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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 of resins that differed markedly in their properties were
Panneman and Beenackers (1995b) showed that the compared at the same experimental conditions.
catalytic activity of an ion-exchange resin on the same The second goal of this paper is to know the deacti-
reaction depends on its three-dimensional structure, vating effect of ammonium and Fe(III) on the etherifi-
which is influenced by the level of cross-linking, the cation reaction. To test catalytic activity of partially
porosity, the internal surface area, the sulfonic acid sulfonated ion exchangers, reaction rates were compared
content, and its distribution within the particles. at the same experimental conditions.
On the other hand, another important factor in
commercial operation that influences the catalytic activ- Experimental Section
ity is the deactivation of the catalyst. The acid sites of
the cation-exchange resin catalyst may easily be poi- (i) Continuous Operation. Twelve commercial
soned by different ions that can be present in the feeds macroporous styrene-divinylbenzene ion exchangers
due to corrosion in pipelines or can be carried to the were used as catalysts in MTBE synthesis. Their
reactor through misoperations in preceding units. morphological properties are summarized in Table 1.
Brockwell et al. (1991) make a distinction between Prior to use, all ion exchangers were washed with
two different modes of catalyst deactivation. The first distilled water and dried at 110 °C for more than 14 h
mode is plug flow neutralization and the second is at atmospheric pressure. Afterward they were stored
diffused flow neutralization. With plug flow neutraliza- in a desiccator over sulfuric acid (98%). The water
tion, the poison accumulates on the catalyst in a plug- content in all resins, measured by Karl Fischer titration,
flow manner as it impinges on the catalyst bed. The was less than 3%. Before the experiment, the catalyst
uptake of deactivator is rapid and stoichiometric. As bed was preheated in the reactor at operating temper-
deactivation progresses, plug flow neutralization results ature in the presence of the methanol stream to ensure
in a foreshortening of the active catalyst bed length. that an amount of methanol greater than 10 times the
Examples of plug-flow deactivators are all salts and reactor volume was passed through it. As a result, the
other Lewis and Brönsted bases. Diffused flow neu- residual water content in the resin was reduced to less
tralization is a mode of deactivation in which catalytic than 1.6%. tert-Butyl alcohol produced from this amount
sites are neutralized uniformly throughout the bed of water was not detected in the experiments. Other
rather than in progression from the point of impinge- byproducts (dimethyl ether and diisobutylene) were not
ment. Diffusional deactivators are generally very weak found in the runs.
bases that either weakly bind the catalytic sites or are In all experiments, carried out in the steady state,
species that generate more strongly binding species in commercial particle sizes of different resins have been
situ. Examples of diffusional deactivators are propi- used to study their behavior in operating conditions of
onitrile, dimethylformamide, dimethyl sulfide, hydrogen industrial reactors. Fresh dry catalyst sample (0.874
sulfide, and amine formers such as acetonitrile, which g) was always placed in a continuous packed-bed mi-
is responsible for most of the catalyst deactivation croreactor (15 cm length; 4.4 mm i.d.) and the small
experienced in MTBE reactors due to formation of remaining reactor volume was filled with quartz of 0.63
ammonium ion (Marston, 1994). < dp < 0.8 mm to avoid bed expansion.
It has not been possible to find experimental studies The experiments in the continuous regime were
about the catalytic behavior of an ion exchanger partly carried out in a setup made of stainless steel at 1.6 MPa
deactivated by ammonium or Fe(III) in MTBE synthe- and 323 K by feeding an appropriate methanol-C4
sis. Krause and Hammarström (1987) propose that the olefinic cut mixture. This pressure was enough to
loss of the activity of the resin partly deactivated by maintain the reacting system in liquid phase and this
sodium or ammonium ions is the same for tert-amyl temperature was chosen to avoid temperature axial
methyl ether (TAME) synthesis in liquid phase, and gradients. The methanol molar flow rate was always
Kmosták and Setinek (1981) found that sodium ions 0.874 mol/h, the molar ratio of isobutylene/methanol
deactivate the catalyst more than Fe(III) ions for employed was 0.91, and the liquid hourly space velocity
isomerization of cyclohexene and dehydration of 1-pro- (LHSV) used was 85 h-1. C4 cut from a steam cracking
panol in the gas phase. (SC) plant containing 45-55% isobutylene was supplied
So, the first aim of this work is to contribute further by Repsol Petróleo S.A. Methanol for high-performance
to the elucidation of the effect of different morphologic liquid chromatography (HPLC) (<0.01% water, 99%
properties of an ion exchanger (surface area, average pure) was supplied by Romil Chemicals Ltd.
pore diameter, and acidic capacity) on its catalytic Two sampling valves injected 0.2 µL into an HP 5890
activity in MTBE synthesis. For this purpose, a number gas-liquid chromatography (GLC) apparatus equipped
Ind. Eng. Chem. Res., Vol. 37, No. 9, 1998 3577
with flame ionization detector (FID). One valve took free of external mass transport processes. Runs carried
samples from the reactor inlet and the other one from out by maintaining feed composition and catalyst mass,
the reactor outlet. A 50 m × 0.2 mm × 0.5 µm methyl but using different molar flow rates, demonstrated that
silicone capillary column was used to separate MTBE, for LHSV > 60 h-1 reaction rate does not depend on
methanol, and C4 cut compounds (isobutylene and flow rate. As a result, a LHSV ) 85 h-1 was used.
