US4388221A
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Vanadium-phosphorus-tin-mordenite oxidation catalysts
Assignee: Union Oil Company of California
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Filing: 1981-08-03
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Granted: 1983-06-14
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Expires: 2001-08-03
Abstract
Abstract Oxidation catalysts having large surface areas and which are suitable for converting C 4 to C 10 hydrocarbons to maleic anhydride are disclosed, comprising the oxides of vanadium, phosphorus and tin in combination with hydrogen mordenite having a surface area between 100 M 2 /g to 450 M 2 /g and wherein the vanadium has an average valence in the range of from 3.5 to 4.95.
Inventors
- 👤 Eric L. Moorehead
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 02:41
CPC Classifications
C; C07; C07C; C07C51/00; C07C51/16; C07C51/21; C07C51/25; C07C51/252; B; B01; B01J; B01J23/00; B01J23/002; B01J27/00; B01J27/14; B01J27/186; B01J27/195; B01J27/198; C07C51/215; B01J2523/00
Claims Analysis
Total Claims: 36
Claim 1
Independent Claim
44 words
An oxidation catalyst described by the formula: V.sub.a P.sub.b Sn.sub.c O.sub.d X wherein X is mordenite, a is 0.10 to 1, b is 1, c is 0.001 to 0.30, and d is a number which satisfies the valence requirements of the other elements present.
Claim 2
Dependent Claim
44 words
An oxidation catalyst described by the formula: V.sub.a P.sub.b Sn.sub.c O.sub.d X wherein X is mordenite, a is 0.10 to 1, b is 1, c is 0.001 to 0.30, and d is a number which satisfies the valence requirements of the other elements present.
Claim 3
Dependent Claim
12 words
The oxidation catalyst defined in claim 1 wherein X is hydrogen mordenite.
Claim 4
Dependent Claim
18 words
The oxidation catalyst defined in claim 1 wherein the vanadium has an average valence between +3.50 and +4.95.
Claim 5
Dependent Claim
18 words
The oxidation catalyst defined in claim 1 wherein the vanadium has an average valence between +4.10 and +4.70.
Claim 6
Dependent Claim
17 words
The oxidation catalyst defined in claim 1 wherein the vanadium:phosphorus:tin atomic ratio is from 0.20:1:0.002 to 1:1:0.20.
Claim 7
Dependent Claim
35 words
The oxidation catalyst defined in claim 1 wherein from 15 to 50 weight percent of V, P, Sn and O as the metal oxides is combined with from 50 to 85 weight percent of X.
Claim 8
Dependent Claim
32 words
The oxidation catalyst defined in claim 1 optionally containing from 0 to 10 weight percent of a binder selected from the group consisting of silica, methyl cellulose and alumina, and mixtures thereof.
Claim 9
Dependent Claim
43 words
The oxidation catalyst defined in claim 1 having a surface area of from 100 M 2 /g to 450 M 2 /g, a pore volume of from 0.1 cc/g to 0.8 cc/g, and a compacted bulk density of from 0.50 to 1.50 g/cc.
Claim 10
Dependent Claim
146 words
An oxidation catalyst described by the formula: V.sub.a P.sub.b Sn.sub.c O.sub.d X wherein X is hydrogen mordenite, a is 0.10 to 1, b is 1, c is 0.001 to 0.30, and d is a number which satisfies the valence requirements of the other elements present, vanadium has an average valence between +3.50 and +4.95, wherein said oxidation catalyst contains from 15 to 50 weight percent of V, P, Sn and O as the metal oxides, from 50 to 85 weight percent of X, and from 0 to 10 weight percent of a binder selected from the group consisting of silica, methyl cellulose and alumina and mixtures thereof, said oxidation catalyst having a surface area of from 100 M 2 /g to 450 M 2 /g, a pore volume of from 0.1 cc/g to 0.8 cc/g, and a compacted bulk density of from 0.50 to 1.50 g/cc.
Claim 11
Dependent Claim
146 words
An oxidation catalyst described by the formula: V.sub.a P.sub.b Sn.sub.c O.sub.d X wherein X is hydrogen mordenite, a is 0.10 to 1, b is 1, c is 0.001 to 0.30, and d is a number which satisfies the valence requirements of the other elements present, vanadium has an average valence between +3.50 and +4.95, wherein said oxidation catalyst contains from 15 to 50 weight percent of V, P, Sn and O as the metal oxides, from 50 to 85 weight percent of X, and from 0 to 10 weight percent of a binder selected from the group consisting of silica, methyl cellulose and alumina and mixtures thereof, said oxidation catalyst having a surface area of from 100 M 2 /g to 450 M 2 /g, a pore volume of from 0.1 cc/g to 0.8 cc/g, and a compacted bulk density of from 0.50 to 1.50 g/cc.
Claim 12
Independent Claim
91 words
A method of preparing a vanadium, phosphorus, tin, oxygen and mordenite, oxidation catalyst which comprises: (A) contacting a vanadium compound and a phosphorus compound with an acidic-aqueous medium and a divalent tin compound under reaction conditions which will produce vanadium having an average valence of from +3.50 to +4.95, to form a catalyst precursor; (B) mixing the catalyst precursor with mordenite, to form an impregnated mordenite; and (C) calcining the oxidation catalyst at temperatures in the range of from 400° F. to 1,200° F., for from 1/4 hour to 6 hours.
