj dF j T gj
AC

dz


 pD 

j
av j hf T sj  T gj 
U T g2  T g1 0
AC

14

15

where Fi,j and T gj are the uid-phase ith-component molar ow rate


and temperature in jth side of the reactor, respectively. In Eq. (15),
the positive sign for the third term is related to the exothermic side
and the negative sign is used for the endothermic one.
4.3. Ergun equation
The pressure drop through the catalytic beds is calculated based
on the Ergun equation [45]. The related equation for tubular reactors is:

Table 4
The reaction rate constant, the adsorption equilibrium constant, and the reaction
equilibrium constant for dehydrogenation of cyclohexane reaction.
k = A exp (B/T)

B (K)

k
KB
Kp

0.221 mol m3 Pa1 s1


2.03  1010 Pa1
4.89  1035 Pa3

4270
6270
3190

dP 150l 1  e2 Q 1:75q 1  e Q 2

2 2
dz
e3 Ac /s dp e3 A2c
/s dp

16

where dP is the pressure gradient, Q is the volumetric ow rate, dp is


the particle diameter, /s is the sphericity (for spherical particles is
unity), and l and q are the uid viscosity and density, respectively.

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6.1. Base case

Table 5
Physical properties and mass and heat transfer correlations.
Parameter

Equation

Ref.
2

Component heat capacity


Gas density

Cp = a + bT + cT + dT
q RTP
P
M W av e
MW i yi

Average molecular weight


Viscosity of reaction mixtures

[46]

l 1C1CT3 2C4
T

Mixture thermal conductivity


Mass transfer coefcient between
gas and solid phases

T2

kgi 1:17Re0:42 Sc0:67


ug  103
i

[47]
[48]

2R u

Re lp g
l
Sci qD 10
4
im

1yi
Dim P
yi

[49]

p
107 T 3=2 1=M i 1=M j


Dij

[50]

ij Dij

Overall heat transfer coefcient


Heat transfer coefcient between
gas phase and reactor wall

3=2
v 3=2
v cj
ci

o =Di
h1i Ai lnD
AAoi h1o
2pLK w
 2=3


Cp l
qudp 0:407
h
0:458
K
eB
l
C p ql

1
U

[51]

4.4. Boundary conditions


At the entrance of the reactor, the inlet temperature, pressure
and molar ow rate of the reactant gas (in the both sides) are
known. Therefore, the following boundary conditions are applied
to the differential equations system:

z 0;

F i;j F i0;j

T gj T g0j

Pgj Pg0j

17

4.5. Auxiliary correlations


To complete the simulation procedure, auxiliary correlations
should be added to the modelling section. These auxiliary correlations which estimate physical properties as well as the mass and
heat transfer coefcients are summarized in Table 5. The heat
transfer coefcient between gas phase and the reactor wall is
applicable for heat transfer between gas phase and solid catalyst
phase.
5. Numerical solution
MATLAB software is used to solve the ordinary differential
equations in axial direction. The related set of ODEs are converted
to nonlinear algebraic equations by using backward nite difference method. The reactor length is divided to 100 separate sections
and nonlinear algebraic equations are solved for both reactor sides
in each section, simultaneously.
6. Results and discussion
In this section, various observed behaviours for co-current ow
in a thermally coupled reactor (TCR) are discussed. The effects of
operational and design parameters variations on the exothermic
and endothermic mole fractions, carbon monoxide and cyclohexane conversions and temperature proles during the process are
investigated. Two denitions are introduced as follows to examine
the carbon monoxide and cyclohexane conversions through the
reactor length:

XCO

F CO;in  F CO;out
F CO;in

XC6 H12

F C6 H12 ;in  F C6 H12 ;out


F C6 H12 ;in

In order to establish a reference point for the coupled reactor, so


that the inuence of various parameters can be evaluated, calculations are rst carried out for a base case. The operating conditions used for both sides of this mentioned case have been given
in Tables 1 and 2 previously.

