Ind. Eng. Chem. Res.

1998, 37, 3575-3581 3575

Catalytic Activity and Deactivation of Acidic Ion-Exchange Resins

in Methyl tert-Butyl Ether Liquid-Phase Synthesis
D. Parra,† J. F. Izquierdo,*,† F. Cunill,† J. Tejero,† C. Fité,† M. Iborra,† and M. Vila‡
Chemical Engineering Department, Faculty of Chemistry, University of Barcelona, C/Martı́ i Franqués 1,
08028 Barcelona, Spain, and Escombreras Research Center, Repsol Petróleo S.A., 30350 Valle de Escombreras,
Cartagena (Murcia), Spain

This paper presents a comparative study of catalytic activity of 12 different styrene-

divinylbenzene ion-exchange resins as catalysts for MTBE (methyl tert-butyl ether) liquid-phase
synthesis. Experiments were carried out at 1.6 MPa and 323 K using a stationary fixed-bed
fed with methanol and C4 olefinic cut as the source of isobutylene. The isobutylene/methanol
molar ratio studied was 0.91 and the LHSV employed in the continuous operation was 85 h-1.
Experimental data show that ion exchangers with higher acidic capacity were the most active
ones. It seems that this parameter plays the greatest influence on the catalytic activity for
MTBE synthesis whereas other properties such as surface area and average pore diameter hardly
influence it.

Introduction There are several published approaches to explain the

It is hard to explain the kinetic mechanism of the
etherification reaction of isobutylene with methanol in
liquid phase. At low concentrations of methanol, the
catalysis is by the polymer-bound -SO3H groups, which
are very active, but if the concentration of methanol is
increased, the alcohol dissociates the acid groups and
solvated protons become now the catalytic agents, which
are catalytically less active (Gates and Rodriguez, 1973;
Chakrabarti and Sharma, 1993). A proof of the dif-
ficulty to explain methyl tert-butyl ether (MTBE) mech-
anism synthesis is found in the literature itself because
researchers have used both pseudohomogeneous and
heterogeneous kinetic models to describe the kinetics
of this reaction (Voloch et al., 1986; Subramanian and
Bathia, 1987; Colombo and Dalloro, 1983; Rehfinger and
Hoffman, 1990; Gicquel and Tork, 1983; Parra et al.,
1994; Tejero et al., 1996; Panneman and Beenackers,
1995a). Information in the available literature about
the influence of catalyst morphology, acid concentration,
and solvent effect on catalytic activity of an ion ex-
changer in MTBE synthesis is rather scarce (Colombo
and Dalloro, 1983; Jerábek et al., 1993; Rehfinger and
Hoffmann, 1990; Panneman and Beenackers, 1995b).
In general, the reaction rate of an ion-exchanger
catalyzed reaction in a nonaqueous medium depends
both on changes of the polymer structure and on
changes in the concentration of accessible acid groups
(Rodriguez and Setinek, 1975; Jerábek and Setinek,
1987). In nonaqueous medium, the polymer matrix
structure influences directly the reaction course since
the possibility of forming undissociated sulfonic groups
depends necessarily on the conformation of polymer
chains. Depending on the polarity of the medium and
on the size of the reactant and product molecules, steric
restrictions may also influence the catalytic activity
(Jerábek and Setinek, 1987) because some of the inner
active centers could not participate in the reaction.
* To whom correspondence should be addressed. Fax: +34-
3-4021291. E-mail: felipe@angel.qui.ub.es.
† University of Barcelona.
‡ Escombreras Research Center, Repsol Petróleo S.A.
