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Thermodynamic and kinetic study of tert-amyl


methyl ether (TAME) synthesis

Article in Chemical Engineering and Processing May 2008


DOI: 10.1016/j.cep.2006.12.014

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Chemical Engineering and Processing 47 (2008) 761769

Thermodynamic and kinetic study of tert-amyl


methyl ether (TAME) synthesis
Wei Mao, Xiaolei Wang, Hua Wang, Heying Chang, Xiangwen Zhang, Jinyu Han
Key Laboratory for Green Chemical Technology of State Education Ministry, School of Chemical Engineering and Technology,
Tianjin University, Tianjin 300072, PR China
Received 1 August 2006; received in revised form 21 December 2006; accepted 21 December 2006
Available online 2 February 2007

Abstract
The etherification of methanol (MeOH) with 2-methyl-1-butene (2M1B) and 2-methyl-2-butene (2M2B) catalyzed by the macroporous cation
ion-exchange resin (D005II) was studied in a batch reactor. The thermodynamic properties and kinetic data were obtained under different initial
molar ratio of methanol and isoamylenes (0.52) in the temperature range between 323 and 353 K with pressure (1 MPa) constant. Because
of the nonideal property of the reaction, activities were adopted to calculate equilibrium constants and the activity coefficients were estimated
by Wilson method. There were three mechanisms adopted for simulating reaction rate equations, containing homogeneous reaction mechanism,
LangmuirHinshelwood (LH) type mechanism and EleyRideal (ER) type mechanism and the equations based on the LH type mechanism was found
to get better fit with the experimental data. The results showed that the experimental data for thermodynamics agreed with the theoretical predications
well, and the activation energy was 88.1 and 102.1 kJ mol1 for the etherification of 2M1B and 2M2B, respectively, by kinetic calculation.
2007 Elsevier B.V. All rights reserved.

Keywords: TAME; Isoamylene; Etherification; Thermodynamic; Kinetic

1. Introduction MTBE. TAME is catalytically synthesized in the liquid phase


by the reaction of methanol (MeOH) and active isoamylenes,
Fuel oxygenates are produced to improve the burning including 2-methyl-1-butene (2M1B) and 2-methyl-2-butene
efficiency of gasoline and counteract the gas emission impact (2M2B).
over environment, such as organic volatile compounds (VOC). The prime process involves three simultaneous reversible
The amendments to Clean Air Act (AAC), introduced in USA reactions, two etherification reactions and the isomerization
beginning with 1990, push the worldwide increasing interest between 2M1B and 2M2B, over an acidic macroreticular ion-
in their production for environmental friendly gasoline [1,2]. In exchange resin. The networks and notations for the reactions are
the last decade, MTBE, the most economic gasoline blending presented in Fig. 1 in which the reaction pairs shown establish
oxygenate, has attracted the highest attention to increase the the reaction equilibria. In fact, there also occur additional side
octane number of RON and MON and dominated the oxygenate reactions in the reaction system. The primary of these side reac-
market [3]. However, the high water solubility of this ether tions is the etherification reaction of methanol to dimethylether
has contaminated the underground waters, which has led a ban (DME) and water. Then water reacts in a consecutive reaction
on the use of MTBE in America and must be wholly replaced with an olefin to tert-amyl alcohol.
around the world in the future. As a substitute for MTBE, heavier Originally, the equilibrium constants were calculated in terms
tertiary ether, namely TAME, has already been used as octane of concentrations [4], but it was fail to represent the real equi-
boosters. It not only has similar octane number to MTBE, but librium. In the work of Verevkin [5], he concluded that reactive
also substantially lowers blending Reid vapor pressure (RVP) mixtures of TAME synthesis behave strongly nonideally, espe-
in comparison to MTBE, which is only one-eighths of that of cially when the mole fractions of methanol are low. Thus,
activities should be used instead of concentrations to evaluate
the equilibrium constants.
Corresponding author. Tel.: +86 22 27890859; fax: +86 22 27890859. At present, the used activity coefficient methods in context
E-mail address: hanjinyu@tju.edu.cn (J. Han). with etherification reaction system contain group-contribution

0255-2701/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2006.12.014
762 W. Mao et al. / Chemical Engineering and Processing 47 (2008) 761769

1.0 and 2.0) in a batch autoclave reactor. At the same time,


some other variables, such as agitation speed, sizes of cata-
lyst, were also taken into account to find the optimum reaction
circumstances.

