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US4370490A Expired / Lapsed US ⏱️ 0.0 years remaining

Process for producing methacrylic acid by oxidative dehydration of isobutyric acid and catalyst therefor

Assignee: Roehm GmbH Darmstadt
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Filing: 1981-08-28
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Granted: 1983-01-25
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Expires: 2001-08-28
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Abstract

Abstract Isobutyric acid is oxidatively dehydrogenated to methacrylic acid by passing a gaseous mixture of isobutyric acid, oxygen, nitrogen and optionally water vapor at temperatures of 300°-450° C. and pressures of 0.5 to 5 bar over a catalyst comprising molybdenum oxide, which also contains vanadium, phosphorous and a metal selected from the group consisting of alkali metals, alkaline earth metals, zinc, silver, aluminum, titanium, lead, manganese, iron, cobalt, nickel and tin, preferably precipitated on a solid silica support and calcined at 200° to 400° C. At conversion levels of 80 to 100% of the isobutyric acid used, a methacrylic acid selectivity of 60 to 74% is attained.

Inventors

  • 👤 Wilhelm Gruber
  • 👤 Gunter Schroder

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-30 21:59
CPC Classifications
B; B01; B01J; B01J23/00; B01J23/002; B01J27/00; B01J27/14; B01J27/186; B01J27/195; B01J27/198; B01J27/199; C; C07; C07C; C07C51/00; C07C51/347; C07C51/377; B01J2523/00

Claims Analysis

Total Claims: 22
Claim 1
Independent Claim 69 words
A process for producing methacrylic acid or an ester thereof comprising contacting in gaseous phase in presence of oxygen isobutyric acid or the corresponding ester thereof with a metal oxide catalyst substantially free of sulfate and consisting essentially of oxides of molybdenum, vanadium, phosphorus, and a metal selected from the group consisting of alkali metals, alkaline earth metals, zinc, silver, aluminum, titanium, lead, manganese, iron, cobalt, nickel, and tin.
Claim 2
Dependent Claim 69 words
A process for producing methacrylic acid or an ester thereof comprising contacting in gaseous phase in presence of oxygen isobutyric acid or the corresponding ester thereof with a metal oxide catalyst substantially free of sulfate and consisting essentially of oxides of molybdenum, vanadium, phosphorus, and a metal selected from the group consisting of alkali metals, alkaline earth metals, zinc, silver, aluminum, titanium, lead, manganese, iron, cobalt, nickel, and tin.
Claim 3
Dependent Claim 99 words
The process of claim 1, wherein said metal oxide catalyst has the formula: M.sub.a Mo.sub.b V.sub.c P.sub.d O.sub.e wherein M is a metal selected from the group consisting of K, Rb, Cs, Be, Mg, Ba, Zn, Ca, Ag, Al, Ti, Pb, Mn, Fe, Co, Ni, and Sn; a is a number from 0.4 to 2.5; b is a number about equal to 12; c is a number from 1 to 2; d is a number from 0.5 to 3; and e is a number chosen to satisfy the valences and amounts of the other elements present in the catalyst.
Claim 4
Dependent Claim 36 words
The process of claim 1 or 2, wherein said metal oxide catalyst has the formula: A.sub.1.5-2 Mo.sub.12 V.sub.1.5 P.sub.2 O.sub.45-46 wherein A is an alkali metal selected from the group consisting of potassium, rubidium and cesium.
Claim 5
Dependent Claim 24 words
The process of claim 1 or 2, wherein the metal oxide catalyst is supported on a solid support comprising silicon dioxide and activated silica.
Claim 6
Dependent Claim 20 words
The process of claim 4, wherein said silicon dioxide is diatomaceous earth and said activated silica is submicroscopic pyrogenic silica.
Claim 7
Dependent Claim 19 words
The process of claim 4, wherein the ratio of silicon dioxide/activated silica in said support is 14:2 to 9:2.
Claim 8
Dependent Claim 10 words
The process of claim 6, wherein said ratio is 5:1.
Claim 9
Dependent Claim 28 words
The process of claim 1 or 2, wherein said metal oxide catalyst comprises 5 to 80% by weight of the total weight of support plus metal oxide catalyst.
Claim 10
Dependent Claim 26 words
The process of claim 8 wherein said metal oxide catalyst comprises 20 to 70% by weight of the total weight of support plus metal oxide catalyst.
Claim 11
Dependent Claim 25 words
The process of claim 1 or 2, wherein said catalyst is calcined at temperatures between 200° and 400° C. before being used in the process.
Claim 12
Dependent Claim 19 words
The process of claims 1 or 2, wherein said isobutryic acid or ester thereof is in the gas phase.
Claim 13
Dependent Claim 23 words
The process of claim 11, wherein said isobutyric acid or ester thereof is present in a mixture together with water, oxygen and nitrogen.
Claim 14
Dependent Claim 23 words
The process of claim 12, wherein the molar ratio of isobutyric acid or ester thereof to water to oxygen to nitrogen is (1-2.5):(0-3):(1-2):(4-10).
Claim 15
Dependent Claim 11 words
The process of claim 13, wherein said molar ratio is 1:2:1.7:20.
Claim 16
Dependent Claim 22 words
The process of claim 1 or 2, wherein said oxidative dehydrogenation is performed in a temperature range of 300° to 450° C.
Claim 17
Dependent Claim 14 words
The process of claim 15, wherein said temperature range is 340° to 450° C.
Claim 18
Dependent Claim 14 words
The process of claim 15, wherein said temperature range is 340° to 370° C.
Claim 19
Dependent Claim 29 words
The process of claim 12, wherein said gaseous mixture is introduced at a space velocity of about 100 to 15,000 liters of gas per liter of catalyst per hour.
Claim 20
Dependent Claim 17 words
The process of claim 11, wherein the pressure of said gas is from 0.5 to 5 bar.
Claim 21
Dependent Claim 17 words
The process of claim 12, wherein the pressure of said gas mixture is 0.5 to 5 bar.
Claim 22
Dependent Claim 25 words
The process of claim 1 or 2, wherein said metal oxide catalyst contains a metal selected from the group consisting of magnesium, calcium and aluminum.

References Cited (Backward Citations)

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DE2722375A1 Cited
US4061673A Cited
US4249020A Cited
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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) 1986-01-24 1986-07-26 1987-01-25 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1990-01-24 1990-07-26 1991-01-25 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1994-01-24 1994-07-26 1995-01-25 $7700.00 Window Closed / Lapsed

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