Chemistry of inorganic compounds – Zeolite – Organic compound used to form zeolite
Reexamination Certificate
2003-04-11
2004-09-28
Sample, David (Department: 1755)
Chemistry of inorganic compounds
Zeolite
Organic compound used to form zeolite
C423S709000, C423S718000, C423S335000, C208S046000
Reexamination Certificate
active
06797254
ABSTRACT:
TECHNICAL FIELD OF THE INVENTION
The present invention refers to microporous crystalline materials, particularly materials of a zeolitic nature, and specially materials of a zeolitic nature useful in the separation and transformation of organic compounds.
STATE OF THE ART BEFORE THE INVENTION
Zeolites are microporous crystalline materials formed by a crystalline network of tetrahedrons TO4 that share all their vertices leading to a three dimensional structure that contains channels and/or cavities of molecular dimensions. They are of a variable composition, and T generally represents atoms with a formal +3 or +4 oxidation status, such as, for example Si, Ge, Ti, Al, B, Ga, . . . If any of the T atoms has an oxidation status of less than +4, the crystalline network formed shows negative charges that are compensated by means of the presence of organic or inorganic cations in the channels and cavities. Organic molecules and H
2
O can also be lodged in said channels and cavities, for which, in a general manner, the chemical composition of the zeolites can be represented by means of the following empirical formula:
x
(M
1
XO
2
):
y
YO
2
:z
R:
w
H
2
O
wherein M is one or various organic or inorganic cations with +n charge; X is one or various trivalent elements; Y is one or various tetravalent elements, generally Si; and R is one or various organic substances. Although by means of post-synthesis treatments 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 after its calcination) possesses a characteristic range for each zeolite and its method of being obtained.
On the other hand, the crystalline structure of each zeolite, with a specific system of channels and cavities, leads to a characteristic X-ray diffraction pattern. Therefore, the zeolites are differentiated among themselves through their range of chemical composition plus their X-ray diffraction pattern. The two characteristics (crystalline structure and chemical composition) also determine the physical and chemical properties of each zeolite and its possible application in different industrial processes.
DESCRIPTION OF THE INVENTION
The present invention refers to a microporous crystalline material of a zeolitic nature, (also identified as “ITQ-15”), to its method of preparation and its uses in processes for the separation and transformation of organic compounds.
This material is characterised by its X-ray diffraction pattern and by its chemical composition. In its anhydrous and calcinated form, the chemical composition of ITQ-15 can be represented by means of the empirical formula
x
(M
1
XO
2
):
y
YO
2
:z
GeO
2
:(1
−z
)TO
2
wherein
x has a value of less than 0.2;
y has a value of less than 0.1;
z has a value of less than 1,
with at least one of x, z and y being greater than zero;
M is H+ or one or various inorganic cations with a +n charge;
X is at least one chemical element with a +3 oxidation status;
Y is one or various chemical elements with a + oxidation status; and
T is at least one chemical element with a +4 oxidation status;
The existence of defects in the crystalline network is possible, however, in terms of the method of synthesis and of its calcination or later treatments, which are shown by the presence of Si-OH groups (silanols). These defects have not been included in the above empirical formula.
The material of the invention is also characterised by its X-ray diffraction pattern as synthesised, obtained by the powder method using a slit of fixed divergence characterised by the following values of interplanar spacings (d) and relative intensities (I/I
0
) of the most intense reflections.
TABLE I
d(Å) ± 0.3
I/I
0
14.01
VS
12.36
VS
9.15
W
4.94
M
3.92
VS
3.57
M
3.37
VS
On the other hand, the material according to the invention is also characterised because, in a calcinated and anhydrous state, it has the following X-ray diffraction pattern.
TABLE II
d(Å) ± 0.3
I/I
0
14.11
VS
12.42
VS
9.13
M
4.96
W
3.91
M
3.59
W
3.38
M
The positions, widths and relative intensities of some secondary peaks can depend to a certain extent on the chemical composition of the material. In this way, when the network of materials is composed exclusively of silicon and germanium oxide, with a Si/Ge=10 ratio and synthesised using a quaternary ammonium cation as a structure directing agent, the material, as it is synthesised has the ray diffraction pattern shown in table III.
