The invention is directed to mordenites having a high mesoporosity,
to the preparation of such mordenites, and to their use.
Zeolites and more in particular mordenites, are used in
many catalytic and separation processes due to unique properties such as uniform
pores of molecular dimensions, intrinsic acidity, and the ability to confine active
metal species. However, the microporous character of these materials often leads
to intracrystalline diffusion limitations, which adversely affect catalytic performance.
A breakthrough was the synthesis of mesostructured aluminosilicates. Emerging mesoporous
materials however generally do not comply with most practical requirements as a
result of limited thermal stability and poor acidic properties.
Consequently, new synthesis procedures for preparation
of small zeolitic crystals or post-treatment procedures to create extra-porosity
are increasingly investigated. Conventional steaming and acid leaching methods or
the less-known treatments in alkaline media have been applied to alter various properties
of zeolites. The last method removes preferentially Si from the zeolite framework
(desilication), while the former ones lead to dealumination. Desilication was firstly
applied to study chemical changes of MFI crystals upon contact with NaOH solutions,
but only recently this treatment has shown to induce a significant mesoporosity
in MFI-type zeolites.
Groen et al, On
the introduction of intracrystalline mesoporosity in zeolites upon desilication
in alkaline medium, Microporous and Mesoporous Materials, 69 (2004) pp 29-34,
describe the influence of the extraction of silicon from zeolite frameworks on their
In general, results from this type of treatments often
cannot be extrapolated directly from one type of zeolites to other zeolite types,
or even within one family due to e.g. different framework properties, stability,
and typical Si- to-A1 ratios.
Mordenites are a separate class of zeolites and are applied
frequently as catalyst or catalyst support in chemical reactions, such a the alkylation
of aromatic compounds, (hydro-)isomerization, esterification, dehydration of alcohols,
amine production from NH3 and olefins, acetal or ketal formation, aldol
condensation reactions, and the like.
More in particular mordenite can be used as a solid acid
catalyst, or as a catalyst support for those reactions wherein both acidic properties
and the properties of the applied catalytically active material (bifunctional catalyst)
are required. In addition thereto mordenite is also useful as a catalyst support
in case the trivalent metal (aluminum) is needed as anchoring site for the catalytically
active material (usually a metal).
The mordenite structure is defined in the Atlas of zeolite
framework types, 5th revised edition (2001). In this context the term
mordenite not only includes the materials based on silicon and aluminum, but also
those materials with the same structure, wherein the trivalent aluminum has been
replaced in whole or in part by other trivalent atoms, such as iron, boron or gallium.
As indicated above, it would be advantageous if the pore
structure of the mordenite could be improved, especially with respect to surface
area in mesopores. Because of the pore structure of mordenite, consisting of relatively
wide unidirectional pores and relatively narrow pores connecting these wide pores,
the material is rather susceptible to disturbances of the pore structure. Increase
of mesoporosity in mordenites would result in a better accessibility of the pores
and would allow for transport between parallel pores, thereby making the material
less susceptible to disturbances of the pore structure.
Further it would be advantageous if the catalytic properties
of the mordenite in general could be improved, more in particular with respect to
activity, selectivity and stability.
In the modification of mordenites it is important that
the process proceeds smoothly, and that the resulting material has predictable properties
in terms of structure, reproducibility of acidic character, strength and framework
Si-to-trivalent metal atomic ratio in the end product. When used as catalyst or
catalyst support, it is often important that the original acidity of the mordenite
Accordingly it is an object of the present invention to
provide a process for increasing the mesoporosity of mordenites (MOR), while substantially
maintaining the acidity thereof, and to improve the catalytic properties thereof.
The present invention is based on the surprising discovery, that in order to meet
these objects it is essential that the atomic Si-to-Al ratio in the mordenite exceeds
15, preferably exceeds 20 and more preferably is between 25 and 35.
For ease of definition, whenever mention is made of aluminum
herein, it is to be understood that the trivalent aluminum may have been replaced
in whole or in part by other trivalent atoms, such as iron, boron or gallium, unless
it is clearly indicated that only aluminum is intended.
In a first embodiment the present invention is directed
to a process for the preparation of a mesoporous mordenite, which process comprises
subjecting a non-dealuminated mordenite having an atomic ratio of Si-to-Al of least
15 to an alkaline treatment in order to create mesoporosity by removal of silicon.
The atomic Si-to-Al ratio is defined as the ratio of the atoms in the mordenite
framework. Atoms present in free alumina or silica are not included herein.
