Chemistry of hydrocarbon compounds – Aromatic compound synthesis – By condensation of entire molecules or entire hydrocarbyl...
Reexamination Certificate
2000-11-03
2002-05-14
Dang, Thuan D. (Department: 1764)
Chemistry of hydrocarbon compounds
Aromatic compound synthesis
By condensation of entire molecules or entire hydrocarbyl...
Reexamination Certificate
active
06388157
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to an alkylation process using a family of related crystalline aluminosilicate zeolites, examples of which have been designated UZM-5, UZM-5P and UZM-6. These zeolites are structurally different from other zeolites.
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. One such process is the alkylation of aromatics with olefins and especially the alkylation of benzene with ethylene or propylene. The reaction between benzene and propylene produces mostly cumene. Cumene is an important industrial compound because it is a source of phenol, acetone, which are obtained by the oxidation of Cumene and subsequent acid-catalyzed decomposition of the intermediate hydroperoxide. Acid catalysts are used to catalyze this reaction with the most common catalysts being zeolites and particularly zeolite beta.
Applicants have synthesized a new family of crystalline aluminosilicate zeolites which have good activity for the alkylation of aromatics. These crystalline zeolitic compositions have a unique x-ray diffraction pattern 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 and 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, Cr, In 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 0 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.
SUMMARY OF THE INVENTION
This invention relates to a process for the alkylation of aromatic compounds using a new family of zeolites. Accordingly, one embodiment of the invention is a process for alkylating an aromatic compound comprising reacting under alkylation conditions and under at least partial liquid phase conditions an olefin with an alkylatable aromatic compound to provide an alkylated compound in the presence of a crystalline aluminosilicate zeolite having a composition in the as synthesized and anhydrous 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, Cr, In and B, “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 O to (Al+E) and has a value determined by the equation:
z
=(
m·n+r·p+
3+4
·y
)/2
the zeolite 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 catalyst has been designated UZM-5 and has the x-ray 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
One specific embodiment involves the alkylation of benzene with propylene to give cumene.
Another embodiment of the invention is a transalkylation process comprising reacting under transalkylation reaction conditions a polyalkylated aromatic compound with a nonalkylated aromatic compound in the presence of the zeolites described above, wherein at least one alkyl group is transferred from the polyalkylated aromatic compound to the nonalkylated aromatic compound.
These and other objects and embodiments will become more apparent after the following detailed description of the invention.
DETAILED DESCRIPTION OF THE INVENTION
An essential feature of applicants' process is 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
Where 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 1.2. R is a nitrogen containing organic cation and is selected from the group consisting of pronated 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, chromium, indium, boron 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
+
m
3
…
.
Similarly when only one R organic cation is present, the weighted average valence is the valence of the single R cation, i.e., +1 or +2. When more than one R cation is present, the total amount of R is given by the equation:
R
r
p+
=R
r1
(p1)+
+R
r2
(p2)+
+R
r3
(p3)+
and the weighted average valence “p”
Jan Deng-Yang
Lewis Gregory J.
Miller Mark A.
Moscoso Jaime G.
Dang Thuan D.
Molinaro Frank S.
Tolomei John G.
UOP LLC
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