Title of Invention	A PROCESS TO SYNTHESIZE A POROUS CRYSTALLINE MATERIAL
Abstract	The invention relates to a porous crystalline material which, in the calcined state, has a composition: X2O3 : nY02 : mZ02 wherein: X represents a trivalent element; Z represents Ge; and Y represents at least one tetravalent element other than Ge. Furthermore, in the chemical composition, (n+m) is equal to at least 5 and the Y/Z ratio is equal to at least 1. Moreover, in the calcined state, said material has an X-ray diffraction pattern which coincides substantially with (1) , wherein VS is a very strong relative intensity corresponding to a percentage of between 80 and 100 with respect to the most intense peak; M is a mean relative intensity corresponding to a percentage of between 40 and 60 with respect to the most intense peak; and W is a mean relative intensity corresponding to a percentage of between 20 and 40 with respect to the most intense peak.

Title of Invention

A PROCESS TO SYNTHESIZE A POROUS CRYSTALLINE MATERIAL

Abstract

The invention relates to a porous crystalline material which, in the calcined state, has a composition: X2O3 : nY02 : mZ02 wherein: X represents a trivalent element; Z represents Ge; and Y represents at least one tetravalent element other than Ge. Furthermore, in the chemical composition, (n+m) is equal to at least 5 and the Y/Z ratio is equal to at least 1. Moreover, in the calcined state, said material has an X-ray diffraction pattern which coincides substantially with (1) , wherein VS is a very strong relative intensity corresponding to a percentage of between 80 and 100 with respect to the most intense peak; M is a mean relative intensity corresponding to a percentage of between 40 and 60 with respect to the most intense peak; and W is a mean relative intensity corresponding to a percentage of between 20 and 40 with respect to the most intense peak.