S0888-5885(98)00007-4 CCC: $15.00 © 1998 American Chemical Society
Published on Web 08/14/1998
behavior of an ion exchanger as a catalyst. From a
morphological point of view, it is to be noted that in the
model proposed by Guyot (1988), who claims that
macroporous resins are composed of three families of
pores, the structure contains large agglomerates of
microspheres (100-200 nm), which look like cauliflow-
ers, and each microsphere shows smaller nuclei (10-
30 nm) more or less fused together. In betweeen the
nuclei, there is a family of very small pores (5-15 nm),
which are mainly responsible for the high surface area
(> 500 m2/g) of these materials. Between the micro-
spheres, a second family of intermediate pores is
observed (20-50 nm), which may account for moderate
surface areas (up to 100 m2/g). A third family of large
pores (50-100 nm) is located between the agglomerates;
this kind of pores yields very low surface area but large
pore volume up to 3 mL/g. Resins are able to swell to
varying degrees in different solvent media. So, the
catalytic behavior of a resin may be analyzed in terms
of accessibility of its functional groups in different media
taking into account their situation inside the resin.
Other theories emphasize the dependence of the
catalytic activity on the acidity and on the accessibility
(Widdecke 1988; Buttersack, 1988). The acidity de-
pends on the type and number of acid groups within
the resin and is affected by the degree of cross-linking.
The accessibility is related to the permeability of the
resin and it can be influenced by the interaction of the
solvent and adsorbed molecules with the functionalized
polymer.
So, it can be drawn from the general theories that
the catalytic activity of the resins depends mainly on
its initial morphology and on its interaction with the
reacting medium including the solvent and the com-
pounds that can be found in the reacting system.
The properties of the MTBE reacting system change
with the reaction progress. In this context, contradic-
tory papers can be found, probably due to the different
initial mixtures and kinds of resins used to study this
reaction. Rehfinger and Hoffman (1990) and Jerábek
et al. (1993) found no influence of the degree of cross-
linking, the internal surface area, and the exchange
3576 Ind. Eng. Chem. Res., Vol. 37, No. 9, 1998

Table 1. Physical Properties of Different Ion Exchangers, Methanol Conversions, and Reaction Rates Obtained at 323
K
trade name C (mequiv/g) A (m2/g) A′ (m2/g) V (mL/g) D (Å) dp (mm) XM (%) r (mol/h‚mequiv)
Bayer K2631 4.83 41.5 ---- 0.67 650 0.63 6.9 0.0143
Bayer OC-1501 5.47 25.0 163.8 0.52 832 0.66 11.0 0.020
Amberlyst 15 4.75 42.0 156.9 0.36 343 0.74 7.2 0.0151
Amberlyst 35 5.32 34.0 165.7 0.28 329 0.51 10.4 0.0195
Dowex M32 4.78 29.0 0.33 455 0.63 6.8 0.0143
Purolite CT151 5.40 25.0 151.2 0.30 252 0.43 8.1 0.0150
Purolite CT165 5.00 6.2 0.16 1148 0.43 4.1 0.0081
Purolite CT169 4.90 48.1 0.38 342 0.43 7.7 0.0158
Purolite CT171 4.94 31.0 0.47 597 0.40 7.8 0.0158
Purolite CT175 4.98 29.0 0.48 662 0.40 8.2 0.0164
Purolite CT175/2824 5.30 24.1 157.4 0.44 745 0.43 10.4 0.0196
Purolite CT179 5.25 35.0 220.1 0.33 386 0.43 9.6 0.0182

capacity of the resin on the rate of MTBE synthesis, but
Panneman and Beenackers (1995b) showed that the
catalytic activity of an ion-exchange resin on the same
reaction depends on its three-dimensional structure,
which is influenced by the level of cross-linking, the
porosity, the internal surface area, the sulfonic acid
content, and its distribution within the particles.
On the other hand, another important factor in
commercial operation that influences the catalytic activ-
ity is the deactivation of the catalyst. The acid sites of
the cation-exchange resin catalyst may easily be poi-
soned by different ions that can be present in the feeds
due to corrosion in pipelines or can be carried to the
reactor through misoperations in preceding units.
Brockwell et al. (1991) make a distinction between
two different modes of catalyst deactivation. The first
mode is plug flow neutralization and the second is
diffused flow neutralization. With plug flow neutraliza-
tion, the poison accumulates on the catalyst in a plug-
flow manner as it impinges on the catalyst bed. The
uptake of deactivator is rapid and stoichiometric. As
deactivation progresses, plug flow neutralization results
in a foreshortening of the active catalyst bed length.
