Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Metal – metal oxide or metal hydroxide
Reexamination Certificate
2000-08-17
2002-10-01
Wood, Elizabeth D. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Metal, metal oxide or metal hydroxide
C502S300000
Reexamination Certificate
active
06458742
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an improved catalyst for use in the ammoxidation of an unsaturated hydrocarbon to the corresponding unsaturated nitrile. In particular, the present invention is directed to an improved process and catalyst for the ammoxidation of propylene and/or isobutylene to acrylonitrile and/or methacrylonitrile, respectively. More specifically, the invention relates to a novel and improved ammoxidation catalyst comprising a complex of catalytic oxides of iron, bismuth, molybdenum, cobalt, cerium, antimony, at least one of nickel or magnesium, and at least one of lithium, sodium, potassium, rubidium, or thallium.
2. Description of the Prior Art
There are many patents related to the production of acrylonitrile by the use of bismuth-molybdenum-iron fluidized bed catalysts. In particular, Great Britain Patent 1436475; U.S. Pat. Nos. 4,766,232: 4,377,534; 4,040,978; 4,168,246; 5,223,469 and 4,863,891 are each directed to bismuth-molybdenum-iron catalysts which may be promoted with the Group II elements to produce acrylonitrile. In addition, U.S. Pat. No. 4,190,608 discloses similarly promoted bismuth-molybdenum-iron catalyst for oxidation of olefins. U.S. Pat. Nos. 5,093,299 and 5,212,137 are directed to bismuth-molybdenum promoted catalysts which show high yields of acrylonitrile.
Catalysts containing oxides of iron, bismuth and molybdenum, promoted with suitable elements, as described in the aforementioned patents have long been used for the conversion of propylene at elevated temperatures in the presence of ammonia and oxygen (usually in the form of air) to manufacture acrylonitrile.
An object of the instant invention is a novel catalyst comprising a unique combination of promoters offering better performance in the catalytic ammoxidation of propylene, isobutylene or mixtures thereof, to acrylonitrile, methacrylonitrile and mixtures thereof, respectively.
SUMMARY OF THE INVENTION
The present invention is directed to an improved catalyst and process for the ammoxidation of propylene and/or isobutylene to acrylonitrile and/or methacrylonitrile, respectively. The present invention is a novel catalyst characterized by the following empirical formula:
A
a
B
b
C
c
Fe
d
Bi
e
Co
f
Ce
g
Sb
h
Mo
m
O
x
wherein
A is at least one of Cr, P, Sn, Te, B, Ge, Zn, In, Mn, Ca, W, or mixtures thereof
B is at least one of Li, Na, K, Rb, Cs, Ti, or mixtures thereof
C is least one of Ni, Mg or mixtures thereof
a is 0 to 4.0
b is 0.01 to 1.5
c is 1.0 to 10.0
d is 0.1 to 5.0
e is 0.1 to 2.0
f is 0.1 to 10.0
g is 0.1 to 2.0
h is 0.1 to 2.0
m is 12.0 to 18.0 and
x is a number determined by the valence requirements of the other elements present.
The present invention is also directed to a process for the conversion of an olefin selected from the group consisting of propylene, isobutylene or mixtures thereof, to acrylonitrile, methacrylonitrile and mixtures thereof, respectively, by reacting in the vapor phase at an elevated temperature and pressure said olefin with a molecular oxygen containing gas and ammonia in the presence of an mixed metal oxide catalyst, wherein the catalyst has the empirical formula shown above.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to an ammoxidation catalyst comprising a complex of catalytic oxides of iron, bismuth, molybdenum, cobalt, cerium, antimony, at least one of nickel or magnesium, and at least one of lithium, sodium, potassium, rubidium, or thallium, characterized by the following empirical formula:
A
a
B
b
C
c
Fe
d
Bi
e
Co
f
Ce
g
Sb
h
Mo
m
O
x
wherein
A is at least one of Cr, P, Sn, Te, B, Ge, Zn, In, Mn, Ca, W, or mixtures thereof
B is at least one of Li, Na, K, Rb, Cs, Tl, or mixtures thereof C is least one of Ni, Mg or mixtures thereof
a is 0 to 4.0
b is 0.01 to 1.5
c is 1.0 to 10.0
d is 0.1 to 5.0
e is 0.1 to 2.0
f is 0.1 to 10.0
g is 0.1 to 2.0
h is 0.1 to 2.0
m is 12.0 to 18.0 and
x is a number determined by the valence requirements of the other elements present.
