Journal of Industrial and Engineering Chemistry: Mohammad Ghavipour, Reza Mosayebi Behbahani
Journal of Industrial and Engineering Chemistry: Mohammad Ghavipour, Reza Mosayebi Behbahani
Journal of Industrial and Engineering Chemistry: Mohammad Ghavipour, Reza Mosayebi Behbahani
A R T I C L E I N F O
Article history:
Received 11 June 2013
Accepted 12 September 2013
Available online 19 September 2013
Keywords:
Methanol dehydration
DME
g-Alumina
Fixed-bed reactor modeling
Reaction rate
A B S T R A C T
Dimethyl ether (DME) synthesis reaction rate was studied over a commercial sample of g-Alumina to
investigate the accuracy of the most applicable rate models. Due to the deviation of the former proposed
models especially at temperatures below 593 K, a new simple empirical rate model was proposed.
Besides, previous proposed correlations for methanol dehydration equilibrium constant were examined
experimentally and a new equation was developed. Subsequently, one dimensional unsteady state
heterogeneous model was applied to simulate adiabatic and non-adiabatic xed-bed reactors.
Temperature prole and methanol conversion along the reactors were predicted while varying feed
rate and feed temperature.
2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.
1. Introduction
Considering environmental pollution, energy security and
future oil supplies, the global community is seeking new
alternative fuels. A promising alternative fuel could be dimethyl
ether (DME) due to low NOx and SOx emission and because it
does not have large issues with toxicity, production, infrastructure, and transportation [13]. It also can be used as hydrogenrich feed of fuel-cells [4,5] or as a substitute fuel in domestic
appliances [6]. DME synthesis can be performed through two
routes: direct synthesis (i.e. syngas to DME over hybrid
catalysts) and indirect synthesis (i.e. methanol dehydration to
DME) [7]. g-Alumina and HZSM-5 are the most common
catalysts for DME indirect synthesis reaction. g-Alumina tends
to adsorb water on its surface and thereby loses its activity
because of its hydrophilic nature. When pure methanol is used
as the process feed, the catalyst deactivation occurs very slowly
and this hydrophilic nature is not a considerable problem [8].
The g-Alumina modied by silica or phosphorous has shown
better performance compared to the untreated one. The best
operating temperatures are from 523 to 673 K and the amounts
of coking and by-products are very low [911]. The activity of
HZSM-5 is higher than the g-Alumina because of more strong
acidic sites. Unlike the g-Alumina, which exhibits only Lewis
acidity, HZSM-5 has both Lewis (due to the extra-framework
1226-086X/$ see front matter 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2013.09.015
M. Ghavipour, R.M. Behbahani / Journal of Industrial and Engineering Chemistry 20 (2014) 19421951
Nomenclature
Table 1
Methanol dehydration reaction rate models.
Bercic and Levec (1992) [15]
av
Ci
Cp
dp
dt
hf
kgi
K
Keq
L
Q
r
R
Re
Sci
T
Tin
Tr
t
us
U
W
WHSV
X
z
Greek letters
m
viscosity of uid phase (kg/m s)
r
density (kg/m3)
e
catalyst bed void fraction
h
effectiveness factor (dimensionless)
DHr
heat of reaction (J/molMeOH)
Subscripts
bulk of solid phase (catalyst bed)
B
in bulk of gas phase
g
gaseous chemical species involved in the reaction
i
methanol
M
solid phase
s
water
W
Superscripts
at the catalyst surface
s
1943
rM
rM
2 C D C W
ks k2
CM
K
M
I
4
12kM C M 0:5 kW C W
ks k2
C2
M M
II
0:5
k s k M CM
0:5
M CM kW C W
III
C 0:5
IV
1kM C M kW C W 2
rM k 1k
M
rM k C 0:5 k
M
2 CW
0:5
0:5
k 2 CW
rM k1 CM
rM k1 k2 C M
VI
VII
C
rM k0 expEa =RT C MeOH KW
eq
M. Ghavipour, R.M. Behbahani / Journal of Industrial and Engineering Chemistry 20 (2014) 19421951
1944
Table 2
Catalyst characterizations.