Examples of plug-flow deactivators are all salts and
other Lewis and Brönsted bases. Diffused flow neu-
tralization is a mode of deactivation in which catalytic
sites are neutralized uniformly throughout the bed
rather than in progression from the point of impinge-
ment. Diffusional deactivators are generally very weak
bases that either weakly bind the catalytic sites or are
species that generate more strongly binding species in
situ. Examples of diffusional deactivators are propi-
onitrile, dimethylformamide, dimethyl sulfide, hydrogen
sulfide, and amine formers such as acetonitrile, which
is responsible for most of the catalyst deactivation
experienced in MTBE reactors due to formation of
ammonium ion (Marston, 1994).
It has not been possible to find experimental studies
about the catalytic behavior of an ion exchanger partly
deactivated by ammonium or Fe(III) in MTBE synthe-
sis. Krause and Hammarström (1987) propose that the
loss of the activity of the resin partly deactivated by
sodium or ammonium ions is the same for tert-amyl
methyl ether (TAME) synthesis in liquid phase, and
Kmosták and Setinek (1981) found that sodium ions
deactivate the catalyst more than Fe(III) ions for
isomerization of cyclohexene and dehydration of 1-pro-
panol in the gas phase.
So, the first aim of this work is to contribute further
to the elucidation of the effect of different morphologic
properties of an ion exchanger (surface area, average
pore diameter, and acidic capacity) on its catalytic
activity in MTBE synthesis. For this purpose, a number
of resins that differed markedly in their properties were
compared at the same experimental conditions.
The second goal of this paper is to know the deacti-
vating effect of ammonium and Fe(III) on the etherifi-
cation reaction. To test catalytic activity of partially
sulfonated ion exchangers, reaction rates were compared
at the same experimental conditions.
Experimental Section
(i) Continuous Operation. Twelve commercial
macroporous styrene-divinylbenzene ion exchangers
were used as catalysts in MTBE synthesis. Their
morphological properties are summarized in Table 1.
Prior to use, all ion exchangers were washed with
distilled water and dried at 110 °C for more than 14 h
at atmospheric pressure. Afterward they were stored
in a desiccator over sulfuric acid (98%). The water
content in all resins, measured by Karl Fischer titration,
was less than 3%. Before the experiment, the catalyst
bed was preheated in the reactor at operating temper-
ature in the presence of the methanol stream to ensure
that an amount of methanol greater than 10 times the
reactor volume was passed through it. As a result, the
residual water content in the resin was reduced to less
than 1.6%. tert-Butyl alcohol produced from this amount
of water was not detected in the experiments. Other
byproducts (dimethyl ether and diisobutylene) were not
found in the runs.
In all experiments, carried out in the steady state,
commercial particle sizes of different resins have been
used to study their behavior in operating conditions of
industrial reactors. Fresh dry catalyst sample (0.874
g) was always placed in a continuous packed-bed mi-
croreactor (15 cm length; 4.4 mm i.d.) and the small
remaining reactor volume was filled with quartz of 0.63
< dp < 0.8 mm to avoid bed expansion.
The experiments in the continuous regime were
carried out in a setup made of stainless steel at 1.6 MPa
and 323 K by feeding an appropriate methanol-C4
olefinic cut mixture. This pressure was enough to
maintain the reacting system in liquid phase and this
temperature was chosen to avoid temperature axial
gradients. The methanol molar flow rate was always
0.874 mol/h, the molar ratio of isobutylene/methanol
employed was 0.91, and the liquid hourly space velocity
(LHSV) used was 85 h-1. C4 cut from a steam cracking
(SC) plant containing 45-55% isobutylene was supplied
by Repsol Petróleo S.A. Methanol for high-performance
liquid chromatography (HPLC) (<0.01% water, 99%
pure) was supplied by Romil Chemicals Ltd.
