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Dynamic Analysis of Adsorption Equilibrium and Rate

Parameters of Reactants and Products in MTBE, ETBE and

TAME Production

* Chemical Engineering Department, Gazi University, Ankara, Turkey

Department of Chemical Engineering, Middle East Technical University, Ankara, Turkey
Adsorption equilibrium constants of ethanol, methanol, isobutylene, isoamylenes (2M2B, 2M 1B), MTBE and TAME
on Amberlyst 15 catalyst were evaluated from the packed bed moment technique. Adsorption equilibrium constants of
alcohols were found to be two orders of magnitude greater than the adsorption equilibrium constants of i-olefins and the
corresponding tertiary ethers. However, their apparent heat of adsorption values are quite low ( 4 , 7 kJ/mol and -8.3
kJ/mol for methanol and ethanol, respectively). Among the i-olefins, isobutylene gave the highest adsorption equilibrium
constant and the heat of adsorption (-54.2 kJ/mol). The adsorption equilibrium constant of 2M2B on a catalyst, which
was pretreated with ethanol, was about three times greater than the corresponding value obtained on fresh catalyst.
Second moment analysis indicated that diffusion resistance in both macropores and microspheres of the catalyst are
equally significant.

Les constantes d’equilibre d’adsorption de I’ethanol, methanol, isobutylene, isoamylene (2M2B, 2M 1 B) MTBE et
TAME, avec le catalyseur Amberlyst 15,ont ete evaluees par la methode du moment de couche. Les constantes d’equilibre
d’adsorption des alcools ainsi determinees sont superieures de deux puissances (102) aux valeurs correpondantes pour
des olefines i et ethers tertiaires equivalents. Cependant, leurs valeurs apparentes de chaleur d’adsorption sont assez basses,
(-6.7 kJ/mol et -8.3 kJ/mol, respectivement pour le methanol et I’ethanol). En ce qui concerne les olefines i,
l’isobutylene a des constantes d’equilibre et de chaleur d’adsorption les plus elevees (-54,2 kJ/mol). La constante
d’adsorption du 2M2B sur un catalyseur pretraite I’ethanol, est environ 3 fois superieure celle obtenue avec un catalyseur
frais. Une analyse avec le moment du 2e ordre indique que la resistance la diffusion est la mme dans les macropores et
les microspheres du catalyseur.

Keywords: adsorption, MTBE, TAME, difhsivities, Amberlyst 15.

ethyl tert-butyl ether (MTBE), ethyl tert-butyl ether Iborra et al., (1992), Subramaniam and Bhatia (1987), Ali
M ( E T B E ) and tert-amyl methyl ether (TAME) are the and Bhatia (1990), Zhang and Datta (1995) and Linnekoski
major oxygenates used as gasoline blending components. et al., (1997) Langmuir-Hinshelwood type rate models were
Octane enhancing and emission lowering characteristics of shown to describe the experimental results best. On the
these oxygenates attracted wide attention of he1 producers other hand, in some other studies (Al-Jarallah et al., 1998;
and researchers in recent years. These ethers can be pro- Parra et al., 1994; Fite et al., 1994; Rihko et al., 1997; Rihko
duced by the reaction of C4 and Csi-olefins with alcohols. and Krause, 1995) Rideal-Eley type mechanisms involving
Strongly acidic macroreticular resin catalysts are generally i-olefin from the bulk fluid phase were considered. Tejero
used in the production of MTBE and ETBE by the reaction et al. (1996) suggested a transition between Rideal-Eley and
of isobutylene with methanol or ethanol respectively. In the Langmuir-Hinshelwood mechanisms with a decrease of
production of TAME and tert-amyl ethyl ether (TAEE), alcohol concentration.
isoamylenes such as 2-methyl 2-butene (2M2B) and 2- To our knowledge, no independent adsorption data were
methyl 1-butene (2MlB) were used instead of isobutylene. quoted in the literature for isobutylene, isoamylenes,
More than 20% of FCC light gasoline constitutes Cs, C6 MTBE, ETBE and TAME on such acidic resin catalysts. As
and C7 reactive olefins (Pescarollo et al., 1993). Production for the alcohols, Sola et al. (1997) and Fite et al. (1994)
of oxygenates from the FCC tertiary olefins and direct ether- reported heat of adsorption values which were extracted
ification of FCC light gasoline with methanol or ethanol from kinetic data. In a recent work, Zhang and Datta (1 995)
attracted the attention of researchers in recent years (Rihko reported some information about adsorption of liquid
and Krause, 1996; Ignatus et al., 1995; Sola et al., 1997; ethanol in n-heptane as solvent, and C6 olefins on Amberlyst
Zhang and Datta, 1995; Linnekoski et al., 1997). 15. For the verification of proposed reaction mechanisms
In the etherification of i-olefins, alcohols are generally and for the evaluation of adsorption parameters which
considered to be adsorbed strongly on the acidic ion- appear in the rate expressions, a detailed investigation of
exchange resin catalysts. However, the controversy between adsorption of i-olefins, alcohols and the corresponding
the kinetic models involving adsorbed i-olefins (Langmuir- ethers on the acidic macroreticular resin catalysts is
Hinshelwood type reaction mechanisms) and Rideal-Eley required. The macroreticular ion exchange resin catalyst
type mechanisms involving i-olefins from the fluid phase is used in these etherification reactions show bidisperse struc-
still open to further investigation. In the kinetic studies of tures (Ihm et al., 1996; Oost and Hoffman, 1996; Caetano
et al., 1995). The catalyst particle is considered as an ensemble
*Author to whom correspondence may be addressed. E-mail address: of gellular microspheres. Most of the active sites are reported
tdogu@rorqual.cc.metu.edu.tr to lie within these microspheres. The reactant species should

