Chemistry of inorganic compounds – Zeolite – Structure defined x-ray diffraction pattern
Reexamination Certificate
2000-11-03
2003-09-02
Sample, David (Department: 1755)
Chemistry of inorganic compounds
Zeolite
Structure defined x-ray diffraction pattern
C423S705000, C208S046000
Reexamination Certificate
active
06613302
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to a family of related crystalline aluminosilicate zeolites examples of which have been designated UZM-5, UZM-5P and UZM-6. These compositions are structurally different from other zeolites and can catalyze various hydrocarbon processes.
BACKGROUND OF THE INVENTION
Zeolites are crystalline aluminosilicate compositions which are microporous and which have a three-dimensional oxide framework formed from corner sharing AlO
2
and SiO
2
tetrahedra. Numerous zeolites, both naturally occurring and synthetically prepared are used in various industrial processes. Zeolites are characterized by having pore openings of uniform dimensions, having a significant ion exchange capacity, and being capable of reversibly desorbing an adsorbed phase which is dispersed throughout the internal voids of the crystal without significantly displacing any atoms which make up the permanent zeolite crystal structure.
The number of synthetic zeolites is well over a hundred as evidenced by the Atlas of Zeolite Structure Types published by the International Zeolite Association (IZA). As is well known, zeolites are distinguished from each other on the basis of their composition, crystal structure and adsorption properties. One method commonly used in the art to distinguish zeolites is x-ray diffraction.
Applicants have synthesized a family of crystalline zeolitic compositions which have unique x-ray diffraction patterns and have an empirical formula on an anhydrous basis in terms of molar ratios of:
M
m
n+
R
r
p+
Al
(1−x)
E
x
Si
y
O
z
where M is at least one exchangeable cation selected from the group consisting of alkali and alkaline earth metals, “m” is the mole ratio of M to (Al+E) and varies from about 0 to about 1.2, R is a nitrogen-containing organic cation selected from the group consisting of quaternary ammonium ions, protonated amines, protonated diamines, protonated alkanolamines, quaternary alkanolammonium ions, diquaternary ammonium ions, and mixtures thereof, “r” is the mole ratio of R to (Al+E) and has a value of about 0.25 to about 3.0, E is an element selected from the group consisting of Ga, Fe, In, Cr, and B, “x” is the mole fraction of E and varies from 0 to about 0.5, “n” is the weighted average valence of M and has a value of +1 to about +2, “p” is the weighted average valence of R and has a value of +1 to about +2, “y” is the mole ratio of Si to (Al+E) and varies from about 5 to about 12, and “z” is the mole ratio of O to (Al+E) and has a value determined by the equation:
z
=(
m·n+r·p
+3+4
·y
)/2
Specific members of this family of zeolites are: UZM-5, UZM-5P and UZM-6. These zeolites can catalyze various hydrocarbon conversion processes such as alkylation of benzene and isomerization of xylene.
SUMMARY OF THE INVENTION
This invention relates to a new family of zeolite, a process for preparing the zeolites and a process using the zeolites. Accordingly, one embodiment of the invention is a microporous crystalline zeolite having a composition in the as synthesized form in terms of mole ratios of the elements given by
M
m
n+
R
r
p+
Al
(1−x)
E
x
Si
y
O
z
where M is at least one exchangeable cation selected from the group consisting of alkali and alkaline earth metals, “m” is the mole ratio of M to (Al+E) and varies from about 0 to about 1.2, R is a nitrogen-containing organic cation selected from the group consisting of protonated amines, protonated diamines, protonated alkanolamines, quaternary ammonium ions, diquaternaryammonium ions, quaternized alkanolamines and mixtures thereof, “r” is the mole ratio of R to (Al+E) and has a value of about 0.25 to about 3.0, E is an element selected from the group consisting of Ga, Fe, In, Cr, B, and mixtures thereof “x” is the mole fraction of E and varies from 0 to 0.5, “n” is the weighted average valence of M and has a value of about +1 to about +2, “p” is the weighted average valence of R and has a value of +1 to about +2, “y” is the mole ratio of Si to (Al+E) and varies from about 5 to about 12 and “z” is the mole ratio of 0 to (Al+E) and has a value determined by the equation:
z
=(
m·n+r·p
+3+4
·y
)/2
the material characterized in that it has at least two x-ray diffraction peaks, one at a d-spacing of 3.9±0.12 Å and one at 8.6±0.20 Å.