Two sampling valves injected 0.2 µL into an HP 5890
gas-liquid chromatography (GLC) apparatus equipped

with flame ionization detector (FID). One valve took
samples from the reactor inlet and the other one from
the reactor outlet. A 50 m × 0.2 mm × 0.5 µm methyl
silicone capillary column was used to separate MTBE,
methanol, and C4 cut compounds (isobutylene and
1-butene could not be separated; as a consequence, only
methanol and MTBE were used as the reference com-
pounds to measure the reaction progress). More de-
tailed information about setup, procedure, and sample
analysis can be found elsewhere (Parra et al., 1994).
Catalyst activity was measured as methanol conver-
sion and also as a reaction rate at steady-state condi-
tions to know the efficiency of the resins from an
industrial point of view. To reduce the effect of reacting
medium and the development of temperature gradients,
the methanol conversion was lower than 11%. Reaction
rates were also calculated to look into, from a scientific
point of view, the influence of different properties of the
resins. In each run the flow rates were maintained (3-4
h) until chromatographic analysis was the same within
the limits of the experimental error to ensure that
steady state was reached. Some experiments were
repeated to determine the experimental error.
(ii) Batch Operation. The experiments in batch
mode were carried out in a stainless steel jacketed 250
mL autoclave. A calculated amount of methanol and
about 2.9 g of dry resin (water content less than 3%)
were first charged into the reactor and, after checking
for leakages, heated to the desired temperature (always
333 K) and then an amount of C4 liquid, given by the
desired isobutylene/methanol ratio, was introduced
directly from a cylinder. At this time, the magnetic-
drive turbine was switched on at 500 rpm and the
reactor pressure was set at 1.6 MPa throughout the
experiment in order to maintain the liquid phase. The
time of introduction of the olefinic fraction into the
reactor was considered as the starting point for the
reaction. Further information on this apparatus is
described elsewhere (Izquierdo et al., 1992).
The reactor was connected directly to the sampling
valve (Valco 4-CL4WE) which injects a small pressur-
ized liquid volume (0.2 µL) to the gas chromatograph
(HP5890A). The same capillary column described above
was used for sample analysis. No byproducts (tert-butyl
alcohol, dimethyl ether, and diisobutylene) were de-
tected in the experiments.
Catalytic activity was measured as initial reaction
rate calculated from the slope of methanol conversion
versus time data. Some experiments were repeated to
evaluate the experimental error on reaction rate.
(iii) Partial Neutralization of Ion Exchangers.
Four resins were chosen to be partially neutralized by
Fe(III) and ammonium ions. Two standards of iron and
one of ammonium were used. A known amount (always
60 g) of a given dried ion exchanger was placed into a
beaker and 400 mL of solution, either FeCl3‚6H2O or
ammonium hydroxide, was added. After standing for
24 h with stirring, the catalyst was washed with water
in a column until there was negative reaction on the
corresponding anion. After this, the resin was redried
in a oven at 105 °C for 14 h. The concentrations of
exchangeable acid sites left were measured by the same
method as for the fresh resin (Bayer, 1990).
Results and Discussion
(i) Fresh Catalysts. Preliminary experiments were
made at 323 K to ensure that rate data were generated
Ind. Eng. Chem. Res., Vol. 37, No. 9, 1998 3577
free of external mass transport processes. Runs carried
out by maintaining feed composition and catalyst mass,
but using different molar flow rates, demonstrated that
for LHSV > 60 h-1 reaction rate does not depend on
flow rate. As a result, a LHSV ) 85 h-1 was used.
Fourteen different replicated experiments were made
to calculate the experimental error of methanol conver-
sion ((0.2% with a probability level of 95%).