first diffuse through the macropores to the external surface
of microspheres and then penetrate into the microspheres. -- (Microsphereequation) (3)
The pore size distribution of such a catalyst depends upon
the degree of cross-linking of the polymer matrix. The activ-
ity of these catalysts are due to the S O , H groups which q=KCA; at r=ro ..................... (4)
have strong proton donor-acceptorproperties. These S O , H
groups form a dense network structure by forming hydrogen Model B :
bonds between them. In the presence of polar compounds
(i.e. alcohols), sulfonic groups and the polar compounds
form a hydrogen bonded network structure and the micros-
pheres start to swell. Diffusion of such polar compounds
into the microspheres is expected to be strongly influenced (Pellet equation). . . . . . . . . . . . . . . . . . . . . . . . . . . (5)
by the interaction with the catalyst structure. Modelling of
diffusion and reaction in such bidisperse catalysts are dis-
cussed in the review article of Dogu (1998).
In the present study, packed bed moment technique was
used for the evaluation of adsorption equilibrium constants
(Microsphere equation) . . . . . . . . . . . . . . . . . . . . . (6)
and effective diffbsivities of isobutylene, 2M2B, 2MlB,
MTBE and TAME, methanol and ethanol in Amberlyst 15
resin. Heats of adsorption were evaluated from the sorption A major assumption involved in both of these models is
data obtained in the temperature range of 323 to 373 K. the linear adsorption relation (Henry's law) between the
fluid phase and adsorbed concentrations of the tracer. Such
AND THEORY an assumption may in general be justified at sufficiently low
concentrations of the tracer. At higher concentrations, lin-
In the chromatographictechnique used in this work, pulses earization of the adsorption isotherm is necessary at the con-
of adsorbing tracers were injected into the carrier gas (helium) centration level of the experiment.
flowing through a column packed with Amberlyst 15. The macroreticular resin catalysts are generally consid-
Moments of the response peaks were then used for the eval- ered as an ensemble of gellular microspheres (Ihm et al.,
uation of adsorption equilibrium constants and effective dif- 1996; Oost and Hoffmann, 1996; Dogu, 1998). For these
hsivities. catalysts, diffusion within the microspheres is expected to
be strongly influenced by the interactions with the polymer
As it was mentioned in the introduction section above,
both macro and micropore diffusion resistance should be matrix. Consequently, an approach similar to Model A is a
considered in the modelling of transport processes in more suitable representation of this system.
The first absolute moment (time delay of the response
macroreticular resin catalysts. The species conservation
curve) and the second central moment (variance) expres-
equations for the adsorbing tracer in the packed bed is
sions derived for Model A, are reported in the early work of
Kawazoe et al. (1974).
a2c ac 3(i- Eb) ac, ac
U o -az- - R, Da T I = €b -
.......................................... (1)
Generally, two different approaches are used in the
description of diffision and adsorption in the bidisperse
porous catalysts. In the first approach, diffusing species are
assumed to be adsorbed on the external surface of micro-
spheres and these adsorbed species penetrate into the micro-
spheres by diffusion (Model A). This approach is generally
used in molecular sieve pellets and similar solids having
micropore dimensions comparable to the molecular size of
diffusing species. Two of the earlier papers which adopt this 2
approach are Kawazoe et al., (1974) and Shah and Ruthven ............
(1977). In the second approach (Model B), diffusion and
adsorption terms within the microspheres are separately
included into the conservation equation for the microporous
particle (Haynes and Sarma, 1973; Hashimoto and Smith,
1974). For these two models, species conservation equations
in the macropores of the catalyst pellet and for the micro-
spheres are expressed as follows:
Model A :

