Professional Documents
Culture Documents
A R T I C L E I N F O A B S T R A C T
Article history: Dimethyl ether (DME) synthesis reaction rate was studied over a commercial sample of g-Alumina to
Received 11 June 2013 investigate the accuracy of the most applicable rate models. Due to the deviation of the former proposed
Accepted 12 September 2013 models especially at temperatures below 593 K, a new simple empirical rate model was proposed.
Available online 19 September 2013
Besides, previous proposed correlations for methanol dehydration equilibrium constant were examined
experimentally and a new equation was developed. Subsequently, one dimensional unsteady state
Keywords: heterogeneous model was applied to simulate adiabatic and non-adiabatic xed-bed reactors.
Methanol dehydration
Temperature prole and methanol conversion along the reactors were predicted while varying feed
DME
g-Alumina rate and feed temperature.
Fixed-bed reactor modeling 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Reaction rate reserved.
1. Introduction aluminum) and Brnsted acid sites. The reaction takes place at
the temperature range of 423523 K. The HZSM-5 catalyst is
Considering environmental pollution, energy security and deactivated sooner than the g-Alumina because a layer of coke
future oil supplies, the global community is seeking new covers its strong acid sites and it has lower DME selectivity
alternative fuels. A promising alternative fuel could be dimethyl especially at higher temperatures. Modication of the strong
ether (DME) due to low NOx and SOx emission and because it acidic sites by Na, Si or P inhibits hydrocarbon formation (such
does not have large issues with toxicity, production, infrastruc- as methane) and thereby enhances the catalyst stability [1014].
ture, and transportation [13]. It also can be used as hydrogen- By taking all of the above facts into account, it seems that the g-
rich feed of fuel-cells [4,5] or as a substitute fuel in domestic Alumina is a better choice and its commercial use in large extent
appliances [6]. DME synthesis can be performed through two for this reaction proves this opinion.
routes: direct synthesis (i.e. syngas to DME over hybrid The mechanism of methanol adsorption, dehydration and
catalysts) and indirect synthesis (i.e. methanol dehydration to specially, formation of the rst C-C bond and the nature of the
DME) [7]. g-Alumina and HZSM-5 are the most common intermediates involved, are still not fully understood, but they
catalysts for DME indirect synthesis reaction. g-Alumina tends have been studied extensively and different rate equations have
to adsorb water on its surface and thereby loses its activity been developed till now (see Table 1) [15]. Most of these rate
because of its hydrophilic nature. When pure methanol is used equations have been derived from experiments conducted at
as the process feed, the catalyst deactivation occurs very slowly conditions far away from an industrial reactor. Almost all of these
and this hydrophilic nature is not a considerable problem [8]. experiments were performed with diluted methanol by nitrogen
The g-Alumina modied by silica or phosphorous has shown and/or water, as the reactor feed. In spite of that, to meet the
better performance compared to the untreated one. The best highest production in the industrial reactors, pure methanol is
operating temperatures are from 523 to 673 K and the amounts consumed as the feed. However, water in the reactor feed will
of coking and by-products are very low [911]. The activity of deactivate the g-Alumina by covering the catalyst active sites [8]
HZSM-5 is higher than the g-Alumina because of more strong and also will retard the DME production reaction (i.e. forward
acidic sites. Unlike the g-Alumina, which exhibits only Lewis reaction as indicated below) and speed up the DME consumption
acidity, HZSM-5 has both Lewis (due to the extra-framework reaction (i.e. backward reaction) according to Le Chateliers
principle in equilibrium reactions
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 1943
Table 1
Nomenclature Methanol dehydration reaction rate models.
Bercic and Levec (1992) [15] ks k2
M
2 C D C W
CM K
I
rM
av specic catalyst surface area (m2/m3) 12kM C M 0:5 kW C W
4
dp catalyst particle diameter (m) Kallo and Knozinger (1967) [39] C 0:5 IV
rM k C 0:5 k
M
dt reactor diameter (m) M 2 CW
hf overall heat transfer coefcient between gas and Rubio et al. (1980) [40] 0:5
rM k1 CM 0:5
k 2 CW V
solid (J/m2 K s) Schmitz (1978) [41] rM k1 k2 C M VI
kgi mass transfer coefcient for component i (m/s) This work C
rM k0 expEa =RT C MeOH KW VII
eq
In our experiments, a commercial sample of g-Alumina from ln K P 3440=T 1:67 ln T 2:39 104 T 0:055
Engelhard Corporation in powder form was used. Several catalyst 106 T 2 5:496 (1)
characterization tests have been performed such as BET, NH3-TPD,
Bulk density and particle size distribution that are listed in Table 2. Diep and Walnwright (1987) determined thermodynamic
A multipurpose micro reactor and catalyst test setup was equilibrium constant of the methanoldimethyl etherwater
employed for this work. Pure liquid methanol was injected to a pre system experimentally at temperatures from 498 to 623 K over
heater by means of a HPLC metering pump (working range of 0.1 a commercial g-Alumina catalyst in a ow reactor maintained at a
99.9 mL/min), then evaporated in the pre heater at the constant constant pressure of 200 kPa [27]
temperature of 453 K. The reactor consisted of two heating zones.