18

19

6.1.1. Molar behaviour


(a) Exothermic side:
Fig. 3af shows components mole fraction changes in exothermic side of coupled reactor in CDR proposed by Hu et al. [21].
Fig. 3a illustrates the mole fraction of DME in the exothermic side
of TCR and CDR versus the dimensionless reactor length. It is obvious that the DME mole fraction is enhanced by about 0.8% in TCR
compared with the CDR which leads to a higher production rate
of 600 Ton/year. Fig. 3bf presents similar results for the other
components in the exothermic section of the TCR. Among DME
synthesis reactions (Eqs. (4)-(6)), the reversible reaction representing the hydrogenation of carbon dioxide occurs in backward direction which leads to carbon dioxide production as demonstrated in
Fig. 3c. Also, outlet water content from the TCR is higher than that
of the CDR (see Fig. 3e) which is related to higher DME (in Eq. (6))
and lower carbon dioxide production (in Eq. (5)) in the TCR.
Although the proles of mole fractions along the TCR and CDR
are not the same under steady-state conditions, there are not considerable differences between the outlet values from the TCR and
CDR. The TCR and CDR simulation results related to the study of
Hu et al. [21] are summarized in Table 6. As it is illustrated, the
maximum relative error obtained is about 3.8% which is feasible
and acceptable.
(b) Endothermic side:
Fig. 3g reveals simultaneously the plots of cyclohexane, benzene and hydrogen mole fractions in the endothermic side of the
TCR as functions of the reactor dimensionless length. The cyclohexane conversion reaches to 64% with a total hydrogen production
rate of 860 kmol/h.
(c) Total molar ow rate:
In recent studies on the coupled reactors [35,52,53], a constant
molar ow rate during the modelling has been considered, which
reduces the accuracy in prediction of reactor outlet mole fractions.
In the CDR the total molar ow rate decreases along the reactor
length continuously. Therefore, in this work total molar ow rate
is considered to be variable along the reactor length. The total molar ow rates (for both sides of TCR) are depicted in Fig. 4. As it is
illustrated, the variations of the molar ow rates are obtained 17%
and 36% for exothermic and endothermic sides, respectively. The
molecular weights, heat capacities, viscosity, density and the other
properties are considered to be variable during the mathematical
modelling.
6.1.2. Thermal behaviour
Fig. 5 illustrates the axial temperature proles for CDR and TCR
in both the exothermic and endothermic sides, respectively. Fig. 5a
shows the temperature proles in the exothermic side of both the
TCR and CDR. As it can be understood, the maximum temperature
in the TCR is about 4K lower and the temperature prole is improved in comparison with the ones of the CDR. This lower temperature permits a higher DME conversion. Along the exothermic side,
temperature increases smoothly and a hot spot develops Because
of the amount of the generated heat (in exothermic side) is higher
than the amount of the consumed one in endothermic side. The
rates of the exothermic reactions are reduced by temperature increase at the end of the reactor due to the equilibrium limitations.
Thus, the consumed heat in endothermic side will be higher than
the generated one in exothermic side and consequently the

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-3

0.05
0.045

DME mole fraction

x 10
11

10

Coupled reactor
Hu et al. [21]

0.04

Methanol mole fraction

0.035
0.03

0.05

0.025
0.048

0.02
0.046
0.95

0.015

0.98

0.01

8
7
6
5

Coupled reactor
Hu et al. [21]

4
3

0.005
0

0.2

0.4

0.6

0.8

2
0

0.2

Dimensionless Length

0.18
0.17

Coupled reactor
Hu et al. [21]

0.15
0.14
0.13
0.12
0.11

0.03
0.025
0.02
Coupled reactor
Hu et al. [21]

0.015

0.005
0

0.2

0.4

0.6

0.8

0.2

Dimensionless Length

0.4

0.6

0.8

Dimensionless Length

0.08

f
Coupled reactor
Hu et al. [21]

0.075

0.44
Coupled reactor
Hu et al. [21]

0.42

0.07

H2 mole fraction

CO2 mole fraction

0.01

0.09

0.8

0.04

0.1

0.08

0.6

0.035

H2O mole fraction

CO mole fraction

0.16

0.4

Dimensionless Length

0.065
0.06
0.055
0.05

0.4
0.38
0.36
0.34

0.045

0.32
0.04

0.2

0.4

0.6

0.8

0.6

0.8

0.35
C6H12
C6H6
H2

0.3

Mole fraction

0.4

Dimensionless Length

Dimensionless Length

0.2

0.25
0.2
0.15
0.1
0.05
0
0

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

Dimensionless Length
Fig. 3. Comparison of: (a) DME, (b) CO, (c) CO2, (d) methanol, (e) H2O and (f) H2 mole fraction along the reactor length between exothermic sides of TCR and CDR, (g) mole
fraction of cyclohexane, benzene, and hydrogen in the endothermic side along the reactor length.

