US Patent 6,337,298 — Deeply reduced oxidation catalyst and its use for catalyzing liquid phase oxidation reactions

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Abstract

This invention relates to an improved catalyst, comprising a carbon support having a noble metal at its surface, for use in catalyzing liquid phase oxidation reactions, especially in an acidic oxidative environment and in the presence of solvents, reactants, intermediates, or products which solubilize noble metals; a process for the preparation of the improved catalyst; a liquid phase oxidation process using such a catalyst wherein the catalyst exhibits improved resistance to noble metal leaching, particularly in acidic oxidative environments and in the presence of solvents, reactants, intermediates, or products which solubilize noble metals; and a liquid phase oxidation process in which N-(phosphonomethyl)iminodiacetic acid (i.e., PMIDA) or a salt thereof is oxidized to form N-(phosphonomethyl)glycine (i.e., glyphosate) or a salt thereof using such a catalyst wherein the oxidation of the formaldehyde and formic acid by-products into carbon dioxide and water is increased.

Claims

144 · 8 independent · depth 4

144 granted claims

›1.independentAn oxidation catalyst comprising a carbon support having a noble metal and a promoter at a surface of the carbon support, wherein: the catalyst is cha…+12

›2.↳ 1The oxidation catalyst of claim 1 wherein the promoter is more easily oxidized than the noble metal.d2

›3.↳ 1The oxidation catalyst of claim 1 wherein the promoter comprises a metal selected from the group consisting of tin, bismuth, lead, cadmium, magnesium,…d2

›4.↳ 1The oxidation catalyst of claim 1 wherein the promoter comprises tin.d2

›5.↳ 1The oxidation catalyst of claim 1 wherein the promoter comprises iron.d2

›6.↳ 1The oxidation catalyst of claim 1 wherein the promoter comprises titanium.d2

›7.↳ 1The oxidation catalyst of claim 1 wherein the catalyst comprises two promoters at the surface of the carbon support, each said promoter constituting a…d2+1

›9.↳ 1The oxidation catalyst of claim 1 wherein noble metal atoms at the surface are alloyed with the promoter.d2

›10.↳ 1The oxidation catalyst of claim 1 wherein a majority of the noble metal atoms at the surface are alloyed with the promoter.d2

›11.↳ 1The oxidation catalyst of claim 1 wherein substantially all of the noble metal atoms at the surface are alloyed with the promoter.d2

›12.↳ 1The oxidation catalyst of claim 1 wherein said carbon monoxide yield is no greater than about 0.3 mmole of carbon monoxide per gram of catalyst.d2

›137.↳ 1The catalyst of claim 1 wherein noble metal constitutes no greater than about 7.5% by weight of the catalyst.d2

›13.independentAn oxidation catalyst comprising a carbon support having a noble metal, a promoter, carbon, and oxygen at a surface of the carbon support, wherein: th…+17

›14.↳ 13The oxidation catalyst of claim 13 wherein said ratio of carbon atoms to oxygen atoms is at least about 40:1.d2

›15.↳ 13The oxidation catalyst of claim 13 wherein said ratio of carbon atoms to oxygen atoms is at least about 50:1.d2

›16.↳ 13The oxidation catalyst of claim 13 wherein said ratio of carbon atoms to oxygen atoms is at least about 60:1.d2

›17.↳ 13The oxidation catalyst of claim 13 wherein the catalyst is further characterized as having a ratio of oxygen atoms to noble metal atoms at the surface…d2+2

›20.↳ 13The oxidation catalyst of claim 13 wherein the promoter is more easily oxidized than the noble metal.d2

›21.↳ 13The oxidation catalyst of claim 13 wherein the promoter comprises a metal selected from the group consisting of tin, bismuth, lead, cadmium, magnesium…d2

›22.↳ 13The oxidation catalyst of claim 13 wherein the promoter comprises tin.d2

›23.↳ 13The oxidation catalyst of claim 13 wherein the promoter comprises iron.d2

