US4455388A
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Catalyst and process for producing diolefins
Assignee: Union Oil Company of California
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Filing: 1981-12-29
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Granted: 1984-06-19
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Expires: 2001-12-29
Abstract
Abstract High surface area oxidative dehydrogenation catalysts which are suitable for converting C 4 to C 8 monoolefins to diolefins are disclosed, comprising the oxides of an alkali metal, vanadium, phosphorus, potassium and tin in combination with a crystalline silica having a surface area between 30 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
- 👤 Paul R. Robinson
- 👤 Eric L. Moorehead
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 13:34
CPC Classifications
C; C07; C07C; C07C5/00; C07C5/42; C07C5/48; B; B01; B01J; B01J23/00; B01J23/002; B01J27/00; B01J27/14; B01J27/186; B01J27/195; B01J27/198; B01J2523/00
Claims Analysis
Total Claims: 47
Claim 1
Independent Claim
57 words
An oxidative dehydrogenation catalyst defined by the formula: Me.sub.a V.sub.b P.sub.c Sn.sub.d O.sub.e X wherein X is crystalline silica, Me is an alkali metal, a is 0.10 to 2, b is 0.10 to 1, c is 1, d is 0.001 to 0.30 and e is a number which satisfies the valence requirements of the other elements present.
Claim 2
Dependent Claim
57 words
An oxidative dehydrogenation catalyst defined by the formula: Me.sub.a V.sub.b P.sub.c Sn.sub.d O.sub.e X wherein X is crystalline silica, Me is an alkali metal, a is 0.10 to 2, b is 0.10 to 1, c is 1, d is 0.001 to 0.30 and e is a number which satisfies the valence requirements of the other elements present.
Claim 3
Dependent Claim
20 words
The oxidative dehydrogenation catalyst defined in claim 1 wherein the vanadium has an average oxidation state between +3.5 and +4.95.
Claim 4
Dependent Claim
29 words
The oxidative dehydrogenation catalyst defined in claim 1 wherein Me is a member selected from the group consisting of lithium, sodium, potassium, rubidium, or cesium or a mixture thereof.
Claim 5
Dependent Claim
37 words
The oxidative dehydrogenation catalyst defined in claim 1 wherein from 15 to 50 weight percent of Me, V, P, Sn, and O as the metal oxides are combined with from 50 to 85 weight percent of X.
Claim 6
Dependent Claim
32 words
The oxidative dehydrogenation catalyst defined in claim 1 including from 0.1 to 10 weight percent of a binder selected from the group consisting of silica, methyl cellulose and alumina, and mixtures thereof.
Claim 7
Dependent Claim
45 words
The oxidative dehydrogenation catalyst defined in claim 1 having a surface area of from 30 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 0.35 g/cc to 1.50 g/cc.
Claim 8
Dependent Claim
14 words
The oxidative dehydrogenation catalyst defined in claim 1 wherein the crystalline silica is silicalite.
Claim 9
Dependent Claim
156 words
An oxidative dehydrogenation catalyst defined by the formula: K.sub.a V.sub.b P.sub.c Sn.sub.d O.sub.e X wherein X is silicalite, a is 0.10 to 2, b is 0.10 to 1, c is 1, d is 0.001 to 0.30, and e is a number which satisfies the valence requirements of the other elements present, vanadium has an average oxidation state between 3.50 and 4.95, wherein said dehydrogenation catalyst contains from 15 to 50 weight percent of K, V, P, Sn and O as the metal oxides, from 50 to 85 weight percent of X and from 0.1 to 10 weight percent of a binder selected from the group consisting of silica, methyl cellulose and alumina and mixtures thereof, said oxidative dehydrogenation catalyst having a surface area of from 30 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 0.35 g/cc to 1.50 g/cc.
Claim 10
Dependent Claim
156 words
An oxidative dehydrogenation catalyst defined by the formula: K.sub.a V.sub.b P.sub.c Sn.sub.d O.sub.e X wherein X is silicalite, a is 0.10 to 2, b is 0.10 to 1, c is 1, d is 0.001 to 0.30, and e is a number which satisfies the valence requirements of the other elements present, vanadium has an average oxidation state between 3.50 and 4.95, wherein said dehydrogenation catalyst contains from 15 to 50 weight percent of K, V, P, Sn and O as the metal oxides, from 50 to 85 weight percent of X and from 0.1 to 10 weight percent of a binder selected from the group consisting of silica, methyl cellulose and alumina and mixtures thereof, said oxidative dehydrogenation catalyst having a surface area of from 30 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 0.35 g/cc to 1.50 g/cc.