Here, 6 , 6 ,6, and represent the contributions of axial

dispersion, fikmass transfer resistance, macropore diffu-
(Pellet equation) . . . . . . . . . . . . . . . . . . . . . . . . . . (2) sion resistance and microsphere diffusion resistance to the

- 288

216 -

54 -

36 -


I I I 0.00 0.40 0.80 1.20 1.60 2.00
0.00 0.40 0.80 1.20 1.60 2.00

L/U,,S L/U,,S

Figure 1 -First absolute moment data for 2M2B. Figure 2 - First absolute moment data obtained with different
tracers (T= 323 K).

variance of the response peak, respectively. The definition The packed column was placed into the oven of the chro-
of ordinary moments (m,)is given by Equation (14). The matograph (Varian 6000) and the response peaks were
time delay of the response curve (first absolute moment) is detected using an FID detector. With the data acquisition
a function of adsorption equilibrium constant (Equation 7). system connected to the chromatograph response peaks
On the other hand, the rate processes invo!ved in this system were analyzed with high precision. The moments of the
influence the variance of the response peak. As it is shown response peaks were then evaluated by the numerical inte-
in Equations (7 to 12), film mass transfer, macro and micro- gration of,
pore difhsion rates might have significant contributions to
the second central moments. In the case of plug flow, the
axial dispersion contribution can be neglected. The contri-
bution of each of these terms to the second central moment
m, =
Ct"dt ............................. (14)

values obtained in our work are discussed in the Results and

discussions section of this paper. For large values of adsorp- Initial experimentscarried out with different liquid sample
tion equilibrium constant (pp HE,>> l), the moment expres- sizes (in the range of 1.0 to 0.2 pL) gave reproducible
sions derived from the two models (Models A and B) results, especially for sample amounts less than 0.5 pL.
become very similar. For this case, the only difference Basing on this observation, 0.2 pL sample size was used in
between the two models appears in the 6iterm. The relation most of the experiments. Only for isobutylene, samples
were injected in the vapor phase, and 100 to 200 pL sample
between the microsphere diffusivities in models A and B is
volumes were used.
Moments of the response peaks contain contributions due
D;= Di(ppK)l( 1 - EJ ...................... (13) to dead volumes in the injection and detection lines. In order
to make corrections to the moments, a set of pulse-response
In principle, the adsorption equilibrium constant of an experiments were carried out in the same system, but with-
adsorbing tracer may be evaluated from the first moment out the packed column. This analysis showed that the second
data (Equation 7) and second moments may be used for the central moments due to dead volumes were much less than
evaluation of the rate parameters. 1% of the second moments obtained with the Amberlyst 15
column. It was concluded, that no correction was necessary
Experimental work for the second central moments. However, for the first
absolute moments, correction was made by taking the dif-
Pulse response experiments were carried out using ferences of moments obtained with and without the packed
ethanol, methanol, isobutylene, 2M2B, 2M1B, TAME and column. Results showed that first moment corrections were
MTBE tracers. Experiments were repeated using 0.1 to 0.5 g less than 10% with i-olefins, MTBE and TAME. In the case
Amberlyst 15 catalyst packed into a column of (3/16) inch of alcohols, first absolute moments were so high that no cor-
inside diameter. Bed void fraction was determined as 0.47. rection was necessary.
Due to large adsorption equilibrium constants of ethanol The pore size distribution of the Amberlyst 15 catalyst
and methanol, very high first absolute moment values were (Sigma) was determined with a Quantachrome 60 mercury
obtained with these tracers. For these alcohols, response intrusion porosimeter. It showed a rather narrow distribution
peaks were very wide with long tails. Therefore, only 0.1 with an average macropore diameter of 2.28 x 10-8 m. The
gram of catalyst was enough for the analysis. However, with macroporosity average diameter and the apparent density of
the other tracers, higher amounts of catalyst (0.5 g) were the catalyst particles are 0.32, 7.4 x lo" m and 0.99 g/mL,
necessary to obtain reproducible results. For all these trac- respectively. The macropore surface area of the catalyst was
ers, pulse response experiments were repeated at different found as 59.2 m2/g from mercury porosimeter. This value
temperatures ranging between 323 to 373 K. In these exper- corresponds to pores having diameters greater than 6.7 x
iments carrier gas (Helium) flow rate was changed in the 10-9 m. The surface area determined from nitrogen adsorp-
range of 30 to 200 mL/min. Before each set of experiments, tion is somewhat smaller than the porosimeter area. These
the column was conditioned for 3 h at 373 K while carrier results indicated that nitrogen could not penetrate into the
gas was flowing through. gellular microspheres at the liquid nitrogen temperature.

