Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Metal – metal oxide or metal hydroxide
Reexamination Certificate
1997-06-27
2002-09-17
Solola, T A (Department: 1626)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Metal, metal oxide or metal hydroxide
C502S350000, C502S352000
Reexamination Certificate
active
06451730
ABSTRACT:
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention is directed to a method for the preparation of promoted VSbO
x
based catalyst useful in the catalytic vapor phase ammoxidation of propylene or isobutylene to acrylonitrile or methacrylonitrile. In addition, the present invention is directed to a method for catalytic vapor phase ammoxidation of propylene or isobutylene to acrylonitrile or methacrylonitrile in a fluid bed reactor by contacting with a fluid bed ammoxidation catalyst made by the process of the present invention.
U.S. Pat. No. 4,162,992 discloses the ammoxidation of olefins, especially propylene, using a catalyst containing vanadium, antimony and titanium. However, the amount of antimony is far outside the range of the catalyst made by the present claimed process.
In U.S. Pat. No. 3,681,421 to Barclay et al there is disclosed the vapor phase catalytic ammoxidation of propylene over an oxide composition comprising antimony, vanadium and one or more additional poly-valent metals selected from the group of tin, iron, cobalt and titanium. The catalyst disclosed by Barclay et al overlap with the empirical formula of the compositions of the catalyst of the present invention. However, the catalyst of the present invention are made by a different method than the catalyst disclosed by Barclay et al.
Finally, in U.S. Pat. No. 5,258,543 to Suresh et al, assigned to the assignee of the instant application, there is disclosed a suitable procedure for making a VSbO
x
promoted catalyst useful in the ammoxidation of propylene to acrylonitrile. The present invention is directed to an improvement in the procedure for making the VSbO
x
promoted catalyst of the U.S. Pat. No. 5,258,543. The properties of the catalyst prepared by the present invention have superior properties than those disclosed in the prior art.
SUMMARY OF THE INVENTION
It is the primary object of the present invention to provide a novel process for the preparation of promoted VSbO
x
based catalyst useful in the ammoxidation of propylene or isobutylene to produce acrylonitrile or methacrylonitrile.
It is another object of the present invention to provide a novel procedure for the catalytic vapor phase ammoxidation of propylene or propane to acrylonitrile or methacrylonitrile.
Additional objects, advantages and novel features of the invention, will be set forth in part in the description which follows, and, in part, will become apparent to those skilled in the art upon examination of the following or may be learned by the practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
To achieve the foregoing and other objects and in accordance with the purpose of the present invention as embodied and broadly described herein, the process of the present invention comprises preparing a supported catalyst wherein said catalyst comprises the elements and proportions indicated by the following empirical formula:
V
1.0
Sb
a
M
b
O
x
wherein
M equals Sn, Ti, Fe, Cu, Nb, Ta, Co, Ni, Mg, Li, Na, Ga and mixtures thereof,
a is from about 0.5 to about 5.0,
b is from about 0.1 to 5.0, and
x is the number of oxygen atoms required to satisfy the valency requirement of the other elements,
comprising (1) mixing the vanadium compound, at least a portion of the antimony compound, at least a portion of the M compound and an aqueous sol containing a portion of the support material to form an aqueous slurry, heating the slurry to remove the water, and calcining at a temperature of at least about 150° C. to form a catalyst precursor; (2) mixing the catalyst precursor with an aqueous sol containing the remaining portion of the support material and any remaining portion of the antimony and M compounds to form a second slurry, (3) drying the second slurry to remove the water to form a dry mixture, and (4) calcining the dried mixture at a temperature of at least 150° C. to form the finished catalyst.
In a preferred embodiment of the present invention the portion of the support material added during the formation of the catalyst precursor is between 1 to 79% of the total amount of support material present in the finished catalyst.
In a further preferred embodiment of the present invention the remaining portion of support material present in the aqueous sol to which the catalyst precursor is mixed is between 1 to 79% of the total amount of support material present in the finished catalyst.
In still another preferred embodiment of the present invention all of the antimony compound is added during the formation of the catalyst precursor.
In still a further preferred embodiment of the present invention all of the M compound is added during the formation of the catalyst precursor.
In another further preferred embodiment of the present invention the catalyst precursor is calcined at a temperature of between about 150° to about 900° C., preferably between about 250° to 800° C., especially preferred being between about 300° to about 600° C.
In another preferred embodiment of the present invention the support material is selected from the group consisting of silica, alumina, titanium, zirconia, and mixtures thereof.
In a still further preferred embodiment of the present invention, the process further comprises forming the first aqueous slurry by mixing an aqueous dispersion containing the vanadium compound and at least a portion of the antimony compound while the vanadium is in solution prior to calcining to form the catalyst precursor.
In accordance with additional aspects of the present invention as embodied and broadly described herein, the method of manufacture of acrylonitrile or methacrylonitrile from propylene or isobutylene comprises introducing in the vapor state a hydrocarbon selected from the group consisting of propylene and propane, an oxygen-containing gas and ammonia into a fluid bed reactor containing an ammoxidation catalyst, wherein the catalyst contains elements in proportions indicated in the empirical formula set forth above. Wherein the catalyst is prepared by a process comprising (1) mixing the vanadium compounds, at least a portion of the antimony compound, at least a portion of the M compound and an aqueous sol containing a portion of the support material to form an aqueous slurry, heating the slurry to remove the water, and calcining at a temperature of at least about 150° C. to form a catalyst precursor; (2) mixing the catalyst precursor with an aqueous sol containing the remaining portion of the catalyst and any remaining portion of the antimony and M compounds to form a second slurry, (3) drying the second slurry to remove the water to form a dry mixture, and (4) calcining the dried mixture at a temperature of at least 150° C. to form the finished catalyst.
In a preferred embodiment of this aspect of the present invention the olefin is selected to be propylene.
In a still further preferred embodiment of this aspect of the present invention the olefin is selected to be isobutylene.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a method of preparing a supported catalyst useful in the ammoxidation of acrylonitrile or methacrylonitrile. The catalyst comprises the elements in proportions indicated by the following empirical formula:
V
1.0
Sb
a
M
b
O
x
wherein
M equals Sn, Ti, Fe, Cu, Nb, Ta, Co, Ni, Mg, Li, Na, Ga and mixtures thereof,
a is from about 0.5 to about 5.0,
b is from about 0.1 to 5.0, and
x is the number of oxygen atoms required to satisfy the valency requirement of the other elements.
The process of preparing the above-identified catalyst comprises mixing the vanadium compound, at least a portion of the antimony compound, at least a portion of the M compound in an aqueous sol containing a portion of the support material to form an aqueous slurry, heating the slurry to remove the water and calcining in a temperature of at least about 150° C. to form a catalyst precursor; (2) mixing the catalyst precursor with aqueous sol containing
Friedrich Maria Strada
Seely Michael J.
Suresh Dev Dhanaraj
Murray Joseph
Solola T A
The Standard Oil Company
Yusko David P.
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