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US4333853A
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Mixed vanadium phosphorus oxide catalysts and preparation thereof
Assignee: Standard Oil Co
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Filing: 1980-05-05
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Granted: 1982-06-08
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Expires: 2000-05-05
Abstract
Abstract The present invention provides improved oxidation catalysts containing mixed oxides of vanadium and phosphorus and the method for the preparation thereof, which catalysts are particularly effective in the oxidation of n-butane, n-butenes, 1,3-butadiene or a mixture thereof with molecular oxygen or an oxygen-containing gas in the vapor phase to produce excellent yields of maleic anhydride with very good selectivity. At least one vanadium compound, a substantial portion of which is in the pentavalent state, and at least one phosphorus-containing compound is added to an organic liquid medium capable of reducing at least a portion of the vanadium to a +4 valence state, to form a reaction mixture. Partial reduction of the vanadium is effected in the presence of the phosphorus-containing compound and a highly ordered and uniform mixed vanadium phosphorus oxide-containing catalyst precursor is formed.
Inventors
- 👤 Ernest C. Milberger
- 👤 Noel J. Bremer
- 👤 Dennis E. Dria
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 17:02
CPC Classifications
B; B01; B01J; B01J23/00; C; C07; C07C; C07C51/00; C07C51/16; C07C51/21; C07C51/215; B01J23/002; B01J23/16; B01J23/20; B01J23/22; B01J27/00; B01J27/14; B01J27/186; B01J27/195; B01J27/198; B01J2523/00
Claims Analysis
Total Claims: 30
Claim 1
Independent Claim
119 words
A process for the preparation of oxidation catalysts containing the mixed oxides of vanadium and phosphorus which comprises the steps of (a) introducing a substantially pentavalent vanadium-containing compound and a pentavalent phosphorus-containing compound into an organic liquid medium capable of reducing the vanadium to a valence state less than +5; (b) effecting the reduction of at least a portion of the vanadium to a valence state of +4 while in the presence of the phosphorus-containing compound and in the absence of a corrosive reducing agent by heating the vanadium-containing reducing medium of step (a); (c) recovering the mixed vanadium phosphorus oxide-containing catalyst precursor; (d) drying the catalyst precursor; (e) calcining the catalyst precursor to form the active oxidation catalyst.
Claim 2
Dependent Claim
119 words
A process for the preparation of oxidation catalysts containing the mixed oxides of vanadium and phosphorus which comprises the steps of (a) introducing a substantially pentavalent vanadium-containing compound and a pentavalent phosphorus-containing compound into an organic liquid medium capable of reducing the vanadium to a valence state less than +5; (b) effecting the reduction of at least a portion of the vanadium to a valence state of +4 while in the presence of the phosphorus-containing compound and in the absence of a corrosive reducing agent by heating the vanadium-containing reducing medium of step (a); (c) recovering the mixed vanadium phosphorus oxide-containing catalyst precursor; (d) drying the catalyst precursor; (e) calcining the catalyst precursor to form the active oxidation catalyst.
Claim 3
Dependent Claim
15 words
A process as recited in claim 1 wherein said organic liquid medium is essentially anhydrous.
Claim 4
Dependent Claim
26 words
A process as recited in claim 1 wherein reduction of said vanadium is effected by heating the vanadium-containing reaction medium of step (a) under reflux conditions.
Claim 5
Dependent Claim
27 words
A process as recited in claim 1 wherein said vanadium-containing compound is added to a solution or dispersion of said phosphorus-containing compound in the organic liquid medium.
Claim 6
Dependent Claim
27 words
A process as recited in claim 1 wherein said phosphorus-containing compound is added to a slurry or suspension of said vanadium-containing compound in the organic liquid medium.
Claim 7
Dependent Claim
31 words
A process as recited in claim 1 wherein said phosphorus-containing compound is added to the reaction medium in the form of a solution of said phosphorus-containing compound in said organic liquid.
Claim 8
Dependent Claim
25 words
A process as recited in claim 1 wherein said organic liquid is selected from the group consisting of alcohols, ketones, aldehydes, ethers and mixtures thereof.
Claim 9
Dependent Claim
14 words
A process as recited in claim 1 wherein said organic liquid is an alcohol.
Claim 10
Dependent Claim
13 words
A process as recited in claim 8 wherein said organic liquid is isobutanol.
Claim 11
Dependent Claim
14 words
A process as recited in claim 1 wherein said vanadium-containing compound is vanadium pentoxide.
Claim 12
Dependent Claim
14 words
A process as recited in claim 1 wherein said phosphorus-containing compound is orthophosphoric acid.
Claim 13
Dependent Claim
41 words
A process as recited in claim 1 wherein said oxidation catalyst is represented by the empirical formula: V.sub.1 P.sub.a O.sub.x wherein a=1.0 to 1.2 and x is the number of oxygens required to satisfy the valence requirements of the other elements.