Full Text	TITLE OF THE INVENTION PROCESS TO SYNTHESIZE A porous crystalline material (ITO-21) AND THE METHOD OF OBTAINING-THE SAME IN THE ABSENCE OF FLUORIDE IONS TECHNICAL FIELD OF THE INVENTION The present invention belongs to the field of porous crystalline materials and particularly to zeolitic materials. More particularly, the invention fits in the sector of zeolitic materials useful as catalysts or components__of catalysts in processes of conversion of feedstock formed by organic compounds, such as catalytic cracking processes of hydrocarbons, catalytic hydrocracking of hydrocarbons, alkylation of aromatic olefins and in esterification processes, alkylation of aromatics with olefins and in esterification processes, acylation, reaction of aniline with formaldehyde in its acid form and/or exchanged with suitable cations. PRIOR ART Zeolites are porous crystalline aluminosilicates that have found important uses such as catalysts, adsorbing agents and ionic exchangers. Many of these zeolitic materials have well defined structures that form channels and cavities inside of a uniform size and shape that permit adsorption of certain molecules, whereas they prevent from passing inside the crystal other molecules that are too big from spreading through the pores. This characteristic gives these materials properties of molecular sieve. These molecular sieves can include Si and other elements of the group IIIA of the periodic table in the lattice, all of them tetrahedrally coordinated. The tetrahedron are bonded by their vertexes by oxygen atoms forming a three-dimensional lattice. The negative charge generated by the elements of the IIIA group tetrahedrally coordinated in lattice positions is compensated by the presence of cations, such as for example, alkaline or alkaline earth cations, in the crystal. A type of cation may be totally or partially exchanged by another type of cation by means of ionic exchange techniques, being thus possible to vary the properties of a given silicate by selecting the desired cations. Many zeolites have been synthesized in the presence of an organic molecule that acts as a structure directing agent (SDA). The organic molecules that act as structure directing agents (SDA) generally contain nitrogen in their composition and can give rise to organic cations stable in the reaction medium. The mobilization of silica can be carried out in the presence of OH" groups and a basic medium, that can be introduced as a hydroxide of the SDA itself, such as for example, tetrapropylammonium hydroxide in the case of zeolite ZSM-5. The fluoride ions can also act as mobilizing agents of silica in the synthesis of zeolites, such as is described, for example, in patent application EP-A-337479 in accordance with which HF is used in H2O at a low pH as a mobilizing agent of the silica for the synthesis of ZSM-5. However, the use of fluoride ions in the synthesis is less desired from an 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 a specific treatment with waste waters and gases. DESCRIPTION OF THE INVENTION The present invention refers to a microporous crystalline material (hereinafter also called ITQ-21) and the process for obtaining the same in a basic medium, in the absence of added fluoride. This new material has, in the calcined form as well as in the uncalcined synthesized form, an X-ray diffraction pattern that is different from that of other known zeolitic materials. The most important diffraction lines of the material for its calcined are shown in Table 1. TABLE 1 2? (°) (a) Relative _______________________intensity 6.4 VS 11.2 M 18.4 W 19.6 W 21.6 M 26.3 M __________29.3______________ W_______________ (a)±0.2 The crystalline material of this invention named ITQ-21 has a molar composition in its calcined and anhydrous state represented by the equation: X X2O3 : y YO2 : Z ZO2 wherein X is a trivalent element such as Al, B, Fe, In, Ga, Cr or combinations thereof, Y is a tetravalent element such as Si, Ti, Sn or combinations thereof, although Si is preferred, and Z is Ge; wherein the value of (y+z)/x is less than 5, and can be comprised between 7 and a and the value y/z is at least 1. From the values given, it is clearly inferred that the crystalline material ITQ-21 can be synthesized in the absence of added trivalent elements. In turn, the most important diffraction lines for the uncalcined form of the material are the ones given in These diffractograms were obtained with a Philips X'Pert diffractometer equipped with a graphite monochromator and an automatic divergence slot using Ka radiation of copper. The diffraction data were registered by a passing of 20 of 0.01° wherein 0 is the Bragg angle and a count time of 10 seconds per passing. The relative intensity of the lines is calculated as the percentage regarding the most intense peak, and a percentage of 80-100 is considered very strong (vs). a percentage of 60-80 is considered strong (s) , a percentage of 40-60 is considered medium, a percentage of 2 0-40 is considered weak (w) and a percentage of 0-20 is considered very weak (vw). The compensation cations in the material in its uncalcined form, or after thermal treatment, can be exchanged, in the case of being present, by other metallic ions, H+ and H+ precursors such as for example NH+4. Among the cations that can be introduced by ionic exchange, those that can have a positive role in the activity of the material as a catalyst are preferred, and more specifically, cations such as H+' rare earth cations and metals of the group VIII, as well as of group