›24.↳ 13The oxidation catalyst of claim 13 wherein the promoter comprises titanium.d2

›25.↳ 13The oxidation catalyst of claim 13 wherein the catalyst comprises two promoters at the surface of the carbon support each said promoter constituting a…d2+1

›27.↳ 13The oxidation catalyst of claim 13 wherein noble metal atoms at the surface are alloyed with the promoter.d2

›28.↳ 13The oxidation catalyst of claim 13 wherein a majority of the noble metal atoms at the surface are alloyed with the promoter.d2

›29.↳ 13The oxidation catalyst of claim 13 wherein substantially all of the noble metal atoms at the surface are alloyed with the promoter.d2

›138.↳ 13The catalyst of claim 13 wherein noble metal constitutes no greater than about 7.5% by weight of the catalyst.d2

›30.independentAn oxidation catalyst prepared by a process comprising depositing a noble metal at a surface of a carbon support, and then heating the surface at a te…+22

›31.↳ 30The oxidation catalyst of claim 30 wherein the promoter is more easily oxidized than the noble metal.d2

›32.↳ 30The oxidation catalyst of claim 30 wherein the promoter comprises a metal selected from the group consisting of tin, bismuth, lead, cadmium, magnesium…d2

›33.↳ 30The oxidation catalyst of claim 30 wherein the promoter comprises tin.d2

›34.↳ 30The oxidation catalyst of claim 30 wherein the promoter comprises iron.d2

›35.↳ 30The oxidation catalyst of claim 30 wherein the promoter comprises titanium.d2

›36.↳ 30The oxidation catalyst of claim 30 wherein the catalyst comprises two promoters at the surface of the carbon support, each promoter constituting at le…d2+1

›38.↳ 30The oxidation catalyst of claim 30 wherein noble metal atoms at the surface are alloyed with the promoter.d2

›39.↳ 30The oxidation catalyst of claim 30 wherein a majority of the noble met atoms at the surface are alloyed with the promoter.d2

›40.↳ 30The oxidation catalyst of claim 30 wherein substantially all of the noble metal atoms at the surface are alloyed with the promoter.d2

›41.↳ 30The oxidation catalyst of claim 30 wherein said temperature is at least about 500 C.d2

›42.↳ 30The oxidation catalyst of claim 30 wherein said temperature is from about 550 to about 1,200 C.d2

›43.↳ 30The oxidation catalyst of claim 30 wherein said temperature is from about 550 to about 900 C.d2

›44.↳ 30The oxidation catalyst of claim 30 wherein the heating is conducted in a non-oxidizing environment.d2+7

›139.↳ 30The catalyst of claim 30 wherein noble metal constitutes no greater than about 7.5% by weight of the catalyst.d2

›52.independentAn oxidation catalyst prepared by a process comprising depositing a noble metal at a surface of a carbon support, and then exposing the surface to a r…+13

›53.↳ 52The oxidation catalyst of claim 52 wherein the promoter is more easily oxidized than the noble metal.d2

›54.↳ 52The oxidation catalyst of claim 52 wherein the promoter comprises a metal selected from the group consisting of tin, bismuth, lead, cadmium, magnesium…d2

›55.↳ 52The oxidation catalyst of claim 52 wherein the promoter comprises tin.d2

›56.↳ 52The oxidation catalyst of claim 52 wherein the promoter comprises iron.d2

›57.↳ 52The oxidation catalyst of claim 52 wherein the promoter comprises titanium.d2

›58.↳ 52The oxidation catalyst of claim 52 wherein the catalyst comprises two promoters at the surface of the carbon support, each said promoter constituting …d2+1

›60.↳ 52The oxidation catalyst of claim 52 wherein noble metal atoms at the surface are alloyed with the promoter.d2

›61.↳ 52The oxidation catalyst of claim 52 wherein a majority of the noble metal atoms at the surface are alloyed with the promoter.d2