2.1. Apparatus

The experiments were carried out in a stainless steel batch


reactor (280 mL) equipped with automatic acquisition of tem-
perature, pressure, and stirring speed (Fig. 2). In all experiments,
the initial volume of the reagents was kept at 200 mL, and the
Fig. 1. Scheme of the TAME reaction triangle.
reaction mixture was stirred magnetically. To reduce the influ-
ence of temperature fluctuation, it was controlled within 0.5 K
method (UNIFAC) [6,7], UNIQUAC [8,9] method and Wilson by a thermistor. In addition, the experimental system also com-
[1012] method. As the above literatures shown, both UNIFAC prises a cooler, thermocouples, a manometer and a sampling
method and UNIQUAC method are not sufficient to calculate device for determining the effluent composition. The needed
activity coefficients accurately, but Wilson method can describe amount of resin and methanol was placed in the autoclave at first
the compound activities very well in all ranges of MeOH mole and then the working temperature was achieved with a thermal
fraction. Therefore, the liquid-phase activity coefficients were agent provided by the thermostat. Meanwhile, an amount of the
calculated by the Wilson method using the binary parameters. isoamylenes (2M1B and 2M2B), given by the desired isoamy-
The kinetic behavior of the reactions in the presence of an lene/methanol ratio, was preheated in a hermetical stainless steel
ion-exchange resin is complex to describe and there is not vessel to the experiment temperature. Then the isoamylenes
a precise model to describe the mechanics. As a result, sev- were purged by nitrogen into the reactor, and the experiment
eral approximate kinetic models have been published for the started. The pressure was kept constant at 0.91.0 MPa to guar-
synthesis of TAME, containing LangmuirHinshelwood type antee a liquid phase at all temperatures. The samples were
(LH) [9,13,14], EleyRideal type (ER) [10,15,16], Modified withdrawn from the reactor in a shorter interval at the beginning
EleyRedial type (MER) and LewisBronstedt type (LB). In of the reactions, which would grow longer with the process, espe-
the work of Kiviranta-Paakkonen and Krause [17], a compari- cially when the reactions reached the equilibrium, the intervals
son of various kinetic models was presented for TAME and LH may be up to 2 h.
type was considered to be fitter to the experiment data. But the
objective to select the best mechanism is not achieved for the 2.2. Analytical methods
comparison data is limited. Therefore, a comparison between
three models was developed in this work. A Beifen gas chromatograph (GC) SP-2100, equipped with
a flame ionization detector, was used for analyzing the samples.
2. Experimental The compounds were separated in a 50 m 0.20 mm 0.5 m
nonpolar capillary column (AT.PONA, LanZhou Zhongke Kaidi
The etherification of TAME and the isomerization of Chemical New Technology Co. Ltd, China). A flame ion-
isoamylenes were measured as a function of temperature (323, ization detector (FID) operating at 250 C was utilized. An
333, 343 and 353 K) and the MeOH/isoamylene molar ratio (0.5, oven temperature program starting at 60 C for 8 min and then

Fig. 2. Experimental unit: (1) gas cylinder; (2) (9) (12) valves; (3) thermocouples; (4) batch reactor; (5) bracket; (6) thermistor; (7) lab jack; (8) motor; (10) sampling
point; (11) cooler; (13) exhaust; (14) operating board.
W. Mao et al. / Chemical Engineering and Processing 47 (2008) 761769 763

increasing to 120 C at a rate of 15 C/min, which was held


for 1 min, was sufficient to provide the necessary separation.
Nitrogen acted as the carrier gas, and the ratio of the flow
velocity of nitrogen, hydrogen, air was 1:1:10. GC samples
were taken until the successive compositions remained con-
stant over time, at which point the reaction was regarded to be
equilibrium.

