Catalyst compositions and the method of manufacturing them

• US 4,171,288 A
• Filed: 09/23/1977
• Issued: 10/16/1979
• Est. Priority Date: 09/23/1977
• Status: Expired due to Term

• Current Assignee: Engelhard Corporation (BASF SE)
• Original Assignee: Engelhard Minerals & Chemicals Corporation
• Inventors: Keith, Carl D., Shimrock, Thomas, Larsen, William R.
• Primary Examiner(s): Shine, W. J.
• Application Number:
  US05/836,649
• Time in Patent Office: 753 Days
• Field of Search: 252/462, 252/466 PT, 252/466 B, 423/213.5
• US Class Current: 502/304
• CPC Class Codes: B01D 53/945 characterised by a specific catalyst
• CPC Class Codes: B01J 23/6567 Rhenium
• CPC Class Codes: B01J 23/8986 with manganese, technetium or rhenium
• CPC Class Codes: Y02T 10/12 Improving ICE efficiencies

Abstract

Catalysts are disclosed which have good activity and life when used to promote the conversion of hydrocarbons, carbon monoxide and nitrogen oxides contained in small concentrations in gaseous streams, to obtain the less noxious materials, carbon dioxide, water and nitrogen. The catalysts contain a catalytically promoting, platinum group metal component, a catalytically promoting, base metal component and an alumina support component, deposited on a high surface area, particulate, macrosize carrier. The base metal component contains a metal selected from the group consisting of metals having an atomic number from 25 to 28 and rhenium.

Claims

1. A catalyst composition having a catalytically-promoting material comprising an alumina support, a catalytically-promoting, base metal component, the base metal of which is selected from the group consisting of base metals having an atomic number from 25 to 28 and rhenium, and a catalytically-promoting, platinum group metal component, said catalytically-promoting material being deposited on a particulate, macrosize, solid carrier having a surface area of at least about 50 square meters per gram, and said base metal component being present in said catalyst composition in an amount greater than said platinum group metal component, said catalyst composition being prepared by combining said platinum group metal component, said base metal component, and said alumina support on said carrier, said platinum group metal component being combined with said support by contacting said support in solid, finely divided form with a liquid containing therein at least one compound of a platinum group metal, and said base metal component being combined with said support by at least one of (1) admixing finely divided particles of a solid compound of at least one base metal with said solid, finely divided alumina support and (2) contacting said support with a liquid containing therein at least one compound of said base metal, which liquid may be the same or different from that which contains said compound of said platinum group metal, heating said alumina support, after the aforesaid contacting with said liquid or liquids containing said platinum group metal and, optionally, said base metal compound or compounds, at a temperature sufficiently high to provide thereon said platinum group metal component and, optionally, said base metal component, forming a mixture of said solid, finely divided alumina support and a liquid, forming in a gaseous medium dispersed particles of said mixture containing said liquid and said solid, finely divided alumina support, contacting said dispersed particles with said particulate solid carrier to deposit said alumina support on said carrier, and drying said particulate carrier so coated with said alumina support.

2. The catalyst of claim 1 wherein said platinum group metal comprises one or both of platinum and palladium, and one or more of rhodium, ruthenium and iridium.

3. The catalyst of claim 2 in which platinum comprises the major amount of the platinum group metal.

4. The catalyst of claim 3 wherein said platinum group metal comprises platinum and rhodium.

22. The method of claim 1 wherein said heating and said drying of said support are carried out after the contacting of said support with said liquid or liquids and the depositing of the resultant contacted support and, optionally, said solid finely-divided base metal component on said carrier.

23. The method of claim 22 wherein said heating is carried out at a temperature of at least about 250°

C.

5. A catalyst composition having a catalytically-promoting material comprising an alumina support a catalytically-promoting, base metal component comprising one or more of nickel, cobalt and manganese, and a catalytically-promoting, platinum group metal component, the platinum group metal of which comprises one or both of platinum and palladium and one or more of rhodium, ruthenium and iridium, said catalytically-promoting material being deposited on a particulate, macrosize, solid carrier having a surface area of at least about 50 square meters per gram, said base metal component being present in said catalyst composition in an amount greater than said platinum group metal component, said catalyst being prepared by combining said platinum group metal component, said base metal component, and said alumina support to provide a composite thereof, said platinum group metal component being combined with said support by contacting said support with a compound of a platinum group metal comprising one or both of a compound of platinum and a compound of palladium and one or more of a compound of rhodium, a compound of ruthenium and a compound of iridium, said compounds of platinum group metals being contained in a liquid during said contacting, and said base metal component being combined with said support by at least one of (1) admixing finely divided particles of solid compounds of one or more of nickel, cobalt and manganese with said support, and (2) contacting said support with a liquid containing therein a compound of one or more of nickel, cobalt and manganese which liquid may be the same as or different from that which contains compounds of the platinum group metals as aforesaid, heating said alumina support, after the aforesaid contacting with said liquid or liquids containing said platinum group metal and, optionally, said base metal compound or compounds, at a temperature sufficiently high to provide thereon said platinum group metal component and, optionally, said base metal component, and depositing the resulting composite on said carrier by forming a mixture of said solid, finely divided alumina support and a liquid, forming in a gaseous medium dispersed particles of said mixture containing said liquid and said solid, finely divided alumina support, and contacting said dispersed particles with said particulate solid carrier to deposit said alumina support upon said carrier, and drying said particulate carrier so coated with said alumina support.