Claim 14
Dependent Claim
114 words
An oxidation catalyst comprising the mixed oxides of vanadium and phosphorus prepared by the steps comprising: (a) introducing a substantially pentavalent vanadium-containing compound and a pentavalent phosphorus-containing compound into an organic liquid medium capable of reducing the vanadium to a valence state less than +5; (b) effecting the reduction of at least a portion of the vanadium to a valence state of +4 while in the presence of the phosphorus-containing compound and in the absence of a corrosive reducing agent by heating the vanadium-containing reducing medium of step (a); (c) recovering the mixed vanadium phosphorus oxide-containing catalyst precursor; (d) drying the catalyst precursor; (e) calcining the catalyst precursor to form the active oxidation catalyst.
Claim 15
Dependent Claim
114 words
An oxidation catalyst comprising the mixed oxides of vanadium and phosphorus prepared by the steps comprising: (a) introducing a substantially pentavalent vanadium-containing compound and a pentavalent phosphorus-containing compound into an organic liquid medium capable of reducing the vanadium to a valence state less than +5; (b) effecting the reduction of at least a portion of the vanadium to a valence state of +4 while in the presence of the phosphorus-containing compound and in the absence of a corrosive reducing agent by heating the vanadium-containing reducing medium of step (a); (c) recovering the mixed vanadium phosphorus oxide-containing catalyst precursor; (d) drying the catalyst precursor; (e) calcining the catalyst precursor to form the active oxidation catalyst.
Claim 16
Dependent Claim
16 words
An oxidation catalyst as recited in claim 13, wherein said organic liquid medium is essentially anhydrous.
Claim 17
Dependent Claim
26 words
An oxidation catalyst as recited in claim 13 wherein said organic liquid is selected from the group consisting of alcohols, ketones, aldehydes, ethers and mixtures thereof.
Claim 18
Dependent Claim
15 words
An oxidation catalyst as recited in claim 13 wherein said organic liquid is an alcohol.
Claim 19
Dependent Claim
14 words
An oxidation catalyst as recited in claim 16 wherein said organic liquid is isobutanol.
Claim 20
Dependent Claim
15 words
An oxidation catalyst as recited in claim 13 wherein said vanadium-containing compound is vanadium pentoxide.
Claim 21
Dependent Claim
15 words
An oxidation catalyst as recited in claim 13 wherein said phosphorus-containing compound is orthophosphoric acid.
Claim 22
Dependent Claim
42 words
An oxidation catalyst as recited in claim 13 wherein said oxidation catalysts is represented by the empirical formula: V.sub.1 P.sub.a O.sub.x wherein a=1.0 to 1.2 and x is the number of oxygens required to satisfy the valence requirements of the other elements.
Claim 23
Dependent Claim
30 words
An oxidation catalyst as recited in claim 13, wherein at least 75 percent of the particles of the catalyst precursor have an average diameter of less than about 25 microns.
Claim 24
Dependent Claim
30 words
An oxidation catalyst as recited in claim 13, wherein at least 75 percent of the particles of the catalyst precursor have an average diameter of less than about 20 microns.
Claim 25
Dependent Claim
28 words
An oxidation catalyst as recited in claim 13, wherein said catalyst has an intrinsic surface area of about 25 m 2 /g to about 60 m 2 /g.
Claim 26
Dependent Claim
58 words
An oxidation catalyst comprising the mixed oxides of vanadium and phosphorus characterized by an average valence state of vanadium from about +3.9 to about +4.6, and a phosphorus to vanadium ratio of about 1:1 to about 1.2:1, wherein the macrostructure of the catalyst predominantly comprises generally spheroid particles consisting of stacks of integrally associated sheets of catalytic material.
Claim 27
Dependent Claim
58 words
An oxidation catalyst comprising the mixed oxides of vanadium and phosphorus characterized by an average valence state of vanadium from about +3.9 to about +4.6, and a phosphorus to vanadium ratio of about 1:1 to about 1.2:1, wherein the macrostructure of the catalyst predominantly comprises generally spheroid particles consisting of stacks of integrally associated sheets of catalytic material.
Claim 28
Dependent Claim
26 words
An oxidation catalyst as recited in claim 24 wherein at least 75 percent of the particles have an average diameter of less than about 25 microns.
Claim 29
Dependent Claim
26 words
An oxidation catalyst as recited in claim 24 wherein at least 75 percent of the particles have an average diameter of less than about 20 microns.
Claim 30
Dependent Claim
28 words
An oxidation catalyst as recited in claim 24 wherein said catalyst has an intrinsic surface area of about 25 m 2 /g to about 60 m 2 /g.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1985-06-07 | 1985-12-07 | 1986-06-08 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-06-07 | 1989-12-07 | 1990-06-08 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-06-07 | 1993-12-07 | 1994-06-08 | $7700.00 | Window Closed / Lapsed |