US4392986A
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US
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Catalyst for carboxylic anhydride production
Assignee: ExxonMobil Technology and Engineering Co
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Filing: 1981-12-02
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Granted: 1983-07-12
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Expires: 2001-12-02
Abstract
Abstract A vanadium, phosphorus oxygen containing catalyst compositions capable of partially oxidizing hydrocarbons (e.g., n-butane) to form a carboxylic anhydride (e.g., maleic anhydride), a process for preparing this catalyst, and a process for using this catalyst to form such anhydrides is disclosed. The catalyst composition is prepared by an organic heterogeneous technique followed by a water treatment step and activation.
Inventors
- 👤 Tai-Cheng Yang
- 👤 Krishna K. Rao
- 👤 I-Der Huang
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-07 11:16
CPC Classifications
C; C07; C07C; C07C51/00; C07C51/16; C07C51/21; C07C51/255; C07C51/265; B; B01; B01J; B01J23/00; B01J23/002; B01J27/00; B01J27/14; B01J27/186; B01J27/195; B01J27/198; C07C51/215; C07C51/25; C07C51/252; B01J2523/00
Claims Analysis
Total Claims: 32
Claim 1
Independent Claim
189 words
A process for preparing a catalyst composition comprising vanadium, phosphorus and oxygen capable of catalyzing the oxidation of hydrocarbons comprising: (1) reacting in the presence of a liquid organic media, a vanadium containing compound present in said liquid organic media as a heterogeneous suspension and a phosphorus containing compound, in a manner and under conditions sufficient to form in said liquid organic media a heterogeneous vanadium-phosphorus-oxygen containing first catalyst precursor composition having an atomic ratio of phosphorus to vanadium of from about 0.5:1 to about 2:1, and an average vanadium valence of from about 3.9 to about 4.7; (2) separating said first catalyst precursor composition from said liquid organic media; (3) treating said first catalyst precursor composition with at least one part by weight liquid water per part by weight first catalyst precursor composition at a temperature of at least about 30° C. for a period of at least about 0.5 hour to form a second vanadium-phosphorus-oxygen catalyst precursor composition; (4) separating said second catalyst precursor composition from said water; and (5) activating said second catalyst precursor composition in an atmosphere which excludes the presence of air alone therein.
Claim 2
Dependent Claim
189 words
A process for preparing a catalyst composition comprising vanadium, phosphorus and oxygen capable of catalyzing the oxidation of hydrocarbons comprising: (1) reacting in the presence of a liquid organic media, a vanadium containing compound present in said liquid organic media as a heterogeneous suspension and a phosphorus containing compound, in a manner and under conditions sufficient to form in said liquid organic media a heterogeneous vanadium-phosphorus-oxygen containing first catalyst precursor composition having an atomic ratio of phosphorus to vanadium of from about 0.5:1 to about 2:1, and an average vanadium valence of from about 3.9 to about 4.7; (2) separating said first catalyst precursor composition from said liquid organic media; (3) treating said first catalyst precursor composition with at least one part by weight liquid water per part by weight first catalyst precursor composition at a temperature of at least about 30° C. for a period of at least about 0.5 hour to form a second vanadium-phosphorus-oxygen catalyst precursor composition; (4) separating said second catalyst precursor composition from said water; and (5) activating said second catalyst precursor composition in an atmosphere which excludes the presence of air alone therein.
Claim 3
Dependent Claim
29 words
The process of claim 1 wherein said liquid organic media comprises at least one member selected from the group consisting of alcohol, ether, aldehyde, ketone, amine, amide, and thiol.
Claim 4
Dependent Claim
14 words
The process of claim 1 wherein said activation is conducted in a non-oxidizing atmosphere.
Claim 5
Dependent Claim
37 words
The process of claim 1 wherein the vanadium containing compound comprises vanadium and oxygen, the phosphorus containing compound comprises at least one phosphoric acid, and the liquid organic media comprises at least one primary or secondary alcohol.
Claim 6
Dependent Claim
43 words
The process of claim 4 wherein the vanadium containing compound is V 2 O 5 ; the phosphorus containing compound is substantially anhydrous phosphoric acid, the liquid organic media is isobutanol, and the reaction of Step 1 is conducted under substantially anhydrous conditions.
Claim 7
Dependent Claim
54 words
The process of claim 1 wherein the first catalyst precursor forming reaction is conducted by admixing V 2 O 5 , substantially anhydrous phosphoric acid and isobutanol to form a slurry and refluxing this slurry while removing water formed in-situ during refluxing, said refluxing being conducted until the color of the slurry is blue.
Claim 8
Dependent Claim
29 words
The process of claim 1 wherein the first catalyst precursor is separated from the liquid organic media by filtration to form a filter cake, and drying said filter cake.
Claim 9
Dependent Claim
27 words
The process of claim 1 wherein the second catalyst precursor is separated from water by evaporation, and drying the resulting evaporated solids constituting the second catalyst precursor.
Claim 10
Dependent Claim
27 words
The process of claim 1 wherein the second catalyst precursor is separated from said water by filtration to form a filter cake, and drying said filter cake.
Claim 11
Dependent Claim
24 words
The process of claim 1 wherein the second catalyst precursor is separated from water by centrifuging, recovering the centrifuged solids and drying these solids.