Particle size
distribution
Bulk
density
(g/cm3)
0.869
BET surface
area (m2/gcat)
183.2
NH3-TPD
Temp (K)
mmolNH3 =g cat
402
666
0.295
0.452
conductivity detectors. The column was TRB-5 (Teknokroma Co.(95%) Dimethyl-(5%) diphenylpolysiloxane bonded and cross
linked phase-length 30 m-inside diameter 0.53 mm) with helium
as the carrier gas. The oven temperature was kept constant at
313 K and run time was 3 min. The 6-port gas sampling valve with
a 0.05 mL sample loop was used to inject the gas samples into the
capillary column. A calibration curve was used to determine the
gas samples composition. The compositions of the reactor outlet
gases were monitored via the Gas Chromatograph until no change
observed by time and steady state conditions were obtained.
3. Equilibrium constant estimation
Equilibrium constant of the methanol to dimethyl ether
reaction has been studied previously and some correlations have
been derived based on the experimental works or thermodynamic
calculations. Hayashi and Moffat (1982) developed the equilibrium
constant using thermodynamic properties at 298 K and heat
capacity data at higher temperatures as following [27]:
ln K P 3440=T 1:67 ln T 2:39 104 T 0:055
106 T 2 5:496
(1)
(2)
They also calculated the enthalpy of formation (DHf 298) and the
free Gibbs energy of formation (DGf 298) of dimethyl ether by use of
published thermochemical data together with the experimental
data to be 180.22 and 109.66 kJ/mol, respectively.
Finally, the equilibrium constant which is coupled to Bercic and
Levec model and has been used extensively in xed-bed reactor
modeling papers [2226].
ln K P 3138=T 0:86 log T 1:33 103 T 1:23
105 T 2 3:5 1010 T 3
(3)
ln
K
1
K0 R
ZT
T0
DHr
T2
dT
&
DHr DHr0
ZT
rC P dT
(4)
T0
rC P rC 1 rC 2 T rC 3 T 2 rC 4 T 3 rC 5
T4
Cn
&
DME
rC n
Cn
H2 O
K 0 expDG0r =R T 0
2C n
MeOH
(5)
(6)
M. Ghavipour, R.M. Behbahani / Journal of Industrial and Engineering Chemistry 20 (2014) 19421951
1945
Table 3
Thermodynamic properties of pure substances.
Substance
C2
C3
C4
C5
MeOH
DME
H2O
1.0580e5
1.1010e5
2.7637e5
3.6223e2
1.5747e2
2.0901e3
9.3790e1
5.1853e1
8.125
0
0
1.4116e2
0
0
9.3701e6
K0 R
T0
2
6
rC 4 3
rC 5 4
T T03
T T04
12
20
rC 2 2 rC 3 3 rC 4 4 rC 5 5
T0
T0
T0
T0
DH0r rC 1 T 0
2
3
4
5
1=T 1=T 0
Finally, the following expression is obtained:
1
T
174870 ln
761:555T 298
K eq 863:2 exp
8314
298
1:127955T 2 2982 0:00117633T 3 2983 4:68550
107 T 4 2984 44789470:261=T 1=298
To nd the best correlation of equilibrium constant, the
correlations mentioned above have been used to calculate
methanol conversion at different temperatures as bellow:
h
K eq
i2
eq
0
2
Xeq
C DME C H2 O
2 CMeOH
2
2
0
CMeOH
41 X eq 2
1 X eq CMeOH
(9)
0
is the
Xeq is the equilibrium conversion of methanol and CMeOH
initial concentration of methanol.