IIA. IIIA, IVA, Va, IB, IIB, IIIB, IVB, VB, VIIB of the periodic chart of elements are preferred. For the purpose of preparing catalysts, the crystalline material of the present invention can be combined closely with hydrogenating-dehydrogenating agents such as platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chrome, manganese, iron. The introduction of these elements can be carried out in the crystallization step, by exchange (if appropriate), and/or by impregnation or by physical mixing. These elements can be introduced in their cationic form and/or as of salts or other compounds which by decomposition produce the metallic component or oxide in its suitable catalytic form. The material ITQ-21 can be prepared in a basic medium and in the absence of added fluoride ions, from a reaction mixture that contains H20, optionally an oxide or a source of the trivalent element X, such as for example Al and/or B, an oxide or source of the element or tetravalent elements Y, such as for example Si; a source of Ge, such as for example GeO2 and an organic structure directing agent (R) generally a salt of N(16)- methylsparteinium, preferably the hydroxide. The composition of the reaction mixture has the following composition in terms of molar ratios of oxides: Crystallization of the material ITQ-21 can be carried out statically or with stirring, in autoclaves at a temperature between 80 and 200°C, at sufficient times to achieve crystallization, for example, between 12 hours and 3 0 days. When the crystallization step ends, the ITQ-21 crystals are separated from the mother liquors and are recovered. It should be taken into account that the components of the synthesis mixture can come from different sources and depending thereon, crystallization times and conditions can be varied. For the purpose of facilitating synthesis, material ITQ-21 crystals can be added as seeds to the synthesis mixture, in amounts up to 15% by weight with respect to the total oxides. These can be added before or during crystallization of the material ITQ-21. The organic agent can be eliminated, for example by extraction and/or by thermal treatment heating at a temperature above 250°C for a period of time between 2 minutes and 25 hours. The material of the present invention can be made into pellets in accordance with known techniques, and can be used as a component of catalysts of catalytic cracking of hydrocarbons, catalytic hydrocracking of hydrocarbons, alkylation of aromatics with olefins and in processes of esterification, acylation, aniline reaction with formaldehyde in its acid form and/or exchanged with suitable cations. EMBODIMENTS OF THE INVENTION Several examples that illustrate aspects of ways of carrying out the invention will be described hereinafter. EXAMPLES Example 1.- Preparation of N(16)-methylsparteinium hydroxide. 20.25 g of (-)-sparteine are mixed with 100 ml of acetone. 17.58 g of methyl iodide are added, drop by drop, to this mixture while the mixture is stirred. After 24 hours, a cream color precipitate appears. 200 ml of diethyl ether are added to the reaction mixture, which is filtered and the solid obtained is vacuum dried. The product is N(16)-methylsparteinium iodide with a yield higher than 95%. The iodide is exchanged by hydroxide using ionic exchange resin, according to the following process: 31.50 g of N(16)-methylsparteinium iodide are dissolved in 92.3 8 g of water. 85 g of Dowes BR resin are added to the solution and kept with stirring until the next day. Subsequently, it is filtered, washed with distilled water and we obtain 124.36 g of a N(16)-methylsparteinium hydroxide solution with a concentration of 0.65 moles/kg. Example 2. 2.08 g of GeO2 are dissolved in 25.43 g of a N- methylsparteinium hydroxide solution with a concentration of 0.59 moles/1000 g. Once dissolved, 4.16 g of tetraethylorthosilicate are hydrolyzed in said solution, allowing to evaporate with stirring until the ethanol formed evaporates. 0.15 g of ITQ-21 crystals suspended in 1.86 g of water are added. The final composition of the synthesis mixture is: 0.67 SiO2 : 0.33 6eO2 : 0.50 C16H29NOH : 4 H2O It is heated at 175°C in steel autoclaves with an inside Teflon casing for 12 days. The solid obtained after filtering, washing and drying at l00°C is ITQ-21, and the most important lines of its diffraction pattern are shown in table 3. In this table VS is a very strong relative intensity corresponding to a percentage of 80-100 with respect to the most intense peak, S is a strong relative intensity, corresponding to a percentage of 60-80 with respect to the most intense peak, M is a medium relative intensity, corresponding to a percentage of 40-60 with respect to the most intense peak, W is a relative weak intensity, corresponding to a percentage of 2 0-40 with respect to the most intense peak, VW is a very weak relative intensity, corresponding to a percentage of 0-20, with respect to the most intensive peak. When the material is calcined at 540°C for 3 hours, the most important diffraction lines of the material are the ones that appear in table 4. Example 3 : 5.21 g of tetraethylorthosilicate are hydrolyzed in 25.43 g of N-methylsparteinium hydroxide solution with a concentration of 0.59 moles/1000 g, wherein 0.54 g of GeO2 have been previously dissolved. The mixture is allowed to evaporate with stirring until the ethanol formed is eliminated. 