TABLE1 100000 t
Adsorption Equilibrium Constants (pp K ) of Methanol, Ethanol,
C, and C, i-olefins and the Corresponding Tertiary Ethers
Tracer 323 K 340 K 358 K 373 K
Ethanol 1.43 104 1.13 104 1.05 104 1.85 x 104 l o ETHANOL

Methanol 0.97 x lo4 0.88 x lo4 0.76 x lo4 1.09 x lo4

lsobutylene 635 260 1 I3 38
2M1B 133 63 40 19
2M2B 94 68 42 24
MTBE 238 124 43 26
TAME 56 37 32 21

innn 1
0.260 0.275 0.290 0.305 0 320

(I/T)xlO', K-'

Figure 5 - Temperature dependence of adsorption equilibrium

constants of ethanol and methanol on Amberlyst 15.

Heat of Adsorption Values of Methanol, Ethanol, C, and C,
i-olefins and the Corresponding Tertiary Ethers
(Temperature range: 323 to 373 K)
Tracer Heat of Adsorption, kJ/mol
lsobutylene -54.2
2M2B -26.8
0.260 0.275 0.290 0.305 0.320 2MlB -37.2
MTBE -44.9
(I/T)X loz,K-' TAME -1 8.1
Figure 3 - Temperature dependence of adsorption equilibrium Ethanol 43*
constants of isobutylene, 2M2B and 2M 1B on Arnberlyst 15. Methanol -6.7*
(*) For these tracers apparent heat of adsorption values correspond
to the temperature range of 323 to 358 K.
'Oo0 I
The first absolute moments and the corresponding values
of adsorption equilibrium constants of alcohols were found
to be two orders of magnitude greater than the corresponding
values for i-olefins and tert-ethers. Adsorption equilibrium
constants evaluated for all these tracers are given in Table 1.
The temperature dependence of adsorption equilibrium
constants of C4, Cs i-olefms (isobutylene, 2M2B, 2MlB),
tertiary ethers (MTBE and TAME) and alcohols (ethanol
and methanol) are shown in Figures 3 , 4 and 5, respectively.
The heats of adsorption, evaluated from the slopes of these
10 '
0 260


figures are given in Table 2.
Adsorption equilibrium constant of isobutylene was
( I / T ) x l O z , K-' found to be higher than the adsorption equilibrium constants
Figure 4 - Temperature dependence of adsorption equilibrium of C, i-olefins (2M2B and 2MlB). The heat of adsorption of
constants of MTBE and TAME on Amberlyst 15. isobutylene is also quite high (-54.2 kJ/mol), indicating
chemisorption. As it is discussed by Tejero et al. (1987),
Results and discussions isobutylene is expected to adsorb on two centers. Isobutylene
chemisorptiondata were not found in the literature. Fite et al.
For all the tracers used in this work, corrected first (1 994), reported an estimated value of -72.64 kJ/mol for the
absolute moment data showed linear dependence on space heat of adsorption of isobutylene from the analysis of kinetic
time within the packed column. Typical first moment data data in ETBE synthesis.
obtained for 2M2B in the temperature range of 323 to 373 K The adsorption equilibrium constants of isoamylenes
are shown in Figure 1. The slopes of the linear relations (2M2B and 2MlB) are found to be close to each other
(passing from the origin) between first absolute moments (Figure 3). The heat of adsorption of 2M1B is higher than
and LIU, were then used for the evaluation of adsorption 2M2B. In a separate study carried out in our laboratory, it
equilibrium constants (Equation 7). The R values of regres- was found out that the reactivity of 2M1B is also higher than
sion analysis for the first moment data ranged between the reactivity of 2M2B in the etherification reaction. 2M 1B
0.985 and 0.996. A comparison of first moment data is a less stable molecule than 2M2B and consequently, it is
obtained for isobutylene, 2M2B, 2MlB, MTBE and TAME more reactive.
tracers are illustrated in Figure 2. Among these tracers, A comparison of adsorption equilibrium parameters of
isobutylene gave the highest first absolute moments and MTBE and TAME showed higher adsorption equilibrium
consequently, the highest adsorption equilibrium constant. constant and heat of adsorption values for MTBE (Figure 4,