Claim 11
Dependent Claim
39 words
An oxidative dehydrogenation catalyst comprising promoters of one or more alkali metals, vanadium, phosphorus and tin in combination with crystalline silica, said promoters being present in an alkali metal, vanadium, phosphorus and tin ratio between about 0.10:0.10:1:0.001 and 2:1:1:0.30.
Claim 12
Dependent Claim
39 words
An oxidative dehydrogenation catalyst comprising promoters of one or more alkali metals, vanadium, phosphorus and tin in combination with crystalline silica, said promoters being present in an alkali metal, vanadium, phosphorus and tin ratio between about 0.10:0.10:1:0.001 and 2:1:1:0.30.
Claim 13
Dependent Claim
23 words
The oxidative dehydrogenation catalyst defined in claim 9 wherein the alkali metal is lithium, sodium, potassium, rubidium or cesium or a mixture thereof.
Claim 14
Dependent Claim
14 words
The oxidative dehydrogenation catalyst defined in claim 9 wherein the crystalline silica is silicalite.
Claim 15
Dependent Claim
14 words
The oxidative dehydrogenation catalyst defined in claim 10 wherein the crystalline silica is silicalite.
Claim 16
Independent Claim
102 words
A method of preparing an alkali metal, vanadium, phosphorus, tin, oxygen and crystalline silica, oxidative dehydrogenation catalyst which comprises: (A) contacting an alkali metal, a vanadium compound, and a phosphorus compound with an acidic-aqueous medium and a divalent tin compound under reaction conditions which will provide vanadium having an average oxidation state of from +3.50 to +4.95 to form a catalyst precursor; (B) admixing the catalyst precursor with crystalline silica, to form an impregnated crystalline silica; and (C) calcining the oxidative dehydrogenation catalyst at temperatures in the range of from 400° F. to 1,200° F. for from 1/4 hour to 6 hours.
Claim 17
Independent Claim
102 words
A method of preparing an alkali metal, vanadium, phosphorus, tin, oxygen and crystalline silica, oxidative dehydrogenation catalyst which comprises: (A) contacting an alkali metal, a vanadium compound, and a phosphorus compound with an acidic-aqueous medium and a divalent tin compound under reaction conditions which will provide vanadium having an average oxidation state of from +3.50 to +4.95 to form a catalyst precursor; (B) admixing the catalyst precursor with crystalline silica, to form an impregnated crystalline silica; and (C) calcining the oxidative dehydrogenation catalyst at temperatures in the range of from 400° F. to 1,200° F. for from 1/4 hour to 6 hours.
Claim 18
Dependent Claim
27 words
The method defined in claim 13 wherein the oxidation catalyst contains an alkali metal, vanadium, phosphorus and tin in an atomic ratio of from 0.10:0.10:1:0.001 to 2:1:1:0.30.
Claim 19
Dependent Claim
29 words
The method defined in claim 13 wherein from 15 to 50 weight percent of the catalyst precursor is mixed with from 50 to 85 weight percent of crystalline silica.
Claim 20
Dependent Claim
21 words
The method defined in claim 13 wherein the alkali metal is lithium, sodium, potassium, rubidium or cesium or a mixture thereof.
Claim 21
Dependent Claim
31 words
The method defined in claim 13 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 22
Dependent Claim
31 words
The method defined in claim 13 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 23
Dependent Claim
32 words
The method defined in claim 13 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 24
Dependent Claim
42 words
The method defined in claim 13 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 25
Dependent Claim
39 words
The method defined in claim 13 including mixing from 3 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 crystalline silica in step (B).
Claim 26
Dependent Claim
27 words
The method defined in claim 21 wherein the binding agent is a member selected from the group consisting of silica, methyl cellulose and alumina, and mixtures thereof.
Claim 27
Dependent Claim
26 words
The method defined in claim 21 wherein the solvent is a member selected from the group consisting of ethanol, propanol, isopropanol, and butanol, and mixtures thereof.
Claim 28
Dependent Claim
26 words
The method defined in claim 13 wherein the reaction conditions comprise temperatures from 100° F. to 220° F. and pressures from atmospheric pressure to 50 p.s.i.g.
Claim 29
Dependent Claim
48 words
The method defined in claim 13 wherein the oxidative dehydrogenation catalyst has a surface area of from 30 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 0.35 g/cc to 1.50 g/cc.
Claim 30
Dependent Claim
12 words
The method described in claim 13 wherein the crystalline silica is silicalite.
Claim 31
Dependent Claim
12 words
The method described in claim 15 wherein the crystalline silica is silicalite.
