1348 Ind. Eng. Chem. Res.

2001, 40, 1348-1354

The Effect of Ether on the Reaction Rate of MTBE Synthesis

Carles Fité,* Javier Tejero, Montserrat Iborra, Fidel Cunill, and J. Felipe Izquierdo
Chemical Engineering Department, Faculty of Chemistry, University of Barcelona, Martı́ i Franquès 1,
08028 Barcelona, Spain

The influence of the product on the kinetics of the MTBE synthesis reaction has been investigated.
Experimental reaction rates for the MTBE synthesis reaction in the liquid phase by addition of
methanol (MeOH) to isobutene (IB) were determined on the sulfonic macroporous resin Bayer
K2631 at 45-90 °C for a wide range of IB, MeOH, and MTBE concentrations and operating in
the differential regime in a tubular reactor system. The affinity between the bulk phase and
the resin depends on the composition of the reaction medium, and it plays an important role in
the catalyst activity. This effect has been implemented into the kinetic equation as a function
of the resin and the medium solubility parameters. Experimental data are well described through
a LHHW mechanism, the surface reaction being the limiting step. The obtained kinetic equation
correctly predicted the additional experimental data obtained in a batch reactor. The apparent
activation energy was estimated to be 84.31 ( 1.09 kJ/mol, and the resin solubility parameter
was estimated as 23.79 ( 0.83 MPa1/2 at 25 °C.

Introduction the reaction rates is hindered by the high degree of

In the recent past, some studies involving the kinetics
of the synthesis of methyl tert-butyl ether (MTBE) from
isobutene (IB) and methanol (MeOH) have been pub-
lished. These works mainly deal with the simulation of
industrial MTBE multitubular reactors and reactive
distillation. Obviously, these tasks require the imple-
mentation of an accurate kinetic description in terms
of reaction rates. As the reaction progresses toward
chemical equilibrium in such industrial equipment, the
reaction proceeds in the presence of the product. Hith-
erto, kinetic equations available in the open literature
have been obtained by working in a narrow range, if
any, of MTBE concentrations.
Up to now, the most widely used kinetic equation is
that proposed by Rehfinger and Hoffmann.1 It was
obtained by means of experiments carried out in the
temperature range 323-363 K by two different proce-
dures: (i) determination of the forward reaction rate by
reacting MeOH with IB, as a component of the C4
fraction, in the absence of MTBE (IB conversion at the
reactor inlet equal to zero), and (ii) decomposition of
MTBE in the absence of IB and MeOH (further away
from chemical equilibrium). Indirectly, the situation for
which the reaction rate vanishes is also included
through the equilibrium constant estimated from ther-
modynamic data. As a consequence, no experiments
have been performed at the usual conditions reached
inside the bulk of the industrial equipment.
The majority of the published MTBE kinetic studies
are engaged in determining initial reaction rates,
namely, in the absence of the product. Only two pub-
lished works appear to be concerned with the influence
of the MTBE content on the reaction rate. Parra et al.2
determined experimental reaction rates in the presence
of MTBE by using a C4 olefinic cut as the IB source. In
this case, the analysis of the influence of the ether on
* Author to whom correspondence should be addressed.
Phone: +34 93 402 1308. Fax: +34 93 402 1291. E-mail:
fite@angel.qui.ub.es.
10.1021/ie000300p CCC: $20.00 © 2001 American Chemical Society
Published on Web 02/06/2001
dilution because of the hydrocarbons other than IB
contained in the C4 cut. Panneman and Beenackers3
performed experiments with equimolar amounts of IB
and MeOH and variable MTBE contents (0-50% molar),
and reaction rates were found to decrease with increas-
ing MTBE content, as expected because of the increasing
importance of the reverse reaction. However, this de-
crease is lower than that estimated by Rehfinger and
Hoffmann.1 Along with the results obtained in the
absence of product, this fact was assumed to be caused
by a significant interaction between the catalyst and the
reaction medium. Kinetic analysis was performed as-
suming a first-order rate equation expressed in terms
of activities of the following species: IB, MeOH-solvated
resin acidic groups, and the activated complex. The
authors proposed a composition-dependent kinetic con-
stant because of variations in the Gibbs energy of the
activated complex depending on the reaction medium
composition. It was concluded that the presence of the
product stabilizes the activated complex and, therefore,
that the kinetic constant increases with increasing
MTBE contents, which is equivalent to saying that the
reaction rate is higher than expected.
More recently, a significant influence of the reaction
medium composition on the catalyst activity in the
forward reaction was also observed.4,5 Experimental
conditions were 45-90 °C and an IB/MeOH molar ratio
between 0.5 and 2.0. Several conventional Langmuir-
Hinshelwood-Hougen-Watson (LHHW) and Eley-
Rideal (ER) type rate equations in terms of activities
were analyzed, and it was concluded that they did not
accurately predict the reaction rate. Therefore, a modi-
fication of such rate equations was proposed, consisting
of splitting the kinetic constant into two factors that are
related to two different observed aspects: temperature
dependence and reaction medium influence. The second
factor corresponds to a quantification of the affinity
between the reaction medium and the catalyst in terms
of solubility parameters. This modification produced a
significant improvement in the prediction of experimen-
tal reaction rates.
 Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1349