Claim 12
Dependent Claim
38 words
The process of claim 1 wherein Step 3 is conducted by heating the first catalyst precursor in water at a temperature of from about 40° to about 100° C. for a period of at least about 0.5 hour.
Claim 13
Dependent Claim
32 words
The process of claim 11 wherein said heating of Step 3 is conducted for a period of at least 1 hour at a temperature of from about 40° to about 100° C.
Claim 14
Dependent Claim
19 words
The process of claim 1 wherein activation is conducted at temperatures of from about 200° to about 450° C.
Claim 15
Dependent Claim
19 words
The process of claim 1 wherein activation is conducted at temperatures of from about 250° to about 450° C.
Claim 16
Dependent Claim
19 words
The process of claim 1 wherein activation is conducted at temperatures of from about 300° to about 410° C.
Claim 17
Dependent Claim
17 words
The process of claim 3 wherein said non-oxidizing atmosphere comprises a gaseous mixture of air and hydrocarbon.
Claim 18
Dependent Claim
33 words
The process of claim 16 wherein activation is conducted in a non-explosive gaseous mixture comprising air and a hydrocarbon selected from the group consisting of methane, butane, butene, butadiene, pentane and mixtures thereof.
Claim 19
Dependent Claim
39 words
The process of claim 3 wherein activation is conducted in a gaseous mixture comprising air and from about 0.1 to about 1.8 mole % butane based on the total number of moles of the components in the gaseous mixture.
Claim 20
Dependent Claim
14 words
The process of claim 3 wherein the non-oxidizing atmosphere additionally contains an inert gas.
Claim 21
Dependent Claim
23 words
The process of claim 19 wherein the inert gas is selected from the group consisting of steam, nitrogen, helium, argon, and mixtures thereof.
Claim 22
Dependent Claim
77 words
The process of claim 20 wherein the non-oxidizing atmosphere comprises at least one member selected from the group consisting of carbon monoxide, mixtures of carbon monoxide and at least one inert gas, carbon dioxide, mixtures of carbon dioxide and at least one inert gas, hydrogen, mixtures of hydrogen and at least one inert gas, mixtures of hydrocarbon and at least one inert gas and hydrocarbon alone, said hydrocarbon being capable of being oxidized by said catalyst composition.
Claim 23
Dependent Claim
17 words
The process of claim 1 wherein the second catalyst precursor is shaped into structures prior to activation.
Claim 24
Dependent Claim
56 words
The process of claim 1 wherein said process is conducted in a manner and under conditions sufficient to impart to said activated catalyst a phosphorus to vanadium atomic ratio of from about 1:1 to about 1.4:1, an average vanadium valence of from about 3.9 to about 4.2, and a % B-Phase of not greater than 10%.
Claim 25
Dependent Claim
24 words
The process of claim 1 wherein the water of Step 3 is employed as an aqueous solution of mixed oxides of vanadium and phosphorus.
Claim 26
Dependent Claim
39 words
The process of any one of claims 1 to 10 and 11 to 24 wherein in Step (3) each part by weight of said first catalyst precursor composition is contacted with at least 2 parts by weight of water.
Claim 27
Dependent Claim
39 words
The process of any one of claims 1 to 10 and 11 to 24 wherein in Step (3) each part by weight of said first catalyst precursor composition is contacted with at least 4 parts by weight of water.
Claim 28
Dependent Claim
178 words
The process of claim 1 which comprises: (1) admixing V 2 O 5 , substantially anhydrous phosphoric acid and isobutanol to form a slurry having V 2 O 5 suspended therein and phosphoric acid dissolved therein; (2) refluxing under substantially anhydrous conditions said slurry until the color thereof turns blue to form a heterogeneous first catalyst precursor composition suspended in said slurry having a phosphorus to vanadium atomic ratio of from about 1:1 to about 1.3:1; (3) separating said first catalyst precursor composition from said isobutanol; (4) contacting each part by weight of said first catalyst precursor composition with at least 2 parts by weight water at a temperature of from about 50 to about 150° C. for a period of at least about 1 hour to form a second catalyst precursor composition; (5) separating said second precursor composition from said water; (6) activating said second precursor composition in a gaseous mixture comprising air and from about 0.1 to about 1.8 mole %, n-butane, based on the total number of moles of gaseous components in said gaseous mixture.
Claim 29
Dependent Claim
38 words
The process of claim 27 wherein the V 2 O 5 and phosphoric acid are admixed in amounts sufficient to achieve an initial phosphorus to vanadium atomic ratio in said admixture of from about 1:1 to about 1.3:1.
Claim 30
Dependent Claim
21 words
The process of claim 4 wherein the vanadium containing compound and the phosphorus containing compound are reacted under substantially anhydrous conditions.
Claim 31
Dependent Claim
40 words
The process of claim 1 wherein the vanadium containing compound is reduced in the presence of the phosphorus containing compound and liquid organic media and the reduced vanadium containing compound reacted with the phosphorus containing compound in a single step.
Claim 32
Dependent Claim
23 words
The process of claim 1 wherein Step 3 is conducted by contacting the first catalyst precursor with a liquid consisting essentially of water.
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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) | 1986-07-11 | 1987-01-10 | 1987-07-12 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-07-11 | 1991-01-10 | 1991-07-12 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-07-11 | 1995-01-10 | 1995-07-12 | $7700.00 | Window Closed / Lapsed |