Claim 13
Independent Claim
91 words
A method of preparing a vanadium, phosphorus, tin, oxygen and mordenite, oxidation catalyst which comprises: (A) contacting a vanadium compound and a phosphorus compound with an acidic-aqueous medium and a divalent tin compound under reaction conditions which will produce vanadium having an average valence of from +3.50 to +4.95, to form a catalyst precursor; (B) mixing the catalyst precursor with mordenite, to form an impregnated mordenite; and (C) calcining the oxidation catalyst at temperatures in the range of from 400° F. to 1,200° F., for from 1/4 hour to 6 hours.
Claim 14
Dependent Claim
24 words
The method defined in claim 10 wherein the oxidation catalyst contains vanadium, phosphorus and tin in an atomic ratio of from 0.20:1:0.002 to 1:1:0.20.
Claim 15
Dependent Claim
28 words
The method defined in claim 10 wherein from 15 to 50 weight percent of the catalyst precursor is mixed with from 50 to 85 weight percent of mordenite.
Claim 16
Dependent Claim
31 words
The method defined in claim 10 wherein the vanadium compound is a member selected from the group consisting of ammonium vanadate, vanadyl sulfate, vanadium pentoxide and vanadium oxytrichloride, and mixtures thereof.
Claim 17
Dependent Claim
31 words
The method defined in claim 10 wherein the phosphorus compound is a member selected from the group consisting of phosphoric acid, phosphorus pentoxide, ammonium phosphate and diammonium phosphate, and mixtures thereof.
Claim 18
Dependent Claim
32 words
The method defined in claim 10 wherein the tin compound is stannous chloride, stannous fluoride, stannous bromide, stannous oxide, stannous sulfate, stannous acetate, stannous pyrophosphate, or stannous oxalate, or a mixture thereof.
Claim 19
Dependent Claim
42 words
The method defined in claim 10 wherein the acidic-aqueous medium comprises water and an acid selected from the group consisting of hydrochloric acid, hydroiodic acid, hydroformic acid, acetic acid, oxalic acid, maleic acid, citric acid or formic acid, or a mixture thereof.
Claim 20
Dependent Claim
38 words
The method defined in claim 10 comprising mixing from 0 to 10 weight percent of a binding agent and solvent in a weight ratio of from 1:20 to 20:1, with the catalyst precursor and mordenite in step (B).
Claim 21
Dependent Claim
27 words
The method defined in claim 17 wherein the binding agent is a member selected from the group consisting of silica, methyl cellulose and alumina, and mixtures thereof.
Claim 22
Dependent Claim
26 words
The method defined in claim 17 wherein the solvent is a member selected from the group consisting of ethanol, propanol, isopropanol, and butanol, and mixtures thereof.
Claim 23
Dependent Claim
26 words
The method defined in claim 10 wherein the reaction conditions comprise temperatures from 100° F. to 220° F. and pressures from atmospheric pressure to 50 p.s.i.g.
Claim 24
Dependent Claim
46 words
The method defined in claim 10 wherein the oxidation catalyst has a surface area of from 100 M 2 /g to 450 M 2 /g, a pore volume of from 0.1 cc/g to 0.8 cc/g, and a compacted bulk density of from 0.50 to 1.50 g/cc.
Claim 25
Independent Claim
133 words
A method of preparing a vanadium, phosphorus, tin, oxygen and mordenite oxidation catalyst which comprises: (A) contacting a pentavalent vanadium compound, a pentavalent phosphorus compound and a divalent tin compound, at an atomic ratio of from 0.10:1:0.001 to 1:1:0.30 with an acidic-aqueous medium at a temperature of from 100° F. to 220° F., and a pressure from atmospheric pressure to 50 p.s.i.g., to form a catalyst precursor and produce vanadium having an average valence of from +3.50 to +4.95; (B) mixing from 15 weight percent to 50 weight percent of said catalyst precursor with from 50 weight percent to 85 weight percent of mordenite to form an impregnated mordenite; and (C) calcining the oxidation catalyst at temperatures in the range of from 400° F. to 1,200° F., for 1/2 hour to 6 hours.
Claim 26
Independent Claim
133 words
A method of preparing a vanadium, phosphorus, tin, oxygen and mordenite oxidation catalyst which comprises: (A) contacting a pentavalent vanadium compound, a pentavalent phosphorus compound and a divalent tin compound, at an atomic ratio of from 0.10:1:0.001 to 1:1:0.30 with an acidic-aqueous medium at a temperature of from 100° F. to 220° F., and a pressure from atmospheric pressure to 50 p.s.i.g., to form a catalyst precursor and produce vanadium having an average valence of from +3.50 to +4.95; (B) mixing from 15 weight percent to 50 weight percent of said catalyst precursor with from 50 weight percent to 85 weight percent of mordenite to form an impregnated mordenite; and (C) calcining the oxidation catalyst at temperatures in the range of from 400° F. to 1,200° F., for 1/2 hour to 6 hours.