20.0940e7
18.4100e7
24.1814e7
16.2320e7
11.2800e7
22.8590e7
rB C ps 1 e
@T s
hi rB DHr r i h f av gTss T
@t
(13)
(15)
C P rm
K
eB
m
hf
(16)
dP
1 e3 mus
1 erus 2
150
1:75
l
d2p e3
d p e3
(17)
@C i
@C
us i kgi av C i Ciss
@t
@z
rg C pg e
@T
@T
U
us rg C p
h f av Tss T 4 T T r
dt
@t
@z
(10)
(11)
@C is
hi rB r i kgi av C i Ciss
@t
&
CP
(18)
The differential equations were converted to algebraic equations by means of Finite Difference method. The reactor length was
divided into equal discrete intervals, and the algebraic equations
were solved by 4th order RungeKutta method for every segment
at each time step [34]. Calculations were repeated at the next time
step with the initial values which were the results of the previous
time step and the iteration continued until no changes observed by
time (i.e. steady state condition). Because, the reactor length was
divided into separate segments that conversion through each one
was small enough, differential reactor assumption could be applied
for each segment. For each run in a differential reactor, the plug
ow performance equation is used as the following form:
W
F A0
X AZ out
X A in
dX A
1
r A r A ave
X AZ out
XA
dX A
X A
out X A
r A ave
in
(19)
in
Solid phase:
1 e
C Pi c1 c2 T c3 T 2 c4 T 3 c5 T 4
X
yi C Pi
(12)
M. Ghavipour, R.M. Behbahani / Journal of Industrial and Engineering Chemistry 20 (2014) 19421951
1946
1
0.9
0.9
experiment
0.8
modeling
0.8
0.7
0.7
Exp. Data WHSV=90
0.5
0.4
0.4
0.3
0.3
0.5
0.6
0.6
0.2
0.2
Equi. Conv. (Diep & Walnwright)
0.1
0.1
523
548
573
598
623
648
498
T(K)
Fig. 1. Methanol conversion (experimental data) and methanol equilibrium
conversion versus temperature.
the reaction and lower WHSV means more retention time to let the
reaction to proceed. For exothermic reactions, temperature rising
has a negative effect too. It shifts the reaction to the backward
direction and methanol equilibrium conversion decreases. This
effect defeats the positive effect (i.e. speeding up the forward
reaction rate) near equilibrium points. Conversion drops at 598
623 K in lower WHSVs (i.e. WHSV = 15 or 7.5) conrm this fact.
DME selectivity was almost 100% at the temperature range of 523
623 K. The optimum reaction temperature is a function of WHSV
and as the WHSV decreases, the best operating temperature
decreases too. Roughly, 570620 K can be known as the optimum
operating temperature range.
The equilibrium conversions which are calculated from the
correlations presented earlier, and our experimental data have
been depicted together to nd the best equilibrium constant
model. From Fig. 1, it is clear that our correlation and the
correlation proposed via Diep and Walnwright match the
experimental data better than other correlations.
The reactor modeling program was conducted at the experimental conditions as the same as experiments (i.e. the same
temperature, WHSV and feed composition) while Bercic and Levec
rate model was used. In Fig. 2, both of the experimental and
modeling results have been depicted. From this Figure, it can be
concluded that Bercic and Levec model is not valid for temperatures below 593 K, because the parameters in this model were
evaluated from the experimental data at three temperatures of
593, 613 and 633 K with an impure methanol as the feed.
Therefore, another rate equation should be developed, especially
for lower temperatures. At rst, reaction rate as a function of
temperature and methanol conversion should be calculated.
Integral reactor method was used for this goal. Differential reactor
assumption is used when the rate is considered to be constant at all
points through the reactor. Since the rate is concentrationdependent, this assumption is reasonable only for small conversions or small reactors. But, for pure methanol as used in this study,
conversion was so large that differential reactor assumption was
not acceptable. Therefore, an integral reactor was assumed and the
differential analysis was used to nd the rate equation:
dX
r A A
d FWA0
(20)
523
548
573
598
623
648
T(K)
Fig. 2. Methanol conversion versus reactor temperature. Comparison between
experimental data and modeling results based on Bercic rate model (WHSV = 15 g/
h gcat).
Table 4
Calculated rate values at different conditions based on experimental data.
