Title of Invention

A MICROPOROUS CRYSTALLINE MATERIAL OF ZEOLITIC NATURE AND A METHOD OF SYNTHESISING A MICROROROUS CRYSTALLINE MATERIAL

Abstract The present invention refers to a microporous crystalline material of zeolitic nature (ITQ-22) which, in the calcined state, has the empirical formula wherein M is H+ or at least one inorganic cation of charge +n; X is at least one chemical element of oxidation state +3, preferably selected from the group consisting of Al, Ga, B, Fe and Cr; Y is at least one chemical element with oxidation state + 4 other than Si and Ge, preferably selected from the group consisting of Ti, Sn and V; x has a value less than 0.2, preferably less than 0.1 and can take the value zero, y has a value less than 0.1, preferably less than 0.05 and can take the value zero, z has a value less than 0.8, preferably between 0.005 and 0.5 and can take the value zero, with a characteristic X-ray diffraction pattern, to the method of preparation and to the use of the material in separation and transformation processes of organic compounds.
Full Text A MICROPOROUS CRYSTALLINE MATERIAL OF ZEOLITIC NATURE
AND A METHOD OF SYNTHESISING A MICROPOROUS
CRYSTALLINE MATERIAL
TECHNICAL FIELD OF THE INVENTION
This invention belongs to the technical field of
microporous crystalline materials of zeolitic nature,
useful as catalysts or components of catalysts for
separation and transformation processes of organic
compounds.
STATE OF THE ART PRIOR TO THE INVENTION
Zeolites are microporous crystalline materials
formed from a crystal lattice of TO4 tetrahedra which
share all their vertices giving rise to a three-
dimensional structure containing channels and/or cavities
of molecular dimensions. Their composition is variable
and T in general represents atoms with formal oxidation
state +3 or +4, such as for example Si, Ge, Ti, Al, B,
Ga, and so on. When any of the T atoms has an oxidation
state less than + 4, the crystal lattice formed displays
negative charges which are compensated by means of the
presence of organic or inorganic cations in the channels
or cavities. Organic molecules and H2O can also be housed
in those channels and cavities so, in a general manner,
the chemical composition of the zeolites can be
represented by means of the following empirical formula:


wherein M is one or several organic or inorganic cations
of charge +n; X is one or several trivalent elements; Y
is one or several tetravalent elements, generally Si; and
R is one or several organic substances. Although by means
of post-synthesis treatment the nature of M, X, Y and R
and the values of x, y, z and w can be varied, the
chemical composition of a zeolite (as synthesised or
following its calcination) possesses a range
characteristic of each zeolite and of its method of
preparation.
The crystalline structure of each zeolite, with a
specific system of channels and cavities, gives rise to a
characteristic X-ray diffraction pattern, which enables
them to be differentiated from each other.
Many zeolites have been synthesised in the presence
of an organic molecule which acts as a structure
directing agent. The organic molecules which act as
structure directing agents (SDA) generally contain
nitrogen in their composition and can give rise to stable
organic cations in the reaction medium.
The mobilisation of precursor species during the
synthesis of zeolites can be carried out in the presence
of OH- groups and basic medium, which can be introduced
as the hydroxide of the SDA itself, such as for example
tetrapropylammonium hydroxide in the case of zeolite ZSM-
5. Fluoride ions can also act as mobilising agents in the
synthesis of zeolites, for example patent EP-A-337479
describes the use of HF in H2O at low pH as a mobilising
agent of silica for the synthesis of zeolite ZSM-5.
Nevertheless, the use of fluoride ions in the synthesis
is less desirable from the industrial point of view than

the use of OH-, given that the presence of fluoride ions
requires the use of special materials in the synthesis
equipment as well as specific treatment of the waste
waters and gases.
Fluid catalytic cracking (FCC), or its variant deep
catalytic cracking (DCC), together with steam cracking,
are the units which most contribute to the production of
C3-C5 olefins. Moreover, FCC contributes approximately
30% of the gasoline stream in the refinery. The
production of propylene in the FCC can be incremented by
modifying the operating conditions of the unit, such as
increasing the temperature of the reactor, for example.
Nevertheless, this solution entails a considerable
increase in gases and especially in undesired dry gas.
Better results are obtained using new compositions of
catalysts involving the use of zeolite mixtures. The use
of zeolite ZSM-5 as additive in FCC catalysts also leads
to an increase in C3 and C4 olefins (see for example
patents US-3758403, US-3769202; US-3894931; US-3894933;
US-3894934; US-3926782; US-4309280; US-4309279; and US-
437458 and Buchanan, J.S. and Adewuyi, Y-G., Applied
Catalysis: A General, 134, 247 (1996); Madon, R.J.,
Journal of Catalysis 129 (1), 275 (1991). Nevertheless,
it is known {Studies in Surface Science and Catalysis,
vol. 16, 499 (1993)) that the introduction of zeolite
ZSM-5 produces a decrease in dry gas, and an increase in
the proportion of aromatics in the gasoline. This is
particularly important from the point of view both of
producing an increase in the yield of C3-C5 olefins, and
especially propylene, and of obtaining a high yield of
high octane/barrel gasoline with a low aromatics content,

finding other alternative zeolites to zeolite ZSM-5
which, acting as an additive of zeolite faujasite Y,
would provide light olefins with minimum loss of
gasoline. Numerous zeolites have been studied in this
direction such as zeolite MCM-22, Omega, L, mordenite BEA
and ITQ-7 (see for example: J. Catal. 165, 102 (1997);
Stud. Surf. Sci. and Catal. 46, 115 (1989); the patents:
US-5314612; EP-489324; US-474292; US-4137152; EP-350331;
FR-2661621; WO-0170905).
Nevertheless, the need persists to improve known
procedures by means of using new catalysts with better
performance in cracking.
With regard to the use of zeolites as catalysts in
alkylation processes of aromatics, cumene is of
particular interest as a raw material for the production
of phenol and acetone. Numerous works have been developed
using acid catalysts. A general reference on catalysts
and processes used can be found in: "Encyclopedia of
Chemical Processing and Design", J.J. McKezta and W.A.
Cunningham Editors, V.14, pp. 33-55 (1982). The
alkylation process of benzene with propylene, as well as
seeking a high conversion of propylene and a high
selectivity to the monoalkylated product isopropylbenzene
(cumene), also requires minimising the quantity of n-
propyl benzene (NPB) formed. Given that it is difficult
to separate cumene and NPB by conventional methods, such
as by distillation, it can be understood that the yield
of NPB has to be as low as possible and in all cases very
low, during the alkylation of benzene with propylene.
Zeolites have been used as catalysts for the
alkylation of aromatics and so, for example, patent US-

429457 describes zeolite ZSM-5 as a catalyst for
alkylation of benzene with propylene.
Nevertheless, due probably to the small diameter of
its channels, this zeolite displays low selectivity for
the desired process. There also exist numerous patents
which describe the use of Faujasite and modified
Faujasites as catalysts for the production of cumene by
alkylation of benzene with propylene. Zeolite Y can be
used as a catalyst but it is necessary to work with high
benzene/propylene ratios in the feed. This leads to high
costs in the recycling of benzene. Zeolite Beta has also
been claimed as a catalyst for alkylation of benzene with
propylene in various patents such as for example: US-
4891458, US-5030786, EP-432814, EP-439632; EP-629599.
This zeolite produces good results in activity and
selectivity, but its behaviour could be better both with
regard to selectivity towards NPB and as far as the
stability of the catalyst is concerned. The use of a new
zeolite (MCM-22) has recently been claimed.
The object of the present invention is to provide a
material of a nature that can advantageously be applied
in processes of separation and transformation of organic
compounds, and more particularly its use as an active
zeolitic compound for the cracking of organic compounds
and more specifically hydrocarbon fractions derived from
natural or synthetic petroleums, as well as in the
alkylation process of aromatics.
The pore topology of this new zeolite confers on it
properties for acting as an additive of zeolite faujasite
Y in catalysts for fluid catalytic cracking (FCC) units,
providing high yields of light olefins with a high

octane-barrel number of the gasoline produced, as well as
reduction in the content of aromatics in the gasoline in
comparison with the base catalyst.
DESCRIPTION OF THE INVENTION
The present invention achieves the objectives
defined above by means of a microporous crystalline
material of zeolitic nature, also identified as "ITQ-22"
or "zeolite ITQ-22", its method of preparation in the
absence of fluoride ions and its applications. This
material, in both its calcined form and synthesised
uncalcined, has an X-ray diffraction pattern that is
different from that of other known zeolitic materials and
which is therefore characteristic of this material.
The X-ray diffraction pattern of the material ITQ-
22, as synthesised, has been obtained by the powder
method employing a fixed divergence slit and using Ka
radiation from Cu. This pattern is characterised by the
values of angle 2θ (degrees) and relative intensities
(I/I0) of the most intense reflections which are shown in
Table I, with I0 being the intensity of the most intense
peak which is assigned a value of 100. The relative
intensities have been expressed in the following terms: m
= medium intensity (between 20 and 40%); s = strong
intensity (between 40 and 60%) and vs = very strong
intensity (between 60 and 100%).