2.3. Catalyst

The catalyst used was a commercial, strong cation-exchange


resin, D005II (Dandong Mingzhu Special Type Resin Co. Ltd,
China), which had similar properties to Amberlyst types cata-
lysts of Rohm and Hass. According to the supplier, the cationite
had the following characteristics:

Exchange capacity (mmol/g [H+ ]) 5.2. Fig. 3. Effect of agitation speed on yield of TAME (RM/IA = 1:1, T = 353 K).
Average porosity size (nm): 3845.
Particle size (mm): 0.351.25. 3.1.2. Effect of resin particle size on reaction rates
Specific area (m2 ): 4050. The catalyst was sieved as dry form into four size groups:
(I) 0.350.42 mm, (II) 0.420.50 mm, (III) 0.500.85 mm,
Before the reaction, the resin was treated several times by and (IV) 0.851.25 mm. Experiments were carried out at
methanol, then dried in a vacuum dryer at 80 C for 24 h and 400 rpm and other conditions were the same as agitation
cooled in a desiccator for 1 h. speed studying. The result of yield of TAME with different
particle size fractions were presented in Fig. 4 which indi-
cates that the particle size influences the reaction rate most
2.4. Materials remarkably when the particle size is over 0.85 mm, but no
significant effect is observed with the other three particle
The reagents utilized in this work were methanol (MeOH, sizes.
Fisher Scientific, p.a. Grade, 99.9 wt%) and isoamylenes To justify this result, the diffusion in D005II catalyst was
(8.22 wt% of 2M1B, 90.78 wt% of 2M2B, and 1.00 wt% of calculated following the methods published by Paakkonen and
other inert C5 compounds, Shangdong Hengyuan Petrochem- Krause [18] and Silva and Rodrigues [19]. As the result shown,
ical Corporation, China). For calibration solutions, methanol the effectiveness factor () decreases with the increasing of
(MeOH, 99.9 wt%), 2M1B (99 wt%, JK chemicals), TAME the particle size. When the particle size is between 0.85 and
(96 wt%, by distillation) were used. 1.25 mm, the effectiveness factor only equals to 0.81. That indi-
cates there is internal mass transfer effect in the catalyst to
3. Results and discussion

3.1. Inuence of operating variables

3.1.1. Effect of agitation speed on reaction rates


Preliminary experiments were performed to study the effect
of external diffusion of reactants to the catalyst surface by
varying the agitating speed with the other variables constant,
including 200, 300, 400 and 500 rpm. And the catalyst used in
this experiment was under 0.85 mm.
As the result shown in Fig. 3, the 400 rpm agitation speed is
sufficient to avoid external mass transfer resistances. Although
the TAME yields at an agitation speed of 500 rpm seems as well
as 400 rpm, it would intensify the damaged degree of the cata-
lyst particles, which is possible to block the chromatograph and
decrease the activity of the catalyst. Therefore, 400 rpm is cho-
sen for kinetic studies. In addition, the TAME yields at 300 rpm
and above are close for long reaction time, so it indicates that an
agitation speed of 300 rpm is sufficient for the thermodynamic Fig. 4. Effect of resin particle size on yield of TAME (RM/IA = 1:1, T = 353 K,
studies. 400 rpm).
764 W. Mao et al. / Chemical Engineering and Processing 47 (2008) 761769

3.2. Chemical reaction equilibrium

The equilibrium constants for the reactions of MeOH and


2M1B to TAME (R1) and of MeOH and 2M2B to TAME (R2)
are defined in terms of activities as following [20]:
  N
r Goim
Kai = exp = (aje )ji
RT
j=1