As a consequence, the following needs arise: deter-

mination of experimental reaction rates in a wide range
of IB, MeOH, and MTBE concentrations and validation
of the inclusion of the reaction medium influence in the
kinetic constant. Hence, the aim of this study is to
obtain a reliable rate equation based on experimental
data in a wide range of concentrations, from which
mechanistic conclusions can be inferred.

Experimental Section
Materials. Experiments were performed using metha-
nol, MTBE (both 99.9% pure, <0.01% water; Romil
Chemicals Ltd., Shepsted, U.K.), and isobutene (99%
pure; Carburos Metálicos, Barcelona, Spain). As the
catalyst, the sulfonated ion-exchange resin Bayer K2631
(styrene-divinylbenzene matrix, 15-25 wt % degree of
cross-linking, BET surface area of 36 m2/g, exchange
capacity of 4.83 equiv of H+/kg) was used.
Experimental Setup. Differential and integral ki-
netic experiments were performed in two different
experimental setups:
(i) The differential operating reactor consisted of an
upflow packed-bed tubular reactor (15 cm length, 4.4
mm i.d.) submerged in a thermostatic bath. Reactants
were fed with a positive displacement duplex-type
pump. Assayed temperatures were 45, 60, 75, and 90
°C, and the pressure was kept at 1.6 MPa in order to
ensure that all of the components of the reacting
mixture were in the liquid phase. Samples at the reactor
inlet and outlet were taken by liquid sampling valves,
and analysis was carried out with a gas chromatograph
Figure 1. Effect of the isobutene, methanol, and MTBE concen-
equipped with a capillary column and an FID detector.
trations on the experimental reaction rate at 75 °C.
More detailed information about this experimental
setup can be found elsewhere.4 A total of 63 experiments
were performed in the present work to study the effect < 0.16 mm) used ensured that the reactor operated in
of the product on the MTBE synthesis kinetics, by the differential regime and that both internal and
feeding MeOH-MTBE mixtures of different composi- external mass-transfer effects were negligible.4 Byprod-
ucts did not appear at any operating conditions.
tions (MTBE molar fractions, x/MTBE, of about 0.2, 0.4,
and 0.5) instead of pure MeOH. In addition, previously As no compounds other than IB, MeOH, and MTBE
available experiments obtained with the same experi- were introduced into the system, only the concentrations
mental setup, but with a reactor feed free of ether,4 have of two compounds can be freely fixed. Therefore, the
been included in the present study. effect of each particular compound on the reaction is
(ii) The integral operating reactor consisted of a substantially difficult to separate. Nevertheless, some
jacketed stainless steel batch reactor. Catalyst and general facts have been observed at all of the experi-
methanol were introduced into the reactor, and the bath mental temperatures and for the different MTBE con-
temperature was set to the desired value. Isobutene was centrations in the reactor feed. For example, Figure 1
added, and the system was pressurized up to 1.6 MPa shows the experimental results at 75 °C.
with nitrogen. In the course of an experiment, several (i) Isobutene Concentration. The reaction rate was
samples of the reaction mixture were taken by auto- found to increase with cIB for all compositions of the fed
matic valves at different reaction times and then MeOH-MTBE mixtures. This behavior agrees with the
analyzed by gas chromatography. From these data, the available data in terms of concentrations: a positive,
evolution of the reaction mixture composition was close to 1, partial reaction order in a power-law kinetic
determined. Liquid samples were analyzed until the equation is reported by Colombo and Dalloro;7 and for
system was close to the equilibrium. Further details of mechanistic-based kinetic equations, the partial reaction
the experimental setup, procedure, and analysis can be order is positive and equal to 1 in absence of ether.8-10
found elsewhere.6 The influence of the isobutene concentration is stronger
at higher MTBE contents. At cIB values higher than
about 4 mol/L, the experimental reaction rate obtained
Results and Discussion
in the absence of product is lower than that obtained
Differential Regime Experiments. Kinetic experi- when MTBE is present at the reactor inlet, and this
ments were performed by feeding IB-MeOH and IB- difference increases as the MTBE content increases.
MeOH-MTBE mixtures to the reaction system in the This trend seems to become inverted at cIB < 4 mol/L.