Once calcined and in the anhydrous state, the
material accords with the general formula
x (H X 02) : y YO2 z GeO2 (1 - z) SiO2
wherein "x" possesses a value less than 0.2, preferably
less than 0.1 and can take the value zero; "y" has a
value less than 0.1, preferably less than 0.05 and can
take the value zero; "z" possesses a value less than 0.8,
preferably between 0.005 and 0.5 and can take the value
zero; X is one or several chemical elements of oxidation
state +3 (Al, Ga, B, Fe, Cr) and Y is one or several
chemical elements with oxidation state +4 other than Si
and Ge (Ti, Sn, V) .
Nevertheless, depending on the synthesis method and
on the calcination or later treatments, it is possible
for defects to exist in the crystal lattice, which are
manifested by the presence of Si-OH (silanol) groups.
These defects have not been included in the above
empirical formula.
Table II shows the values of angle 29 (degrees) and
relative intensities (I/I0) of the most intense
reflections of the powder X-ray diffractogram zeolite

ITQ-22 after being calcined in order to eliminate organic
compounds occluded in its interior, where m, s, and vs
have the same meanings as in Table I.

The positions, widths and relative intensities of
the peaks depends to a certain degree on the chemical
composition of the material, as well as on the degree of
hydration and crystal size. In particular, when the
lattice is composed solely of silicon and germanium
oxides, with a ratio Si/Ge = 3.8 and it has been
synthesised using the quaternary ammonium cation 1,5-bis
(methylpyrrolidinium) pentane as structure directing
agent, the material as synthesised displays an X-ray
diffraction pattern like that shown in Figure I. This
diagram is characterised by the values of angle 29
(degrees) and relative intensities (I/I0) that are shown
in Table III. The relative intensities have been
expressed in the following terms: w = weak intensity
(between 0 and 20%); m = medium intensity (between 20 and

40%); s = strong intensity (between 40 and 60%) and vs =
very strong intensity (between 60 and 100%).



The X-ray diffraction pattern of the above sample of
ITQ-22, after being calcined at 580°C in order to
eliminate organic compounds occluded in its interior, is
shown in Figure 2. This diffractogram is characterised by
the values of angle 29 (degrees) and relative intensities
(I/I0) that are shown in Table IV, where w, m, s and vs
have the same meanings as in Table III. The comparison of
the X-ray diffractograms corresponding to zeolite ITQ-22
as synthesised and in the calcined state demonstrate the
thermal stability of the material.




The present invention also refers to the preparation
method of ITQ-22. This is carried out in basic medium, in
the absence of fluoride ions and comprises heat treatment
at a temperature between 80 and 200°C, preferably between
130 and 200°C, of a reaction mixture containing a source
of SiO2 (such as for example tetraethylorthosilicate,
colloidal silica, amorphous silica), optionally a source
of GeO2, 1,5-bis (methylpyrrolidinium) pentane, and
water. The organic cation 1,5-bis (methylpyrrolidinium)
pentane is added to the reaction mixture in the form of
salt (for example, a halide, preferably, chloride or
bromide) or hydroxide.
Optionally, it is possible to add a source of
tetravalent element or elements Y other than Si and Ge,
preferably Ti, V, Sn and/or trivalent elements X,
preferably Al, B, Ga, Fe, Cr The addition of this element
or elements can be done prior to heating of the reaction
mixture or in an intermediate moment during that heating.
It can occasionally be convenient to also add crystals of
ITQ-22 (between 0.01 and 20% by weight with respect to
the inorganic oxides taken as a whole, preferably between
0.05 and 10% by weight) as promoters of the
crystallisation (sowing) at some stage of the
preparation. The composition of the reaction mixture
accords with the general empirical formula:

wherein X is one or several trivalent elements,
preferably Al, B, Ga, Fe, Cr; Y is one or several
tetravalent elements other than Si and Ge, preferably Ti,
Sn, V; R is 1,5-bis (methylpyrrolidinium) pentane; and
the values of r, t, u, v and w vary in the ranges

r = ROH/SiO2 = 0.01-1.0, preferably 0.1-1.0
t = X2O3/SiO2 = 0-0.1, preferably 0-0.05
u = YO2/SiO2 = 0-0.1, preferably 0-0.05
v = GeO2/SiO2 = 0-4, preferably 0.005-1
w = H2O/SiO2 = 1-50
The heat treatment of the reaction mixture can be
done statically or with stirring of the mixture. Once the
crystallisation is complete, the solid product is
separated by filtration or centrifugation and dried. The
later calcination at temperatures above 350°C, preferably
between 400 and 900°C, produces the decomposition of
organic remains occluded in the interior of the zeolite
and their exit, leaving the zeolitic channels free. The
calcination can be done in the presence of N2 followed by
calcination in air, or direct calcination in air can be
carried out, or an extraction of the organic matter with
mineral or organic acids can be performed, or the organic
material can be eliminated by treatment with ozone.
After having been calcined, the material is
pelletised. The means by which the catalyst is pelletised
are well known in the literature, using a diluent such as
for example SiO2 or Al203 or a clay, zirconium, magnesium
oxide or mixture thereof, in proportions of
zeolite/diluent of between 20 and 95%, preferably between
40 and 90% by weight.

In an alternative embodiment, the calcined catalyst
can be treated with an aqueous solution of a mineral acid
such as for example HNO3, H2SO4, H3PO4, HClO4.
By means of treatment of that aqueous solution of
mineral acid, a pH of between 0 and 1.5 is reached, at
temperatures between 20 and 100°C in a time period
between 10 and 400 minutes, depending on the
concentrations of acid and the treatment temperature. The
ratio of catalyst to aqueous solution of acid lies
between 0.05 and 1, and preferably between 0.1 and 0.5 by
weight.
The resulting material, whether or not treated with
acid, but containing acid centres in its structure, once
it has been calcined at a temperature between 450 and
700°C, is used as a catalyst.
The ITQ-22 material can be used in the following
applications:
As an additive of catalytic cracking catalysts for
hydrocarbons, and for organic compounds in general.
As a component of hydrocracking and gentle hydrocracking
catalysts.
As a component or additive of isomerisation catalysts for
light paraffins.
As a component of deparaffining and isodeparaffining
catalysts.
As an alkylation catalyst of isoparaffins with olefins
and alkylation of aromatics and aromatics substituted