Liquid
Methanol
Catalyst
Rate
Temperature Methanol
(K)
concentration conversion methanol weight (g) (mol/gcat h)
ow rate
(%)
(mol/L)
(mL/min)
523
523
523
523
548
548
548
548
573
573
573
573
0.0709
0.0653
0.0549
0.0486
0.0677
0.0522
0.0361
0.0250
0.0647
0.0340
0.0223
0.0117
0.0000
0.0793
0.2264
0.3160
0.0000
0.2295
0.4668
0.6309
0.0000
0.4742
0.6555
0.8203
2.00
2.00
2.00
2.00
2.00
2.00
2.00
2.00
2.00
2.00
2.00
2.00
0.00
1.05
6.32
12.6
0.00
1.05
6.32
12.6
0.00
1.05
6.32
12.6
0.1460
0.1361
0.0862
0.0268
0.2710
0.2483
0.1343
0.0016
0.3750
0.3381
0.1528
0.0679
M. Ghavipour, R.M. Behbahani / Journal of Industrial and Engineering Chemistry 20 (2014) 19421951
1947
0.9
R-squared = 0.997
y = -8038x + 15.966
R = 0.9868
0.7
0.5
0
0.0017
0.00175
0.00185
0.0018
0.0019
0.00195
1/T
Fig. 3. Arrhenius plot for constants obtained by non-linear regression for reversible
rst order equation rate.
Experimental Conversion
Ln(K)
1.5
0.8
0.6
0.5
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Modeling Conversion
Fig. 4. Accuracy assessment of the modeling results with the experimental data.
Fig. 5. Reactor modeling results. Temperature prole along the non-adiabatic reactor at different feed ow rates (mcat = 40 g and Tr = Tin = 523 K). (a) Q = 19 mL/min;
WHSV = 22.5. (b) Q = 38 mL/min; WHSV = 45. (c) Q = 76 mL/min; WHSV = 90.
M. Ghavipour, R.M. Behbahani / Journal of Industrial and Engineering Chemistry 20 (2014) 19421951
1948
Table 5
Comparing the modeling and experimental results of non-adiabatic reactor at different conditions.
Tin = Tr (K)
Liquid methanol
ow rate (mL/min)
Catalyst
weight (g)
WHSV (gMeOH/gcat h)
Modeling
conversion (%)
Experimental
conversion (%)
523
523
523
498
523
548
573
598
623
498
523
548
573
598
19.0
38.0
76.0
25.4
25.4
25.4
25.5
25.4
25.4
12.7
12.7
12.7
12.7
12.7
40.00
40.00
40.00
40.00
40.00
40.00
40.00
40.00
40.00
40.00
40.00
40.00
40.00
40.00
22.50
45.00
90.00
30.00
30.00
30.00
30.00
30.00
30.00
15.00
15.00
15.00
15.00
15.00
0.2135
0.1341
0.0701
0.0745
0.1771
0.3212
0.5073
0.7318
0.8144
0.1003
0.3038
0.5439
0.8210
0.8336
0.2211
0.1299
0.0734
0.0769
0.1655
0.3109
0.5298
0.7474
0.7903
0.1103
0.2853
0.5603
0.8067
0.8198
3.44
3.23
4.49
3.12
7.01
3.31
4.25
2.09
3.05
9.07
6.48
2.93
1.77
1.68
Fig. 6. Reactor modeling results. Temperature prole along the adiabatic reactor at different feed ow rates (mcat = 40 g and Tin = 523 K). (a) Q = 19 mL/min; WHSV = 22.5. (b)
Q = 38 mL/min; WHSV = 45. (c) Q = 76 mL/min; WHSV = 90.
M. Ghavipour, R.M. Behbahani / Journal of Industrial and Engineering Chemistry 20 (2014) 19421951
527
526.5
Temperature(K)
526
525.5
525
524.5
Q=19 ml/min
524
Q=38 ml/min
523.5
Q=76 ml/min
523
0
10
15
20
Q=19 ml/min
Q=38 ml/min
Methanol Conversion
0.2
Q=76 ml/min
0.15
0.1
0.05
0
0
10
15
20
1949
Fig. 7. Reactor modeling results. (a) Temperature prole along the non-adiabatic
reactor. (b) Conversion changes along the non-adiabatic reactor (Q = 19, 38, 76 mL/
min (mcat = 40 g and Tr = Tin = 523 K)).