Adsorption Equilibrium Constants (pp K ) of 2M2B on Fresh and Second Central Moment Analysis for Methanol and Isobutylene
Ethanol Pretreated Amberlyst 15 Catalyst ( T = 50°C) Tracers (T= 358 K)
Fresh catalyst : 94 Methanol Isobutylene
Ethanol pretreated catalyst : 268 LIUO? (s) 0.132 0.5
(experiment E)
Ethanol pretreated catalyst : 291 Pi, (s2) 5.04 105 1.41 x lo2
(experiment F) 0.86 1.58
- +-
(calculated i o m Eq. 8)
Table 2). The heat of adsorption of MTBE is more than
twice the value found for TAME. No chemisorption data D, (cm2/s) 0.0024 0.00 18
were found in the literature for these molecules. In a sepa- (estimated from Eq. 17)
rate study conducted in our laboratory with ETBE, heat of 2.5 x I @ I x 10-3
adsorption was found as -47.4 kJ/mol, which is close to the (s-9
value obtained for MTBE. Some decomposition of tertiary e
- 1

ethers were expected in the presence of Amberlyst 15 cata- Di (Model A), (cm2/s) 5.6 x 1.56 10-l~
lyst. The contact time of the tracer with the catalyst is quite Dr (Model B), (cm2/s) 6.3 x lo-'* 2.6 x ICY'*
low in our system and no indication of such a decomposition
was observed from the response peaks. Also, with the
olefins no indication of any side reactions were observed at clearly measured over the shallow alcohol peak. From the
the operating conditions of this study. A major advantage of time delay of this response peak, adsorption equilibrium
moment techniques over the conventional batch adsorption constant of 2M2B was determined. In the second type of
studies in the evaluation of the adsorption equilibrium con- experiment (Experiment F), Amberlyst 15 catalyst packed
stants is the short contact time of the tracer with the adsorbent into the column was soaked in ethanol for 18 h. Then, excess
in the pulse-response studies. alcohol was drained. The column was heated to the desired
The response peaks obtained with alcohols were very temperature (50°C) with helium gas flowing through the
wide with long tails. Even with 0.1 g of catalyst, more than column at a rate of 75 mL/min. After 15 min, pulse response
1 h was necessary to obtain the complete response peak. As experiments were carried out with the 2M2B tracer to eval-
it is shown in Table 1 adsorption equilibrium constants of uate the adsorption equilibrium constant. At this tempera-
alcohols are about two orders of magnitude higher than the ture, and with the small amount of catalyst used in this work,
adsorption equilibrium constants of other tracers. The tem- conversion of 2M2B to ethers is small and did not create a
perature dependence of alcohol adsorption equilibrium con- significant error in the evaluation of time delay of the
stants are very weak (Figure 5). The heat of adsorption values response peak of 2M2B. Results of these experiments
estimated from the adsorption data obtained between 323 showed that the adsorption equilibrium constants of 2M2B
and 358 K a r e 4 . 7 kJ/mol and-8.3 kJ/mol for methanol and obtained with alcohol pretreated catalysts are more than
ethanol, respectively. twice the corresponding values obtained with fresh catalyst
In the spectroscopic study of Thornton and Gates (1974), (Table 3). Swelling of the catalyst in the presence of alco-
it was shown that polar compounds like alcohols form a hols may allow easier penetration of i-olefins to the active
hydrogen bonded network structure with the S O , H groups sites. Also, a bridged adsorbed structure of 2M2B is possi-
on the catalyst surface. Up to three S O , H sites are reported ble between the S O , H sites and adsorbed alcohols. A
to be involved in the adsorption of one alcohol molecule. detailed spectroscopic investigation of the adsorbed species
Alcohols enter the gellular microspheres of the catalyst par- is necessary for further justification of this observation.
ticles and cause swelling. The desorption of these hydrogen In principle, the second central moment data can be used
bonded alcohol molecules from the network of gellular for the estimation of rate parameters. As it is shown in
microspheres is not highly temperature sensitive. The adsorp- Equation (8), four different terms namely, the axial disper-
tion equilibrium constants and heat of adsorption values sion, external film mass transfer resistance, macropore d i f i -
reported here for alcohols should be considered as apparent sion resistance and micropore d i h i o n resistance contribute
values. Due to the swelling of the catalyst in the presence of to the second central moment. Evaluation of difision terms,
alcohol molecules, the number of sites available for adsorp- from the second moment data would require an independent
tion might change. estimation of axial dispersion and film mass transfer terms.
An unexpected increase of adsorption equilibrium con- Also, one should note that second moment data are usually
stants of both ethanol and methanol was observed with an more scattered than the first moment data.
increase of temperature from 358 K to 373 K. One possible By estimating the film mass transfer coefficient from the
reason for this increase might be the swelling of the catalyst. well known correlation proposed by Carberry (1976)
Zhang and Datta (1995) also reported a similar observation (Equation 15), contribution of the external film mass transfer
with an increase of temperature over 323 K. resistance to the second central moments was found to be
All the adsorption data reported above correspond to single less than 1% for all the tracers used in this work.
tracers. In order to see the effect of alcohol presence on the
adsorption equilibrium constants of i-olefins on Amberlyst 1/2
15, two different kinds of dynamic experimentswere carried 2kf%
= . . . . . . . . . . . . (15)
out. In the first case (Experiment E), a pulse-response exper-
iment was carried out with the desired tracer ( e.g. 0.2 pL of
2M2B ) five min after the injection of 10 p1 of ethanol to the Also, by using the packed bed correlations for axial dis-
inlet of the packed bed. The response peak of 2M2B was persion (Smith, 1981), the value of 0,was estimated and