with olefins, alcohols or polyalkylated aromatics, and
more specifically as a catalyst for the alkylation of
benzene with propylene.
As a catalyst in acylation reactions, preferably in
acylation reactions of substituted aromatic compounds
using acids, acid chlorides or anhydrides of organic
acids as acylating agents.
As catalysts in oxidation reactions, preferably of the
Meerwein-Pondorf-Verley type.
An especially preferred use is as an additive of
catalytic cracking catalysts for hydrocarbons, and for
organic compounds in general. Zeolite ITQ-22 has a three-
dimensional topology with a system of pores and
dimensions different from any other zeolite used so far
in FCC catalysts. This zeolite contains pores formed by
of 8, 10 and 12 membered rings connected, and it is
precisely this topology which gives rise to a specific
behaviour in cracking catalysts.
In its use as a cracking catalyst, the zeolitic material
ITQ-22 can be the only zeolitic component of the catalyst
embedded in a matrix, or it can be accompanied by at
least one second zeolitic component, both embedded in a
matrix.
When ITQ-22 is accompanied by another zeolitic component
or components, said second zeolitic component can be
formed of zeolitic structures selected among zeolitic
structures containing pores delimited by rings of 14
members, such as for example SSZ-24, CIT-5, UTD-1;
zeolitic structures containing pores delimited by rings
of 12 members, such as for example zeolite Beta, ITQ-7,
zeolite faujasite Y, SSZ-33; zeolitic structures

containing pores delimited by rings of 11 members, such
as for example NU-86; zeolitic structures containing
pores delimited by rings of 10 members, such as for
example ITQ-13, ZSM-5, SAPO-11, MCM-22, and mixtures
thereof.
Moreover, for the cracking process the catalyst can
consist partially or wholly of a single type of particle
with the material ITQ-22 and the said at least second
component being present in the catalyst in the same
particle, embedded in a matrix. Said particle preferably
comprises at least two zeolitic components which are ITQ-
22 and zeolite faujasite Y in one or more of its variants
selected from the group formed from zeolite faujasite Y,
ultrastable zeolite faujasite Y, zeolite faujasite Y
fully exchanged with rare earths, zeolite faujasite Y
partially exchanged with rare earths, ultrastable zeolite
faujasite Y fully exchanged with rare earths, ultrastable
zeolite faujasite Y partially exchanged with rare earths
and mixtures thereof. Preferably, said second zeolitic
component of the type faujasite Y is present in
quantities between 0.1 and 99.9% by weight with respect
to the total weight of zeolitic components, with the
weight of zeolite ITQ-22 being between 0.1 and 60% by
weight with respect to the total weight of zeolitic
components. The rest of the catalyst composition is
formed by the matrix containing components well known in
the art, such as kaolin, alumina and silica, being able
to also contain P2O5.
When zeolite ITQ-22 is used in cracking together
with at least one other zeolitic component and wherein
the zeolitic components are embedded in the same

particle, at least some of the particles of the catalytic
cracking catalyst preferably comprise:
- 0.1-40% by weight of the zeolitic material ITQ-22 with
respect to the total weight of zeolitic components
- 0.1-99.9% by weight of the zeolite faujasite Y with
respect to the total weight of zeolitic components.
In its use in cracking processes, zeolite ITQ-22 can
form part of a catalyst partially or wholly constructed
of at least two types of particle in which the zeolitic
material ITQ-22 and said at least one second zeolitic
material are embedded in a matrix, the zeolitic material
ITQ-22 and said second zeolitic component being present
in different particles, the catalyst being a physical
mixture of particles of different nature. So, in this
case, each zeolite would be incorporated separately into
a matrix. The final mixture of the catalyst would be
formed by a mixture of at least two types of particle,
with each type of particle incorporating a different
zeolitic component. The final mixture would preferably be
formed by a type of particle that includes ITQ-22 in a
matrix, and by a second type of particle that includes
zeolite faujasite Y in any of the different forms of
faujasite Y, embedded in a second matrix. An FCC catalyst
would be formed by this type of said mixture of
particles; particles with ITQ-22 and particles with
zeolite faujasite Y in any of its two forms.
When zeolite ITQ-22 is used in a cracking process
with another zeolitic component or components, with the
zeolitic components being embedded in different types of
particle, the catalytic cracking catalyst preferably
comprises:

- 0.1-40% by weight of particles containing zeolite ITQ-
22 with respect to the sum of zeolitic components, in
which each particle comprises 10-70% by weight of zeolite
ITQ-22;
0.1-99.9% by weight of particles containing a
conventional catalytic cracking catalyst based on
faujasite type zeolite, in which the percentages are
indicated on the sum of zeolitic components.
In the case that the catalyst for use in cracking
comprises ITQ-22 and another zeolitic component or
components, contained in particles of different type,
said catalyst can have a composition in which there
exists at least a third type of particle, in which a
third zeolite would be included in a matrix. This third
zeolite is preferably ZSM-5.
Of course, and as is known in the art, a final
catalyst could also contain other particles with the aim
of, for example, and without being limiting, improving
fluidisation, trapping contaminants (such as for example
metals, nitrogen, Na+) , converting beds, trapping SOx. In
particular, an FCC catalyst could contain these types of
additional particles mentioned.
In the catalytic cracking catalyst described which
contains ITQ-22, zeolite faujasite Y and ZSM-5, a
physical mixture of separate particles is preferred in
which the zeolitic components are to be found in the
following proportions: Zeolite faujasite Y at no less
than 20% by weight with respect to the total weight of
zeolitic components; zeolite ITQ-22 + ZSM-5 at a maximum
of 80% by weight, the ratio by weight between zeolite
ZSM-5 and zeolite ITQ-22 lying between 10 and 0.

When the catalyst contains zeolite ITQ-22 and at
least two other zeolitic components, contained in
particles of different type, the third component is
preferably zeolite ZSM-5.
For its use in cracking, the catalyst can comprise
more than three types of different particles, in
particular FCC catalysts which can also contain other
particles for improving fluidisation, etc.
The catalyst particles include components that are
not active in the catalytic process though they are
necessary in order to conform them, such as binders
and/or conventional additives such as clays, among
others.
The zeolitic components can include one or more TIV
elements, such as for example Si and also other TIII
element or elements, preferably selected from the group
made up of Al, Fe, Ge, Ga, Zn, Ti, B and mixtures
thereof. It can also include phosphorus. Likewise, they
can be exchanged with divalent and/or trivalent ions or
with rare earths. Also optionally, they can contain
compounds of vanadium, and optionally cerium, added in a
stage subsequent to the synthesis of the zeolite.
Both when the zeolitic components are to be found in the
same particle and when the zeolitic components are to be
found in separate particles, zeolite faujasite Y can be
added to the cracking catalyst in various forms, such as
zeolite HY, ultrastable zeolite faujasite Y (USY),
zeolite faujasite Y totally exchanged with rare earths
(REY) or with rare earths and H+ (HREY), zeolite USY
partially exchanged with rare earths (REUSY), or zeolite
type Y exchanged with rare earths and calcined (CREY).

When a catalytic cracking catalyst comprises ITQ-22 with
at least two other zeolitic components in separate
particles, each type of catalyst particle can comprise
one or more or the zeolitic components.
Both in the case of the catalyst containing ITQ-22 as the
sole zeolitic component and in the case of its containing
another zeolitic component or components, in order to
form the catalyst particles a matrix is used containing
at least one binder such as silica, alumina, silica-
alumina, P2O5 and mixtures thereof. The final particles
of catalyst can also contain conventional additives for
catalytic cracking such as clays.
In particular, in FCC catalysts, the catalyst can
contain any conventional material, such as for example
kaolin, in order to conform catalysts with various sizes
of particle. When an FCC catalyst is prepared, a
suspension can be made and atomised in order to form the
particles of the catalyst. In the case of FCC units,
particles of between 60 and 200 micrometres are
preferred.
The different zeolitic components of the zeolitic
material ITQ-22 which form part of a catalyst for use in
cracking can include one or more TIV elements, such as
for example Si and Ge and also include at least one TIII
element. Said TIII element is preferably selected from the
group made up of Al, Fe, Ge, Ga, Zn, Ti, B and mixtures
thereof.
In the case of catalytic cracking in FCC units,
zeolite ITQ-22 can be modified by means of the addition
of phosphorus. In its initial composition, the molar
ratio between TIV and TIII lies between 8 and 10000 and