0.10 g of ITQ-21 crystals suspended in 2.05 g of water are added. The final composition of the mixture is: 0.83 SiO2 t 0.17 6eO2 : 0.50 C16H29NOH : 4 H20 It is heated at 175°C in steel autoclaves with an inside Teflon casing for 13 days. The solid obtained after filtering, washing and drying at 100°C is ITQ-21 with amorphous material. Example 4: 0.33 g of GeO2 are dissolved in 27.95 g of a N- methylsparteinium hydroxide solution with a concentration of 0.59 moles/1000 g. Once dissolved, 6.25 g., of tetraethylorthosilicate are hydrolyzed in said solution, allowing it to evaporate with stirring until the ethanol formed evaporates. 0.15 g of ITQ-21 crystals suspended in 1.86 g of water are added. The final composition is: 0.91 SiO2 t 0.09 GeO2 : 0.50 C16H29NOH : 4 H2O The mixture is heated at 175°C in steel autoclaves with an inside Teflon casing for 24 days. The product obtained is ITQ-21 with amorphous material. Example 5: 0.245 g of aluminum isopropoxide and 5.213 g of tetraethylorthosilicate are hydrolyzed in 26.576 g of a N-methylsparteinium hydroxide solution with a concentration of 0.564 moles/1000 g, wherein 0.528 g of GeO2 have been previously dissolved. The mixture is allowed to evaporate with stirring until the ethanol is eliminated and the isopropanol formed in the hydrolysis. 0.10 g of ITQ-21 crystals suspended in 2.05 g of water are added. The final composition of the mixture is: 0.83SiO2 : 0.17 6eO2 : 0.02 A12O3 t 0.50 C16H29NOH : 6 H2O It is heated at 175°C in steel autoclaves with an inside Teflon casing for 13 days. The product obtained after filtering, washing and drying at 100°C is Al-ITQ-21 with amorphous material. We Claim: 1. A process to synthesize a porous crystalline material that, in a calcined state has a composition X2O3 : n Y02 : m Z02 wherein X is a trivalent element, Z is Ge, Y is at least one tetravalent element other than Ge, (n + m) is at least 5, and the Y/Z ratio is at least 1, and the material, in its calcined form, has an X-ray diffraction pattern substantially coinciding with wherein VS is a very strong relative intensity corresponding to a percentage of 80-100 with respect to the most intense peak; M is a medium relative intensity, corresponding to a percentage of 40-60 with respect to the most intense peak, and W is a weak relative intensity, corresponding to a percentage of 20-40 of the most intense peak, said process comprising: - a synthesis step taking place in a basic medium in the absence of added fluoride wherein a synthesis mixture that comprises a source of the trivalent material X, H20, a source of the tetravalent material Y, a source of the tetravalent material Z and a structure directing agent (R) , whose synthesis mixture has a composition, in terms of molar ratios of oxides of is subjected to reaction at a temperature between 80 and 200°C until crystals of the synthesized material are obtained; - a recovery step wherein the crystals of the synthesized material are separated from the mother liquor; and a calcination step, wherein the crystals of the synthesized material that have been recovered are calcined. 2. The process as claimed in claim 1, wherein the process comprises an elimination step, wherein organic material occluded inside the recovered material, is eliminated through an elimination method, selected among an extraction method, thermal treatments at temperatures higher than 250°C for a period of time comprised between 2 minutes and 25 hours, and combinations thereof. 3. The process as claimed in any of the claims 1 and 2, wherein the mixture has a composition, in terms of molar ratio of 4. The process as claimed in one of the claims 1 to 3, wherein R is a salt of N(16)-methylsparteinium. 5. The process as claimed in any one of claims 1 to 3 wherein Y is an oxide of the tetravalent material. 6. The process as claimed in any of the claims 1 to 3, wherein Z is an oxide of the tetravalent material. 7. The process as claimed in any one of the claim 1 to 6, wherein the prorous crystalline material in its uncalcinated form, has an X-ray diffraction pattern substantially coinciding with wherein VS is a very strong relative intensity, corresponding to a percentage of 80-100 with respect to the most intense peak, S is a strong relative intensity, corresponding to a percentage of 60-80 with respect to the most intense peak, M is a medium relative intensity, corresponding to a percentage of 40-60 with respect to the most intense peak, and W is a weak relative intensity, corresponding to a percentage of 20-40 with respect to the most intense peak. 8. The process as claimed in any one of the claims 1 to 7, wherein X is at least one trivalent element selected from the group consisting of Al, B, In, Ga, Fe; Y is at least one tetravalent element selected from the group consisting of Si, Sn, Ti and V. 9. The process as claimed in any one of the claims 1 to 8, wherein X is B, Al or B+Al and Y is Si. The invention relates to a porous crystalline material which, in the calcined state, has a composition: X2O3 : nY02 : mZ02 wherein: X represents a trivalent element; Z represents Ge; and Y represents at least one tetravalent element other than Ge. Furthermore, in the chemical composition, (n+m) is equal to at least 5 and the Y/Z ratio is equal to at least 1. Moreover, in the calcined state, said material has an X-ray diffraction pattern which coincides substantially with (1) , wherein VS is a very strong relative intensity corresponding to a percentage of between 80 and 100 with respect to the most intense peak; M is a mean relative intensity corresponding to a percentage of between 40 and 60 with respect to the most intense peak; and W is a mean relative intensity corresponding to a percentage of between 20 and 40 with respect to the most intense peak.