Claim 32
Dependent Claim
12 words
The method described in claim 21 wherein the crystalline silica is silicalite.
Claim 33
Independent Claim
142 words
A method of preparing an alkali metal, vanadium, phosphorus, tin, oxygen and crystalline silica dehydrogenation catalyst which comprises: (A) contacting an alkali metal, a pentavalent vanadium compound, a pentavalent phosphorus compound and a divalent tin compound, at an atomic ratio of from 0.10:0.10:1:0.001 to 2:1:1:0.30 with an acidic-aqueous medium 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 and produce vanadium having an average oxidation state of from +3.50 to +4.95. (B) mixing from 15 percent to 50 weight percent of said catalyst precursor with from 50 weight percent to 85 weight percent of crystalline silica to form an impregnated crystalline silica; and (C) calcining the dehydrogenation catalyst at temperatures in the range of from 400° F. to 1,200° F., for 1/2 hour to 6 hours.
Claim 34
Independent Claim
142 words
A method of preparing an alkali metal, vanadium, phosphorus, tin, oxygen and crystalline silica dehydrogenation catalyst which comprises: (A) contacting an alkali metal, a pentavalent vanadium compound, a pentavalent phosphorus compound and a divalent tin compound, at an atomic ratio of from 0.10:0.10:1:0.001 to 2:1:1:0.30 with an acidic-aqueous medium 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 and produce vanadium having an average oxidation state of from +3.50 to +4.95. (B) mixing from 15 percent to 50 weight percent of said catalyst precursor with from 50 weight percent to 85 weight percent of crystalline silica to form an impregnated crystalline silica; and (C) calcining the dehydrogenation catalyst at temperatures in the range of from 400° F. to 1,200° F., for 1/2 hour to 6 hours.
Claim 35
Dependent Claim
28 words
The method defined in claim 29 wherein the alkali metal is a member selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium and mixtures thereof.
Claim 36
Dependent Claim
31 words
The method defined in claim 29 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 37
Dependent Claim
31 words
The method defined in claim 29 wherein the phosphorus compound is a member selected from the group consisting of phosphoric acid, phosphorus pentoxide, ammounium phosphate, and diammonium pnosphate, and mixtures thereof.
Claim 38
Dependent Claim
32 words
The method defined in claim 29 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 39
Dependent Claim
43 words
The method defined in claim 29 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 40
Dependent Claim
39 words
The method defined in claim 29 including admixing from 0.1 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 crystalline silica in step (B).
Claim 41
Dependent Claim
24 words
The method defined in claim 35 wherein the binding agent is a member selected from the group consisting of silica, methyl cellulose and alumina.
Claim 42
Dependent Claim
26 words
The method defined in claim 35 wherein the solvent is a member selected from the group consisting of ethanol, propanol, isopropanol, and butanol, and mixtures thereof.
Claim 43
Dependent Claim
47 words
The method defined in claim 29 wherein the oxidative dehydrogenation catalyst has a surface area of from 30 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 g/cc to 1.50 g/cc.
Claim 44
Dependent Claim
12 words
The method described in claim 29 wherein the crystalline silica is silicalite.
Claim 45
Dependent Claim
12 words
The method described in claim 35 wherein the crystalline silica is silicalite.
Claim 46
Independent Claim
228 words
A method of preparing an alkali metal, vanadium, phosphorus, tin, oxygen and silicalite dehydrogenation catalyst having a surface area of from 30 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 g/cc to 1.50, which comprises: (A) Contacting potassium metaphosphate, ammonium metavanadate, phosphoric acid and stannous chloride at an atomic range of from 0.10:0.10:1:0.001 to 2:1:1:0.30 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 oxidation state of from +3.50 to +4.95; (B) admixing from 15 weight percent to 50 weight percent of said catalyst precursor and from 50 weight percent to 85 weight percent of crystalline silica, 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 cryatalline silica; 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 47
Independent Claim
228 words
A method of preparing an alkali metal, vanadium, phosphorus, tin, oxygen and silicalite dehydrogenation catalyst having a surface area of from 30 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 g/cc to 1.50, which comprises: (A) Contacting potassium metaphosphate, ammonium metavanadate, phosphoric acid and stannous chloride at an atomic range of from 0.10:0.10:1:0.001 to 2:1:1:0.30 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 oxidation state of from +3.50 to +4.95; (B) admixing from 15 weight percent to 50 weight percent of said catalyst precursor and from 50 weight percent to 85 weight percent of crystalline silica, 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 cryatalline silica; 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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