In a particular embodiment, the zeolite is designated UZM-5 and has the diffraction pattern having at least the d-spacings and intensities set forth in Table A:
TABLE A
UZM-5
2-&thgr;
d(Å)
I/I
o
%
6.31-5.89
14.00-15.00
w-m
7.96-7.58
11.10-11.65
m-s
10.40-10.01
8.50-8.83
w-m
12.11-11.59
7.30-7.63
m
16.10-15.53
5.50-5.70
m-vs
19.28-18.55
4.60-4.78
w-m
22.26-21.60
3.99-4.11
m
23.20-22.43
3.83-3.96
w-s
24.16-23.33
3.68-3.81
vs
30.48-29.55
2.93-3.02
w-m
31.94-30.92
2.80-2.89
w-m
44.83-43.47
2.02-2.08
w
Another embodiment of the invention is a process for preparing the above-described zeolites which comprises forming a reaction mixture containing reactive sources of R, Al, Si and optionally E and/or M and heating the reaction mixture at a temperature of about 100° C. to about 175° C., the reaction mixture having a composition expressed in terms of mole ratios of the oxides of:
a
M
2
O:
b
R
2/p
O:(1
−c
)Al
2
O
3
:c
E
2
O
3
:d
SiO
2
:e
H
2
O
where “a” has a value of about 0 to about 2.0, “b” has a value of about 1.5 to about 30, “c” has a value of about 0 to about 0.5, “d” has a value of 5 to about 30, and “e” has a value of about 30 to about 6000.
Yet another embodiment of the invention is a hydrocarbon conversion process using the above-described zeolites. More specifically the hydrocarbon conversion process is the alkylation of benzene with an olefin or the isomerization of xylenes.
These and other objects and embodiments will become more apparent after the following detailed description of the invention.
DETAILED DESCRIPTION OF THE INVENTION
Applicants have synthesized a new family of zeolites. In its as-synthesized form, this family of zeolites has a composition on an anhydrous basis that is represented by the formula:
M
m
n+
R
r
p+
Al
(1−x)
E
x
Si
y
O
z
M is an exchangeable cation and is selected from the group consisting of alkali and alkaline earth metals. Specific examples of the M cations include but are not limited to lithium, sodium, potassium, cesium, strontium, calcium, magnesium, barium and mixtures thereof. The value of “m” which is the mole ratio of M to (Al+E) varies from 0 to about 1.2. R is a nitrogen containing organic cation and is selected from the group consisting of protonated amines, protonated diamines, protonated alkanolamines, quaternary ammonium ions, diquaternary ammonium ions, quaternized alkanolammonium ions and mixtures thereof. The value of “r” which is the mole ratio of R to (Al+E) varies from about 0.25 to about 3.0. The value of “n” which is the weighted average valence of M varies from +1 to about +2. The value of “p”, which is the average weighted valence of the organic cation has a value from about +1 to about +2. E is an element which is present in the framework and is selected from the group consisting of gallium, iron, boron chromium, indium and mixtures thereof. The value of “x” which is the mole fraction of E varies from 0 to about 0.5. The ratio of silicon to (Al+E) is represented by “y” which varies from about 5 to about 12, while the mole ratio of O to (Al+E) is represented by “z” and ” has a value given by the equation:
z
=(
m·n+r·p
+3+4
·y
)/2
When M is only one metal, then the weighted average valence is the valence of that one metal, i.e. +1 or +2. However, when more than one M metal is present, the total amount of:
M
m
n
+
=
M
m1
(
n1
)
+
+
M
m2
(
n2
)
+
+
M
m3
(
n3
)
+
+
…
and the weighted average valence “n” is given by the equation:
n
=
m
1
·
n
1
+
m
2
·
n
2
+
m
3
·
n
3
+
⋯
m
1
+
m
2
+
Jan Deng-Yang
Lewis Gregory J.
Miller Mark A.
Moscoso Jaime G.
Patton R. Lyle
Molinaro Frank S.
Sample David
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