The “A” component is an optional element in the above catalyst. If “A” is present, “A” is preferably selected from the group comprising Cr, P, Ge, Ca or mixtures thereof. In a preferred embodiment of the present invention, “B” is selected to be one or more of Li, Na, K, Cs, or mixtures thereof, especially preferred being Li, Cs, K or mixtures thereof. In a preferred embodiment of the present invention, “C” is a mixture of Ni and Mg, i.e. the catalyst contains both Ni and Mg.
In other preferred embodiments of the present invention, “a” may independently range from about 0.1 to 4.0, especially preferred being about 0.1 to 3.0; “b” may independently range from ab out 0.05 to 1.2, especially preferred being about 0.1 to 1.0; “c” may independently range from about 2.0 to 9.0, especially preferred being about 2.0 to 8.0; “d” may independently range from about 0.5 to 5.0, especially preferred being about 1.0 to 4.0; “e” may independently range from about 0.1 to 1.5 especially preferred being about 0.1 to 1.0, “f” may independently range from about 1.0 to 7.0, especially preferred being about 1.0 to 1.5; “g” may independently range from about 0.3 to 1.5, especially preferred being about 0.3 to 1.2; “h” may independently range from about 0.3 to 1.5, especially preferred being about 0.3 to 1.2; and “m” may independently range from about 13.0 to 16.0.
The catalyst of the present invention can be used either supported or unsupported. Preferably the catalyst is supported on silica, alumina, zirconium, titania, or mixtures thereof, especially preferred as a catalyst support is silica. The amount of catalyst support employed may vary. Typically the support comprises between about 30 and 70 percent of total catalyst weight, more preferably about 50 percent of total catalyst weight.
Examples of catalyst compositions of this invention include:
K
0.2
Ni
3.0
Mg
2.0
Fe
2.0
Bi
0.5
Co
3.5
Ce
1.0
Sb
0.5
Mo
13.6
O
x
+50 wt % SiO
2
K
0.2
Ni
4.5
Mg
1.5
Fe
2.0
Bi
0.5
Ca
0.2
Co
1.7
Ce
0.5
Sb
0.5
Mo
13.6
O
x
+50 wt. % SiO
2
Cs
0.1
K
0.1
Mg
2.0
Fe
2.0
Bi
0.5
Co
6.2
Ce
0.5
Sb
0.3
Mo
13.0
O
x
+50 wt. % SiO
2
Cs
1.15
Ni
3.0
Mg
2.5
Fe
1.5
Bi
0.3
Co
3.0
Ce
0.5
Sb
0.5
W
0.2
Mo
13.0
O
x
+50 wt. % SiO
2
Cs
0.15
Ni
2.5
Mg
2.5
Fe.
1.5
Bi
0.3
Li
1.0.2
Co
2.8
Ce
1.0
Sb
0.5
Mo
13.0
O
x
+50 wt. % SiO
2
Cs
0.1
K
0.1
Ni
5.0
Mg
2.5
Fe
1.5
Bi
0.3
P
0.2
Co
1.0
Ce
0.5
Sb
0.5
Mo
13.0
O
x
+50 wt. % SiO
2
Cs
0.1
K
0.1
Ni
4.0
Mg
2.0
Fe
2.0
Bi
0.5
Co
2.2
Ce
0.3
Cr
0.2
Sb
0.3
Mo
13.6
O
x
+50 wt. % SiO
2
The catalysts of the present invention may be prepared by any of the numerous methods of catalyst preparation which are known to those of skill in the art. For example, the catalyst may be manufactured by co-precipitating the various ingredients. The co-precipitating mass may then be dried and ground to an appropriate size. Alternatively, the co-precipitated material may be slurried and spray dried in accordance with conventional techniques. The catalyst may be extruded as pellets or formed into spears in oil as is well known in the art. Alternatively, the catalyst components may be mixed with a support in the form of the slurry followed by drying or they may be impregnated on silica or other supports. For particular procedures for manufacturing the catalyst, see U.S. Pat. Nos. 5,093,299; 4,863,891 and 4,766,232 assigned to the Assignee of the present invention, herein incorporated by reference.
The “A” component of the catalyst (i.e. at least one of Cr, P, Sn, Te, B, Ge, Zn, In, Mn, Ca, W, or mixtures thereof) may be derived from any suitable source. For example, cobalt, nickel and magnesium may be introduced into the catalyst using nitrate salts. Additionally, magnesium may be introduced into the catalyst as an insoluble carbonate or hydroxide which upon heat treating results in an oxide. Phosphorus may be introduced in the catalyst as an alkaline metal salt or alkaline earth metal salt or the ammonium salt but is preferably introduced as
Friedrich Maria S.
Paparizos Christos
Seely Michael J.
Suresh Dev D.
The Standard Oil Company
Wood Elizabeth D.
Yusko David P.
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