Table 1 shows the morphological properties of ion
exchangers used along with the results of methanol
conversion and reaction rates obtained after the experi-
ments carried out in steady-state mode. The reaction
rates were calculated by taking into account that for
the methanol conversion values obtained, the reactor
was differential (Parra et al., 1994). So, the reaction
rates were determined by
XMF
r) (1)
100CW
At first sight, the following differences about the
properties of the resins must be pointed out: Purolite
CT165 has a particular morphology, its Brunauer-
Emmett-Teller (BET) surface area (A) and pore volume
are the smallest in the group but its average pore
diameter is the highest one. It seems to be a mi-
croporous resin. Despite the fact that Purolite CT151
has a high acidic capacity, it has a surprisingly small
average pore diameter in comparison with the other
resins studied. Bayer OC-1501, Amberlyst 35, and
Purolite CT175/2824 have the highest acidic capacity
of ion exchangers selected. Finally, Purolite CT 169 has
the largest value of surface area (A), but its other
properties are similar to the other resins.
As can be seen in Table 1, the catalytic behavior of
the resins differs greatly. Methanol conversions vary
from 4.1% (Purolite CT165) to 11.0% (Bayer OC-1501).
Equal conversion values for Amberlyst 35 and Purolite
CT175/2824 are found, close to that for Bayer OC-1501.
Traditional catalysts in MTBE synthesis such as
Bayer K2631 or Amberlyst 15 show lesser catalytic
activities than the new generation of commercial resins
from the same manufacturers, Bayer OC-1501 and
Amberlyst 35. This fact could be explained because of
the increase of density of sulfonic groups produced after
a special sulfonation procedure which added a second
sulfonic group to the aromatic rings already sulfonated
rather than sulfonate the unsulfonated aromatic rings.
So, this sulfonation procedure makes it possible to
achieve a higher number of acidic groups per unit of
mass of these new resins.
To assess the quantitative influence of morphological
properties in dried state of the different resins on
methanol conversion, different polynomials were fitted
to the data. From a statistical point of view, the best
significant polynomial fitted to the data was
XM ) (2.924 × 10-3)C3A - (1.751 × 10-4)C2A2 +
(1.598 × 10-5)C3D (2)
This fourth-order polynomial only contains three vari-
ables, namely, acid capacity (C), BET surface area (A),
and average pore diameter (D). We have not considered
in this mathematic analysis pore volume (V), because
it depends on the surface area and average pore
diameter, or approximate average particle diameter (dp),
3578 Ind. Eng. Chem. Res., Vol. 37, No. 9, 1998
Figure 1. Reaction rates of MTBE synthesis at 323 K versus
average pore diameter.
Figure 2. Reaction rates of MTBE synthesis at 323 K versus BET
surface area.
because the values obtained from manufacturers are not
accurate enough.
It can be seen from this polynomial that the positive
influence of acidic capacity on methanol conversion is
stronger than that of the other two variables. It seems
that the accessibility of methanol and isobutylene to the
greater part of the acidic active centers is quite good
for the majority of the resins chosen.
Several authors assure that kinetics of MTBE syn-
thesis catalyzed by strong acidic ion exchangers pro-
ceeds with the participation of ensembles of sulfonic
groups (Parra et al., 1994; Tejero et al., 1996; Jerábek
et al., 1993). Most of these ensembles are placed within
the polymeric matrix and their accessibility to reactants
may be sometimes limited.
On the whole, the strong influence of acidic capacity
on catalytic activity of the resins studied for MTBE
synthesis can be explained by supposing that the
polymeric mass of ion exchanger, which suffers a
moderate swelling due to the presence of significant
quantities of methanol, allows reactants to permeate
with relative freedom and to react faster as the density
of active centers increases. Because of that, the weak
influence of average pore diameter and BET surface
area on catalytic activity, whose values have been
obtained from dry state, could be explained by supposing
that the initial structure of dry ion exchanger would
have changed due to the reaction microenvironment,
and so pore sizes and surface area would have changed
after the moderate swelling. Figures 1 and 2 demon-
strate this affirmation because there are not significant
and defined relationships either between reaction rate
and surface area or between reaction rate and average
pore volume for the resins studied. The results of
Figure 3. Reaction rates of MTBE synthesis at 323 K as a
function of acidic capacity.
surface area for the swollen state of some of the resins
studied (Jerábek, 1997) by inverse steric exclusion
chromatography (ISEC) corroborate this affirmation (see
Table 1). As can be seen, there is not a relationship
between the BET surface area, determined in dry state,
and the surface area in the swollen state.