First zone was to raise the feed temperature to a desirable level and ln K P 2835:2=T 1:675 ln T 2:39 104 T 0:21
the other one was to maintain the reactor surrounding at a proper 106 T 2 13:360 (2)
temperature to minimize the heat losses. The thermocouples at the
second zone were arranged in a way that the operator could x the They also calculated the enthalpy of formation (DHf 298) and the
outer surface of the stainless steel reactor at a constant free Gibbs energy of formation (DGf 298) of dimethyl ether by use of
temperature (non-adiabatic reactor). There were other thermo- published thermochemical data together with the experimental
couples to report the temperatures of the pre heater, the feed, the data to be 180.22 and 109.66 kJ/mol, respectively.
reactor center and other critical sections. Finally, the equilibrium constant which is coupled to Bercic and
The experimental data were obtained from three different Levec model and has been used extensively in xed-bed reactor
sizes of reactors (i.e. outside diameter of 3/8, 1/2 and 3/4 inches modeling papers [2226].
with heights of 0.4, 1 and 1.5 inches respectively). Catalyst
weights of 1.05, 6.32, 12.64 g with the constant liquid methanol ln K P 3138=T 0:86 log T 1:33 103 T 1:23
ow rate of 2 mL/min were used (weight hourly space velocities
of 90, 15 and 7.5, respectively). The temperatures of the reactor 105 T 2 3:5 1010 T 3 (3)
zones were adjusted in a way that the reactor center temperature
A model based on the thermodynamic calculations has been
varied from 523 to 623 K. All of these reactors were assumed to
developed in the present work using the thermodynamic proper-
be isothermal at their center temperatures which were
ties of the pure substances which are listed in Table 3 [28]. It
measured through the submerged thermocouple. For the
should be mentioned that the pressure is not an effective
assessment of our xed bed reactor modeling, the biggest size
parameter in this reaction due to the conversion of two moles
reactor was used (i.e. outside diameter of 1/2 with height of 8
of methanol to one mole of water and one mole of DME (i.e. the
inches), 40 g catalyst was loaded and with different liquid
reaction occurs with no changes in gaseous moles).
methanol ow rates, various WHSVs were adjusted. Reactor
If the variation of the reaction heat with temperature is taken
pressure was maintained constant at 3 bar via a back pressure
into account, temperature dependency of the equilibrium constant
regulator installed at the reactor exit. Activity of the commercial
(Keq) will be found by using the integrated form of Vant Hoff
catalyst decreased during the rst day (activity depletion of 1
equation:
3% that was attributed to the strong unstable acidic sites) and the
conversion remained almost constant during 120 h. Therefore, ZT ZT
K 1 DHr
the experimental data were recorded during 3060 h after ln dT & DHr DHr0 rC P dT (4)
reactor startup. For every specic temperature or WHSV, fresh
K0 R T2
T0 T0
catalyst was used and data gathering started after 30 h of
reaction. The effect of coke formation on the catalyst activity was
rC P rC 1 rC 2 T rC 3 T 2 rC 4 T 3 rC 5
neglected, because the experiments were not long enough that
the deactivation of the catalyst could be monitored. Conse- T4 & rC n
quently, the proposed model of the present work is applicable to Cn Cn 2C n (5)
DME H2 O MeOH
predicting the activity of the fresh catalyst.
Gas sample analysis was performed by means of Agilent 6890
Gas Chromatograph equipped with ame ionization and thermal K 0 expDG0r =R T 0 (6)
M. Ghavipour, R.M. Behbahani / Journal of Industrial and Engineering Chemistry 20 (2014) 19421951 1945
Table 3
Thermodynamic properties of pure substances.
Substance Heat capacity (J/kmol K) Enthalpy of formation (J/kmol) Gibbs energy of formation (J/kmol)
C1 C2 C3 C4 C5
1 0.9
X
0.4 Exp. Data WHSV=7.5 0.4
2 0.9
R-squared = 0.997
y = -8038x + 15.966 0.8
1.5 R = 0.9868
0.7
Ln(K)
Experimental Conversion
0.6
0.5 0.5
0.4
0
0.0017 0.00175 0.0018 0.00185 0.0019 0.00195
0.3
1/T
0.2
Fig. 3. Arrhenius plot for constants obtained by non-linear regression for reversible
rst order equation rate.
