Beruflich Dokumente
Kultur Dokumente
Applied Energy
journal homepage: www.elsevier.com/locate/apenergy
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
1212
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
Kw
L
Mi
N
P
Pi
rCO
rCO2
rDME
rC
ri
R
Rp
Re
Sci
T
u
ug
U
vi
yi
z
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
1213
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.
1214
Table 1
Operational conditions and properties of catalyst for conventional DME reactor [21].
Parameter
Value
Unit
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.
/5 5
1200
0.455
mm
kg/m3
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
Argon
Syngas
Endothermic Side
Exothermic Side
rDME
b1
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
1215
Table 2
Operational conditions and properties of catalyst for benzene synthesis process.
a
b
Parameter
Value
Unit
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
b2
fCH3 OH fH2 O
K f 2 fCO2 fH32
b3
fDME fH2 O
2
K f 3 fCH
3 OH
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:
C6 H12 $ C6 H6 3H2
10
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
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
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
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
1216
Table 5
Physical properties and mass and heat transfer correlations.
Parameter
Equation
Ref.
2
Cp = a + bT + cT + dT
q RTP
P
M W av e
MW i yi
[46]
l 1C1CT3 2C4
T
T2
[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
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]
z 0;
F i;j F i0;j
T gj T g0j
Pgj Pg0j
17
XCO
F CO;in F CO;out
F CO;in
XC6 H12
18
19
1217
0.05
0.045
x 10
11
10
Coupled reactor
Hu et al. [21]
0.04
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
0.01
0.09
0.8
0.04
0.1
0.08
0.6
0.035
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
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
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
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.
490
0.2
0.4
0.6
0.8
0.8
Dimensionless Length
515
510
Temperature,K
0.6
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
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
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
tively. Fig. 9b reveals the simultaneous effects of endothermic molar ow rate and inlet temperature on the hydrogen yield
(cyclohexane conversion).
1220
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
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.
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-
1221
CO conversion
0.55
0.5
0.45
0.4
0.35
0.3
0.25
0.2
495
490
480 0.1
0.2
0.12 0.14 0.16 0.18
0.22 0.24
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
0.18 0.2
0.12 0.14 0.16
Cyclohexane conversion
1.8
0.22 0.24
T 02=470K
4.5
T =480K
02
T 02=493K
4
3.5
3
2.5
2
1.5
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.
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
DEff
aP
i
DEff
ij
es 2 8RT
s 3 pM i
es
D
s ij
1=2
A:2
A:3
1222
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
Xk 0 at r 0
A:11
yi ysi at r RP
A:12
P Ps at r RP
A:13
R Rp
gk
r k dr
Rp rsk
A:14
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