After this, we studied in detail the influence of acidic
capacity on reaction rate for all resins and we found out
some behavior deviations. Figure 3 shows the reaction
rate against the acidic capacities of the resins studied.
As a general rule, it can be seen that the higher the
acidic capacity, the higher the reaction rate, but there
are two resins that do not fulfill this trend, namely,
Purolite CT 151 and especially Purolite CT 165. Despite
the fact that Purolite CT 151 has a high acidic capacity,
it has the smallest average pore diameter in the dry
state. It seems that this resin could not suffer a
significant swelling in contact with the MTBE reaction
mixture, and so the accessibility of reactants to the
ensembles of sulfonic groups placed inside the polymer
mass is not satisfactory. Purolite CT 165 has a high
acidic capacity and the smallest BET surface area,
though its average pore diameter in the dry state is the
largest one. It seems that this resin, which is mi-
croporous (Jerábek, 1997), could have a small density
of accessible sulfonic groups and so concerted mecha-
nisms are difficult to form.
(ii) Deactivated Catalysts. Four representative
resins (Bayer K 2631, Bayer OC-1501, Amberlyst 35,
and Purolite CT 175) were chosen to be partially
neutralized by Fe(III) and ammonium ions in batch
operation. These cations were selected because they can
frequently be found in industrial reactors for MTBE
synthesis, so it is expedient to measure the loss of
activity of these resins due to partial neutralization by
both cations. Two neutralization standards for Fe(III)
and only one for ammonium were used. To measure
the deactivation produced, initial reaction rates of
MTBE formation were determined from the slope of the
curve at zero time of experimental values of methanol
conversion versus time. Figure 4 shows the plots of
methanol conversion against time for fresh and partly
deactivated resin K2631. It can be seen that the initial
slope of the curve for fresh resin is higher than those
for resins neutralized by, respectively, low standard of
Fe(III), high standard of Fe(III), and ammonium. Some
experiments were repeated to evaluate the experimental
error on initial reaction rate, which was (0.0011 mol
h-1 mequiv-1.
The concentrations of pollutants in the contaminated
resins, the remaining acidic capacity after deactivation,
 Ind. Eng. Chem. Res., Vol. 37, No. 9, 1998 3579

Figure 4. Methanol conversion values versus time at 333 K for

fresh and deactivated K2631.
Figure 5. Initial reaction rates of MTBE synthesis at 333 K
Table 2. Remainig Acidic Capacities and Initial versus acidic capacities of the resins before and after being polluted
Reaction Rates at 333 K for the Four Resins Used in by iron and ammonium.
MTBE Synthesis as a Function of Fe(III) and Ammonium
Contents Table 3. Loss of Activity for Different Resins Partially
Neutralized by Iron and the Corresponding Values of
acidic
capacity r0 (mol/ Effective Exchange Capacity for Fe(III)
resin pollutant cFe(III) cam (mequiv/g) h‚mequiv) resin ppm Fe(III) L (mequiv/g) nFe(III)
Bayer K-2631 none 4.83 0.037
Bayer K-2631 3613 0.11 1.70
low Fe(III) 3613 4.72 0.036
15904 0.67 2.35
high Fe(III) 15904 4.16 0.033
Bayer OC-1501 3152 0.14 2.48
ammonium 8433 4.38 0.026 14368 0.55 2.13
Bayer OC-1501 none 5.47 0.041 Purolite CT 175 2915 0.13 2.48
low Fe(III) 3152 5.33 0.041 13630 0.57 2.34
high Fe(III) 14368 4.92 0.040 Amberlyst 35 3386 0.14 2.31
ammonium 9653 4.59 0.027 13890 0.36 1.45
Purolite CT175 none 4.98 0.037
low Fe(III) 2915 4.85 0.036 significantly greater than that of Fe(III). An explana-
high Fe(III) 13630 4.41 0.034
tion for this fact is that the presence of ammonium in
ammonium 9696 4.57 0.025 the catalyst besides neutralization could lead to the
Amberlyst 35 none 5.32 0.042
low Fe(III) 3386 5.18 0.041 formation of hydrogen bonds with some sulfonic groups.