1218

R. Vakili et al. / Applied Energy 88 (2011) 12111223

Table 6
Comparison between steady state simulation results and Hu et al. [21].

Output composition
CO
CO2
DME
CH3OH
H2O
H2
Temperature (K)

Hu et al. [21]
(mole fraction)
0.0877
0.0671
0.0491
0.0106
0.0338
0.033
516.60

Simulation results

Relative error (%)

0.089
0.064
0.0495
0.0103
0.0351
0.0333
510.70

1.5
3.7
0.8
2.8
3.8
0.9
1.1

535
530
525

Temperature,K

Components

520
515
510
505

coupled reactor
Hu et al. [21]

500

0.22

0.55

0.2

0.5

0.18

0.45

0.16

0.4
0

0.2

0.4

0.6

0.8

0.14
1

dimensionless length
Fig. 4. Changes of molar ow rate of exothermic and endothermic stream along the
reactor length.

temperature decreases to 511 K (see Fig. 5a). The temperature of


the endothermic side in the TCR is always lower than that of the
exothermic side in order to make a driving force for heat transfer
from the solid wall. At the reactor entrance, the transferred heat
from the solid wall is lower than the consumed heat by the endothermic side, which is due to low temperature difference. Therefore, temperature begins to decrease and a cold spot forms as
demonstrated in Fig. 5b. Afterward, the endothermic temperature
starts to increase in order to increase the exothermic temperature
and the heat transfer from the exothermic side to the endothermic
section. Considering that the consumed heat in endothermic side is
higher than the generated in exothermic side the temperature decreases to 501 K at the end part of the shell side (endothermic
section).
6.2. Inuence of inlet temperature of endothermic stream
Fig. 6a and b depict the inuence of various inlet temperature of
endothermic stream on the temperature proles in the exothermic
and endothermic sides along the TCR. By decreasing the inlet temperature of endothermic side, the temperature driving force between the shell and tube sides increases. Besides, the rate of
dehydrogenation decreases. Consequently, the endothermic temperature starts to increase and the cold spot is vanished as it is
illustrated in Fig. 6a. Higher inlet temperatures create a bigger
maximum for the exothermic section (see Fig. 6b). The carbon
monoxide and cyclohexane conversions decrease signicantly
from 48% to 39.5% and 64% to 54%, respectively for a 13 C depletion the inlet temperature of the endothermic side.
6.3. Inuence of molar ow rate of endothermic stream
Fig. 7a and b examines the inuence of the molar ow rates in
endothermic stream on the temperature proles in the exothermic

490

0.2

0.4

0.6

0.8

0.8

Dimensionless Length

515
510

Temperature,K

0.6

Molar flow rate of endothermic stream,


mol/s

Molar flow rate of exothermic stream,


mol/s

495

505
500
495
490
485

0.2

0.4

0.6

Dimensionless Length
Fig. 5. Variation of temperature for CDR and TCR in: (a) exothermic side, (b)
endothermic side along the reactor length.

and endothermic sides. With increasing the ow rate of endothermic stream, axial temperature variations become lower due to
higher transferred heat through the solid wall (Fig. 7a). The temperature of the endothermic side is always lower than that of the
exothermic one in order to make a temperature driving force.
Therefore, the temperature of endothermic side changes pursuant
to the exothermic one (Fig. 7b). Fig. 7c illustrates how the carbon
monoxide and cyclohexane conversions vary when the ow rate
of endothermic stream increases from 0.1 to 0.24 mol s1. Carbon
monoxide and cyclohexane conversion decrease from 53.3% to
40.2% and from 89% to 39.5% respectively. Decreasing of carbon
monoxide is due to lower axial temperature prole (see Fig. 7a)
and consequently lower reaction rates. Decreasing of cyclohexane
conversion is an obvious consequence of the fact that the amount
of catalyst on endothermic side is not enough for these higher ow
rates.
6.4. Inuence of molar ow rate of exothermic stream
In this section, the reactor thermal behaviour and performance
are studied for different exothermic stream molar ow rates. By
increasing the ow rate of exothermic stream lower degree of reaction is taken owing to lower residence time. Hence, the temperature of exothermic side decreases. Consequently, hot spot which
is due to the equality of generated and consumed heats is approached to end of reactor length as it can be seen in Fig. 8a. In
the entrance of the reactor, the consumed heat (for endothermic
side) is higher than the transferred one, therefore the system starts
to cool down and thus a minimum in temperature is observed for
the endothermic side. By further increasing the exothermic ow
rate, this minimum becomes bigger which is due to lower heat