N
 N

= (xje )ji (je )ji = Kxi Ki (1)
j=1 j=1

where xje is the equilibrium molar fraction of component j, aje


the activity of species j at equilibrium, and je is the liquid-
Fig. 5. Yield of TAME at different temperature (RM/IA = 1:1).
phase activity coefficients calculated by Wilson method. In the
definition, the equilibrium constants are based on molar frac-
tions and the mole fractions of side products were low (less
some extent which is in line with the result obtained in Fig. 4. than 2%), so the influence of side products was neglected in this
For the other three size groups, the effectiveness factors are work.
0.96, 0.95 and 0.89 for group (I) to (III). So it could be made In Table 1 the activity coefficients and equilibrium constants
the conclusion that the internal diffusion is neglectable when for each experiment are presented. The values in Table 1 showed
the particle size is lower than 0.5 mm. In this way, the cata- that Ka1 and Ka2 decreased dramatically with the increase of
lyst of group (I) and group (II) will be adopted in the kinetic temperature, but Ka3 seemed independence of temperature.
study. This fact may be related to the characteristics of the three
reactions. The etherification is reversible exothermic chemical
reactions with high heat changes: the higher is the temper-
3.1.3. Effect of temperature on the reactions ature, the heavier block the yield of TAME meets. On the
The temperatures adopted were from 323 to 353 K in accor- other hand, the isomerization reaction has relatively low heat
dance with the optimum temperature range of D005II catalyst. changes, so K3 varies only a little during the whole temper-
As an example, Fig. 5 shows the effect of temperature on the ature ranges. Another obvious conclusion that can be taken
formation of TAME with RM/IA = 1:1. The equilibrium point from the values of Table 1 is that K2 is much smaller than K1 ,
decreases as temperatures increasing, whereas an opposite ten- only equaling to one-tenths of the latter one. That is because
dency is observed for the reaction rate of TAME formation by the carbocations formed from 2M2B are more stable than the
the slope: its rate grows remarkably with the increase of tem- carbocations formed from 2M1B in the process of TAME
perature. For the experiment at 323 K, it followed an almost synthesis.
linear increase until equilibrium point and the time reaching the Fig. 6 shows the linear relationship between ln Kai and 1/T in
equilibrium is extremely long. As the result shown, the ether- Vant Hoff coordinates, representing the three equilibria whose
ification reactions for TAME is exothermic, which indicates a equations regressed by ORIGIN are given below.
compromise temperature near 353 K. In addition, there are sim-
ilar tendencies for the TAME synthesis with RM/IA = 1:2 and 4747.278
lnKa1 = 10.301 + (2)
2:1. T

Table 1
Experimental reaction conditions (initial mole of methanol/isoamylene, temperature), mole fractions of methanol (1), 2-methyl-1-butene (2), 2-methyl-2-butene (3),
TAME (4), calculated activity coefficients and equilibrium constants
RM/IA T (K) Equilibrium molar fractions (%) Wilson activity coefficients Ka1 Ka2 Ka3

X1 X2 X3 X4 1 2 3 4

0.5 323 0.0229 0.0383 0.4787 0.4601 6.0257 1.0916 1.0304 0.9796 78.13 6.62 11.80
0.5 333 0.0310 0.0425 0.4822 0.4443 5.5927 1.0989 1.3069 0.9730 53.39 3.96 13.49
1.0 333 0.2140 0.0161 0.1915 0.5784 2.4636 1.2733 1.2555 1.0141 54.27 4.63 11.73
2.0 333 0.5652 0.0063 0.0770 0.3514 1.3536 2.1785 2.1364 1.4163 47.40 3.95 11.99
0.5 343 0.0406 0.0467 0.4909 0.4217 5.2368 1.1085 1.0445 0.9648 36.97 3.73 9.90
1.0 343 0.2425 0.0199 0.2090 0.5286 2.3106 1.3196 1.2944 1.0149 36.46 3.54 10.30
2.0 343 0.5916 0.0072 0.0769 0.3242 1.3094 2.2895 2.2378 1.4472 36.74 3.52 10.44
0.5 353 0.0798 0.0515 0.4826 0.3861 4.3643 1.1464 1.0798 0.9412 17.67 2.00 8.83
1.0 353 0.3101 0.0217 0.2155 0.4527 2.0206 1.4394 1.4027 1.0366 23.98 2.48 9.68
2.0 353 0.5652 0.0101 0.1007 0.3240 1.3516 2.1628 2.1078 1.3594 26.39 2.72 9.72
W. Mao et al. / Chemical Engineering and Processing 47 (2008) 761769 765