preferably between 20 and 1000. The cracking catalyst can
also contain one or more alkaline metals. In no case may
the quantity of alkaline metal, if there is any, exceed
0.25% by weight of Na2O.
The zeolitic components that can form part of the
cracking catalyst, including the zeolitic material ITQ-
22, as has been stated earlier, can contain phosphorus.
The quantity of phosphorus present preferably lies
between 0 and 8% by weight with respect to zeolite ITQ-
22. The phosphorus can be incorporated by impregnation in
a, for example aqueous, solution of at least one acid or
salt chosen from the group consisting of H3PO4, (NH4)3PO4,
(NH4)2HPO4, (NH4)H2PO4. The product obtained is calcined at
a temperature between 350 and 700 °C.
The zeolitic components that can form part of the
cracking catalyst, including the zeolitic material ITQ-
22, can be exchanged with divalent and/or trivalent ions
or they can be exchanged wholly or partially with rare
earths.
For use in cracking, the catalyst can contain compounds
of vanadium and optionally cerium added in a stage
subsequent to the synthesis of zeolite ITQ-22.
For use in cracking the catalyst particles can have
a size between 20 and 400 micrometres. In a preferred
embodiment the catalyst is formed from particles with a
size between 60 and 200 micrometres.
The zeolite ITQ-22 can be used in an FCC cracking
process and in deep catalytic cracking (DCC), a process
which consists of placing the feed in contact with the
catalyst in a reactor for a length of time between 0.1
and 80 s and recovering the resulting product.

By means of using zeolite ITQ-22, gasoline is
obtained with a lower content of aromatics, with a higher
content of olefins and isoparaffins, less dry gas, higher
octane-barrel number and a greater propylene/propane
ratio than when a catalyst that does not contain ITQ-22
is used.
An especially preferred additional use for zeolite
ITQ-22 is as a catalyst in an alkylation reaction. In
said alkylation reaction, a suitable quantity of the
catalyst is used along with an alkylating agent selected
among olefins, alcohols, polyalkylated aromatic compounds
and mixtures thereof in the alkylation of aromatic
compounds.
Said alkylation reaction is preferably conducted
with a molar ratio of alkylating agent to starting
aromatic compound of between 2 and 20, in the presence of
the catalyst.
When the alkylating agent is selected among an
olefin, alcohol and mixtures thereof, said olefin and
said alcohol preferably contain from between 2 to 20
carbon atoms.
In a preferred manner, the starting aromatic
compound is selected among a group formed of benzene,
naphthalene, anthracene, phenanthrene and substituted
derivatives thereof, and still more preferably, the
starting aromatic compound is benzene.
The starting aromatic compound can also be selected among
alkylbenezene, alkylanthracene, alkylphenanthrene,
hydroxybenzene, hydroxynaphthalene, hydroxyanthracene,
hydroxyphenanthrene, alcoxybenzene, alcoxynaphthalene,
alcoxyanthracene and alcoxyphenanthrene.

The alkylating agent is preferably a polyalkylated
aromatic compound and the starting aromatic compound is a
non-alkylated aromatic compound, so that during the
alkylation at least one alkyl group is transferred from
the polyalkylated aromatic compound to the starting
aromatic compound.
When the alkylating agent is a polyalkylated
aromatic compound, the alkyl group or the alkyl groups of
said polylalkylating agent can contain a variable number
of carbon atoms. In a preferred way, said alkyl group or
groups can contain from 2 up to 20 carbon atoms,
preferably from 6 to 20 carbons atoms.
When the alkylating agent is a polyalkylated
aromatic compound and the starting aromatic compound is a
non-alkylated aromatic compound, said starting aromatic
compound is preferably selected among benzene,
naphthalene, anthracene, phenanthrene, substituted
benzene, substituted naphthalene, substituted anthracene
and substituted phenanthrene.
The alkylating agent is preferably a polyalkylated
aromatic agent and the starting aromatic compound is
benzene. Still more preferably, said polyalkylated
aromatic compound is polyisopropylbenzene and the
starting aromatic compound is benzene, so that the
alkylation of benzene with propylene produces cumene.
A preferred use of ITQ-22 therefore refers to the
alkylation of benzene with an alkylating agent selected
among propylene, ethylene, ethyl alcohol, propyl alcohol
and mixtures thereof.
According to the use of zeolite ITQ-22 in
alkylation, the alkylation reaction is conducted at a

reaction temperature of between 60 and 350°C, and
preferably between 80 and 300°C.
The alkylation reaction is conducted at sufficient
pressure for maintaining a liquid phase, at least
partially, preferably in a range between 1.4 and 7.0 MPa,
and more preferably between 1.4 and 4.1 MPa.
In the alkylation reaction, the spatial velocity
(WHSV) of reagents lies between 0.2 and 150 hours-1 and
preferably between 0.5 and 10 hours"1.
The alkylation reaction of benzene with propylene is
preferably conducted under the following conditions:
reaction temperature lying between 60 and 350°C, and
preferably between 80 and 300°C; the pressure at which it
is carried out is also sufficient for maintaining a
liquid phase, at least partially, preferably being in a
range between 1.4 and 7.0 MPa, and more preferably
between 1.4 and 4.1 MPa; the spatial velocity (WHSV) of
reagents lies between 0.2 and 150 hours-1 and preferably
between 0.5 and 10 hours-1 and the benzene/propylene
molar ratio is between 2 and 20, and preferably 2
and 15.
When ITQ-22 is applied in its acid form in the
alkylation of aromatics with olefins or alcohols, and
more specifically when it is used as a catalyst in the
alkylation of benzene with propylene it turns out to be a
highly active catalyst, and with a surprisingly low
selectivity for the production of NPB. Moreover, the
selectivity to cumene can be increased by introducing
suitable quantities of alkaline or alkaline earth metals
or metallic cations by means of ion exchange in the
material. Its selectivity can also be increased by

eliminating surface acidity by means of extraction of
trivalent cations from the lattice, such as for example
Al and/or B, by means of treatment with mineral acids or
other chemical agents capable of extracting those
elements. The cationic exchange treatments or leaching
stated above permit a reduction in the formation of
polyalkylated products.
When the ITQ-22 material contains Ti, it is especially
useful as a catalyst in epoxidation reactions of olefins,
oxidation of alkanes, oxidation of alcohols and oxidation
of thioethers to sulphoxides and sulphones using organic
or inorganic hydroperoxides, such as for example H2O2,
tertbutylhydroperoxide, cumene hydroperoxide, as
oxidising agents, in the amoximation of ketones, and more
specifically of cyclohexanone to cyclohexanone oxime with
NH3 and H2O2. When the ITQ-22 material contains Sn it is
particularly useful as a catalyst in Baeyer-Villiger
oxidation reactions in which H2O2 is used as an oxidising
agent.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 represents the X-ray diffraction pattern of
a sample of ITQ-22 as synthesised, in which the lattice
consists solely of silicon and germanium oxides, with a
ratio Si/Ge = 3.8 and which has been synthesised using
the quaternary ammonium cation 1,5-bis
(methylpyrrolidinium) pentane as structure directing
agent.
Figure 2 shows the X-ray diffraction pattern of the
same sample of ITQ-22 after being calcined at 580°C in

order to eliminate organic compounds occluded in its
interior.
EXAMPLES
EXAMPLE 1:
This example illustrates the preparation of the
dihydroxide of 1,5-bis (methylpyrrolidinium) pentane.
In a 500 ml flask, 18.7 g of 1,5-dibromopentane, 20 g of
1-methylpyrrolidine and 300 ml of acetone are mixed. The
mixture is left to reflux for 24 hours, after which the
precipitated solid is separated by decantation and then
washed several times with acetone. Finally it is vacuum
dried and 31.9 g of a white solid are obtained. The
analysis of elements and the nuclear magnetic resonance
spectrum in D2O of this solid indicate that it is the
desired product, namely, 1,5-bis (methylpyrrolidinium)
pentane dibromide.
The dihydroxide form of the structure directing agent is
obtained by means of anion exchange using a Dowex SBR
resin (in molar excess). The exchange is carried out with
stirring of the fluid bed of resin in hydroxide form and
an aqueous solution of the bromide of the cation for one
night. The solution obtained is titrated with HC1 (aq.)
using phenolphthalein as indicator, with an exchange
efficiency of 95% being obtained. This solution can be
concentrated in the rotary evaporator for use in the
synthesis of molecular sieves, for example at a
concentration of 0.5-1 N.