›62.↳ 52The oxidation catalyst of claim 52 wherein substantially all of the noble metal atoms at the surface are alloyed with the promoter.d2

›63.↳ 52The oxidation catalyst of claim 52 wherein the reducing environment comprises ammonia.d2

›64.↳ 52The oxidation catalyst of claim 52 wherein the reducing environment comprises NaBH 4 .d2

›140.↳ 52The catalyst of claim 52 wherein noble metal constitutes no greater than about 7.5% by weight of the catalyst.d2

›65.independentA process for the preparation of an oxidation catalyst from a carbon support having carbon and oxygen at a surface of the carbon support, the process …+22

›66.↳ 65The process of claim 65 wherein the promoter is more easily oxidized than the noble metal.d2

›67.↳ 65The process of claim 65 wherein the promoter comprises a metal selected from the group consisting of tin, bismuth, lead, cadmium, magnesium, manganese…d2

›68.↳ 65The process of claim 65 wherein the promoter comprises tin.d2

›69.↳ 65The process of claim 65 wherein the promoter comprises iron.d2

›70.↳ 65The process of claim 65 wherein the promoter comprises titanium.d2

›71.↳ 65The process of claim 65 wherein the catalyst comprises two promoters at the surface of the carbon support each said promoter constituting at least 0.0…d2+1

›73.↳ 65The process of claim 65 wherein noble metal atoms at the surface are alloyed with the promoter.d2

›74.↳ 65The process of claim 65 wherein a majority of the noble metal atoms at the surface are alloyed with the promoter.d2

›75.↳ 65The process of claim 65 wherein substantially all of the noble metals at the surface are alloyed with the promoter.d2

›76.↳ 65The process of claim 65 wherein said temperature is at least about 500 C.d2

›77.↳ 65The process of claim 65 wherein said temperature is from about 550 to about 1,200 C.d2

›78.↳ 65The process of claim 65 wherein said temperature is from about 550 to about 900 C.d2

›79.↳ 65The process of claim 65 wherein said heating is conducted in a non-oxidizing environment.d2+7

›141.↳ 65The catalyst of claim 65 wherein noble metal constitutes no greater than about 7.5% by weight of the catalyst.d2

›87.independentA process for the preparation of an oxidation catalyst from a carbon support having carbon and oxygen at a surface of the carbon support, the process …+17

›88.↳ 87The process of claim 87 wherein the promoter is more easily oxidized than the noble metal.d2

›89.↳ 87The process of claim 87 wherein the promoter comprises a metal selected from the group consisting of tin, bismuth, lead, cadmium, magnesium, manganese…d2

›90.↳ 87The process of claim 87 wherein the promoter comprises tin.d2

›91.↳ 87The process of claim 87 wherein the promoter comprises iron.d2

›92.↳ 87The process of claim 87 wherein the promoter comprises titanium.d2

›93.↳ 87The process of claim 87 wherein the catalyst comprises two promoters at the surface of the carbon support each said promoter constituting at least 0.0…d2+1

›95.↳ 87The process of claim 87 wherein noble metal atoms at the surface are alloyed with the promoter.d2

›96.↳ 87The process of claim 87 wherein a majority of the noble metal atoms at the surface are alloyed with the promoter.d2

›97.↳ 87The process of claim 87 wherein substantially all of the noble metals at the surface are alloyed with the promoter.d2

›98.↳ 87The process of claim 87 wherein the reducing environment comprises ammonia.d2+2

›101.↳ 87The process of claim 87 wherein the reducing environment comprises NaBH 4 .d2+2

›142.↳ 87The process of claim 87 wherein noble metal constitutes no greater than about 7.5% by weight of the catalyst.d2

›104.independentA process for the preparation of an oxidation catalyst from a carbon support having carbon and oxygen at a surface of the carbon support, the process …+19

