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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.
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 in the driving-force term due to the approach to the
from mechanistic based equations,8-10 the partial reac- chemical equilibrium is compensated for, and even
tion order of MeOH in absence of MTBE is equal to 0 overcome by, the increase in the activity of the acidic
and negative for increasing MTBE contents. sites. In practice, this means that the reaction rate
(iii) MTBE Concentration. The general feature is the continuously increases along the reaction course and,
decrease of the reaction rate with increasing MTBE in addition, that it suddenly decreases when the system
concentration, which indicates an inhibiting effect of the is close to equilibrium.
product on the kinetics. Mechanistic Considerations and Kinetic Equa-
A global overview can be achieved by plotting the tion. Analogously to a previous work,5 a large number
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 have been derived by considering different adsorption
mixture, defined as the molar ratio of the reaction types for each isobutene, methanol, and MTBE: no
mixture free of MTBE that would derive from the actual adsorption, one molecule per active center, two mol-
one according to the reaction stoichiometry (Figure 2). ecules per active center, and one molecule on two active
Two zones can be clearly distinguished. For RIB/MeOH o centers. Also, the fact that the adsorption extent of the
lower than approximately 1.5, the reaction rate de- less polar species could be negligible toward methanol
creases with increasing MTBE content, which is usually adsorption has been taken into account. Because MTBE
the expected trend because of the increasing importance was fed to the reactor, the effect of the reverse reaction
of the reverse reaction as the reaction goes forward. For on the reaction rate has been considered in the kinetic
o
RIB/MeOH larger than 1.5, the reaction rate increases equation. Given the nonideallity of the reaction medium,
with the MTBE content. This latter behavior is unex- the kinetic equation must be expressed in terms of
pected, as, under these conditions, the reaction seems activities, which have been estimated through the
to behave autocatalytically. However, this fact can be UNIFAC method. In comparison with the previous
explained by the particular characteristics of the cata- work, the presence of ether in the reactor feed makes
lyst: depending on the composition of the reaction possible a higher variation of IB and MeOH activities,
medium, the backbone of the resin, which consists of a and the MTBE activity is also included in the kinetic
cross-linked polymer with an incompletely rigid struc- equation. As a result, a better discrimination between
ture, acquires a particular conformation. Moreover, its plausible rate equations can be achieved.
active centers present a variable acidity and, therefore, The tested kinetic equations include the factor Ψ with
a changeable activity. Thus, at low methanol contents, a physicochemical meaning that has been found to
o improve the prediction of the experimental reaction
that is, at high RIB/MeOH , and at increasing reaction
rates.5 This factor was defined as
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 h M Φ2P
V
Ψ ) exp (δM - δP)2 (1)
such a way that they form a catalytic cluster with a RT
higher acidity. This fact results in a reaction rate higher
than expected if the resin structure had not changed. and it quantifies the affinity between the catalyst and
Consequently, in the course of the reaction, the decrease the reaction medium. The consideration of such a factor
Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1351
[ ( )]
-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
KMTBE
K′ ) )
KMeOH
( ) ( )
∆SMTBE - ∆SMeOH - ∆HMTBE + ∆HMeOH Figure 4. Reaction rates at 75 °C calculated by means of eq 5 as
o
exp exp a function of RIB/MeOH and MTBE molar fraction.
R RT
(7) eq 8, because twice as many active centers participating
in the surface reaction step are involved and they have
As a consequence, from the experimental data, it to be occupied by the corresponding molecules.