EXAMPLE 2:
This example illustrates the preparation of ITQ-22
by means of using the cation 1,5-bis
(methylpyrrolidinium) pentane.
6.17 g of tetraethylorthosilicate (TEOS) are added
to 23.14 g of a solution of 1,5-bis
(methylpyrrolidinium) pentane dihydroxide (R(OH)2)
containing 0.96 equivalents of hydroxide in 1000 g. In
this mixture 1.55 g of germanium oxide are added, and it
is left to evaporate with stirring until complete
elimination of the ethanol deriving from the hydrolysis
of the TEOS plus the necessary quantity of water so that
the final composition of the gel is:
0.67 SiO2 : 0.33 GeO2 : 0.25 R(OH)2 : 3.5 H2O
The mixture obtained is introduced into an autoclave
internally lined with polytetrafluoroethylene and is
heated at 175°C for 14 days. The autoclave is then
cooled, the contents are filtered, the solid is washed
with water and dried at 100°C. The X-ray diffraction
pattern is shown in Figure I and the list of the most
characteristic peaks appears in Table III. Calcination at
580°C in air for 3 days permits occluded organic species
to be eliminated. The X-ray diffraction pattern of the
calcined zeolite ITQ-22 is shown in Figure 2 and the list
of most characteristic peaks appears in Table IV and
indicates that the material is stable during this
process.
EXAMPLE 3:

The following example illustrates the preparation of
ITQ-22 of different composition.
12 g of tetraethylorthosilicate (TEOS) are added to
27.3 g of a solution of 1,5-bis (methylpyrrolidinium)
pentane dihydroxide (R(OH)2) containing 1.16 equivalents
of hydroxide in 1000 g. In this mixture 0.6 g of
germanium oxide are dissolved, and it is left to
evaporate with stirring until, complete elimination of the
ethanol formed plus the excess of water so that the final
composition is as follows:
0.91 SiO2 : 0.09 GeO2 : 0.25 R(OH)2 : 3.5 H2O
The mixture obtained is heated in autoclaves
internally lined with polytetrafluoroethylene at 175°C
for 14 days. The solid obtained after filtering, washing
with distilled water and drying at 100°C is ITQ-22.
EXAMPLE 4:
This example illustrates synthesis of Al-ITQ-22.
0.09 7 g of Al isopropoxide are added to 9 g of
tetraethylorthosilicate (TEOS). After that, 20.68 g of a
solution of 1,5-bis (methylpyrrolidinium) pentane
dihydroxide (R(OH)2) containing 1.16 equivalents of
hydroxide in 1000 g are added, and then 0.45 g of
germanium oxide are dissolved. The mixture is left to
evaporate with stirring until complete elimination of the
ethanol deriving from the hydrolysis of the TEOS plus the
necessary quantity of water in order to achieve the
stated final composition. The composition of the gel is:
0.91 SiO2 : 0.09 GeO2 : 0.005 Al2O3 : 0.25 R(OH)2
: 3.5 H2O

The mixture obtained is introduced into an autoclave
internally lined with polytetrafluoroethylene and is
heated to 175°C for 12 days.
The X-ray diffraction pattern of the solid obtained after
filtering, washing with distilled water and drying at
100°C indicates that it is ITQ-22.
EXAMPLE 5:
This example illustrates the preparation of a sample
of Al-ITQ-22 with a chemical composition different from
that of the above example.
0.325 g of Al isopropoxide are added to 11.05 g of
tetraethylorthosilicate (TEOS). After that, 34.2 g of a
solution of 1,5-bis (methylpyrrolidinium) pentane
dihydroxide (R(OH)2) containing 1.2 equivalents of
hydroxide in 1000 g are added, and then 2.77 g of
germanium oxide are dissolved. The mixture is left to
evaporate with stirring until complete elimination of the
ethanol deriving from the hydrolysis of the TEOS plus the
necessary quantity of water in order to achieve the
stated final composition. The composition of the gel is:
0.67 SiO2 : 0.33 GeO2 : 0.01 Al2O3 : 0.25 R(OH)2 :
15 H2O
The mixture obtained is introduced into autoclaves
internally lined with polytetrafluoroethylene and is
heated to 175°C for 12 days.
The X-ray diffraction pattern of the solid obtained after
filtering, washing with distilled water and drying at
100°C indicates that it is ITQ-22. The solid obtained is
calcined at 580°C for 3 hours and the X-ray diffraction

pattern shows that the structure is maintained. The
chemical analysis of the calcined zeolite indicates that
it has a composition that accords with the molar ratios
Si/Ge = 5 and (Si + Ge)/Al = 30.
EXAMPLE 6:
This example illustrates the synthesis of Ti-ITQ-22.
0.3 g of Ti(IV) tetraethoxide are added to 9.26 g of
tetraethylorthosilicate (TEOS). After that, 39.97 g of a
solution of 1,5-bis (methylpyrrolidinium) pentane
dihydroxide (R(OH)2) containing 0.85 equivalents of
hydroxide in 1000 g are added, and then 2.32 g of
germanium oxide are dissolved. The mixture is left to
evaporate with stirring until complete elimination of the
ethanol deriving from the hydrolysis of the TEOS plus the
necessary quantity of water in order to achieve the
stated final composition. The composition of the gel is:
0.67 SiO2 : 0.33 GeO2 : 0.02 TiO2 : 0.25 R(OH)2 :
3.5 H2O
The mixture obtained is introduced into an autoclave
internally lined with polytetrafluoroethylene and is
heated to 175°C for 16 days.
The X-ray diffraction pattern of the solid obtained after
filtering, washing with distilled water and drying at.
100°C indicates that it is ITQ-22.
EXAMPLE 7:
This example illustrates the synthesis of Sn-ITQ-22.

To 5.00 g of tetraethylorthosilicate (TEOS), 15.12 g
of a solution of 1,5-bis (methylpyrrolidinium) pentane
dihydroxide (R(OH)2) containing 1.20 equivalents of
hydroxide in 1000 g are added, and then 1.26 g of
germanium oxide are dissolved. After that a solution of
0.105 g of tin (IV) tetrachloride pentahydrate in 2 g of
water is added. The mixture is left to evaporate with
stirring until complete elimination of the ethanol
deriving from the hydrolysis of the TEOS plus the
necessary quantity of water in order to achieve the
stated final composition. The composition of the gel is:
0.67 SiO2 : 0.33 GeO2 : 0.0083 SnO2 : 0.25 R(OH)2
: 3.5 H2O
The mixture obtained is introduced into an autoclave
internally lined with polytetrafluoroethylene and is
heated to 175°C for 23 days.
The X-ray diffraction pattern of the solid obtained after
filtering, washing with distilled water and drying at
100°C indicates that it is ITQ-22.
EXAMPLE 8:
This example illustrates the preparation of a
component of the catalytic cracking catalyst containing
zeolite type ITQ-22 previously activated in order to
obtain the acid form at 580ºC in air.
With the aim of studying the activity and
selectivity of zeolite ITQ-22 in the catalytic cracking
of industrial fractions of petroleum, a catalyst was
prepared mixing ITQ-22 type zeolite, in its acid form, as
was described in example 5 and a silica (BASF D1111),

both in powder form and in a composition of 23% and 77%
by weight of ITQ-22 type zeolite, and SiO2, respectively.
The mixture, thoroughly homogenised, was made into cake
form, crushed in a mortar and sieved taking the fraction
between 0.59 and 0.84 mm in diameter.
EXAMPLE 9:
This example illustrates the use of zeolite ITQ-22
as additive of the catalytic cracking catalyst of a
vacuum gasoil.
The catalytic components described in example 8 were
used as additive of a zeolite US 4 catalyst in the
catalytic cracking of a vacuum gasoil whose
characteristics are given in table V The catalysts are
provided on two separate beds in the reactor as described
in Journal of Catalysis 1997, 165 (1), p. 102. In the
upper zone, 1.5 grams of eolite US 4 catalyst of example
9 are placed, and in the lower zone 1.34 g of catalyst of
example 8.