high Fe(III) 13890 4.96 0.035 Clearly Fe(III) is incapable of doing so. Furthermore,
ammonium 9822 4.90 0.031 it is known that the ionic radius of Fe(III) is 0.064 nm
and the ionic radius of ammonium is 0.143 nm. So it is
and the initial reaction rate values can be seen in Table likely that a part of the so-called active sites, situated
2. From these data it can be pointed up that fresh inside the polymer mass, were difficult to reach for the
Bayer OC-1501 and Amberlyst 35 are more active reactants due to steric hindrance produced by am-
(higher initial reaction rate) than Purolite CT175 and monium ion placed at external layers of the polymeric
Bayer K2631. This fact was already found above in mass.
continuous operation. While the deactivation by low Figure 5 shows that there exists a linear relationship
concentrations of Fe(III) did not affect significantly the between the initial rates and the acidic capacities of the
reaction rate, high concentration values of Fe(III) led fresh resins, but it can be also seen that the catalytic
to a different decrease in both exchange capacity and activity of the resins polluted by iron follows the same
initial reaction rate. For this high iron contamination, trend as the fresh resins. Table 3 shows the effective
the resin Bayer OC-1501 was the strongest one; its loss exchange capacity values for Fe(III) obtained after
of activity was only 2%, whereas Amberlyst 35 suffered analyzing the relationship between the loss (L) of acidic
a loss of 17%. The loss of acidic capacity varied from capacity (difference between the acidic capacity of fresh
7% to 14%. resin and the remaining acidic capacity determined
Surprisingly, the behavior of the resins was different after the neutralization by iron) of the resins and their
when they were deactivated by ammonium ion. In Fe(III) content. To calculate the effective exchange
general, the loss of activity was more pronounced, capacity of Fe(III), the following expression has been
especially for Bayer OC-1501. The decrease on initial used:
reaction rates (catalytic activities) for the four resins
was now from 26% to 34%, whereas the loss of exchange (1000)(55.85)L
capacity ranged from 8% to 16%. It must be considered nFe(III) ) (3)
that the standard of ammonium employed in deactivat- cFe(III)
ing the resins was less than the high iron standard (see
Table 2) used and also that the exchange number for From Table 3 we can see that values of nFe(III) varies
Fe(III) is 3 times higher than that of ammonium. from an unexpected value of 1.45 for Amberlyst 35 at
When deactivation by ammonium is compared to that high standard of Fe(III) to 2.48 for Bayer OC1501 and
produced by Fe(III) high standard, it could be said that Purolite CT 175 at low standard of Fe(III), but for the
ammonium ion leads to a deactivation of the catalyst most part values are close to 2. So, an average value of
3580 Ind. Eng. Chem. Res., Vol. 37, No. 9, 1998
Table 4. Catalytic Exchange Capacity and Fictitious
Loss of Activity Values for Different Resins Partially
Neutralized by Ammonium and the Corresponding
Values of Effective Exchange Capacity for This Ion
ppm CEC L′
resin ammonium (mequiv/g) (mequiv/g) nam
Bayer K-2631 8433 3.40 1.42 3.04
Bayer OC-1501 9653 3.54 1.93 3.60
Purolite CT 175 9696 3.27 1.71 3.17
Amberlyst 35 9822 4.06 1.26 2.31
2 can be considered as the effective exchange capacity
of Fe(III) for these resins.
The results of initial rates for ammonium are signifi-
cantly lower than for iron and it was found that there
is a certain linear relationship between initial rates and
the remaining acidic capacities of the resins polluted
by ammonium (Figure 5). We can see in Table 2 that
resins polluted by ammonium really have lesser effec-
tive exchange capacities, from a kinetic standpoint, than
the ones obtained by titration. It can be inferred again
that ammonium not only neutralizes sulfonic groups but
also obstructs the access of the reactants into the
polymer mass where there is a high density of active
sites. This conclusion can be confirmed after calculating
the acidic capacities that resins would have, taking into
account the initial rates obtained (catalytic exchange
capacity) and analyzing the relationship between the
fictitious loss of activity and the quantities of am-
monium ion found in them.