1219

R. Vakili et al. / Applied Energy 88 (2011) 12111223

550

515

540

F=0.1

510

Temperature,K

Endothermic temperature, K

505
500
495
490

530

F=0.12

520
F=0.15

510
F=0.2

485

500

480
1

495

K
ure,
erat
emp

490

0.5

485

Dimensionless length

0 480

let
ic in

490
0

rm
othe
End

0.2

0.4

0.6

0.8

0.8

Dimensionless Length

520

515

Temperature,K

520
510
500

F=0.12

505

F=0.15

500

F=0.2

495

485
0

495

0.8

0.6

re, K
ratu
mpe

490
0.4

0.2

Dimensionless length

485
0 480

let te
ic in

rm
othe
End

Fig. 6. Inuence of inlet temperature of endothermic stream on the temperature


proles in: (a) endothermic side and (b) exothermic side along the reactor length
for TCR.

transfer from the solid wall to the endothermic side (compare


Fig. 8b and c). Finally, outlet temperature in endothermic side becomes higher due to increase of the transferred heat from the exothermic reaction side. The effect of increasing of the exothermic
stream ow rate on the reactor performance is showed in Fig. 8d.
Carbon monoxide conversion decreases from 58.8% to 24.5% when
molar ow rate increases from 0.2 to 1 mol s1 which is mainly due
to lower residence time for feed to react on the catalyst surface.
Also, cyclohexane conversion is maximized at molar ow
rate = 0.65 mol s1 and then it is reduced which can be dened
by Fig. 8e.
6.5. Simultaneous effects of inlet temperature and molar ow rate of
endothermic stream on the reactor performance
For better understanding of reactor performance, we investigated simultaneous effects of variations in the inlet temperature
and the molar ow rate of endothermic stream on the carbon monoxide and cyclohexane conversions. In this work, inlet temperature
and molar ow rate change from 480 to 493 K and 0.1 to
.24 mol s1. All other parameters are kept at their base case values.
Maximum carbon monoxide conversion is equal to 53.3% when the
inlet temperature and the molar ow rate are 493 K and 0.1 mol
s1, respectively. By increasing the molar ow rate to 0.24 mol s1
and decreasing the inlet temperature to 480 K, carbon monoxide
conversion is reduced to 24.3% as demonstrated in Fig. 9a. This
can be considered for cyclohexane conversion, similarly. Maximum
and minimum cyclohexane conversions are 89% and 27%, respec-

0.2

0.4

0.6

Dimensionless Length

0.54

0.52

0.9

0.5

0.8

0.48

0.7

0.46

0.6

0.44

0.5

0.42

0.4

0.4
0.1

0.12

0.14

0.16

0.18

0.2

0.22

Cyclohexane conversion

490
1

510

490

CO conversion

Exothermic temperature, K

F=0.1

530

0.3
0.24

Molar flow rate of endothermic stream, mol/s


Fig. 7. Inuence of molar ow rate of endothermic stream on: (a) axial temperature
prole in exothermic side, (b) axial temperature prole in endothermic side,
(c) carbon monoxide and cyclohexane conversion.

tively. Fig. 9b reveals the simultaneous effects of endothermic molar ow rate and inlet temperature on the hydrogen yield
(cyclohexane conversion).

6.6. Sensitivity analysis on the reaction rates


Fig. 10a and b illustrates the effect of inlet temperature of the
exothermic and endothermic sides on the main components
(cyclohexane and DME) in the endothermic and exothermic sections, respectively. By increasing the inlet temperature of the exothermic side the related reaction rate increases. Consequently,
more heat is transferred from the solid wall to the endothermic
side and this contributes to more hydrogen production from the
dehydrogenation reaction (see Fig. 10a). At higher inlet temperature of the endothermic side, the heat transfer from the exothermic