absence of inert components. The tubular reactor oper- (ii) Methanol Concentration. In all cases, the reaction
ated isothermally, and the temperature range was 45- rate decreases for increasing cMeOH. The inhibiting effect
90 °C. The flow rates (LHSV > 35 h-1), catalyst masses of MeOH on the reaction rate agrees with the published
(requirement was to keep ∆XIB < 0.10, depending on experimental data and kinetic equations expressed in
the reactor feed and temperature), and particle sizes (dp terms of concentrations: in a power-law equation, the
1350 Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001
o
Figure 2. Reaction rate dependence on RIB/MeOH for different MTBE contents. xMTBE* refers to the MTBE molar fraction of the feed
MeOH-MTBE mixture.
exponent of cMeOH has been found to be negative;7 and
from mechanistic based equations,8-10 the partial reac-
tion order of MeOH in absence of MTBE is equal to 0
and negative for increasing MTBE contents.
(iii) MTBE Concentration. The general feature is the
decrease of the reaction rate with increasing MTBE
concentration, which indicates an inhibiting effect of the
product on the kinetics.
A global overview can be achieved by plotting the
o of kinetic equations based on LHHW and ER formalisms
experimental reaction rates versus RIB/MeOH , namely,
the IB/MeOH molar ratio of the reference reaction
mixture, defined as the molar ratio of the reaction
mixture free of MTBE that would derive from the actual
one according to the reaction stoichiometry (Figure 2).
Two zones can be clearly distinguished. For RIB/MeOH o
lower than approximately 1.5, the reaction rate de-
creases with increasing MTBE content, which is usually
the expected trend because of the increasing importance
of the reverse reaction as the reaction goes forward. For
o
RIB/MeOH larger than 1.5, the reaction rate increases
with the MTBE content. This latter behavior is unex-
pected, as, under these conditions, the reaction seems
to behave autocatalytically. However, this fact can be
explained by the particular characteristics of the cata-
lyst: depending on the composition of the reaction
medium, the backbone of the resin, which consists of a
cross-linked polymer with an incompletely rigid struc-
ture, acquires a particular conformation. Moreover, its
active centers present a variable acidity and, therefore,
a changeable activity. Thus, at low methanol contents,
o improve the prediction of the experimental reaction
that is, at high RIB/MeOH , and at increasing reaction
extension, the polarity of the reaction medium de-
creases, the resin backbone becomes less swollen and
more rigid, and the active centers become shaped in
such a way that they form a catalytic cluster with a
higher acidity. This fact results in a reaction rate higher
than expected if the resin structure had not changed.
Consequently, in the course of the reaction, the decrease
in the driving-force term due to the approach to the
chemical equilibrium is compensated for, and even
overcome by, the increase in the activity of the acidic
sites. In practice, this means that the reaction rate
continuously increases along the reaction course and,
in addition, that it suddenly decreases when the system
is close to equilibrium.
Mechanistic Considerations and Kinetic Equa-
tion. Analogously to a previous work,5 a large number
have been derived by considering different adsorption
types for each isobutene, methanol, and MTBE: no
adsorption, one molecule per active center, two mol-
ecules per active center, and one molecule on two active
centers. Also, the fact that the adsorption extent of the
less polar species could be negligible toward methanol
adsorption has been taken into account. Because MTBE
was fed to the reactor, the effect of the reverse reaction
on the reaction rate has been considered in the kinetic
equation. Given the nonideallity of the reaction medium,
the kinetic equation must be expressed in terms of
activities, which have been estimated through the
UNIFAC method. In comparison with the previous
work, the presence of ether in the reactor feed makes
possible a higher variation of IB and MeOH activities,
and the MTBE activity is also included in the kinetic
equation. As a result, a better discrimination between
plausible rate equations can be achieved.
The tested kinetic equations include the factor Ψ with
a physicochemical meaning that has been found to
rates.5 This factor was defined as
[ ]
h M Φ2P
V
Ψ ) exp (δM - δP)2 (1)
RT
and it quantifies the affinity between the catalyst and
the reaction medium. The consideration of such a factor
 Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1351