›105.↳ 104The process of claim 104 wherein said ratio of carbon atoms to oxygen atoms is at least about 40:1.d2

›106.↳ 104The process of claim 104 wherein said ratio of carbon atoms to oxygen atoms is at least about 50:1.d2

›107.↳ 104The process of claim 104 wherein said ratio of carbon atoms to oxygen atoms is at least about 60:1.d2

›108.↳ 104The process of claim 104 wherein the ratio of oxygen atoms to noble metal atoms at the surface is less than 7:1 as measured by x-ray photoelectron spe…d2+2

›111.↳ 104The process of claim 104 wherein the reducing environment comprises ammonia.d2

›112.↳ 104The process of claim 104 wherein the reducing environment comprises NaBH 4 .d2

›113.↳ 104The process of claim 104 wherein the promoter is more easily oxidized than the noble metal.d2

›114.↳ 104The process of claim 104 wherein the promoter comprises a metal selected from the group consisting of tin, bismuth, lead, cadmium, magnesium, manganes…d2

›115.↳ 104The process of claim 104 wherein the promoter comprises tin.d2

›116.↳ 104The process of claim 104 wherein the promoter comprises iron.d2

›117.↳ 104The process of claim 104 wherein the promoter comprises titanium.d2

›118.↳ 104The process of claim 104 wherein the catalyst comprises at least two promoters at the surface of the carbon support each said promoter constituting at…d2+1

›120.↳ 104The process of claim 104 wherein noble metal atoms at the surface are alloyed with the promoter.d2

›121.↳ 104The process of claim 104 wherein a majority of the noble metal atoms at the surface are alloyed with the promoter.d2

›122.↳ 104The process of claim 104 wherein substantially all of the noble metals at the surface are alloyed with the promoter.d2

›143.↳ 104The process of claim 104 wherein noble metal constitutes no greater than about 7.5% by weight of the catalyst.d2

›123.independentA process for the preparation of an oxidation catalyst, the process comprising depositing a noble metal at a surface of a carbon support, and then exp…+14

›124.↳ 123The process of claim 123 wherein said carbon monoxide yield is no greater than about 0.3 mmole of carbon monoxide per gram of catalyst.d2

›125.↳ 123The process of claim 123 wherein the reducing environment comprises ammonia.d2

›126.↳ 123The process of claim 123 wherein the reducing environment comprises NaBH 4 .d2

›127.↳ 123The process of claim 123 wherein the promoter is more easily oxidized than the noble metal.d2

›128.↳ 123The process of claim 123 wherein the promoter comprises a metal selected from the group consisting of tin, bismuth, lead, cadmium, magnesium, manganes…d2

›129.↳ 123The process of claim 123 wherein the promoter comprises tin.d2

›130.↳ 123The process of claim 123 wherein the promoter comprises iron.d2

›131.↳ 123The process of claim 123 wherein the promoter comprises titanium.d2

›132.↳ 123The process of claim 123 wherein the catalyst comprises at least two promoters at the surface of the carbon support, each said promoter constituting a…d2+1

›134.↳ 123The process of claim 123 wherein noble metal atoms at the surface are alloyed with the promoter.d2

›135.↳ 123The process of claim 123 wherein a majority of the noble metal atoms at the surface are alloyed with the promoter.d2

›136.↳ 123The process of claim 123 wherein substantially all of the noble metal atoms at the surface are alloyed with the promoter.d2

›144.↳ 123The process of claim 123 wherein noble metal constitutes no greater than about 7.5% by weight of the catalyst.d2

Classifications

8 codes

IPC · International Patent Classification

Section B — Performing operations; transporting

B01J2/118

USPC · US Patent Classification

502/185502/177502/182502/180502/184502/174502/183

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Examiner

Elizabeth D. Wood

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Priority chain

1 priority documents

Priority

25 Feb 1998

earliest claimed

›Priority documents — 1

Type	Document	Date
provisional	US 60/075988 00	25 Feb 1998

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