TABLE III
d(Å) ± 0.3
I/I
0
14.01
W
12.36
VS
11.82
M
10.61
W
9.15
W
7.75
VW
7.01
W
6.21
W
5.22
VW
4.94
M
4.56
M
4.33
M
4.15
W
3.97
S
3.92
VS
3.71
W
3.65
W
3.57
M
3.52
W
3.47
M
3.37
VS
3.25
W
3.11
W
3.09
W
3.06
W
On the other hand, table IV shows the values of interplanar spacings (d) and relative intensities of the most intense reflections of the powder X-ray diffractogram of the same sample of ITQ-15 whose values, after having been calcinated at 540° C. to eliminate the organic compounds occluded inside the zeolite, are as follows:
TABLE IV
d(Å) ± 0.3
I/I
0
14.11
VS
12.42
VS
11.81
M
10.56
W
9.13
M
8.15
VW
7.80
VW
7.10
VW
6.94
W
6.08
VW
5.94
VW
5.62
W
5.03
VW
4.96
W
4.58
W
4.33
W
4.16
VW
3.97
M
3.91
M
3.71
W
3.66
W
3.59
W
3.55
W
3.47
W
3.38
M
3.22
VW
3.08
W
3.05
W
In the previous tables, VW means very weak, W weak, M medium, S strong and VS very strong.
In a first embodiment of the material according to the invention, in the empirical formula identified above, T is Si, in such a way that the resulting empirical formula is:
x
(M
1
XO
2
):
y
YO
2
:z
GeO
2
:(1
−z
)SiO
2
wherein x has a value of less than 0.1, preferably less than 0.2, y has a value of less than 0.05 and preferably less than 0.02, z has a value of less than 0.1, M is H+ or one or various inorganic cations with a +n load, X is one or various chemical elements with a +3 oxidation status (preferably Al, Ga, B, Cr) and Y is one or various chemical elements with a +4 oxidation status (preferably Ti, Sn, V).
In a second embodiment of the material according to the invention, in the general empirical formula identified above, T is Si and y is zero, in such a way that the resulting empirical formula is
x
(M
1
XO
2
):
z
GeO
2
:(1
−z
)SiO
2
wherein x has a value of less than 0.2, preferably less than 0.1 and more preferably less than 0.02, z has a value of less than 1 and more preferably less than 0.1; M is H+ or one or various inorganic cations with a +n charge and X is one or various chemical elements with a +3 oxidation status (preferably Al, Ga, B, Cr).
In a third embodiment of the material according to the invention, in the general empirical formula identified above, T is Si and y is zero, in such a way that the resulting empirical formula is
y
YO
2
:z GeO
2
:(1
−z
)SiO
2
wherein y has a value of less than 0.1, preferably less than 0.05 and more preferably less than 0.02, z has a value of less than 1, preferably less than 0.1 and Y is one or various chemical elements with a +4 oxidation status (preferably Ti, Sn or V).
In a fourth embodiment of the material according to the invention, in the general empirical formula identified above, T is Si and x is zero, in such a way that the resulting empirical formula is
x
(HXO
2
):
z
GeO
2
:(1
−z
)SiO
2
in which X is a trivalent element (preferably Al, Ga, B, Cr), x has a value of less than 0.2, preferably less than 0.1, and more preferably less than 0.02, z has a value of less than 1, and more preferably less than 0.1.
In a fifth embodiment of the material according to the invention, in the general empirical formula identified above, T is Si and x is zero, in such a way that the resulting empirical formula is
z
GeO
2
:(1
−z
)SiO
2
wherein z has a value below 1 and preferably below 0.1.
In a sixth embodiment of the material according to the invention, in the general empirical formula identified above, z and y are zero, so that the resulting empirical formula is
X(M
1
XO
2
):TO
2
wherein x has a value of les
Canos Avelino Corma
Diaz Cabañas María José
García Fernando Rey
Consejo Superior de Investigaciones Cientificas
Klauber & Jackson
Sample David
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