Claim 27
Dependent Claim
31 words
The method defined in claim 22 wherein the vanadium compound is a member selected from the group consisting of ammonium vanadate, vanadyl sulfate, vanadium pentoxide, and vanadium oxytrichloride, and mixtures thereof.
Claim 28
Dependent Claim
31 words
The method defined in claim 22 wherein the phosphorus compound is a member selected from the group consisting of phosphoric acid, phosphorus pentoxide, ammonium phosphate, and diammonium phosphate, and mixtures thereof.
Claim 29
Dependent Claim
32 words
The method defined in claim 22 wherein the tin compound is stannous chloride, stannous fluoride, stannous bromide, stannous oxide, stannous sulfate, stannous acetate, stannous pyrophosphate, or stannous oxalate, or a mixture thereof.
Claim 30
Dependent Claim
43 words
The method defined in claim 22 wherein the acidic-aqueous medium consists of water and an acid selected from the group consisting of hydrochloric acid, hydroiodic acid, hydroformic acid, acetic acid, oxalic acid, maleic acid, citric acid or formic acid, or a mixture thereof.
Claim 31
Dependent Claim
39 words
The method defined in claim 22 wherein from 0 to 10 weight percent of a binding agent and solvent in a weight ratio of from 1:20 to 20:1 is mixed with the catalyst precursor and mordenite in step (B).
Claim 32
Dependent Claim
22 words
The method defined in claim 27 wherein the binding agent is selected from the group consisting of silica, methyl cellulose and alumina.
Claim 33
Dependent Claim
26 words
The method defined in claim 27 wherein the solvent is a member selected from the group consisting of ethanol, propanol, isopropanol, and butanol, and mixtures thereof.
Claim 34
Dependent Claim
45 words
The method defined in claim 22 wherein the oxidation catalyst has a surface area of from 100 M 2 /g to 450 M 2 /g, a pore volume of from 0.10 cc/g to 0.80 cc/g, and a compacted bulk density of 0.50 to 1.50 g/cc.
Claim 35
Independent Claim
220 words
A method of preparing a vanadium, phosphorus, tin, oxygen and mordenite, oxidation catalyst having a surface area of from 100 M 2 /g to 450 M 2 /g, a pore volume of from 0.10 cc/g to 0.80 cc/g, and a compacted bulk density of from 0.50 to 1.50, which comprises: (A) Contacting ammonium metavanadate, phosphoric acid and stannous chloride at an atomic ratio of from 0.10:1:0.001 to 1:1:0.30 with aqueous hydrochloric acid at a temperature of from 100° F. to 220° F., and a pressure of from atmospheric pressure to 50 p.s.i.g., to form a catalyst precursor, wherein the vanadium has an average valence of from +3.50 to +4.95; (B) mixing from 15 weight percent to 50 weight percent of said catalyst precursor and from 50 weight percent to 85 weight percent of mordenite with from about 0 to 10 weight percent of a binding agent selected from the group consisting of silica, methyl cellulose and alumina and mixtures thereof, and a solvent selected from the group consisting of ethanol, propanol, isopropanol, and butanol and mixtures thereof in a binding agent and solvent weight ratio of from 1:20 to 20:1 to form an impregnated mordenite; and (C) calcining the oxidation catalyst at a temperature in the range of from 400° F. to 1,200° F., for 1/2 hour to 6 hours.
Claim 36
Independent Claim
220 words
A method of preparing a vanadium, phosphorus, tin, oxygen and mordenite, oxidation catalyst having a surface area of from 100 M 2 /g to 450 M 2 /g, a pore volume of from 0.10 cc/g to 0.80 cc/g, and a compacted bulk density of from 0.50 to 1.50, which comprises: (A) Contacting ammonium metavanadate, phosphoric acid and stannous chloride at an atomic ratio of from 0.10:1:0.001 to 1:1:0.30 with aqueous hydrochloric acid at a temperature of from 100° F. to 220° F., and a pressure of from atmospheric pressure to 50 p.s.i.g., to form a catalyst precursor, wherein the vanadium has an average valence of from +3.50 to +4.95; (B) mixing from 15 weight percent to 50 weight percent of said catalyst precursor and from 50 weight percent to 85 weight percent of mordenite with from about 0 to 10 weight percent of a binding agent selected from the group consisting of silica, methyl cellulose and alumina and mixtures thereof, and a solvent selected from the group consisting of ethanol, propanol, isopropanol, and butanol and mixtures thereof in a binding agent and solvent weight ratio of from 1:20 to 20:1 to form an impregnated mordenite; and (C) calcining the oxidation catalyst at a temperature in the range of from 400° F. to 1,200° F., for 1/2 hour to 6 hours.
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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) | 1986-06-13 | 1986-12-13 | 1987-06-14 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-06-13 | 1990-12-13 | 1991-06-14 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-06-13 | 1994-12-13 | 1995-06-14 | $7700.00 | Window Closed / Lapsed |