Chemistry of inorganic compounds – Zeolite – Organic compound used to form zeolite
Reexamination Certificate
2002-02-12
2004-03-30
Sample, David R (Department: 1755)
Chemistry of inorganic compounds
Zeolite
Organic compound used to form zeolite
C423S706000, C423S708000, C423S718000, C423SDIG002, C423S707000
Reexamination Certificate
active
06713041
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to an aluminosilicate zeolite designated UZM-9 having the LTA topology, but which is thermally stable in an acidic form and has high Si/Al ratio in the range of greater than 3.5 to about 6.0. The zeolite can be used as an adsorbent or an acid catalyst.
BACKGROUND OF THE INVENTION
Zeolites are crystalline aluminosilicate compositions which are microporous and which consist of a negatively charged framework formed from corner sharing AlO
2
and SiO
2
tetrahedra. The negative framework charge is balanced by cations, which usually reside in the pores. 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.
One particular zeolite, designated zeolite A, was first disclosed in U.S. Pat. No. 2,882,243. The '243 patent states that zeolite A has a Si/Al molar ratio of 0.67 to 1.17. U.S. Pat. No. 3,306,922 discloses a zeolite N-A which is identified as an ammonium or alkyl ammonium containing zeolite of LTA topology. The Si/Al ratio is stated to be in the range of 1.25 to 3.0. U.S. Pat. No. 3,314,752 discloses a zeolite identified as ZK-4 which is stated to be zeolite LTA topology with a mixture of methyl ammonium ion or hydronium ion and sodium or potassium. The Si/Al ratio in ZK-4 is stated to be between 1.25 and 2.0. In U.S. Pat. No. 3,375,205 a zeolite Alpha is disclosed which has the zeolite A type lattice but has a Si/Al ratio of greater than 2 to 3.5. Treatment of N-A by ammonium fluorosilicate to increase the Si/Al ratio is disclosed in U.S. Pat. No. 4,610,856. However, substantial loss in crystallinity (see, column 29, lines 1 to 35) with only a small increase in the Si/Al ratio (2.76 to 3.79) is reported. Finally, Fyfe et al. in
J. Chem. Soc., Chem. Commun
., 1093-1094 (1984) report dealumination of zeolite ZK-4, but with the formation of amorphous material.
In contrast to the above references, applicants have prepared a zeolite designated UZM-9 which has the zeolite A topology (LTA), but has a Si/Al ratio of greater than 3.5 to 6 in its as synthesized form. The UZM-9 can also be prepared with organoammonium cations larger than tetramethylammonium. Finally, UZM-9 is stable to calcination up to at least 600° C. and is useful as a catalyst in its acid form.
SUMMARY OF THE INVENTION
As stated, the present invention relates to a new aluminosilicate zeolite designated UZM-9. Accordingly, one embodiment of the invention is a microporous crystalline zeolite having a three-dimensional framework of at least AlO
2
and SiO
2
tetrahedral units and an empirical composition on an as synthesized and anhydrous basis expressed by an empirical formula 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 0 to about 0.95, R is at least two organic cations selected from the group consisting of quaternary ammonium ions, diquaternary ammonium ions, protonated amines, protonated alkanolamines and quaternized alkanolammonium ions and further where at least one of said organic cations contains an organic group having at least two carbon atoms, “r” is the mole ratio of R to (Al+E) and has a value of about 0.5 to about 1.5, “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 about 1 to about 2, E is an element selected from the group consisting of gallium, iron, boron and mixtures thereof, “x” is the mole fraction of E and has a value from 0 to about 0.5, “y” is the mole ratio of Si to (Al+E) and varies from greater than 3.5 to about 6 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
and is characterized in that it has the x-ray diffraction pattern having at least the d spacings and intensities set forth in Table A.
TABLE A
2-&thgr;
d(Å)
I/I
0
%
7.30-7.42
11.9-12.1
m-vs
10.3-10.52
8.4-8.58
m-s
12.65-12.86
6.88-6.99
w-s
14.61-14.85
5.96-6.06
w-m
16.37-16.65
5.32-5.41
w-m
20.74-21.03
4.22-4.28
w-m
21.98-22.38
3.97-4.04
m-vs
23.2-23.64
3.76-3.83
w
24.37-24.78
3.59-3.65
vs
26.51-27.00
3.3-3.36
m
27.51-28.04
3.18-3.24
w-m
30.48-30.81
2.9-2.93
m
31.36-31.82
2.81-2.85
w-m
32.17-33.80
2.65-2.78
w
33.80-34.60
2.59-2.65
w
34.6-35.31
2.54-2.59
w-m
36.19-37.12
2.42-2.48
w
36.96-37.77
2.38-2.43
w
44.83-45.79
1.98-2.02
w-m
48.1-48.93
1.86-1.89
w
48.65-49.5
1.84-1.87
w
Another embodiment of the invention is a process for preparing the crystalline microporous zeolite described above. The process comprises forming a reaction mixture containing reactive sources of M, R, Al, Si and optionally E at a temperature of about 60° C. to about 175° C., the reaction mixture having a composition expressed in terms of mole ratios of the oxides of:
aM
2
O:bR
2/p
O:1-cAl
2
O
3
:cE
2
O
3
:dSiO
2
:eH
2
O
where “a” has a value of 0.0 to about 1.50, “b” has a value of about 1.0 to about 25, “c” has a value of 0 to about 0.5, “d” has a value of about 4 to about 50 and “e” has a value of about 25 to about 15000.
Yet another embodiment of the invention is a hydrocarbon conversion process using the above-described zeolite. The process comprises contacting the hydrocarbon with the zeolite at conversion conditions to give a converted hydrocarbon.
These and other objects and embodiments will become clearer after a detailed description of the invention.
REFERENCES:
patent: 2882243 (1959-04-01), Milton
patent: 3306922 (1967-02-01), Barrer et al.
patent: 3314752 (1967-04-01), Kerr
patent: 3321272 (1967-05-01), Kerr
patent: 3375205 (1968-03-01), Wadlinger et al.
patent: 4205053 (1980-05-01), Rollmann et al.
patent: 4299686 (1981-11-01), Kuehl
patent: 4610856 (1986-09-01), Skeels et al.
patent: 5171556 (1992-12-01), Caullet et al.
patent: 5785947 (1998-07-01), Zones et al.
patent: 6558647 (2003-05-01), Lacombe et al.
Fyfe et al. inJ. Chem. Soc., Chem. Commun., 1093-1094 (1984).
Gisselquist Jana L.
Lewis Gregory J.
Miller Mark A.
Moscoso Jaime G.
Rohde Lisa M.
Molinaro Frank S.
Sample David R
Tolomei John G.
UOP LLC
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