used to predict the value of 6, in Equation (8). The contri- Acknowledgement
bution of axial dispersion term to the second moment was
found to be less than 10%. Typical values of second Financial support of Turkish State Planning Organization (Gazi
moments and the results obtained from second moment University DPT 97 K12 1 1 lo), Gazi University Research Fund
analysis for methanol and isobutylene tracers are given in (06/97-05) and TUBITAK (METU, MISAG-90) are gratefully
Table 4.
The tortuosity factor of the macropores of the Amberlyst Nomenclature
15 catalyst was estimated from the model proposed by Dogu
and Dogu (1991) as 4.9. c = tracer concentration in the packed column, (kmol/m3)
c, = tracer concentration in the macropores, (kmol/m3)
c. = tracer concentration in the microspheres, (kmol/m3)
D, = axial dispersion coefficient, (m2/s)
D, = effective macropore diffusion coefficient, (m2/s)
D. = effective microsphere diffusion coefficient (Model A), (m2/s)
Di = effective microsphere diffusion coefficient (Model B), (m2/s)
The macropore diffusion coefficients were then estimated D = molecular diffusivity, (m2/s)
from D, = Knudsen diffusivity, (m2/s)
k = mass transfer coefficient, ( d s )
k = adsorption equilibrium constant, (m3/kg)
Da = DT-Ea . . , , . . . . . . . . . . . . , . . , . . . . . . L = column length, (m)
T m, = n’th moment defined by Equation (14)
R, = radius of catalyst, (m)
Gas phase diffusion within the macropores is controlled ro = radius of microspheres of catalyst, (m)
by Knudsen diffusion. The estimated values of effective t = time, (s)
macropore diffusivities are given in Table 4. Using the esti- u, = superficial velocity, ( d s )
mated values of D, and the axial dispersion coefficient,
micropore diffusivities are then evaluated from the second Greek letters
moment data using Equation (8). In this calculation average
radius of microspheres was taken as 1.5 x l@ m (Caetano E
, = macroporosity of the catalyst
et al., 1995). 4 = microporosity of the catalyst
E, = bed void fraction
The diffusion coefficient corresponding for Model B was
pi = first absolute moment, (s)
then determined using Equation (13). In Model B, diffusion c‘; = second central moment, (s2)
was considered to take place in the gas phase within the v = kinematic viscosity, (m2/s)
micropores. On the other hand, in Model A, diffusion in the
microspheres was considered to take place in the adsorbed
state. During diffision into the microspheres of macroretic-
z =
catalyst apparent density, (ks/m3)
density of microspheres of catalyst, (kg/m3)
macropore tortuosity (Equation 16)
ular ion exchange resin catalysts, strong interactions of dif-
fusing molecules are expected with the polymer matrix. References
Consequently, Model A seems to be a more realistic repre-
sentation of the system. Ali, A. and S. Bhatia, “Methyl Tertiary Butyl Ether Formation in a
The accuracy of the Di values evaluated from second Catalytic Bed Reactor-Kinetic and Modelling Study”, Chem.
Eng. J. 44, 97-1 06 (1 990).
moment data would strongly depend upon the accuracy of Al-Jarallah, A. M., M. A. B. Siddiqui and A. K. K. Lee, “Kinetics
the data and also the prediction procedures for axial disper- of Methyl Tertiary Butyl Ether Synthesis Catalyzed by Ion
sion, film mass transfer and macropore d i f i i o n coefficients. Exchange Resin”, Can. J. Chem. Eng. 66,802-806 (1988).
Caetano, N. S., J. M. Loureiro and A. E. Rodrigues, “MTBE
Concluding remarks Synthesis Catalyzed by Acid Ion Exchange Resins: Kinetic
Studies and Modelling of Multiphase Batch Reactors”, Chem.
Eng. Sci. 49,45894604 (1995).
Adsorption equilibrium constants of alcohols on Carberry, J. J., Chemical and Catalytic Reaction Engineering,
Amberlyst 15 catalyst are about two orders of magnitude McGraw Hill Book Co., New York, NY 1976.
greater than the adsorption equilibrium constants of C,, Cs Dogu, T., “Diffusion and Reaction in Catalyst Pellets with
i-olefins, MTBE and TAME. Alcohols are expected to enter Bidisperse Pore Size Distribution”, Ind. Eng. Chem. Res. 37,
into the polymer matrix of microspheres of Amberlyst 15 2158-2171 (1998).
forming hydrogen bonds with the S O , H groups and cause Dogu, T. and G. Dogu, “A Grain Model for Catalyst Tortuosity”,
swelling. Their heat of adsorption values are much lower Chem.Eng.Comm. 103, 1-9 (1991).
than the heat of adsorption values of i-olefins. I-olefms are Fite, C., M. Iborra, T. Tejero, J. F. Izquierdo and F. Cunill,
found to be chemisorbed and presence of alcohol caused an “Kinetics of the Liquid-Phase Synthesis of ETBE”, Ind. Eng.
increase in their adsorption equilibrium constants. Chem. Res. 33,581-591 (1994).
Comparison of heat of adsorptions of 2M2B and 2M1B Haynes, H. W. Jr. and P. N. Sanna, “A Model for the Application
showed a higher value of 2M1B which is a more reactive of Gas Chromatography to Measurements of Diffusion in
molecule than 2M2B. The second moment analysis indicat- Bidisperse Structured Catalysts”, AlChE J. 19, 10431046
ed that the ratio of diffusion times in the macro and microp- (1 973).
Hashimoto, N. and J. M. Smith, “Diffusion in Bidisperse Porous
ores is in the order of magnitude of unity. Therefore, in the Catalyst Pellets”, Ind. Eng. Chem. Fund., 13 115, (1974).
analysis of rate data for etherification reactions, both macro Iborra, M., J. F. Izquierdo, F. Cunill and J. Tejero, “Application of
and micropore diffusion resistances should be taken into the Response Surface Methodology to the Kinetic Study of the
consideration. Gas-Phase Addition of Ethanol to lsobutene on a Sulfonated