553
Q=19 ml/min
548
Q=38 ml/min
Temperature(K)
700
Temperature(K)
543
Q=76 ml/min
650
Tin=498K
Tin=523K
600
Tin=548K
Tin=573K
538
Tin=598K
550
Tin=623K
533
500
528
10
15
20
523
0
10
15
20
b
b
0.8
0.35
Q=19 ml/min
0.3
0.7
Q=38 ml/min
Methanol conversion
Methanol conversion
0.9
Q=76 ml/min
0.25
0.2
0.15
0.1
0.6
Tin=498K
0.5
Tin=523K
0.4
Tin=548K
Tin=573K
0.3
Tin=598K
0.2
0.05
Tin=623K
0.1
10
15
20
10
15
20
M. Ghavipour, R.M. Behbahani / Journal of Industrial and Engineering Chemistry 20 (2014) 19421951
1950
700
680
660
Temperature(K)
640
620
Tin=498K
600
Tin=523K
580
Tin=548K
Tin=573K
560
Tin=598K
540
520
500
0
10
15
20
0.9
0.8
Methanol conversion
0.7
0.6
Tin=498K
0.5
Tin=523K
0.4
Tin=548K
0.3
Tin=573K
Tin=598K
0.2
0.1
0
0
10
15
20
Finally, conversion and temperature proles of the nonadiabatic reactor with different reactor temperatures, in two
WHSVs are depicted in Figs. 9 and 10. The results of these
modelings have been compared to the experimental data at Table
6. It is concluded from Figs. 9 and 10 that in our experimental
reactor with 40 grams of catalyst, at WHSV of 30, the minimum
required temperature of reactor outside wall and feed to reach the
equilibrium conversion is 623 K and at WHSV of 15 this value is
573 K. Another point is that in non-adiabatic reactors at a constant
WHSV, as the temperature of the reactor surrounding increases,
the hot spot location shifts to the reactor inlet and this
phenomenon is reasonable because as the medium temperature
increases, the reaction speeds up and most of methanol molecules
will react at the reactor inlet and a bulk of heat will be released as
the reaction heat.
6. Conclusion
The aim of this work was to examine one of the most applicable
rate equations (i.e. Bercic and Levec rate model) by comparing
experimental data with the simulation results. Needless to say that
it was attempted to make the experimental conditions and the
commercial ones close together. Due to the deviation of the
relevant model from the experimental data especially at temperatures below 593 K, non-linear regression was employed to try
the most common rate expressions suggested earlier. Simple
reversible rst order equation had the lowest deviation from the
experimental data. The constants obtained by non-linear regression for this simple reversible rst order equation agreed
reasonably well with Arrhenius equation. Also, one dimensional
unsteady state heterogeneous model was applied to predict the
temperature prole and methanol conversion along the xed-bed
reactor. Adiabatic and non-adiabatic xed-bed reactors were
simulated and methanol conversion and thermal behavior of these
reactors were discussed and the following results were concluded:
The correlations for equilibrium constant of the present work
and that of Diep and Walnwright match the experimental data
better than other correlations.
In non-adiabatic reactors, as the feed ow rate increases, the hot
spot (i.e. maximum temperature) moves to the end of the reactor
and conversion decreases.
In non-adiabatic reactors, due to high rate of heat transfer from
the reactor wall, after that the reaction reaches to its maximum
rate and the hot spot forms, when the reaction rate decreases and
less heat is produced, the temperature will drop. But in adiabatic
reactors, there is no heat loss from the wall and temperature will
rise continuously along the reactor and the conversion is more
than the conversion of non-adiabatic reactors at the same initial
temperature.
It takes more time for adiabatic reactors to reach to the steady
sate conditions in comparison with non-adiabatic reactors.
Conversion and temperature prole of the non-adiabatic reactor
with different temperatures of feed and heating medium at the
range of 498623 K were calculated and the minimum required
temperature of heating medium and feed temperature to reach
the equilibrium conversion at WHSV of 30 and 15, were
estimated.
Another point is that in non-adiabatic reactors at a constant feed
ow, as the heating medium temperature increases, the hot spot
location shifts to the reactor inlet.
Acknowledgements
The authors acknowledge the Iranian Petrochemical Research
and Technology Company for their technical and nancial supports
(Project ID: 0860249001).
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