The reaction conditions were 520°C, reaction time of
30 seconds, 2.34 grams of catalyst and catalyst/feed
ratios by weight of 0.59, 0.73, 0.95, 1.35 and 2.38, the
quantities of gasoil fed being 3.76, 3.07, 2.35, 1.65 and
0.94 grams. The gases produced were analysed by gas
chromatography, the liquids by simulated distillation
(ASTM D-2887) and the coke was measured by analysis (IR)
of the CO2 formed during the combustion. The conversion
is defined as the sum of the yields of gases H2 and C1 -
C4 coke and gasoline (boiling point The composition (PIONA: Paraffins, Isoparaffins, Olefins
and Aromatics) and quality (RON: Research Octane Number)
of the gasoline fraction were determined by gas

chromatography using the "detailed hydrocarbons analysis"
computer program supplied by VARIAN and the correlations
shown in the publication: Lugo, H.J., Ragone, G., and
Zambrano, J., Ind. Eng. Chem. Res. 38, 2111 (1999). The
results obtained by interpolation at 80% of total
conversion are shown in table VI. The use of the zeolite
ITQ-22 as additive of zeolite USY (USY/ITQ-22 Catalyst)
increases the yield of olefins C3 and C4 with respect to
the base catalyst (USY), with a slight drop in the yield
of gasoline. Also, the gasoline obtained has a lower
aromatics content when the catalyst contains the additive
ITQ-22.
It is important to note that the propylene/propane
ratio obtained is greater when ITQ-22 is used as
additive, this result being highly beneficial from the
point of view of a possible industrial process.
Table VI. Selectivities and ratios of interest in the
catalytic cracking of gasoil at 520°C and feed time of 30
s. Fresh additive.





EXAMPLE 10:
The present example illustrates the use of a
material prepared according to example 5 and activated by
calcination in air at 580ºC for 3 hours as a catalyst in
alkylation of benzene with propylene.
An activated sample of the material prepared
according to example 5 was made into cake form, selecting
the particle size between 0.25 and 0.42 mm, in order to
carry out the reaction. The zeolite (0.55 g) was diluted
with silicon carbide (0.59 - 0.84 mm) in a ratio by
weight of SiC/zeolite of 5. The diluted catalyst was
introduced into a tubular steel reactor of diameter 1 cm
and 100 mL.min-1 of N2 was passed under standard
conditions at 150°C for 1.5 hours. The temperature was
then lowered to 20°C and the N2 stream was cut off. At
this point, benzene was fed (1200 uL.min-1) and the
pressure was raised to 3.5 MPa. Once the pressure had
reached 3.5 MPa, the temperature was raised to 125°C and
the propylene started to be fed (270 uL.min-1), the molar
ratio of benzene/propylene being 3.4.
The results of converted propylene are presented in
Table VII.

Table VII: Conversion and selectivity in alkylation of
benzene with propylene at 125°C, B/P = 3.4 mol.mol-1,
WHSV prop = 6 h-1, P = 3.5 MPa for the catalyst Al-ITQ-
22 prepared according to example 5.

In this example, very high values of selectivity to
cumene can be seen along with very low values of NPB and
diisopropylbenzene (DIPB), less than those obtained using
zeolite Beta as catalysts under the same reaction
conditions. The results obtained with a commercial
zeolite Beta of Si/Al = 13 supplied by Zeolyst (code
CP811) are shown in Table VIII.
Table VIII: Conversion and selectivity in alkylation of
benzene with propylene at 125°C, B/P = 3.4 mol.mol-1,
WHSV prop = 6 h-1, P = 3.5 MPa for a commercial catalyst
of zeolite Beta (Si/Al = 13).



From a comparison of the results presented in Tables
VI and VIII, it can be seen that zeolite ITQ-22 displays
greater selectivity to cumene and less to n-propylbenzene
than zeolite Beta, which is the zeolitic catalyst
currently most used for producing cumene.
EXAMPLE 11:
The present example shows the influence of the
reaction temperature on the conversion and selectivity
for alkylation of benzene with propylene using the same
catalyst as in example 10, the rest of the reaction
conditions being the same as in example 10.
The results of the conversion with the reaction time
are presented in Table IX.
Table IX: Conversion and selectivity in alkylation of
benzene with propylene at 150°C, B/P = 3.4 mol.mol-1,
WHSV prop = 6 f-T-1, P = 3.5 MP a for the catalyst Al-ITQ-
22 prepared according to example 5.


EXAMPLE 12:
The present example illustrates the use of a
material prepared according to example 5 and activated by
calcination in air at 580°C for 3 hours as a catalyst in
alkylation of benzene with ethylene.
An activated sample of the material prepared according to
example 5 was made into cake form, selecting the particle
size between 0.25 and 0.42 mm, in order to carry out the
reaction. So, 0.55 g of the zeolite was diluted in 1.57 g
of silicon carbide (0.59 - 0.84 mm). The diluted catalyst
was introduced into a tubular steel reactor of diameter 1
cm. The activation of the catalyst was the same as in
example 10. In the present example the reaction
temperature was 220°C, with 2.90 mmoles of benzene and
0.30 mmoles of ethylene being fed, the pressure of the
process being 3.5 MPa. The results obtained are presented
in Table X.
Table X: Conversion and selectivity in alkylation of
benzene with ethylene at 220°C, B/E =9.6 mol.mol-1, WHSV

ethyl = 1.0 h-1, P = 3.5 MPa for the catalyst Al-ITQ-22
prepared according to example 5.

EXAMPLE 13:
This example illustrates the use of a sample Ti-ITQ-
22 prepared according to example 6 and activated by
calcination in air at 580°C for 3 hours, as a catalyst
for the epoxidation reaction of 1-hexene with hydrogen
peroxide.
1.420 grams of 1-hexene and 0.412 grams of hydrogen
peroxide (35% in water) dissolved in 12.00 g of methanol
are placed in a glass reactor. The reaction mixture is
heated to 60°C and 0.100 grams of activated catalyst Ti-
ITQ-22 are added. After 3 hours of reaction at this
temperature with stirring, a 15% conversion of olefin is
obtained with respect to the maximum possible, bearing in
mind the olefin/oxidising agent molar ratio used in this
example.
EXAMPLE 14:

This example illustrates the use as a catalyst of a
sample Ti-ITQ-22 prepared according to example 6 and
activated by calcination in air at 580°C for 3 hours for
the epoxidation reaction of 1-dodecene with hydrogen
peroxide.
2.780 grams of 1-dodecene and 0.440 grams of
hydrogen peroxide (35% in water) dissolved in 60.00 g of
methanol are placed in a glass reactor. The reaction
mixture is heated to 60°C and 0.100 grams of activated
catalyst Ti-ITQ-22 are added. After 7 hours of reaction
at this temperature with stirring, a 5% conversion of
olefin is obtained with respect to the maximum possible,
bearing in mind the olefin/oxidising agent molar ratio
used in this example.
EXAMPLE 15:
This example illustrates the use of a sample Ti-ITQ-
22 prepared according to example 6 and activated by
calcination in air at 580°C for 3 hours, as a catalyst
for the epoxidation reaction of cyclohexene with terc-
butyl-hydroperoxide.
9.270 grams of cyclohexane and 3.180 grams of terc-
butyl-hydroperoxide are placed in a glass reactor. The
reaction mixture is heated to 60°C and 0.600 grams of
activated catalyst Ti-ITQ-22 are added. After 5 hours of
reaction at this temperature with stirring, a 4%
conversion of olefin is obtained with respect to the
maximum possible, bearing in mind the olefin/oxidising
agent molar ratio used in this example.