is required in the present system, as the polarity of the

reaction medium varies widely, leading to a significant
change in the catalyst activity, as mentioned above.
Mathematical Aspects. The fit of the kinetic equa-
tions to the experimental data has been performed by
means of a nonlinear algorithm based on the Leven-
berg-Marquardt method. The sum of the squares of the
relative deviations between the experimental and cal-
culated values was considered as the objective function
to be minimized. This criterion was chosen because the
analysis of replicated data indicated that the experi-
mental error was proportional to the reaction rate value.
The temperature dependence of the kinetic equation
parameters was implemented in order to fit them at the
same time to all of the experimental data at the different
temperatures. For that purpose, the temperature de- Figure 3. Comparison between experimental rexp and calculated
pendencies of the apparent kinetic constant k′ and of rcalc reaction rates, obtained through eq 5.
the ratio of the adsorption constants K′, if required, were
assumed to be the fitted model, computed as the ratio of the fitted sum

[ ( )]
-Eap 1 1 of squares to the total sum of squares. In a nonlinear
k′(T) ) k′0 exp - (2) model, this is equivalent to the R2 of the linear regres-
R T T h sion (0 e R2 e 1, the coeficient of multiple determina-
A1 1 tion). For both eqs 5 and 6, R2 was greater than 0.99.
K′(T) ) K′0 exp[ ( - )] (3) In addition, the plot of the predicted vs observed values
RT Th
indicates a good agreement between those values (Fig-
where k′0 ) k′(T h ), K′0 ) K′(T
h ), Eap is the apparent ure 3). Therefore, both models can be qualified as
activation energy, and A is a sum of adsorption enthal- significant.
pies that depends on the considered mechanism. On the The lowest value of the objective function, that is, the
other hand, a linear temperature dependence for the weighted sum of the squares of the residuals, was
resin solubility parameter δP was assumed, in agree- attained for eq 5, and the corresponding value for eq 6
ment with the previously obtained results.5 This de- was only a 1.5% larger. The forms of the two equations
pendency is as follows: are very similar, and both give rise to the same equation
for the case in which the reaction medium is free of
δP ) M(T - T
h) + N (4) ether. Thus, the largest differences are disclosed at high
MTBE contents. At low IB/MeOH ratio and high ether
where M and N are parameters to be fitted. In all cases, content, the reaction rates calculated by means of eq 6
the inclusion of the mean experimental temperature T h were systematically 30% larger than the experimental
is done to reduce the cross-correlation between the fitted values, although when eq 5 was used, no significant bias
parameters. was observed. As a consequence, strictly from a math-
All formulated kinetic equations have been system- ematical point of view, eq 5 is more suitable than eq 6
atically fitted to the experimental data. Mathematically, for the prediction of the reaction rates.
the lower the sum of squares, the more suitable the Statistical Aspects. The probability distribution
equation for predicting the experimental values. Glo- functions (pdf’s) of the estimated parameters for eqs 5
bally, the results show that the kinetic equations that and 6 have been calculated by means of a Monte Carlo
better fit the experimental reaction rates are those simulation. Those pdf’s have been processed, and it has
whose driving-force term is (a2IBa2MeOH - a2MTBE/K2). been concluded that the parameter A in eq 3 was
This implies a reaction mechanism wherein the surface statistically not significant for both models. Hence, the
reaction involves the participation of two IB and two temperature dependence of K′ was removed from the
MeOH molecules to yield two MTBE molecules, and it rate equations. The reduced models were then fitted to
is in agreement with the previously obtained results for the experimental data, and the new pdf’s were obtained.
the case when no ether was present at the reactor inlet.5 No significant differences with the previous results were
Two kinetic equations separate from the rest with observed in the parameter values and goodness-of-fit.
regard to the low value of the minimized function. These The standard error of the fitted parameters was calcu-
equations are lated from the obtained pdf’s.
Physicochemical Aspects. The apparent activation
a2MTBE energy can be obtained from the temperature depend-
a2IBa2MeOH - ence of the kinetic constant (eq 2). For both kinetic
K2
r ) k′Ψ (5) equations, the values are practically the same within
(a2MeOH + K′a2MTBE)3 the limits of the experimental error, specifically, 84.3
( 1.1 kJ/mol for eq 5 and 84.5 ( 1.1 kJ/mol for eq 6,
a2MTBE and they agree with the values quoted in the liter-
a2IBa2MeOH - ature.11-12
K2
r ) k′Ψ (6) As no experimental values or correlations were avail-
(aMeOH + K′a2MTBE)6 able in the open literature, the resin solubility param-
eter value was estimated by a contribution group
The appropriateness of the overall model can be tested method,13 which yielded a value of 22.73 MPa1/2 at 298