Surprisingly it has been found that in case an untreated
mordenite is used with an atomic Si-to-Al ratio as defined above, the resulting
mesoporous mordenite meets the requirements in terms of reproducibility and improvement
of catalytic properties.
It is to be noted that the article of Groen, referred to
above, mentions the alkaline treatment of a mordenite having a high Si-to-Al ratio.
However, this material has previously been dealuminated. Further, the data in the
article show that the effect of the treatment is relatively limited, whereas the
reproducibility/predictability of the treatment is low. The conditions for the treatment
described therein are further severe.
In a further embodiment the invention resides in the mesoporous
mordenite produced in accordance with the above process and in a mesoporous mordenite
having a surface area in mesopores of between 50 and 200 m2/g, and an
acidity, as defined herein, of between 0.35 and 0.95 mmol/g.
With respect of the surface area in mesopores, it is to
be noted that the measurement of this values includes some surface area on the outside
of the crystals, as intercrystalline pore-volume is also included in the measurement.
Accordingly, the particle size of the crystals influences the value. Generally,
this outer surface area is rather limited and almost negligible. One solution would
be to distract the outer surface area as determined by SEM measurements from this
value. Another solution would be to define the added surface area in mesopores.
This added surface area should preferably be between 45 and 150 m2/g.
The invention is also embodied in the use of the mordenite
of the invention as catalyst or catalyst support for catalytic chemical reactions,
such as those enumerated in the introductory part. When used as support, it has
been found that the new pore structure leads to advantageous properties in terms
of stabilizing the catalytically active material in the pores. Thanks to the improved
pore structure, metal species (which are the most commonly used catalytically active
materials) are better confined, while at the same time remaining accessible to the
Examples of catalytically active materials to be used in
the present invention are the precious metals, such as Pt, Pd, Ir, Au, Rh and Ag.
Other metals to be used include Ni, Co, Mn, V, Cu, Fe and Zn, to name but a few.
Important classes of reactions to be contemplated in the
context of the present invention are hydro-isomerisation and the alkylation of aromatic
compounds, such as the production of ethylbenzene from benzene and ethylene.
Further important advantages of the modified mordenites
of the present invention are, in addition to the aspects discussed above, that by
the alkaline treatment and the resulting removal of trivalent metal from the mordenite
framework, various important properties of the mordenite may be modified or fine-tuned,
while maintaining other, equally important, properties of the material. More in
particular it is possible to modify the anchoring sites for catalytically active
metals, such as the noble and transition metals, on the internal surface of the
pores. The trivalent metals can function as anchoring sites and by changing the
amount thereof in relation to the amount of Si, the anchoring properties can be
Another aspect thereof is the fine tuning of the balance
between hydrophilicity and hydrophobicity, which is especially important in case
of reactions in a relatively hydrophilic environment.
The starting material for the process is mordenite that
has a high framework Si-to-Al (trivalent metal) ratio as prepared (i.e. not de-aluminated
as in the case of Groen). These materials can be prepared as described in the literature,
by direct hydrothermal synthesis, with or without the use of seed crystals, in the
presence of a suitable template, such as tetraethyl ammoniumhydroxide.
The alkaline treatment of the high silica mordenite is
typically performed in an aqueous environment with a pH above about 11, more preferred
in 0.01 to 1.0 M alkali metal hydroxide, preferably NaOH, more preferably at about
0.2 M NaOH at 310 to 400 K, preferably at 325 to 345 K for 10 to 45 min. The treatment
can be done batch wise or continuous. The temperature and time can be chosen in
dependence of the required treatment level.
In a typical embodiment about 330 mg of sample were vigorously
stirred in 10 ml of 0.2 MNaOH solution in a polypropylene flask for 30 min at a
specific temperature. Subsequently, the reaction was quenched by submersion of the
flask in an ice-water mixture, followed by filtration and thorough washing with
demineralized water. After filtration and washing, the zeolites were dried (preferably
at about 373 K and calcined. Calcination may be done in static air at a temperature
preferably between 673 and 1000 K, such as at about 823 K. The alkaline-treated
samples were converted into the H-form by three successive exchanges with an NH4NO3
solution. Final calcination of the mordenite may be done under the same conditions
The alkali concentration may be varied between the limits
given above. A higher throughput of solid product is obtained at higher concentrations.