0.1
simplies reactor modeling and increases the accuracy of the
results. Fig. 3 indicates that the rate constants obtained by non- 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
linear regression for equation number VII at different tempera-
Modeling Conversion
tures, satisfy reasonably the Arrhenius theory and its temperature
dependency, with pre exponential coefcient of 8,537,681 L/gcat h Fig. 4. Accuracy assessment of the modeling results with the experimental data.
and activation energy of 66,828 J/mol and therefore, this equation
can be considered as the most favorable rate expression.
Two types of reactors were simulated (i.e. adiabatic and non- zones were at the same temperature). Validity of the simulated
adiabatic reactors). In adiabatic reactors, it was assumed that there non-adiabatic reactor by mathematical modeling using the new
was no heat loss in the radial direction and the reactor wall was proposed rate model, was tested by varying the methanol ow rate
insulated completely. In non-adiabatic reactors, the outside and reactor temperatures (i.e. feed temperature and temperature
surface of the reactor wall was maintained at the particular of the outside wall of the reactor) and the experimental data of the
temperature equaled the feed temperature (i.e. rst and second biggest size reactor (i.e. outside diameter of 3/8 with height of 8
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.
1948 M. Ghavipour, R.M. Behbahani / Journal of Industrial and Engineering Chemistry 20 (2014) 19421951
Table 5
Comparing the modeling and experimental results of non-adiabatic reactor at different conditions.
Tin = Tr (K) Liquid methanol Catalyst WHSV (gMeOH/gcat h) Modeling Experimental Relative error (%)
ow rate (mL/min) weight (g) conversion (%) conversion (%)
inches) were compared to the simulation results. Table 5 and Fig. 4 rates, the reaction proceeds in forward direction at the reactor
show the results of both modeling and experiments. The average beginning. As methanol converts to DME, at the end of the reactor,
relative error of the modeling predictions was 4 percent. Fig. 4 and methanol concentration decreases and the forward reaction is
Table 5 conrm the accuracy of the proposed model. Also, the retarded, therefore, much more heat is produced at the reactor
temperature prole along the non-adiabatic reactor was investi- inlet than the reactor outlet. When the feed ow rate increases,
gated. Fig. 5 indicates the modeling results and it shows that as the there is not enough retention time for methanol molecules to react
feed ow rate increases, the hot spot (i.e. maximum temperature and to be consumed at the reactor inlet. So, there are still enough
location) moves to the end of the reactor and the conversion methanol molecules to maintain the reaction rate high along the
decreases. When methanol concentration is high, at low feed ow reactor and the hot spot moves to the end of the reactor. In Fig. 6
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 1949
525.5 decreases and less heat is produced and the temperature drops
525
down. But, in adiabatic reactors, there is no heat loss from the wall
and temperature rises along the reactor, then the conversion is
524.5 more than that of non-adiabatic reactors at the same initial
Q=19 ml/min
524 temperature. The problem will rise at industrial reactors where it is
Q=38 ml/min attempted to maximize the feed ow and conversion. In this
523.5
Q=76 ml/min situation, adiabatic reactors are more sensitive to control [36] and
523 the reactor may run away due to accumulation of the reaction heat.
0 5 10 15 20
Another point is that it takes more time for adiabatic reactors to
Reactor length(number of segments)
reach to the steady sate conditions in comparison with non-
0.25
adiabatic reactors, because in non-adiabatic reactors, temperature
b Q=19 ml/min
of the catalyst bed rises until the temperature difference can cause
Q=38 ml/min enough heat transfer from the reactor wall and also the convective
0.2
Q=76 ml/min heat transfer between catalyst bed and gas bulk ow that
Methanol Conversion
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)). a
700
a 553
650
Temperature(K)
500
528
0 5 10 15 20
Reactor length(number of segments)
523
0 5 10 15 20
Reactor length(number of segments)
b 0.9
b 0.35 0.8
Q=19 ml/min
0.7
0.3
Q=38 ml/min
Methanol conversion
0.6
Q=76 ml/min Tin=498K
Methanol conversion
0.25
0.5 Tin=523K
0.2
0.4 Tin=548K
0.15 Tin=573K
0.3
Tin=598K
0.1
0.2 Tin=623K
0.05 0.1
0 0
0 5 10 15 20 0 5 10 15 20
Reactor length(number of segments) Reactor length(number of segments)
Fig. 8. Reactor modeling results. (a) Temperature prole along the adiabatic reactor. Fig. 9. Reactor modeling results. (a) Temperature prole along the non-adiabatic
(b) Conversion changes along the adiabatic reactor (Q = 19, 38, 76 mL/min reactor. (b) Conversion changes along the non-adiabatic reactor (Q = 25.4 mL/min,
(mcat = 40 g and Tin = 523 K)). mcat = 40 g, WHSV = 30, Tr = Tin).