EXAMPLE 16:
This example illustrates the use as a catalyst of a
sample Sn-ITQ-22 prepared according to example 7 and
activated by calcination in air at 580°C for 3 hours in
the Baeyer-Villiger reaction between cyclohexanone and
hydrogen peroxide.
0.063 grams of cyclohexanone and 0.078 grams of
hydrogen peroxide (35% in water) dissolved in 1.520 g of
dioxane are placed in a glass reactor. The reaction
mixture is heated to 70°C and 0.025 grams of activated
catalyst Sn-ITQ-22 are added. After 7 hours of reaction
at this temperature with stirring, a 47% conversion of
ketone is obtained with respect to the maximum possible,
bearing in mind the ketone/oxidising agent molar ratio
used in this example.
EXAMPLE 17:
This example illustrates the use as a catalyst of a
sample Sn-ITQ-22 prepared according to example 7 and
activated by calcination in air at 580°C for 3 hours for
the Baeyer-Villiger reaction between adamantanone and
hydrogen peroxide.
0.250 grams of adamantanone and 0.259 grams of
hydrogen peroxide (35% in water), dissolved in 1.530 g of
dioxane, are placed in a glass reactor. The reaction
mixture is heated to 90°C and 0.025 grams of activated
catalyst Sn-ITQ-22 are added. After 7 hours of reaction
at this temperature with stirring, a 22% conversion of

ketone is obtained with respect to the maximum possible,
bearing in mind the ketone/oxidising agent molar ratio
used in this example.

WE CLAIM :
1. A microporous crystalline material of zeolitic
nature which, in the calcined state and in the absence of
defects in its crystal lattice manifested by the presence
of silanols, has the empirical formula
x (H X O2) : y YO2 z GeO2 (1 - z) SiO2
in which:
X is at least one chemical element of oxidation
state +3, preferably selected from the group consisting
of Al, Ga, B, Fe and Cr;
Y is at least one chemical element with oxidation state
+ 4 other than Si and Ge, preferably selected from the
group consisting of Ti, Sn and V,
characterised in that
x has a value less than 0.2, preferably less than 0.1 and
can take the value zero,
y has a value less than 0.1, preferably less than 0.05
and can take the value zero,
z has a value less than 0.8, preferably between 0.005 and
0.5 and can take the value zero,
and in that the material, as synthesised, has an X-ray
diffraction pattern with values of angle 29 (degrees) and
relative intensities (I/I0) concordant with



where
m is a medium relative intensity between 20 and 40%;
s is a strong relative intensity between 40 and 60%, and
vs is a very strong relative intensity between 60 and
100%.
2. A microporous crystalline material of zeolitic nature
as claiemd in claim 1, wherein, in the calcined state, it
has an X-ray diffraction pattern with values of angle 28
(degrees) and relative intensities (I/I0) concordant with

where
m is a medium relative intensity between 20 and 40%;
s is a strong relative intensity between 40 and 60%, and
vs is a very strong relative intensity between 60 and
100%.

3. A method for synthesising the microporous
crystalline material as claimed in claim 1 or 2 in which
a reaction mixture containing
a source of SiO2,
optionally a source of GeO2,
optionally a source of other tetravalent element or
elements Y, preferably Ti, V, Sn,
optionally a source of other trivalent element or
elements X, preferably Al, B, Ga, Fe, Cr,
one or several sources of 1,5-bis (methylpyrrolidinium)
pentane ®, and
water,
is subjected to heating with or without stirring at a
temperature between 80 and 200°C, preferably between 130
and 200°C, until achieving crystallisation, characterised
in that the reaction mixture has a composition in terms
of molar ratios of oxides lying in the ranges
ROH/SiO2 = 0.01-1.0, preferably 0.1-1.0
X2O3/SiO2 = 0-0.1, preferably 0-0.05
YO2/SiO2 = 0-0.1, preferably 0-0.05
GeO2/SiO2 = 0-4, preferably 0.005-1
H2O/SiO2 = 1-50.
4. A method as claimed in claim 3, wherein the
organic cation 1,5-bis (methylpyrrolidinium) pentane is
added in dihydroxide form or in the form of a mixture of
hydroxide and another salt, preferably a halide.
5. A method as claimed in claim 4, wherein a
quantity of crystalline material is added to the reaction
mixture, preferably with the characteristics of the

material of one of claims 1 and 2, as promoter of the
crystallisation, said quantity lying in the range 0.01 to
20% by weight with respect to the total of inorganic
oxides added, preferably between 0.05 and 10%.
6. A process selected among processes of cracking,
hydrocracking, gentle hydrocracking of hydrocarbons
and/or functionalised hydrocarbons, a process of
isomerisation of light paraffins, a process of
deparaf fining or isodeparaff ining, a process of
alkylation of isoparaffins with olefins, a process of
alkylation of aromatic compounds with an alkylating agent
selected among olefins, alcohols, polyalkylated aromattcs
or mixtures thereof, an acylation process, and an
oxidation process characterized in that a microporous
crystalline material as claimed in claim 1 or 2 is used
as a component of the catalyst used in such process.
7. A process as claimed in claim 6, which is a catalytic
cracking process of organic compounds wherein the
catalyst comprises the microporcus crystalline material
as claimed in claim 1 or 2, also referred to as zeolite
ITQ-22 as sole zeolitic component embedded in a matrix,
or zeolite ITQ-22 material together with at least one
second zeolitic component embedded in a matrix.
8. A process as claimed in claim 7 wherein the said
second zeolitic component is formed by zeolitic
structures containing pores delimited by rings of 14
members, by rings of 12 members, by rings of 11 members,
by rings of 10 members and mixtures thereof.

9. A process as claimed in claim 1, wherein at least part
of the catalyst particles comprise a second zeolitic
component selected among one or more of the group
comprising zeolite faujasite Y, ZSM-5 and zeolite Beta.
10. A process as claimed in claim. 7, wherein said
catalyst is partially or wholly constituted by a single
type of particle, with the zeolite ITQ-22 material and
said second zeolitic component being present in the same
particle.
11. A process as claimed in claim 10, wherein the said
second zeolitic component is zeolite faujasite Y under
the form of one or more of its variants selected from the
group consisting of zeolite faujasite Y, ultrastable
zeolite faujasite Y, zeolite faujasite Y fully exchanged
with rare earths, zeolite faujasite Y partially exchanged
with rare earths, ultrastable zeolite faujasite Y fully
exchanged with rare earths, ultrastable zeolite faujasite
Y partially exchanged with rare earths and mixtures
thereof, zeolite ITQ-22 being present in quantities
between 0.1 and 60% by weight with respect to the total
of zeolitic components, and zeolite faujasite Y in a
quantity between 0.1 and 99.9% by weight with respect to
the total of zeolitic components, the rest of the
composition of the catalyst up to 100% being formed by
the matrix.
12. A process as claimed in claim 11, wherein at
least part of the particles of the catalyst comprise:

- 0.1-40% by weight of the zeolitic material ITQ-22 with
respect to the total weight of zeolitic components,
and
- 0.1-99.9% by weight of the zeolite faujasite Y with
respect to the total weight of zeolitic components.
13. A process as claimed in claim 7, wherein said
catalyst consists partially or wholly of at least two
types of particle, with ITQ-22 and said at least one
second zeolitic component being present in different
particles.
14. A process as claimed in claim 13, wherein the
catalytic cracking catalyst comprises:
0.1-40% by weight of particles containing zeolite ITQ-22
with respect to the sum of zeolitic components, wherein
each particle comprises 10-70% by weight of zeolite ITQ-
22;
0.1-99.9% by weight of particles of conventional
catalytic cracking catalyst based on zeolite faujasite Y,
wherein the percentages are indicated with respect to the
sum of zeolitic components.
15. A process as claimed in claim 13, wherein said
catalytic cracking catalyst in addition comprises
particles containing zeolite ZSM-5, the composition of
the catalyst being:
- zeolite faujasite Y in a quantity of at least 20%
by weight with respect to the total weight of zeolitic
components,

- quantity of zeolite ITQ-22 + ZSM-5 is a maximum of 80%
by weight, with respect to the total weight of zeolitic
components, and
- the ratio by weight between zeolite ZSM-5 and zeolite
ITQ-22 lies between 10 and 0.