Full Text

TITLE OF THE INVENTION
PROCESS TO SYNTHESIZE A
porous crystalline material (ITO-21) AND THE METHOD OF
OBTAINING-THE SAME IN THE ABSENCE OF FLUORIDE IONS
TECHNICAL FIELD OF THE INVENTION
The present invention belongs to the field of porous
crystalline materials and particularly to zeolitic
materials. More particularly, the invention fits in the
sector of zeolitic materials useful as catalysts or
components__of catalysts in processes of conversion of
feedstock formed by organic compounds, such as catalytic
cracking processes of hydrocarbons, catalytic
hydrocracking of hydrocarbons, alkylation of aromatic
olefins and in esterification processes, alkylation of
aromatics with olefins and in esterification processes,
acylation, reaction of aniline with formaldehyde in its
acid form and/or exchanged with suitable cations.
PRIOR ART
Zeolites are porous crystalline aluminosilicates
that have found important uses such as catalysts,
adsorbing agents and ionic exchangers. Many of these
zeolitic materials have well defined structures that form
channels and cavities inside of a uniform size and shape
that permit adsorption of certain molecules, whereas they
prevent from passing inside the crystal other molecules
that are too big from spreading through the pores. This
characteristic gives these materials properties of
molecular sieve. These molecular sieves can include Si
and other elements of the group IIIA of the periodic
table in the lattice, all of them tetrahedrally
coordinated. The tetrahedron are bonded by their
vertexes by oxygen atoms forming a three-dimensional
lattice. The negative charge generated by the elements
of the IIIA group tetrahedrally coordinated in lattice
positions is compensated by the presence of cations, such
as for example, alkaline or alkaline earth cations, in
the crystal. A type of cation may be totally or
partially exchanged by another type of cation by means of
ionic exchange techniques, being thus possible to vary
the properties of a given silicate by selecting the
desired cations.
Many zeolites have been synthesized in the presence
of an organic molecule that acts as a structure directing
agent (SDA). The organic molecules that act as structure
directing agents (SDA) generally contain nitrogen in
their composition and can give rise to organic cations
stable in the reaction medium.
The mobilization of silica can be carried out in the
presence of OH" groups and a basic medium, that can be
introduced as a hydroxide of the SDA itself, such as for
example, tetrapropylammonium hydroxide in the case of
zeolite ZSM-5. The fluoride ions can also act as
mobilizing agents of silica in the synthesis of zeolites,
such as is described, for example, in patent application
EP-A-337479 in accordance with which HF is used in H2O at
a low pH as a mobilizing agent of the silica for the
synthesis of ZSM-5. However, the use of fluoride ions in
the synthesis is less desired from an 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 a specific treatment
with waste waters and gases.
DESCRIPTION OF THE INVENTION
The present invention refers to a microporous
crystalline material (hereinafter also called ITQ-21) and
the process for obtaining the same in a basic medium, in
the absence of added fluoride. This new material has, in
the calcined form as well as in the uncalcined
synthesized form, an X-ray diffraction pattern that is
different from that of other known zeolitic materials.
The most important diffraction lines of the material for
its calcined are shown in Table 1.
TABLE 1
2? (°) (a) Relative
_______________________intensity
6.4 VS
11.2 M
18.4 W
19.6 W
21.6 M
26.3 M
__________29.3______________ W_______________
(a)±0.2
The crystalline material of this invention named
ITQ-21 has a molar composition in its calcined and
anhydrous state represented by the equation:
X X2O3 : y YO2 : Z ZO2
wherein
X is a trivalent element such as Al, B, Fe, In, Ga,
Cr or combinations thereof,
Y is a tetravalent element such as Si, Ti, Sn or
combinations thereof, although Si is preferred,
and Z is Ge;
wherein the value of (y+z)/x is less than 5, and can be
comprised between 7 and a and the value y/z is at least
1.
From the values given, it is clearly inferred that
the crystalline material ITQ-21 can be synthesized in the
absence of added trivalent elements.
In turn, the most important diffraction lines for
the uncalcined form of the material are the ones given in
These diffractograms were obtained with a Philips
X'Pert diffractometer equipped with a graphite
monochromator and an automatic divergence slot using Ka
radiation of copper. The diffraction data were
registered by a passing of 20 of 0.01° wherein 0 is the
Bragg angle and a count time of 10 seconds per passing.
The relative intensity of the lines is calculated as the
percentage regarding the most intense peak, and a
percentage of 80-100 is considered very strong (vs). a
percentage of 60-80 is considered strong (s) , a
percentage of 40-60 is considered medium, a percentage of
2 0-40 is considered weak (w) and a percentage of 0-20 is
considered very weak (vw).
The compensation cations in the material in its
uncalcined form, or after thermal treatment, can be
exchanged, in the case of being present, by other
metallic ions, H+ and H+ precursors such as for example
NH+4. Among the cations that can be introduced by ionic
exchange, those that can have a positive role in the
activity of the material as a catalyst are preferred, and
more specifically, cations such as H+' rare earth cations
and metals of the group VIII, as well as of group IIA.