Important in this respect is to keep the ratio alkali:mordenite constant in order
to have good control over the silicon extraction process. Altering the ratio will
impact on the degree of silicon extraction, and similar to temperature and time,
enable additional tuning of the mesoporosity. Besides NaOH, other alkali metal hydroxides
or carbonates can successfully be applied, although having a slightly lower efficiency
The mordenite of the present invention may be characterized
by its mesopore surface area, its acidity and, of course, the atomic Si-to-Al ratio.
Suitable characterization methods have been defined herein below. A suitable mordenite,
prepared using the process of the invention is characterized by a combination of
acidity and surface area in mesopores, namely by having a surface area in mesopores
of between 50 and 200 m2/g (taking into account the discussion above
on this subject), and an acidity, as defined herein of between 0.35 and 0.95 mmol/g.
Such a mordenite has a total pore volume of between 0.10 and 0.50 ml/g and an Si-to-Al
atomic ratio of 5 to 30.
The mordenites of the present invention can suitably be
used as catalysts or catalyst supports. It is to be noted that although they have
been treated to remove silicon, their acidity still corresponds to the original
acidity, contrary to expectations. Due to their improved surface area in mesopores,
i.e. pores of between 2 and 50 nm, as defined herein below, they show improved diffusion
characteristics. Also the selectivity, yield and stability (absence of decrease
in activity) of these materials is excellent. As the process of the present invention
allows a good reproducibility, the characteristics of the mordenites produced thereby
is excellent, making them extremely suitably for use in various catalytic processes,
which processes require a very well tuned catalytic activity, that should remain
constant over a long period of time. Further, variations from batch to batch of
catalyst are low, due to the good reproducibility of the process.
Because of their acidic properties, the mordenites of the
present invention are very suitable as catalyst for acid catalyzed reactions, among
which alkylation of aromatic compounds and hydro-isomerisation are important classes.
Especially important is the preparation of ethylbenzene from ethylene and benzene
in the presence of these mordenites. The material is also suitable as support for
bifunctional catalyst, and further as general catalyst support in case the acidic
sites have been covered by metal or in case the acidity plays substantially no role
in the catalytic activity. The material may also be used as an additive in other
catalytic processes, for example as an additive in an FCC catalyst, in order to
improve olefin production.
The reaction conditions for the various catalytic reactions
are well known in the art and they may be applied here too.
The invention is now elucidated on the basis of the following
preparation and use examples, which are intended as exemplification only.
Preparation example of high silica mordenites
High-silica mordenite samples were prepared by direct hydrothermal
synthesis with and without seed crystals.The seed crystals were prepared by mixing
NH4NO3 (Wako Pure Chemical, 99%) with an aqueous solution
of Al(NO3)3 ·9H2O (Wako Pure Chemical, 98%)
and NaOH (Merck Schuchardt, 99%). Subsequently, precipitated hydrated silica (Nipsil,
Nippon Silica Ind., 88% SiO2) and tetraethylammonium hydroxide (Aldrich,
35 wt.%) were added to the mixture and homogenized in a mortar. The chemical composition
of the starting synthesis gel was as follows: Si/Al = 15, NaOH/Al = 3, TEAOH/SiO2
= 0.23. The obtained gel was then transferred to a teflon-lined stainless steel
autoclave and kept at 443 K for 3 days under static conditions. The solid product
obtained was filtered, washed with deionized water, and dried at 393 K. The resulting
mordenite crystals were then added (4 wt.% based on total amount of SiO2
in synthesis gel) to the synthesis mixture of high-silica mordenite with molar composition:
Si/Al = 30, NH4NO3/SiO2 = 0.096, and NaOH/Al =
7. After crystallization at 343 K for 3 days the final high-silica mordenite sample
was obtained (sample code MOR30).
Sample MOR20 was synthesized following a similar protocol
as MOR30, but without seeding and with the following molar composition of the synthesis
gel: NH4NO3/SiO2 = 0.046, Si/Al = 20, and NaOH/Al
= 4. The resulting solids were filtered, washed with demineralized water, dried
at 393 K, and finally calcined in static air at 823 K (heating rate 3 K min-1)
for 5 h.
Prior to further investigations, all samples were brought
into the ammonium form by three successive ion exchanges in 0.1 M NH4NO3,
followed by calcination in static air at 823 K for 5 h.
Alkaline treatment of the mordenite was performed in 0.2
M NaOH at 338 K for 30 min. To this end, 330 mg of sample were vigorously stirred
in 10 ml of NaOH solution in a polypropylene flask for 30 min at a specific temperature.