Table 3
Comparison with experimental and literature parameters in equilibrium constant
equations
ln Kai = Ai +Bi /T

A1 B1 A2 B2

10.301a 4747.278a 9.091a 3527.151a


10.664b 4661.4b 7.377b 2862.3b
8.3881c 4041.2c 8.2473c 3225.3c
8.64d 4330d 8.10d 3360d
8.74435e 4142.069e 8.24371e 3219.118e
a This work.
b Muja et al. [2].
c Su and Chang [8].
d Piccoli and Lovisi [4].
e Kiviranta-Paakkonen and Krause [17].

2.916 102
Fig. 6. Vant Hoff plotting for the ln Kai vs. 1/T. lnKa2 = 24.9421 ln[T (K)]
T (K)
+ 7.356 102 T (K) 4.192 105 [T (K)]2
3527.151
lnKa2 = 9.091 + (3)
T + 1.255 102 (7)

1217.060
lnKa3 = 1.201 + (4) Table 2 shows there are some discrepancies between the
T
experimental data and the theoretical data, where the experimen-
As Ka3 could be calculated by Ka1 and Ka2 , only Ka1 and Ka2 tal data for Ka1 is a little smaller and the experimental data for Ka2
were compared to the theoretical equilibrium constants (Table 2) is a little greater than the counterparts. On average, Eqs. (2) and
in this work. The theoretical equilibrium constant for reaction i (3) provide values with errors of 10.4 and 13.7%, respectively,
could be written as a function of temperature by the form within the studied temperature range. Thus, a fair agreement is
obtained between the experimental data and the theoretical data.
H0 a 1 1 Also, these values are comparable to the ones published in the
lnKai (T ) = + lnT + b T + c T 2 + I
RT R 2R 6R literature which are listed in Table 3.
(5) On the other hand, besides the definition of Eq. (1), GoiT
could also be described by Eq. (8).
where the referential factors had been published by Syed et al.
[20]. The values were submitted into Eq. (5) to obtain the finial GoiT = RT lnKai = T Sio Hio (8)
form (Eqs. (6) and (7)) for the resulting equilibrium constants From Eqs. (1) and (8), the relationship between the reaction
for the TAME reaction network [7]. enthalpies and the equilibrium constants had been established
(Eq. (9)). From the same equations, the value of the standard
1.190 103 reaction entropies were also obtained, which were evaluated by
lnKa1 = 25.801 ln[T (K)]
T (K) the intercept multiplying the ideal gas constant R.
+ 7.599 102 T (K) 4.377 105 [T (K)]2 d(lnKai ) Hio
= (9)
d(1/T ) R
+ 1.299 102 (6)
As Table 4 shown, an excellent agreement is obtained
between experimental and literature data published lately except
Table 2 that So in R3 has deviations from values of literatures. The dif-
Comparison with experimental and theoretical equilibrium constants
ferences were likely due to the different thermodynamic data and
T (K) Experimental data Theoretical data method used in the evaluation.
Ka1 323 81.16 10.44 89.93
333 52.20 6.72 58.82 3.3. Kinetic modeling
343 34.45 4.43 39.29
353 23.27 2.99 26.75 In the published kinetic models for the synthesis of TAME,
Ka2 323 6.23 0.90 5.38 concentration was verified unfit for describing the strongly
333 4.49 0.65 3.88 nonideal kinetic behavior of the reagents, thus rate calcula-
343 3.29 0.47 2.84
tion should be set in terms of activities. In this paper, three
353 2.46 0.35 2.11
correlations based on different mechanisms were evaluated
766 W. Mao et al. / Chemical Engineering and Processing 47 (2008) 761769