in terms of the proportion of the variance explained by K. From the fitted parameters, the values obtained at
1352 Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001
that temperature were 23.79 ( 0.83 MPa1/2 for eq 5 and
23.87 ( 0.84 MPa1/2 for eq 6. As can be seen, both values
are very close to the estimated one. It has also been
found out that δP decreases with increasing tempera-
tures (the M value is negative), similarly to pure
substances in the liquid phase, as it stems from the
definition of the solubility parameter.14
The adsorption enthalpies and entropies are related
to parameters K′0 and A of eq 3. For both eqs 5 and 6,
according to the mechanism from which they stem, the
following relation applies:
KMTBE
K′ ) )
KMeOH
( ) ( )
∆SMTBE - ∆SMeOH - ∆HMTBE + ∆HMeOH
exp exp
R RT
(7)
As a consequence, from the experimental data, it
would only be possible to obtain values for the difference
of the MeOH and MTBE adsorption enthalpies and
entropies. In our case, because of the lack of statistical
significance of the K′ temperature dependence, it can
be concluded that the ∆HMeOH and ∆HMTBE values are
very similar. Therefore, ∆HMTBE on the Bayer K2631
resin should be equal to -3.8 kJ/mol within the limits
of the experimental error, as was determined in a
previous work for MeOH adsorption on the same
catalyst.15
On the other hand, the obtained values of (∆SMTBE -
∆SMeOH) for both eqs 5 and 6 are, respectively, -2.09 (
0.67 and -4.78 ( 0.64 J/(K mol). Neither the ∆SMTBE
nor the ∆SMeOH values for the resin Bayer K2631 were
found in the literature. Nevertheless, a comparison of
this value with the absolute entropies of MeOH and
MTBE, 127.19 J/(K mol)16 and 265.3 J/(K mol),17 re-
spectively, at 25 °C and 1 atm, indicates that it is a
plausible value. In addition, the negative value of this
difference means that, as the adsorption entropy must
be negative, the adsorption process demands a higher
loss of entropy for MTBE than for MeOH.
Equations 5 and 6, respectively, originate from the
following surface reaction steps, which are considered
as the rate-limiting step:
2IBσ + MeOH2σ h MTBE2σ + 2σ (8)
2IBσ2 + 2MeOHσ h MTBE2σ + 5σ (9)
A common feature of both mechanisms is that two
MTBE molecules adsorb on the same active center,
which could be considered as a cluster of acidic groups
rather than an individual one.12 The main difference
between the two are the IB and MeOH adsorption types.
The adsorption of two molecules on one acidic center
would be more likely for a more polar molecule. Because
MTBE presents this adsorption type in both proposed
mechanisms and because its polarity is between that
of MeOH and IB (dipolar moments: MeOH, 1.7 D;
MTBE, 1.2 D; IB, 0.5 D),18 the mechanism described by
eq 8 seems to be more feasible.
Finally, it can be seen that the number of active
centers involved is three for eq 8 and six for eq 9. From
a probabilistic point of view, the requirements of eq 9
are considerably more difficult to fulfill than those of
Figure 4. Reaction rates at 75 °C calculated by means of eq 5 as
o
a function of RIB/MeOH and MTBE molar fraction.
eq 8, because twice as many active centers participating
in the surface reaction step are involved and they have
to be occupied by the corresponding molecules.
Selected Rate Equation. As a consequence of the
mathematical and physicochemical criteria, eq 5 has
been selected as the rate equation, with the mechanism
described by eq 8. The following parameters, with their
respective standard errors, have been obtained from the
fit of eq 5 to the experimental data:
( ) [
mol
k′ ) (0.2566 ( 0.0055) exp (-10141 ( 131)
gh
1
T (K)
- ( 1
340.65 )]
K′ ) 0.778 ( 0.063
1/2
δP (MPa ) ) (-0.0668 ( 0.0126)[T (K) - 340.65] +
(20.95 ( 0.29)
Figure 4 shows a plot of the reaction rates estimated
at 75 °C on the basis of this kinetic equation versus
o
RIB/MeOH and the MTBE molar fraction. Analogous
plots have been obtained at all temperatures. As can
be seen, the calculated reaction rates agree with the
experimental results from the differential regime ex-
periments, as one can distinguish two different regions
o
that are approximately delimited by the value RIB/MeOH
) 1.5. For the lower values, the reaction rate decreases
as the reaction progresses, and for the larger values,
an increase in the reaction rate is observed.
Simulation of the Integral Experiments. Finally,
the validity of eq 5 has been examined by means of
experiments performed in a batch reactor operating in
integral mode. As the actual kinetic equation must be
independent of the experimental setup used, it should
be able to describe accurately the results obtained in
the batch reactor. The main purpose has been to
validate the results observed operating at an initial
RIB/MeOH ratio larger than 1.5, as, under those condi-
tions, unusual behavior had been observed in the
differential regime experiments. Both experimental and
o
simulated results for 75 °C and RIB/MeOH ) 1.5 are
presented in Figure 5, which shows good agreement:
during the initial stage, the slope of the curve, which is
directly related to the reaction rate, slightly increases;
afterward, it suddenly decreases and tends to zero as
equilibrium is approached.