would only be possible to obtain values for the difference Selected Rate Equation. As a consequence of the
of the MeOH and MTBE adsorption enthalpies and mathematical and physicochemical criteria, eq 5 has
entropies. In our case, because of the lack of statistical been selected as the rate equation, with the mechanism
significance of the K′ temperature dependence, it can described by eq 8. The following parameters, with their
be concluded that the ∆HMeOH and ∆HMTBE values are respective standard errors, have been obtained from the
very similar. Therefore, ∆HMTBE on the Bayer K2631 fit of eq 5 to the experimental data:
resin should be equal to -3.8 kJ/mol within the limits
( ) [
of the experimental error, as was determined in a
mol
previous work for MeOH adsorption on the same k′ ) (0.2566 ( 0.0055) exp (-10141 ( 131)
catalyst.15 gh
On the other hand, the obtained values of (∆SMTBE -
∆SMeOH) for both eqs 5 and 6 are, respectively, -2.09 (
1
T (K)
- ( 1
340.65 )]
0.67 and -4.78 ( 0.64 J/(K mol). Neither the ∆SMTBE K′ ) 0.778 ( 0.063
nor the ∆SMeOH values for the resin Bayer K2631 were
1/2
found in the literature. Nevertheless, a comparison of δP (MPa ) ) (-0.0668 ( 0.0126)[T (K) - 340.65] +
this value with the absolute entropies of MeOH and (20.95 ( 0.29)
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 Figure 4 shows a plot of the reaction rates estimated
difference means that, as the adsorption entropy must at 75 °C on the basis of this kinetic equation versus
o
be negative, the adsorption process demands a higher RIB/MeOH and the MTBE molar fraction. Analogous
loss of entropy for MTBE than for MeOH. plots have been obtained at all temperatures. As can
Equations 5 and 6, respectively, originate from the be seen, the calculated reaction rates agree with the
following surface reaction steps, which are considered experimental results from the differential regime ex-
as the rate-limiting step: periments, as one can distinguish two different regions
o
that are approximately delimited by the value RIB/MeOH
2IBσ + MeOH2σ h MTBE2σ + 2σ (8) ) 1.5. For the lower values, the reaction rate decreases
as the reaction progresses, and for the larger values,
2IBσ2 + 2MeOHσ h MTBE2σ + 5σ (9) an increase in the reaction rate is observed.
Simulation of the Integral Experiments. Finally,
A common feature of both mechanisms is that two the validity of eq 5 has been examined by means of
MTBE molecules adsorb on the same active center, experiments performed in a batch reactor operating in
which could be considered as a cluster of acidic groups integral mode. As the actual kinetic equation must be
rather than an individual one.12 The main difference independent of the experimental setup used, it should
between the two are the IB and MeOH adsorption types. be able to describe accurately the results obtained in
The adsorption of two molecules on one acidic center the batch reactor. The main purpose has been to
would be more likely for a more polar molecule. Because validate the results observed operating at an initial
MTBE presents this adsorption type in both proposed RIB/MeOH ratio larger than 1.5, as, under those condi-
mechanisms and because its polarity is between that tions, unusual behavior had been observed in the
of MeOH and IB (dipolar moments: MeOH, 1.7 D; differential regime experiments. Both experimental and
o
MTBE, 1.2 D; IB, 0.5 D),18 the mechanism described by simulated results for 75 °C and RIB/MeOH ) 1.5 are
eq 8 seems to be more feasible. presented in Figure 5, which shows good agreement:
Finally, it can be seen that the number of active during the initial stage, the slope of the curve, which is
centers involved is three for eq 8 and six for eq 9. From directly related to the reaction rate, slightly increases;
a probabilistic point of view, the requirements of eq 9 afterward, it suddenly decreases and tends to zero as
are considerably more difficult to fulfill than those of equilibrium is approached.
Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1353
(15) Solà, L.; Pericàs, M. A.; Cunill, F.; Iborra, M. Reaction (18) Reid, R. C.; Prausnitz, J. M.; Poling, B. E. The Properties
Calorimetry Study of the Liquid-Phase Synthesis of tert-Butyl of Gases & Liquids; McGraw-Hill: New York, 1987.
Methyl Ether. Ind. Eng. Chem. Res. 1994, 33, 2578.
(16) Carlson, H. G.; Westrum, E. F., Jr. Methanol: Heat Received for review March 7, 2000
Capacity, Enthalpies of Transition and Melting, and Thermody-
Revised manuscript received December 7, 2000
namic properties from 5 to 300 K. J. Chem. Phys. 1971, 54, 1464.
(17) Andon, R. J. L.; Martin, J. F. Thermodynamic Properties Accepted December 10, 2000
of Organic Oxygen Compounds. 40. Heat Capacity and Entropy
of Six Ethers. J. Chem. Thermodynam. 1975, 7, 593. IE000300P