Table 4
Liquid phase standard enthalpy and entropy changes of reaction obtained from experimental and literature data
Reaction Experimental data Literature data
1
Ho (kJ mol1 ) So (J mol1 K1 ) GoT (kJ mol ) Ho (kJ mol1 ) So (J mol1 K1 ) GoT (kJ mol1 )

R1 39.5 3.8 85.6 11.0 13.9 4.4 35.8a 82.1b 12.0c


R2 29.3 3.7 75.6 10.9 6.8 2.4 28.1d 78.0b 5.5c
R3 10.12 2.2 10.0 6.58 7.1 11.7 9.46c 4.1b 6.8c

where T in GoT is equal to 298.15 K.


a Serda et al. [21].
b Ferreira and Loureiro [7].
c Syed et al. [20].
d Verevkin [5].

against the data, which are homogeneous reaction mechanism, where


LangmuirHinshelwood (LH) type mechanism and EleyRideal k1 KM K1B k2 KM K2B k3 K1B
(ER) type mechanism. Ka1 = , Ka2 = , Ka3 = .
In the homogeneous reaction mechanism, it assumes the reac- k 1 KT k 2 KT k 3 K2B
tions are presented in the liquid phase without adsorbing on the Calculating the reaction rates by the above equations, we will
catalyst, and then we obtained the activity based net rate. obtain the most convincing results, but the workload is so heavy
that a simplified model is needed. In this work, we assumed the
rT = rTAME1 + rTAME2 adsorption of methanol is dominant for its high ideality and the
   
 aT  aT fractions of unoccupied sites were neglected. Consequently, the
= k1 aM a1B + k2 aM a2B (10)
Ka1 Ka2 kinetic model was simplified as follows:
   
a1B 1 aT 2 a2B 1 aT
rT = k1 + k (16)
r1B = rTAME1 rISO aM Ka1 aM
2 aM Ka2 aM2
       
aT a2B a1B 1 aT
= k1 aM a1B k3 a1B (11) r1B = k1 3 a1B 1 a2B
k (17)
Ka1 Ka3 aM Ka1 aM 2 aM Ka3 aM
   
 a2B 1 aT  a1B 1 a2B
r2B = rTAME2 + rISO r2B = k2 + k3 (18)
aM Ka2 aM 2 aM Ka3 aM
   
 aT  a2B
= k2 aM a2B + k3 a1B (12) For ER type mechanism, we assumed that only alcohol and
Ka2 Ka3 TAME adsorbed on the active sites of the catalyst, so the reaction
where aj is the activity of component j, Kai the equilibrium con- rates can be written as follows:
stants of the reaction, and Ka1 = k1 /k 1 , Ka2 = k2 /k 2 , Ka3 = k1 KM (a1B aM (aT /Ka1 )) k2 KM (a2B aM (aT /Ka2 ))
rT = +
k3 /k 3 . K M aM + K T aT KM aM + KT aT
In the model based on LH mechanism, it involves the com- (19)
petitive adsorption of all reagentsmethanol, isoamylenes and
TAME, and the surface reactions are regarded as the controlling
step. Consequently, reaction rates equations are defined as:
k1 KM K1B (aM a1B (aT /Ka1 )) + k2 KM K2B (aM a2B (aT /Ka2 ))
rT = (13)
(1 + KM aM + K1B a1B + K2B a2B + KT aT )2

 
k1 KM K1B (aM a1B (aT /Ka1 )) k1 KM (a1B aM (aT /Ka1 ))  a2B
r1B = r1B = k3 a1B (20)
(1 + KM aM + K1B a1B + K2B a2B + KT aT )2 KM aM + KT aT Ka3
 