Figure 5. Experimental and calculated (through eq 5) isobutene
conversion vs reaction time obtained in a batch reactor operating
in the integral regime.
Conclusions
The effect of ether on the reaction rate of MTBE
synthesis in liquid phase and in the absence of inert
components measured in a tubular reactor operated in
the differential regime has been studied. From the
experimental results, two different trends are clearly
distinguished as a function of the isobutene content. For
an initial molar IB/MeOH ratio at zero conversion lower
than about 1.5, the reaction rate decreases as the
reaction progresses. For higher values, the reaction rate
increases until conversion is close to equilibrium, and
then, it rapidly decreases. This unusual behavior has
been explained by the influence of the composition of
the reaction medium on the catalyst activity, whose
increase overcomes the expected decrease in the driving
force as the system approaches chemical equilibrium.
Several kinetic equations based on LHHW and ER
formalisms, including a factor that quantifies the reac-
tion medium influence, have been fitted to the experi-
mental data. The best, on the basis of both mathemati-
cal and physicochemical criteria, has been found to stem
from a mechanism in which two isobutene molecules,
each adsorbed on an active center, react with two MeOH
molecules adsorbed on one center to yield two MTBE
molecules adsorbed on one unique center, the surface
reaction being the limiting step.
A different experimental setup, a stirred tank reactor
system operating in the integral regime, was used to
validate the kinetic equation. The simulation of the
evolution of the composition fully agrees with the
experimental results, and therefore, the kinetic equation
has been shown to predict accurately the reaction rate
under the assayed conditions.
Notation
a ) compound activity, dimensionless
A ) parameter of eq 3, J mol-1
c ) molar concentration, mol L-1
Eap ) apparent activation energy, kJ mol-1
∆H ) adsorption enthalpy, J mol-1
k′ ) rate coefficient, mol (g h)-1
K ) equilibrium constant, dimensionless
K′ ) ratio of adsorption constants, dimensionless
LHSV ) liquid hourly space velocity, h-1
r ) intensive reaction rate, mol (g h)-1
R ) gas constant, J (K mol)-1
RIB/MeOH ) IB/MeOH molar ratio of the reaction medium,
dimensionless
Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1353
∆S ) adsorption entropy, J (mol K)-1
t ) reaction time, min
T ) temperature, K
h ) mean experimental temperature, K
T
x ) molar fraction, dimensionless
X ) conversion, dimensionless
Greek Symbols
δ ) solubility parameter, MPa1/2
σ ) active center
Ψ ) parameter of the kinetic equation defined by eq 1,
dimensionless
Subscripts
exp ) experimental
calc ) calculated
M ) reaction medium
P ) resin
0 ) temperature independent
Superscripts
° ) referred to the reaction mixture at zero conversion from
which the present one would arise
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Received for review March 7, 2000
Revised manuscript received December 7, 2000
Accepted December 10, 2000
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