1-butene could not be separated; as a consequence, only Fourteen different replicated experiments were made
methanol and MTBE were used as the reference com- to calculate the experimental error of methanol conver-
pounds to measure the reaction progress). More de- sion ((0.2% with a probability level of 95%).
tailed information about setup, procedure, and sample Table 1 shows the morphological properties of ion
analysis can be found elsewhere (Parra et al., 1994). exchangers used along with the results of methanol
Catalyst activity was measured as methanol conver- conversion and reaction rates obtained after the experi-
sion and also as a reaction rate at steady-state condi- ments carried out in steady-state mode. The reaction
tions to know the efficiency of the resins from an rates were calculated by taking into account that for
industrial point of view. To reduce the effect of reacting the methanol conversion values obtained, the reactor
medium and the development of temperature gradients, was differential (Parra et al., 1994). So, the reaction
the methanol conversion was lower than 11%. Reaction rates were determined by
rates were also calculated to look into, from a scientific
point of view, the influence of different properties of the XMF
resins. In each run the flow rates were maintained (3-4 r) (1)
h) until chromatographic analysis was the same within 100CW
the limits of the experimental error to ensure that
steady state was reached. Some experiments were At first sight, the following differences about the
repeated to determine the experimental error. properties of the resins must be pointed out: Purolite
(ii) Batch Operation. The experiments in batch CT165 has a particular morphology, its Brunauer-
mode were carried out in a stainless steel jacketed 250 Emmett-Teller (BET) surface area (A) and pore volume
mL autoclave. A calculated amount of methanol and are the smallest in the group but its average pore
about 2.9 g of dry resin (water content less than 3%) diameter is the highest one. It seems to be a mi-
were first charged into the reactor and, after checking croporous resin. Despite the fact that Purolite CT151
for leakages, heated to the desired temperature (always has a high acidic capacity, it has a surprisingly small
333 K) and then an amount of C4 liquid, given by the average pore diameter in comparison with the other
desired isobutylene/methanol ratio, was introduced resins studied. Bayer OC-1501, Amberlyst 35, and
directly from a cylinder. At this time, the magnetic- Purolite CT175/2824 have the highest acidic capacity
drive turbine was switched on at 500 rpm and the of ion exchangers selected. Finally, Purolite CT 169 has
reactor pressure was set at 1.6 MPa throughout the the largest value of surface area (A), but its other
experiment in order to maintain the liquid phase. The properties are similar to the other resins.
time of introduction of the olefinic fraction into the As can be seen in Table 1, the catalytic behavior of
reactor was considered as the starting point for the the resins differs greatly. Methanol conversions vary
reaction. Further information on this apparatus is from 4.1% (Purolite CT165) to 11.0% (Bayer OC-1501).
described elsewhere (Izquierdo et al., 1992). Equal conversion values for Amberlyst 35 and Purolite
The reactor was connected directly to the sampling CT175/2824 are found, close to that for Bayer OC-1501.
valve (Valco 4-CL4WE) which injects a small pressur- Traditional catalysts in MTBE synthesis such as
ized liquid volume (0.2 µL) to the gas chromatograph Bayer K2631 or Amberlyst 15 show lesser catalytic
(HP5890A). The same capillary column described above activities than the new generation of commercial resins
was used for sample analysis. No byproducts (tert-butyl from the same manufacturers, Bayer OC-1501 and
alcohol, dimethyl ether, and diisobutylene) were de- Amberlyst 35. This fact could be explained because of
tected in the experiments. the increase of density of sulfonic groups produced after
Catalytic activity was measured as initial reaction a special sulfonation procedure which added a second
rate calculated from the slope of methanol conversion sulfonic group to the aromatic rings already sulfonated
versus time data. Some experiments were repeated to rather than sulfonate the unsulfonated aromatic rings.
evaluate the experimental error on reaction rate. So, this sulfonation procedure makes it possible to
(iii) Partial Neutralization of Ion Exchangers. achieve a higher number of acidic groups per unit of
Four resins were chosen to be partially neutralized by mass of these new resins.