Subsequently, the reaction was quenched by submersion of the flask in an ice-water
mixture, followed by filtration and thorough washing with demineralized water. After
filtration and washing, the mordenites were dried at 373 K and calcined in static
air at 823 K. The alkaline-treated samples were converted into the H-form by three
successive exchanges in 0.1 M NH4NO3 solution. Final calcination
of the mordenites was done in static air at 823 K during 5 h.
N2 adsorption at 77 K was carried out in a Quantachrome
Autosorb-6B apparatus. Samples were previously evacuated at 623 K for 16 h. The
BET surface area was derived from the adsorption isotherm in the adapted relative
pressure range of p/p0 = 0.01-0.1 [S.
Brunauer, P.H. Emmett, E. Teller, J. Am. Chem. Soc. 60 (1938) 309.].
The micropore volume (Vmicro) and the macro- and mesopore surface
area (Smeso) were determined with the t-plot method according
to Lippens and de Boer [B.C. Lippens, J.H.
de Boer, J. Catal. 4 (1965) 319.]. The mesopore size distribution
was calculated from the adsorption branch of the isotherm using the Barret-Joyner-Hallenda
[E.P. Barret, L.G. Joyner, P.H. Hallenda,
J. Am. Chem. Soc. 73 (1951) 373] pore size model.
High-resolution low-pressure argon adsorption measurements
were performed after in-situ vacuum pretreatment at 623 K for 16 h on a Micromeritics
ASAP 2010 to assess the microporous properties. The Saito-Foley [A.
Saito, H.C. Foley, Microporous Mater. 3 (1995) 531] pore size model
was used to calculate the micropore size distribution.
Temperature programmed desorption of ammonia (NH3-TPD)
was carried out in a Micromeritics TPR/TPD 2900 equipped with a thermal conductivity
detector (TCD). The sample (30 mg) was pretreated at 873 K in He for 1 h. Afterwards,
pure NH3 (25 cm3 min-1) was adsorbed at 473 K for
10 min. Subsequently, a flow of He (25 cm3 min-1) was passed
through the reactor during 25 minutes to remove weakly adsorbed NH3 from
the zeolite. This procedure was repeated three times. Desorption of NH3
was monitored in the temperature range of 473-873 K with a ramp rate of 10 K min-1
(defined as mmol NH3 adsorbed per gram of zeolite.
The chemical composition and textural characteristics of
the various zeolites are summarized in Table 1.
Table 1. Physicochemical properties of the parent and alkaline-treated
b BET method;
c t-plot method;
d Determined at p/p0 = 0.99.
* MOR10 is a commercial zeolite obtained from Zeolyst with original sample code
Important features of the alkaline-treated high-silica
mordenite samples are the high degree of mesoporosity coupled to a mostly preserved
micropore volume and acidity. XRD patterns in Figure
1 confirm the high crystallinity of the synthesized mordenite sample, with
sharp reflections at the characteristic 2-theta positions. The alkaline-treated
sample still presents the characteristic fingerprint, though having a slightly lower
intensity, obviously as a result of the introduced mesoporosity.
Alkylation of benzene
The activity of the various zeolites was tested in the
liquid-phase alkylation of benzene (Aldrich, >99%) with ethylene (Hoekloos, >99.9%)
in a 500 cm3 commercial titanium batch autoclave (Premex). First, 200
cm3 of benzene was introduced in the reactor with approximately 1 g of
catalyst that was previously pretreated at 573 K in He for 12 h to remove moisture.
After purging with N2, the reactor was heated to 438 K under vigorous
mechanical stirring (1000 rpm). Subsequently ethylene was introduced in the reactor
until the molar ratio benzene:ethylene was 4:1 and a pressure of 23 bar was obtained.
During the reaction, liquid sample aliquots (0.2 cm3) were extracted
from the reactor, which were analyzed off-line with a GC (Chrompack CP9001) equipped
with a CPSil-8B column and an FID detector.
Table 2 shows the differences in coke content and its impact
on the textural properties of the various catalysts.
Table 2. Textural properties of the MOR30 zeolites before and after
cDetermined at p/p0 = 0.99;
dDetermined by thermogravimetric analysis.
In figure 2, the
results have been given of the alkylation of benzene.
In the figure the following has been shown:
- ethylbenzene (EB) production (open symbols) and selectivity (filled symbols)
of the different mordenite catalysts.
- (o,•) MOR10, (□,▲) MOR30, and (□,■) MOR30-at.
The reported selectivity is based in the selectivity towards
ethylbenzene compared to the total production of ethylbenzene, diethylbenzene, triethylbenzene,
and butylbenzene together.