Styrene-Divinylbenzene Resin”, Ind. Eng. Chem. Res. 31, Smith, J. M., Chemical Engineering Kinetics, 3d ed., McGraw Hill
1840-1848 (1992). Book Co., New York, NY 198 1.
Ignatius, J., H. Jarvelin and P. Lindqvist, “Use TAME and Heavier Sola, L., M. A. Pericas, F. Cunill and J. F. Izquierdo, “A Comparative
Ethers to Improve Gasoline Properties”, Hydrocarbon Processing, Thermodynamic and Kinetic Study of the Reaction between
February, 51-53 (1995). Olefins and Light Alcohols Leading to Branched Ethers.
Ihm, S. K., J. H. Ahn and Y. D. Jo., “Interaction of Reaction and Reaction Calorimetry Study of the Formation of tert-Amy1
Mass Transfer in Ion-Exchange Resin Catalysts”, Ind. Eng. Methyl Ether (TAME) and tert-Butyl Isopropyl Ether (IPTBE)”,
Chem. Res. 35,2946-2954 (1966). Ind. Eng. Chem. Res. 36,2012-2018 (1997).
Kawazoe, K., M. Suzuki and K. Chihara, “Chromatographic Study Subtamaniam, C. and S. Bhatia, “Liquid Phase Synthesis of Methyl
of Diffusion in Molecular-Sieving Carbon”, J. Chem. Eng. tert-Butyl Ether Catalyzed by Ion Exchange Resin”, Can. J.
Japan 7, 151-1 57 (1 974). Chem. Eng. 65,615-622 (1 987).
Linnekoski, J . A. and A. 0. Krause, “Kinetics of the Tejero, J., F. Cunill and M. Iborra, “Molecular Mechanism of
Heterogeneously Catalyzed Formation of tert-Amy1 Ethyl MTBE Synthesis on a Sulphonic Acid Ion Exchange Resin”, J.
Ether”, Ind. Eng. Chem. Res. 36, 3 10-3 16 (1997). Molecular Catal. 42, 257-268 (1 987).
Oost, C. and U. Hoffmann, “The Synthesis of Tertiary Amy1 Tejero, J., F. Cunill, J. F. Izquierdo, M. Iborra and D. Parra, “Scope
Methyl Ether (TAME) : Microkinetics of the Reactions”, Chem. and Limitations of Mechanistic Inferences from Kinetic Studies
Eng. Sci. 51, 329-340 (1996). on Acidic Macroporous Resins. The MTBE Liquid-Phase
Parra, D., J. Tejero, F. Cunill, M. lborra and J. F. Izquierdo, Synthesis Case”, Applied Catalysis, A: General 134, 21-36
“Kinetic Study of MTBE Liquid-Phase Synthesis Using C, (1 996).
Olefinic Cut”, Chem. Eng. Sci. 49,4563-4578 (1994). Thornton, R. and B. C. Gates, “Catalysis by Matrix-Bound Sulfonic
Pescarollo, E., R. Trotta and P. R. Sarathy, “Etherify Light Acid Groups: Olefin and Paraffin Formation from Butyl
Gasolines”, Hydrocarbon Processing, February 53-60 (1 993). Alcohols”, J. Catal. 34, 275-287 (1974).
Rihko, L. K. and A. 0. I. Krause, “Kinetics of Heterogeneously Zhang, T. and R. Datta, “Ethers from Ethanol 4. Kinetics of the
Catalyzed tert-Amy1 Methyl Ether Reactions in the Liquid Liquid-Phase Synthesis of Two tert-Hexyl Ethyl Ethers”, Ind.
Phase”, Ind. Eng. Chem. Res., 34, 1 172-1 180 (1 995). Eng. Chem. Res. 34,2247-2257 (1 995).
Rihko, L. K. and A. 0. I. Krause, “Etherification of FCC Light
Gasoline with Methanol”, Ind. Eng. Chem. Res. 35, 2500-2507
(1 996).
Rihko, L. K., P. K. Kiviranta-Paakonen, and A. 0. I. Krause,
“Kinetic Model for the Etherification of Isoamylenes with
Methanol”, Ind. Eng. Chem. Res. 36,614-621 (1997).
Shah, D. B. and D. M. Ruthven, “Measurements of Zeolitic
Diffusivities and Equilibrium Isotherms by Chromatography”, Manuscript received July 7, 1998; revised manuscript received
AIChE J. 23,804-809 (1977). December 10, 1998; accepted for publication January 26, 1999.