IIIA, IVA, Va, IB, IIB, IIIB, IVB, VB, VIIB of the
periodic chart of elements are preferred.
For the purpose of preparing catalysts, the
crystalline material of the present invention can be
combined closely with hydrogenating-dehydrogenating
agents such as platinum, palladium, nickel, rhenium,
cobalt, tungsten, molybdenum, vanadium, chrome,
manganese, iron. The introduction of these elements can
be carried out in the crystallization step, by exchange
(if appropriate), and/or by impregnation or by physical
mixing. These elements can be introduced in their
cationic form and/or as of salts or other compounds which
by decomposition produce the metallic component or oxide
in its suitable catalytic form.
The material ITQ-21 can be prepared in a basic
medium and in the absence of added fluoride ions, from a
reaction mixture that contains H20, optionally an oxide
or a source of the trivalent element X, such as for
example Al and/or B, an oxide or source of the element or
tetravalent elements Y, such as for example Si; a source
of Ge, such as for example GeO2 and an organic structure
directing agent (R) generally a salt of N(16)-
methylsparteinium, preferably the hydroxide.
The composition of the reaction mixture has the
following composition in terms of molar ratios of oxides:
Crystallization of the material ITQ-21 can be
carried out statically or with stirring, in autoclaves at
a temperature between 80 and 200°C, at sufficient times
to achieve crystallization, for example, between 12 hours
and 3 0 days.
When the crystallization step ends, the ITQ-21
crystals are separated from the mother liquors and are
recovered. It should be taken into account that the
components of the synthesis mixture can come from
different sources and depending thereon, crystallization
times and conditions can be varied. For the purpose of
facilitating synthesis, material ITQ-21 crystals can be
added as seeds to the synthesis mixture, in amounts up to
15% by weight with respect to the total oxides. These
can be added before or during crystallization of the
material ITQ-21.
The organic agent can be eliminated, for example by
extraction and/or by thermal treatment heating at a
temperature above 250°C for a period of time between 2
minutes and 25 hours.
The material of the present invention can be made
into pellets in accordance with known techniques, and can
be used as a component of catalysts of catalytic cracking
of hydrocarbons, catalytic hydrocracking of hydrocarbons,
alkylation of aromatics with olefins and in processes of
esterification, acylation, aniline reaction with
formaldehyde in its acid form and/or exchanged with
suitable cations.
EMBODIMENTS OF THE INVENTION
Several examples that illustrate aspects of ways of
carrying out the invention will be described hereinafter.
EXAMPLES
Example 1.- Preparation of N(16)-methylsparteinium
hydroxide.
20.25 g of (-)-sparteine are mixed with 100 ml of
acetone. 17.58 g of methyl iodide are added, drop by
drop, to this mixture while the mixture is stirred. After
24 hours, a cream color precipitate appears. 200 ml of
diethyl ether are added to the reaction mixture, which is
filtered and the solid obtained is vacuum dried. The
product is N(16)-methylsparteinium iodide with a yield
higher than 95%.
The iodide is exchanged by hydroxide using ionic
exchange resin, according to the following process: 31.50
g of N(16)-methylsparteinium iodide are dissolved in
92.3 8 g of water. 85 g of Dowes BR resin are added to
the solution and kept with stirring until the next day.
Subsequently, it is filtered, washed with distilled water
and we obtain 124.36 g of a N(16)-methylsparteinium
hydroxide solution with a concentration of 0.65 moles/kg.
Example 2.
2.08 g of GeO2 are dissolved in 25.43 g of a N-
methylsparteinium hydroxide solution with a concentration
of 0.59 moles/1000 g. Once dissolved, 4.16 g of
tetraethylorthosilicate are hydrolyzed in said solution,
allowing to evaporate with stirring until the ethanol
formed evaporates. 0.15 g of ITQ-21 crystals suspended
in 1.86 g of water are added. The final composition of
the synthesis mixture is:
0.67 SiO2 : 0.33 6eO2 : 0.50 C16H29NOH : 4 H2O
It is heated at 175°C in steel autoclaves with an
inside Teflon casing for 12 days. The solid obtained
after filtering, washing and drying at l00°C is ITQ-21,
and the most important lines of its diffraction pattern
are shown in table 3.
In this table
VS is a very strong relative intensity corresponding
to a percentage of 80-100 with respect to the most
intense peak,
S is a strong relative intensity, corresponding to a
percentage of 60-80 with respect to the most intense
peak,
M is a medium relative intensity, corresponding to a
percentage of 40-60 with respect to the most intense
peak,
W is a relative weak intensity, corresponding to a
percentage of 2 0-40 with respect to the most intense
peak,
VW is a very weak relative intensity, corresponding
to a percentage of 0-20, with respect to the most
intensive peak.
When the material is calcined at 540°C for 3 hours,
the most important diffraction lines of the material are
the ones that appear in table 4.
Example 3 :
5.21 g of tetraethylorthosilicate are hydrolyzed in
25.43 g of N-methylsparteinium hydroxide solution with a
concentration of 0.59 moles/1000 g, wherein 0.54 g of
GeO2 have been previously dissolved. The mixture is
allowed to evaporate with stirring until the ethanol
formed is eliminated. 0.10 g of ITQ-21 crystals
suspended in 2.05 g of water are added. The final
composition of the mixture is:
0.83 SiO2 t 0.17 6eO2 : 0.50 C16H29NOH : 4 H20
It is heated at 175°C in steel autoclaves with an