The fictitious loss of activity (L′) of a resin can be
determined as a difference between the acidic capacity
of the fresh resin and the catalytic exchange capacity
calculated by using the significant linear correlation
between initial rates and acidic capacities of fresh resins
and polluted by Fe(III). The appropriate expression to
calculate the catalytic exchange capacity (CEC) values
is
r0 - 0.00012
CEC ) (4)
0.0076
To calculate the effective exchange capacity of am-
monium we used the expression:
(1000)(18)L′
nam ) (5)
cam
Results obtained for CEC, L′ and nam are presented in
Table 4. It can be seen that the values of effective
exchange capacity for ammonium range from 2.31 for
Amberlyst 35 to 3.60 for Bayer OC-1501 but an average
value of 3 could be considered as the representative one.
If we compare both average values of effective ex-
change capacity for Fe(III) and ammonium, it can be
inferred that deactivation by ammonium is surprisingly
much higher than by Fe(III). The standard exchange
capacity of Fe(III) is 3 and the effective value obtained
was only 2. So it can be thought that an important
amount of Fe(III) deactivates the resin by ion exchang-
ing but there is a small part of it placed into the resin
that does not affect the active centers of the catalyst.
On the other hand, the standard exchange capacity
of ammonium is 1 and the effective value found was 3.
So this ion deactivates the resin not only by neutraliza-
tion but also by blocking sulfonic groups. So contact of
the reactants with Fe(III) and especially with nitrogen
organic compounds should be avoided in industrial
operation.
Conclusions
After testing of 12 macroporous resins as catalysts
on MTBE synthesis, it has been found that the acidic
capacity is the most significant variable for this reaction
This conclusion agrees with other similar studies (Krause
and Hammarström, 1987; Panneman and Beenackers,
1995b). It seems that the resins which have greater
density of sulfonic groups were the most active because
the reaction of MTBE synthesis involves a concerted
mechanism where some adjacent sulfonic groups par-
ticipate.
Four resins were partially deactivated using Fe(III)
and ammonium ions to evaluate the influence of these
ions on the activity of the resins. The results showed
that for both ions there is a linear relation between the
initial reaction rates and the remaining acidic capacities
of the resins, but while iron fulfils the same correlation
as the fresh resins, ammonium produces standards of
activity much smaller than those produced by Fe(III).
It seems that ammonium could provoke steric hindrance
due to the formation of hydrogen bonds with sulfonic
groups located in outer layers of the polymeric mass of
the resins studied.
Acknowledgment
We thank Repsol Petróleo S.A. for its financial sup-
port and Mr. A. Gonzalez, M. Somoza, and J. A.
Gonzalez for their technical support.
Nomenclature
A ) BET surface area, m2/g
A′ ) ISEC surface area, m2/g
C ) acidic capacity, mequiv/g
cam ) concentration of ammonium in the resin, ppm
cFe(III) ) concentration of Fe(III) in the resin, ppm
CEC ) catalytic exchange capacity, mequiv.g-1
D ) average pore diameter, Å
dp ) approximate value of average particle diameter, mm
F ) methanol flow rate, mol.h-1
L ) loss of acidic capacity by Fe(III), meq.g-1
L′ ) loss of acidic capacity by ammonium, L′ ) C - CEC,
mequiv‚g-1
nam ) effective exchange capacity for ammonium, eq/at-g
ammonium
nFe(III) ) effective exchange capacity for Fe(III), eq/at-g iron
r ) reaction rate, mol h-1 mequiv-1
r0 ) initial reaction rate, mol h-1 mequiv-1
V ) pore volume, mL/g
W ) mass of dry resin, g
XM ) methanol conversion, %
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Received for review January 7, 1998
Revised manuscript received June 8, 1998
Accepted June 10, 1998
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