Fe(III) and ammonium ions. Two standards of iron and To assess the quantitative influence of morphological
one of ammonium were used. A known amount (always properties in dried state of the different resins on
60 g) of a given dried ion exchanger was placed into a methanol conversion, different polynomials were fitted
beaker and 400 mL of solution, either FeCl3‚6H2O or to the data. From a statistical point of view, the best
ammonium hydroxide, was added. After standing for significant polynomial fitted to the data was
24 h with stirring, the catalyst was washed with water
in a column until there was negative reaction on the XM ) (2.924 × 10-3)C3A - (1.751 × 10-4)C2A2 +
corresponding anion. After this, the resin was redried
in a oven at 105 °C for 14 h. The concentrations of (1.598 × 10-5)C3D (2)
exchangeable acid sites left were measured by the same
method as for the fresh resin (Bayer, 1990). This fourth-order polynomial only contains three vari-
ables, namely, acid capacity (C), BET surface area (A),
Results and Discussion and average pore diameter (D). We have not considered
in this mathematic analysis pore volume (V), because
(i) Fresh Catalysts. Preliminary experiments were it depends on the surface area and average pore
made at 323 K to ensure that rate data were generated diameter, or approximate average particle diameter (dp),
3578 Ind. Eng. Chem. Res., Vol. 37, No. 9, 1998
Table 4. Catalytic Exchange Capacity and Fictitious the reactants with Fe(III) and especially with nitrogen
Loss of Activity Values for Different Resins Partially organic compounds should be avoided in industrial
Neutralized by Ammonium and the Corresponding
operation.
Values of Effective Exchange Capacity for This Ion
ppm CEC L′
resin ammonium (mequiv/g) (mequiv/g) nam
Conclusions
Bayer K-2631 8433 3.40 1.42 3.04 After testing of 12 macroporous resins as catalysts
Bayer OC-1501 9653 3.54 1.93 3.60 on MTBE synthesis, it has been found that the acidic
Purolite CT 175 9696 3.27 1.71 3.17 capacity is the most significant variable for this reaction
Amberlyst 35 9822 4.06 1.26 2.31 This conclusion agrees with other similar studies (Krause
and Hammarström, 1987; Panneman and Beenackers,
2 can be considered as the effective exchange capacity 1995b). It seems that the resins which have greater
of Fe(III) for these resins. density of sulfonic groups were the most active because
The results of initial rates for ammonium are signifi- the reaction of MTBE synthesis involves a concerted
cantly lower than for iron and it was found that there mechanism where some adjacent sulfonic groups par-
is a certain linear relationship between initial rates and ticipate.
the remaining acidic capacities of the resins polluted Four resins were partially deactivated using Fe(III)
by ammonium (Figure 5). We can see in Table 2 that and ammonium ions to evaluate the influence of these
resins polluted by ammonium really have lesser effec- ions on the activity of the resins. The results showed
tive exchange capacities, from a kinetic standpoint, than that for both ions there is a linear relation between the
the ones obtained by titration. It can be inferred again initial reaction rates and the remaining acidic capacities
that ammonium not only neutralizes sulfonic groups but of the resins, but while iron fulfils the same correlation
also obstructs the access of the reactants into the as the fresh resins, ammonium produces standards of
polymer mass where there is a high density of active activity much smaller than those produced by Fe(III).
sites. This conclusion can be confirmed after calculating It seems that ammonium could provoke steric hindrance
the acidic capacities that resins would have, taking into due to the formation of hydrogen bonds with sulfonic
account the initial rates obtained (catalytic exchange groups located in outer layers of the polymeric mass of
capacity) and analyzing the relationship between the the resins studied.
fictitious loss of activity and the quantities of am-
monium ion found in them. Acknowledgment
The fictitious loss of activity (L′) of a resin can be
determined as a difference between the acidic capacity We thank Repsol Petróleo S.A. for its financial sup-
of the fresh resin and the catalytic exchange capacity port and Mr. A. Gonzalez, M. Somoza, and J. A.
calculated by using the significant linear correlation Gonzalez for their technical support.
between initial rates and acidic capacities of fresh resins
and polluted by Fe(III). The appropriate expression to Nomenclature
calculate the catalytic exchange capacity (CEC) values
A ) BET surface area, m2/g
is
A′ ) ISEC surface area, m2/g
C ) acidic capacity, mequiv/g
r0 - 0.00012 cam ) concentration of ammonium in the resin, ppm
CEC ) (4)
0.0076 cFe(III) ) concentration of Fe(III) in the resin, ppm
CEC ) catalytic exchange capacity, mequiv.g-1
To calculate the effective exchange capacity of am- D ) average pore diameter, Å
monium we used the expression: 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
(1000)(18)L′
nam ) (5) L′ ) loss of acidic capacity by ammonium, L′ ) C - CEC,
cam mequiv‚g-1
nam ) effective exchange capacity for ammonium, eq/at-g
Results obtained for CEC, L′ and nam are presented in ammonium
Table 4. It can be seen that the values of effective nFe(III) ) effective exchange capacity for Fe(III), eq/at-g iron
exchange capacity for ammonium range from 2.31 for r ) reaction rate, mol h-1 mequiv-1
Amberlyst 35 to 3.60 for Bayer OC-1501 but an average r0 ) initial reaction rate, mol h-1 mequiv-1
value of 3 could be considered as the representative one. V ) pore volume, mL/g
If we compare both average values of effective ex- W ) mass of dry resin, g
change capacity for Fe(III) and ammonium, it can be XM ) methanol conversion, %
inferred that deactivation by ammonium is surprisingly
much higher than by Fe(III). The standard exchange Literature Cited
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