k3 K1B (a1B (a2B /Ka3 )) k2 KM (a2B aM (aT /Ka2 ))  a2B
(14) r2B = + k3 a1B (21)
1 + KM aM + K1B a1B + K2B a2B + KT aT K M aM + K T aT Ka3
where
k2 KM K2B (aM a2B (aT /Ka2 ))
r2B = k1 KM k2 KM k3 K1B
(1 + KM aM + K1B a1B + K2B a2B + KT aT )2 Ka1 = , Ka2 = , Ka3 = .
k 1 KT k 2 KT k 3 K2B
k3 K1B (a1B (a2B /Ka3 )) Values of the kinetic constants ki were calculated by the
+ (15)
1 + KM aM + K1B a1B + K2B a2B + KT aT simplified model from the experimental data on the ini-
W. Mao et al. / Chemical Engineering and Processing 47 (2008) 761769 767

Table 5
Modeling result with D005II as catalyst
Mechanism Parameter Value S.D. S.D.% WSRS

Homogeneous k1 (mol h1 g1


cat (dry)) 0.337 0.012 3.55 0.0455
E1 (kJ mol1 ) 98.877 0.028 0.03
k2 (mol h g1
1
cat (dry)) 0.105 0.004 3.96
E2 (kJ mol1 ) 97.976 0.030 0.03
k3 (mol h gcat
1 1
(dry)) 0.261 0.009 3.27
E3 (kJ mol1 ) 109.380 0.028 0.03
LH k1 (mol h1 g1
cat (dry)) 0.179 0.017 9.40 0.0204
E1 (kJ mol1 ) 88.107 0.064 0.07
k2 (mol h1 g1
cat (dry)) 0.067 0.004 5.41
E2 (kJ mol1 ) 102.054 0.042 0.04
k3 (mol h1 g1
cat (dry)) 0.161 0.012 7.39
E3 (kJ mol1 ) 99.110 0.057 0.06
ER k1 (mol h1 g1
cat (dry)) 0.222 0.026 11.72 0.0309
E1 (kJ mol1 ) 85.131 0.078 0.09
k2 (mol h1 g1
cat (dry)) 0.090 0.002 2.05
E2 (kJ mol1 ) 100.223 0.016 0.02
k3 (mol h1 g1
cat (dry)) 0.193 0.015 7.75
E3 (kJ mol1 ) 110.126 0.067 0.06

tial rates of reactions at different temperature (323353 K) for the etherification of 2M1B and 2M2B, respectively, with
and different mole ratio of materials (RM/IA = 0.5, 1.0, 2.0). D005 catalyst produced in the same corporation as D005II cat-
The particle size of catalyst used in kinetic study was alyst. Since there are only one paper published with D005 type
0.350.50 mm to gain the more favorable data. Finally, the catalyst on kinetic studies, so the reaction energies were also
activation energies for the reactions were obtained from the lin- compared with those obtained by Amberlyst type catalyst and
ear regression fitted to Arrhenius type temperature dependence other catalysts. Rihko et al. [15] reported activation 72.6 and
(Eq. (18)). 94.1 kJ mol1 for the etherification of 2M1B and 2M2B. Piccoli
and Lovisi [4] published values of 85.6 and 92.5 kJ mol1 for
Eai reactions 1 and 2. The values of 77.0, 85.7 and 89.8 kJ mol1 ,
lnki = lnAi (22)
RT respectively, were obtained by Paakkonen and Krause [11] for
The parameters for the regression analysis based on the three the reaction system. Also some other kind resins have been used
kinetic models at 343 K are summarized in Table 5, which are for the kinetic studies of TAME synthesis, and the activation
the values of the parameters, their standard deviations (S.D.). energies published are comparative to the counterparts in this
To optimize the fitting, the modeling parameters were acquired work. In the study of Hoffmann [13], the etherification energies
by minimizing the weighted sum of residual squares (WSAS) were 89.5 kJ mol1 by lumping the isoamylenes together using
between the experimental and calculated rates of reaction and Lewatit SPC 118 catalyst. Paakkonen and Krause [11] also pub-
weight factor (wi ) equaled to 1 for every calculation. lished activation energies for 92.7 and 93.0 kJ mol1 for 2M1B
and 2M2B etherification using SMOPEX-101 catalyst. And the
WSRS = wi (ri,exp ri,calc )2 (23) values of 96.78 and 102.4 kJ mol1 , respectively, were obtained
with NKC-9 catalyst by Jin et al. [23].
According to the statistics, the LH model has the smallest Moreover, in order to validate the application of the cho-
WSAS (0.0204) and the homogeneous model largest (0.0455). sen kinetic mechanism, we used the kinetic equations based
These results are identical to those obtained by others [7,17], on three type mechanisms in order to see whether the derived
which indicated that the mechanism base on the two active sites model describes the experimental results within the experi-
are more appropriate. As the table shown, the value of kinetic mental conditions. In Fig. 7 the experimental and simulated
constant of R1, k1 , is dramatically greater than the value of k2 , molar fractions of the components are presented as a function
and the activation energy of R1 is less than that of R2. Thus, it is of reaction time. In the comparison experiments, the temper-
obvious that TAME synthesis from 2M1B is faster than TAME ature varies from 323 to 353 K and RM/IA contains 1:1, 1:2
synthesis from 2M2B which is in agreement with the conclusion and 2:1, to gain the reliable results. As the results shown in
in the thermodynamic study above. the figure, the homogeneous reaction mechanism is the least
Finally, the activation energies of the reactions, 88.1 kJ mol1 seemly model for its largest deviation. But the experimental
for the etherification of 2M1B, 102.1 kJ mol1 for the ether- results can be simulated by LH model accurately. Therefore,
ification of 2M2B and 99.1 kJ mol1 for the isomerization, we could conclude that the kinetic equations of LH and param-
respectively, are in good agreement with literature values. In eters in Table 5 can satisfactorily describe the synthesis of
1998, Yao et al. [22] reported values of 81.36 and 108.7 kJ mol1 TAME.
768 W. Mao et al. / Chemical Engineering and Processing 47 (2008) 761769