inside Teflon casing for 13 days. The solid obtained
after filtering, washing and drying at 100°C is ITQ-21
with amorphous material.
Example 4:
0.33 g of GeO2 are dissolved in 27.95 g of a N-
methylsparteinium hydroxide solution with a concentration
of 0.59 moles/1000 g. Once dissolved, 6.25 g., of
tetraethylorthosilicate are hydrolyzed in said solution,
allowing it to evaporate with stirring until the ethanol
formed evaporates. 0.15 g of ITQ-21 crystals suspended
in 1.86 g of water are added. The final composition is:
0.91 SiO2 t 0.09 GeO2 : 0.50 C16H29NOH : 4 H2O
The mixture is heated at 175°C in steel autoclaves
with an inside Teflon casing for 24 days. The product
obtained is ITQ-21 with amorphous material.
Example 5:
0.245 g of aluminum isopropoxide and 5.213 g of
tetraethylorthosilicate are hydrolyzed in 26.576 g of a
N-methylsparteinium hydroxide solution with a
concentration of 0.564 moles/1000 g, wherein 0.528 g of
GeO2 have been previously dissolved. The mixture is
allowed to evaporate with stirring until the ethanol is
eliminated and the isopropanol formed in the hydrolysis.
0.10 g of ITQ-21 crystals suspended in 2.05 g of water
are added. The final composition of the mixture is:
0.83SiO2 : 0.17 6eO2 : 0.02 A12O3 t 0.50 C16H29NOH : 6 H2O
It is heated at 175°C in steel autoclaves with an
inside Teflon casing for 13 days. The product obtained
after filtering, washing and drying at 100°C is Al-ITQ-21
with amorphous material.
We Claim:
1. A process to synthesize a porous crystalline material
that, in a calcined state has a composition
X2O3 : n Y02 : m Z02
wherein X is a trivalent element, Z is Ge, Y is at least
one tetravalent element other than Ge, (n + m) is at least
5, and the Y/Z ratio is at least 1, and the material, in
its calcined form, has an X-ray diffraction pattern
substantially coinciding with
wherein
VS is a very strong relative intensity corresponding to a
percentage of 80-100 with respect to the most intense peak;
M is a medium relative intensity, corresponding to a
percentage of 40-60 with respect to the most intense peak,
and
W is a weak relative intensity, corresponding to a
percentage of 20-40 of the most intense peak,
said process comprising:
- a synthesis step taking place in a basic medium in the
absence of added fluoride wherein a synthesis mixture that
comprises a source of the trivalent material X, H20, a
source of the tetravalent material Y, a source of the
tetravalent material Z and a structure directing agent (R) ,
whose synthesis mixture has a composition, in terms of
molar ratios of oxides of
is subjected to reaction at a temperature between 80 and
200°C until crystals of the synthesized material are
obtained;
- a recovery step wherein the crystals of the synthesized
material are separated from the mother liquor; and
a calcination step, wherein the crystals of the
synthesized material that have been recovered are calcined.
2. The process as claimed in claim 1, wherein the process
comprises an elimination step, wherein organic material
occluded inside the recovered material, is eliminated
through an elimination method, selected among an extraction
method, thermal treatments at temperatures higher than 250°C
for a period of time comprised between 2 minutes and 25
hours, and combinations thereof.
3. The process as claimed in any of the claims 1 and 2,
wherein the mixture has a composition, in terms of molar
ratio of
4. The process as claimed in one of the claims 1 to 3,
wherein R is a salt of N(16)-methylsparteinium.
5. The process as claimed in any one of claims 1 to 3
wherein Y is an oxide of the tetravalent material.
6. The process as claimed in any of the claims 1 to 3,
wherein Z is an oxide of the tetravalent material.
7. The process as claimed in any one of the claim 1 to 6,
wherein the prorous crystalline material in its
uncalcinated form, has an X-ray diffraction pattern
substantially coinciding with
wherein
VS is a very strong relative intensity, corresponding
to a percentage of 80-100 with respect to the most intense
peak,
S is a strong relative intensity, corresponding to a
percentage of 60-80 with respect to the most intense peak,
M is a medium relative intensity, corresponding to a
percentage of 40-60 with respect to the most intense peak,
and
W is a weak relative intensity, corresponding to a
percentage of 20-40 with respect to the most intense peak.
8. The process as claimed in any one of the claims 1 to
7, wherein
X is at least one trivalent element selected from the
group consisting of Al, B, In, Ga, Fe;
Y is at least one tetravalent element selected from the
group consisting of Si, Sn, Ti and V.
9. The process as claimed in any one of the claims 1 to
8, wherein X is B, Al or B+Al and Y is Si.
The invention relates to a porous crystalline
material which, in the calcined state, has a composition:
X2O3 : nY02 : mZ02 wherein: X represents a trivalent
element; Z represents Ge; and Y represents at least one
tetravalent element other than Ge. Furthermore, in the
chemical composition, (n+m) is equal to at least 5 and
the Y/Z ratio is equal to at least 1. Moreover, in the
calcined state, said material has an X-ray diffraction
pattern which coincides substantially with (1) , wherein
VS is a very strong relative intensity corresponding to a
percentage of between 80 and 100 with respect to the most
intense peak; M is a mean relative intensity
corresponding to a percentage of between 40 and 60 with
respect to the most intense peak; and W is a mean
relative intensity corresponding to a percentage of
between 20 and 40 with respect to the most intense peak.