Chemical Engineering Research and Design

As part of a cooperative agreement between the Institution of 1 I7 Assessment of Condensation Curves in the Design of Binary
Chemical Engineers (UK) and The Canadian Society for Chemical Vapour Condensers.
Engineering, the table ofcontents of each issue of the respective D. R. Webb, A. J. Dell, R. W. Stevenson and K. Ax
research journals will appear in the other. This journal is available 124 An Experimental and Numerical Investigation of Heat
to members of The Canadian Society for Chemical Engineering for Transfer Fouling and Fluid Flow in Flat Plate Heat
$13 1.00. Exchangers.
T.Kho and H. Miiller-Steinhagen
Chemical Engineering Research Vol. 77, No. A2 13 1 Study of Heat Transfer Process in a Regenerator.
and Design March 1999 S. Muralikrishna

Contents General Papers

87 Editorial 138 Model Selection for Multiresponse System.
Santokh Singh
Special Papers 151 Gas-Solids Contact Efficiency in the Entrance Region of a
89 Single Particles, Bubbles and Drops: Their Velocities and Co-current Downflow Fluidized Bed (Downer).
Mass Transfer Coefficients. J. -X. Zhu, Y. Ma and H. Zhang
J. A . Wesselingh and A. M. Bollen 159 An Experimental Study of Individual Air Bubble Entrainment
97 Manipulation of Bulk Reactions in Muliphase Systems by the at a Planar Plunging Jet.
Use of Microheterogeneous Media. P. D. Cummings and H. Chanson
S. Patel and A . Mehra 165 Book Reviews.
104 Comparison of Mass Transfer Performance for Various 168 Forthcoming Meetings.
Single and Twin Impellers. 170 Contents of CJChE February 1999.
Z. D. Chen and J. J. J. Chen
1 10 A Modification to the Equilibrium Model for Condensation of
Vapours of Immiscible Liquids.
D. A. Webb and J. S. Kim