1220

R. Vakili et al. / Applied Energy 88 (2011) 12111223

530
F=0.3

50

F=0.7

Transferred heat, W

520

F=0.55

Temperature, K

60

510

F=1

500
F=0.9

490

F=1.5

F=0.4

30

F=0.55

20
F=0.7
F=0.3

10

480
470
0

40

0
0.2

0.4

0.6

0.8

0.2

515

0.4

0.6

0.8

Dimensionless length

Dimensionless length

0.7

0.65

0.6

0.6

0.5

0.55

0.4

0.5

0.3

0.45

F=0.55

500
495
F=0.4

F=0.7

490
485

F=0.3

480
475

0.2

0.4

0.6

0.8

0.2
0.2

Dimensionless Length

Cyclohexane conversion

505

CO conversion

Temperature,K

510

0.4
0.3

0.4

0.5

0.6

0.7

0.8

0.9

Molar flow rare of exothermic stream, mol/s

60

Consumed heat , W

55
50
45

F=0.65

F=0.3

40
F=0.55

35
30
25
F=1

20
15
10
0

0.2

0.4

0.6

0.8

Dimensoinless length
Fig. 8. Inuence of molar ow rate of endothermic stream on: (a) axial temperature prole in exothermic side, (b) axial temperature prole in endothermic side, (c)
transferred heat from solid wall to endothermic side, (d) carbon monoxide and cyclohexane conversion and (e) consumed heat in endothermic side along the reactor length.

side decreases owing to the lower temperature difference between


exothermic and endothermic compartments. Consequently, more
DME is produced. The underneath area below the Fig. 10b shows
the DME production rates for various endothermic inlet temperature. These areas are 105.67, 94.93 and 76.71 (mol s1) for inlet
temperatures of 493, 480 and 470 K, respectively.

7. Conclusion
Direct DME synthesis was coupled with dehydrogenation of
cyclohexane to benzene by means of indirect heat transfer. The
reactor considered in this study is composed of two separated sides
for exothermic and endothermic reactions. In this work, a steady-

state heterogeneous one-dimensional model for the mentioned


reactor has been developed. This new conguration represents
some important improvement in comparison to conventional
DME synthesis reactor (CDR) such as: reduction in reactor size;
lowering outlet temperature of product stream; production of
hydrogen and benzene as additional valuable products by about
15,000 and 196,000 Ton/year respectively and achievable autothermal conditions within the reactors. About 600 Ton/year DME
was enhanced by the new proposed coupled conguration. Moreover, hot spot temperature was lowered in about 4 K. The effects
of inlet temperature and the endothermic stream molar ow rate
on the axial temperature prole of exothermic and endothermic
sides as well as carbon monoxide and cyclohexane conversions
were examined. Higher ow rate of endothermic stream results

1221

R. Vakili et al. / Applied Energy 88 (2011) 12111223

CO conversion

0.55

Rate of cyclohexane dehydrogenation,


mol/(m3 s)

0.5
0.45
0.4
0.35
0.3
0.25
0.2
495

490

Inlet temperature 485


,K

480 0.1

0.2
0.12 0.14 0.16 0.18

0.22 0.24

Molar flow rate of endothermic stream, mol/s

1.6

T01=470K

1.4

T01=493K

T01=480K

1.2
1
0.8
0.6
0.4
0.2

0.2

0.4

0.6

0.8

Dimensionless length
1
-3

0.8
0.6
0.4
0.2
495
490

Inlet temperature 485


,K
480 0.1

0.18 0.2
0.12 0.14 0.16

Rate of methanol dehydration.


mol/(kgcats)

Cyclohexane conversion

1.8

0.22 0.24

Molar folw rate of endothermic stream, mol/s

T 02=470K

4.5

Appendix A. Dusty gas model


When reactants diffuse into the pores to react and form products, bulk, Knudsen and surface diffusions may take place simultaneously, depending on the size of the pores, the molecules involved
in the diffusing stream, the operating conditions and the geometry
of the pores [54]. In the dusty gas model which is based on Stefan
Maxwell equations, both diffusional and convective mass transport
terms are considered, and this includes the description of pressure
drop over the catalyst particle resulting from the stoichiometry of

T =480K
02

T 02=493K

4
3.5
3
2.5
2
1.5

Fig. 9. Simultaneous effect of inlet temperature and molar ow rate of endothermic


stream on: (a) carbon monoxide conversion, (b) cyclohexane conversion.