16. A process as claimed in claim 7, whrein the matrix
contains at least one binder selected among silica,
silica-alumina, alumina, P2O5 and combinations thereof,
and optionally also a conventional additive for catalytic
cracking.
17. A process as claimed in claim 7, wherein any of the
zeolitic components also contain a maximum of 8% by
weight of phosphorus.
18. A process as claimed in claim 7, wherein any of the
zeolitic components are exchanged with ions selected
among divalent ions, trivalent ions, divalent and
trivalent ions, and rare earths.
19. A process as claimed in claim 7, wherein any of the
zeolitic components comprise compounds of vanadium
introduced in a post-synthesis stage.
20. A process as claimed in claim 7, wherein any of the
zeolitic components comprise cerium introduced in a post-
synthesis stage.

21. A process as claimed in claim 7, wherein the catalyst
is formed of particles with a size between 20 and 400
micrometres.
22. A process as claimed in claim 7, wherein the
catalytic process is selected between a catalytic
cracking process in fluid bed (FCC) and a deep catalytic
cracking (DCC) process.
23. A process as claimed in claim 6, wherein the organic
compounds are hydrocarbons derived from fractions of
natural or synthetic petroleum.
24. A process as claimed in claim 6 which is a process
for the alkylation of aromatic compounds, wherein an
alkylating agent selected among an olefin, an alcohol, a
polyalkylated aromatic compound and mixtures thereof is
made to react under alkylation conditions with a starting
aromatic compound in the presence of a catalyst, said
catalyst being ITQ-22.

25. A process as claimed in claim 24, wherein the
starting aromatic compound is selected from the group
consisting of benzene, naphthalene, anthracene,
phenanthrene and substituted derivatives thereof.
26. A process as claimed in claim 24, wherein the
starting aromatic compound is selected among
alkylbenzene, alkylanthracene, alkylphenanthrene,
hydroxybenzene, hydroxynaphthalene, hydroxyanthracene,

hydroxyphenanthrene, alcoxybenzene, alcoxynaphthalene,
alcoxyanthracene and alcoxyphenanthrene.
27. A process as claimed in claim 24, wherein the
alkylating agent is selected among an olefin, an alcohol
and mixtures thereof and said olefin and said alcohol
contain from 2 to 20 carbon atoms.
28. A process as claimed in claim 26, wherein the
alkylating agent is a polyalkylated aromatic compound,
the starting aromatic compound is a non-alkylated
aromatic compound, and in which during the alkylation at
least one alkyl group is transferred from the
polyalkylated aromatic compound to the starting aromatic
compound.
29. A process as claimed in claim 28 wherein said
polyalkylated aromatic compound contains at least one
alkyl group which comprises from 2 up to 20 carbon atoms.
30. A process as claimed in claim 28 wherein the
starting aromatic compound is selected among benzene,
naphthalene, anthracene, phenanthrene, substituted
benzene, substituted naphthalene, substituted anthracene
and substituted phenanthrene.
31. A process as claimed in claim 28 wherein the
polyalkylated aromatic compound is polyisopropylbenzene
and the starting aromatic compound is benzene.

32. A process as claimed in claim 24, wherein the
starting aromatic compound is benzene, the alkylating
agent is propylene and in which the alkylation procedure
produces cumene as alkylated aromatic compound.
33. A process as claimed in claim 24, wherein the
alkylation reaction is conducted at a reaction
temperature of between 60 and 350°C.
34. A process as claimed in claim 24, wherein the
alkylation reaction is conducted at a pressure between
1.4 and 7.0 MPa.
35. A process as claimed in claim 24, wherein the
alkylating agent and the starting aromatic compound are
present in a proportion of between 2 and 20, in the
presence of the catalyst.
36. A process as claimed in claim 24, wherein the
starting aromatic compound is benzene and the alkylating
agent is propylene and the alkylated aromatic compound
that is obtained is cumene; the alkylation reaction is
carried out at a reaction temperature between 60 and
350°C; the pressure at which the alkylation reaction is
carried out lies between 1.4 and 7.0 MPa; the spatial
velocity (WHSV) of reagents lies between 0.2 and 10
hours-1 and the benzene/propylene molar ratio is between
2 and 20.
37. A process as claimed in claim 6, wherein the process
is selected among selective oxidation processes of

organic compounds using an oxidising agent selected among
H2O2 or peroxides, hydroperoxides or organic peracids,
and wherein the material contains Ti.
38. A process as claimed in claim 6, wherein the process
is selected among oxidation processes of the Baeyer-
Villiger type, and wherein the material contains Sn.
39. A process as claimed in claim 6, wherein the process
is selected among oxidation processes of the Meerwein-
Pondorf-Verley type.
40. A process as claimed in claim 6, wherein the process
is selected among hydroisomerisation processes of
olefins, alkylation of olefins with isoparaffins and
alkylation of aromatics with olefins or alcohols.

The present invention refers to a microporous crystalline
material of zeolitic nature (ITQ-22) which, in the
calcined state, has the empirical formula
wherein
M is H+ or at least one inorganic cation of charge
+n;
X is at least one chemical element of oxidation state +3,
preferably selected from the group consisting of Al, Ga,
B, Fe and Cr;
Y is at least one chemical element with oxidation state
+ 4 other than Si and Ge, preferably selected from the
group consisting of Ti, Sn and V;
x has a value less than 0.2, preferably less than 0.1 and
can take the value zero,
y has a value less than 0.1, preferably less than 0.05
and can take the value zero,
z has a value less than 0.8, preferably between 0.005 and
0.5 and can take the value zero,
with a characteristic X-ray diffraction pattern, to the
method of preparation and to the use of the material in
separation and transformation processes of organic
compounds.

Documents:

1772-KOLNP-2004-FORM-27.pdf

1772-kolnp-2004-granted-abstract.pdf

1772-kolnp-2004-granted-assignment.pdf

1772-kolnp-2004-granted-claims.pdf

1772-kolnp-2004-granted-correspondence.pdf

1772-kolnp-2004-granted-description (complete).pdf

1772-kolnp-2004-granted-drawings.pdf

1772-kolnp-2004-granted-examination report.pdf

1772-kolnp-2004-granted-form 1.pdf

1772-kolnp-2004-granted-form 13.pdf

1772-kolnp-2004-granted-form 3.pdf

1772-kolnp-2004-granted-form 5.pdf

1772-kolnp-2004-granted-gpa.pdf

1772-kolnp-2004-granted-pa.pdf

1772-kolnp-2004-granted-priority document.pdf

1772-kolnp-2004-granted-reply to examination report.pdf

1772-kolnp-2004-granted-specification.pdf

1772-kolnp-2004-granted-translated copy of priority document.pdf


Patent Number 230353
Indian Patent Application Number 1772/KOLNP/2004
PG Journal Number 09/2009
Publication Date 27-Feb-2009
Grant Date 25-Feb-2009
Date of Filing 23-Nov-2004
Name of Patentee CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS
Applicant Address C/SERRANO,117, E-28006 MADRID
Inventors:
# Inventor's Name Inventor's Address
1 CORMA CANOS AVELINO C/LOS NRANJOS, S/N E-46022 VALENCIA
2 REY GARCIA FERNANDO C/LOS NRANJOS, S/N E-46022 VALENCIA
3 VALENCIA VALENCIA SUSANA C/LOS NRANJOS S/N E-46022 VALENCIA
4 MARTINEZ TRIGUERO LUIS JOAQUIN C/LOS NRANJOS, S/N E-46022 VALENCIA
PCT International Classification Number B01J 29/04
PCT International Application Number PCT/ES03/00246
PCT International Filing date 2003-05-23
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 P200300444 2003-02-14 Spain
2 P200201249 2002-05-23 Spain