1950 M. Ghavipour, R.M. Behbahani / Journal of Industrial and Engineering Chemistry 20 (2014) 19421951
0.6
temperature.
Tin=498K
0.5 It takes more time for adiabatic reactors to reach to the steady
Tin=523K
sate conditions in comparison with non-adiabatic reactors.
0.4 Tin=548K Conversion and temperature prole of the non-adiabatic reactor
0.3 Tin=573K with different temperatures of feed and heating medium at the
Tin=598K range of 498623 K were calculated and the minimum required
0.2
temperature of heating medium and feed temperature to reach
0.1 the equilibrium conversion at WHSV of 30 and 15, were
estimated.
0 Another point is that in non-adiabatic reactors at a constant feed
0 5 10 15 20
ow, as the heating medium temperature increases, the hot spot
Reactor length(number of segments)
location shifts to the reactor inlet.
Fig. 10. Reactor modeling results. (a) Temperature prole along the non-adiabatic
reactor. (b) Conversion changes along the non-adiabatic reactor (Q = 12.7 mL/min,
mcat = 40 g, WHSV = 15, Tr = Tin). Acknowledgements
[22] S.M. Nasehi, R. Eslamlueyan, A. Jahanmiri, Proc. 11th Chem. Eng. Conf. Iran, Kish [33] J.F. Richardson, J.H. Harker, J.R. Backhurst, Chemical Engineering, fth ed.,
Island., 2006. ButterworthHeinemann, 1999.
[23] M. Farsi, R. Eslamloueyan, A. Jahanmiri, Chem. Eng. Process. 50 (2011) 8594. [34] J.D. Hoffman, Numerical Methods for Engineers and Scientists, McGraw-Hill,
[24] M. Fazlollahnejad, M. Taghizadeh, A. Eliassi, G. Bakeri, Chin. J. Chem. Eng. 17 New York, 2001 .
(2009) 630634. [35] C.D. Prater, R.M. Lago, Advances in Catalysis, Academic Press, New York, 1956.
[25] G. Bercic, J. Levec, Ind. Eng. Chem. Res. 32 (1993) 24782484. [36] F.G. Froment, K.B. Bischoff, Chemical Reactor Analysis and Design, John Wiley &
[26] M. Farsi, A. Jahanmiri, R. Eslamloueyan, Int. J. Chem. React. Eng 8 (2010), Article A79. Sons, New York, 1979.
[27] B.T. Diep, M.S. Walnwright, J. Chem. Eng. Data 32 (1987) 330333. [37] B.C. Gates, L.N. Johanson, LungmuirHinshelwood kinetics of the dehydration of
[28] R.H. Perry, D.W. Green, J.O. Maloney, Perrys Chemical Engineers Handbook, 70th methanol catalyzed by cation exchange resin, AICHE J. 17 (1971) 981983.
ed., McGraw-Hill, New York, 1997. [38] F. Figueras, A. Nohl, L. Mourgues, Y. Trambouze, Dehydration of methanol and
[29] S.J. Royaee, C. Falamaki, M. Sohrabi, S.S. Ashraf Talesh, Appl. Catal., A 338 (2008) tert-butyl alcohol on silicaalumina, Trans. Faraday SOC. 67 (1971) 11551163.
114120. [39] D. Kallo, H. Knozinger, Zur Dehydratisierung von Alkoholen an Aliminiumoksid,
[30] E.B. Nauman, Chemical Reactor Design, Optimization and Scale Up, McGraw-Hill, Chem. Ing. Tech. 39 (1967) 676680.
New York, 2002. [40] F.C. Rubio, S.D. Diaz, D.D. Castillo, J.D. Trujillo, R.A. Alvarez, Deshidratacion
[31] E.L. Cussler, Diffusion Mass Transfer in Fluid Systems, Cambridge University Catalitica de Metanol en Fase vapor, Ing. Quim. (Madrid) 12 (1980) 113119.
Press, United Kingdom, 1984. [41] G. Schmitz, Deshydration du Methanol Sur Silice-Alumine, Chim. Phys. (1978)
[32] J.M. Smith, Chemical Engineering Kinetics, McGraw Hill, New York, 1980. 746504355.