in lower carbon monoxide conversion. These are because of lower


temperature prole in exothermic side and also lower cyclohexane
conversion due to the fact that the amount of catalyst in the endothermic side is not enough for these higher ow rates. The inuence of exothermic stream molar ow rate on reactor thermal
behaviour and performance was also studied. By increasing the
molar ow rate of exothermic side, hot spot temperature is approached to the end of the reactor length and carbon monoxide
conversion decreased due to residence time depletion. When molar
ow rate was 0.65 mol s1, cyclohexane conversion was maximized and then decreased due to decrease of consumed heat in
the endothermic side. Rigorous mathematical models are excellent
tools for exploration of the basic characteristics of such novel congurations and are able to provide a good initial sense about what
would be achieved in the coupled reactors. Such an exploration can
contribute to considerable savings in money and time during the
expensive stage of pilot plant development. The continuous development of the model in conjunction with the pilot plant optimal
utilization can also lead to considerable benets on the road towards the successful commercialization of such efcient novel
congurations and would be considered as a future work.

x 10

0.2

0.4

0.6

0.8

Dimensionless length
Fig. 10. Inuence of: (a) exothermic inlet temperature on the rate of cyclohexane
dehydrogenation and (b) endothermic inlet temperature on the rate of methanol
dehydration.

reaction and accompanying convective transport of molecules [55].


The results of sensitivity analysis show that at low pressures (up to
10 bar), Knudsen diffusion is the most important diffusing term,
while at high pressures (100 bar) bulk diffusion predominates
[44]. In this model, it is assumed that pore walls consist of giant
molecules (dust) which are uniformly distributed in the space.
These dust molecules are considered to be dummy, or pseudo species in the mixture [56].
The dusty gas ux relations can be offered as follows, with a
small change in the notation as to avoid conicting with other
notations used in the model [57]:

Ni
DEff
i

N
X
yj Ni  yi N j

DEff
ij

ij

P dyi yi

RT dr RT

B0 P

dP

dr
lDEff
i

A:1

In the above equation, B0 is permeability of catalyst pellet, DEff


i is
effective Knudsen diffusion coefcient and DEff
ij is effective binary
diffusion coefcient which are presented by Eqs. (A.2) and (A.3) below, respectively [58,59]:

DEff
aP
i
DEff
ij

es 2 8RT
s 3 pM i

es
D
s ij

1=2
A:2

A:3

where ap is the mean pore radius.


The dusty gas ux relations (Eqs. (A.1)-(A.3)) contain three
parameters: the mean pore radius, a, the ratio of porosity and tortuosity factors, es/s and the permeability parameter, B0. Using

1222

R. Vakili et al. / Applied Energy 88 (2011) 12111223

Darcys law, combines the two parameters of permeability and the


mean pore radius and gives a two-parameter model using the following correlation [58,59]:

B0

a2P
8

A:4

The reader should note that the ux relations (Eq. (A.1)) could
be rewritten for distinct components to form a set of ordinary differential equations, yielding expressions for dyi/dr [45]. Knowing
the fact that summation of all components equals to 1 (i.e.,
PN
1 yi 1), N  1 ordinary differential equations should be written
for the ux relations.
To complete the mathematical modelling of dusty gas model,
the material balances and the stoichiometric relations have to be
added in order to be able to describe the multi component reactiondiffusion problem. Since we have used the detailed Graaf
kinetics for the system of methanol synthesis process, which is
based on three-independent reactions [44], and cyclohexane dehydrogenation reaction, four material balances are needed to be
added to ux relations. For a spherical and isothermal particle, this
yields [57]:

dXk
r2 r k k 1; 2; 3; 4
dr

A:5

!
3
5
X
dyi
1 X
Xk
v kj F ij ; i 1; 2; . . . ; N  1
 2
r
dr
j1
k1

A:6

RT
F ii
P

1
DEff
i

RT
P

F ij 

w1

yi
DEff
i

5
X

yi

j1;ji

DEff
ij

yi
DEff
j

! !
1
1
Eff
w
lD

yi

B0 P

DEff
i

! !
1
lDEff w
B0 P

i1

A:8

N
B0 P X
yi

A:7

A:9

DEff
i

where Fii, Fij, w and Xk are auxiliary parameters and v is the stoichiometric coefcient.
The pressure drop in radial coordinate is given by:
N
dP
1 RT X
1 X
 2
v ik Xk
dr
r w i1 DEff k
i

!
A:10

The boundary conditions for the set of ordinary differential


equations are given by:

Xk 0 at r 0

A:11

yi ysi at r RP

A:12

P Ps at r RP

A:13

The effectiveness factor for reaction k is given by:

R Rp

gk

r k dr
Rp rsk

A:14

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