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Patent Number

223766

Indian Patent Application Number

00823/KOLNP/2004

PG Journal Number

39/2008

Publication Date

26-Sep-2008

Grant Date

23-Sep-2008

Date of Filing

15-Jun-2004

Name of Patentee

CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS

Applicant Address

CALLE SERRANO, 117, E-28006 MADRID

Inventors:

#	Inventor's Name	Inventor's Address
1	CORMA CANOS AVELINO	INSTITUTO DE TECNOLOGIA QUIMICA, CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS, UNIVERSIDAD POLITECNICA DE VALENCIA C/LOS NARANJOS, S/N E-46022 VALENCIA
2	DIAZ CARBANAS MARIA JOSE	INSTITUTO DE TECNOLOGIA QUIMICA, CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS, UNIVERSIDAD POLITECNICA DE VALENCIA C/LOS NARANJOS, S/N E-46022 VALENCIA
3	REY GARCIA FERNANDO	INSTITUTO DE TECNOLOGIA QUIMICA, CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS, UNIVERSIDAD POLITECNICA DE VALENCIA C/LOS NARANJOS, S/N E-46022 VALENCIA

PCT International Classification Number

C30B

PCT International Application Number

PCT/ES02/00568

PCT International Filing date

2002-11-29

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	P200102753	2001-11-30	Spain