Fig. 7. Comparison of experimental and simulated molar fractions of TAME at different conditions by (a) homogeneous model, (b) LH model and (c) ER model.

4. Conclusions rium constants from thermochemical data, a fair agreement was


obtained. And then the thermodynamic equilibrium constants
In this work, thermodynamic and kinetic properties of TAME for the simultaneous etherification and isomerization reactions
synthesis were studied in a batch reactor. In the primary exper- were regressed in the form of Vant Hoff equation to obtain the
iment, several variables on reactions were studied, including values of enthalpies, entropies and Gibbs energies (at 298.15 K).
agitation speed, particle size and temperature. As the result In the kinetic study, three kinetic mechanisms were used to
shown, 400 rpm is sufficient to avoid external mass transfer evaluate the reaction rate of TAME synthesis, and LH model was
resistances, and the catalyst was used depending on different verified as the best which is based on the assumptions of stronger
experiments. As the most active factor in the system, temperature methanol adsorption. And the data calculated by LH model were
has great influences on TAME formation. When the tempera- able to simulate the experimental data with reasonable accu-
ture turned from 323 to 353 K, the initial reaction rate increased racy. On the other hand, the activation energies obtained for the
dramatically. Whereas the synthesis of TAME is exothermic, a etherification reactions for D005II catalyst in this work are com-
compromise temperature exists near 353 K. parative to those of D005 catalyst and some other type catalysts
In the thermodynamic study, activity was chosen instead of published.
concentration in the calculation of equilibrium constants because
of the nonideal behavior of methanol which varied significantly
during reactions. From experimental equilibrium results, it was Appendix A. Nomenclature
found that Ka1 is larger than Ka2 , which indicates the carboca-
tions formed from 2M2B are more stable than the carbocations
formed from 2M1B. It was also concluded that Ka3 varies a aie activity of species j at equilibrium
little with temperature for the isomerization reaction has low aj liquid-phase activity of component j
heat changes. By comparing the values of calculated equilib- Ei activation energy of reaction i (kJ mol1 )
W. Mao et al. / Chemical Engineering and Processing 47 (2008) 761769 769

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