6. A catalyst composition of claim 5 in which said base metal component comprises an oxide or an oxygen-containing compound which forms an oxide when thermally decomposed.

7. The catalyst of claim 5 in which platinum comprises the major amount of the platinum group metal.

8. The catalyst of claim 7 wherein said platinum group metal comprises platinum and rhodium.

24. The method of claim 5 wherein said heating and said drying of said support are carried out after the contacting of said support with said liquid or liquids and the depositing of the resultant contacted support and, optionally, said solid finely-divided base metal component on said carrier.

25. The method of claim 24 wherein said heating is carried out at a temperature of at least about 250°

C.

9. A catalyst composition having a catalytically-promoting material comprising a finely-divided, solid stabilized, activated alumina support, a catalytically-promoting, finely-divided, solid base metal oxide comprising one or more of oxides of nickel, cobalt and manganese, and a catalytically-promoting platinum group metal component comprising rhodium and a major amount of platinum, said catalytically-promoting material being deposited on a particulate, macrosize, solid, carrier having a surface area of at least about 50 square meters per gram, said base metal oxide being about 0.5 to 10% of said catalyst on a base metal basis and present in an amount greater than said platinum group metal component, said catalyst being prepared by compositing said alumina support with said platinum group metal component and said base metal oxide to provide a composite thereof by contacting said support with a liquid containing therein a compound of rhodium and a compound of platinum, heating said alumina support, after the aforesaid contacting with said liquid containing therein said compound of rhodium and said compound of platinum, at a temperature sufficiently high to provide thereon said platinum group metal component, admixing finely divided solid particles of said base metal oxide with said support in an aqueous liquid to provide an aqueous slurry of the liquid-contacted support and base metal oxide and comminuting said aqueous slurry and depositing the comminuted slurry on said carrier by forming in a gaseous medium dispersed particles of said slurry and contacting said dispersed particles of slurry with said carrier to deposit said alumina support, base metal oxide and platinum group metal component on said carrier, and drying the resulting coated carrier particles to provide said catalyst composition.

10. A catalyst composition of claim 9 in which the stabilized alumina comprises ceria-alumina.

26. The method of claim 9 wherein said heating and drying of said support are carried out after said support is combined with said liquid containing said compounds of rhodium and platinum and the depositing of the resultant contacted support and said solid finely-divided base metal component on said carrier.

27. The method of claim 26 wherein said heating is carried out at a temperature of at least about 250°

C.

11. In a method of manufacturing a catalyst composition comprising depositing a catalytically-promoting material on a solid, macrosize, particulate carrier, said catalytically-promoting material comprising a base metal component containing one or more catalytically-promoting members selected from the group consisting of base metals having an atomic number from 25 to 28 and rhenium, a catalytically-promoting platinum group metal component and an alumina support, the steps which comprise combining said platinum group metal component, said base metal component, and said alumina support on said carrier, said platinum group metal component being combined with said support by contacting said support in solid, finely divided form with a liquid containing therein a compound of at least one platinum group metal, and said base metal component being combined with said support by at least one of (1) admixing finely divided particles of a solid compound of at least one base metal with said solid, finely divided alumina support and (2) contacting said support with a liquid containing therein a compound of at least one base metal, which liquid may be the same or different from that which contains said compound of said platinum group metal, heating said alumina support, after the aforesaid contacting with said liquid or liquids containing said platinum group metal and, optionally, said base metal compound or compounds, at a temperature sufficiently high to provide thereon said platinum group metal component and, optionally, said base metal component, forming a mixture of said solid, finely divided alumina support and a liquid, forming in a gaseous medium dispersed particles of said mixture containing liquid and said alumina support, and contacting said dispersed particles with said solid, macrosize particulate carrier, said carrier comprising particles having a surface area of at least about 50 square meters per gram, to deposit said alumina support on said carrier, and drying the resulting particulate carrier coated with said alumina support component.

12. A method of claim 11 in which at least one platinum group metal component or base metal component is in said dispersed mixture when it is contacted with said macrosize carrier.

13. A method of claim 12 in which the platinum group metal comprises one or both of platinum and palladium, and one or more of rhodium, ruthenium and iridium.

14. A method of claim 13 in which platinum comprises the major amount of the platinum group metal.

15. A method of claim 14 in which said platinum group metal comprises platinum and rhodium and said base metal component comprises one or more nickel, cobalt and manganese oxide components.

16. A method of claim 11 in which said dispersed particles contain platinum group metal and base metal components and the latter is in finely-divided, solid form.

17. A method of claim 11 in which said carrier particles are disposed as a compact bed when contacting said dispersed particles.

28. The method of claim 11 wherein said heating and said drying of said support are carried out after the contacting of said support with said liquid or liquids and the depositing of the resultant contacted support and, optionally, said solid finely-divided base metal component on said carrier.

29. The method of claim 28 wherein said heating is carried out at a temperature of at least about 250°

C.

18. In a method of manufacturing a catalyst composition comprising depositing a catalytically-promoting material on a solid, macrosize, particulate, activated alumina carrier, said catalytically-promoting material comprising a base metal oxide comprising one or more of nickel, cobalt and manganese oxide, a platinum group metal component in which platinum comprises the major amount of platinum group metal, and a stabilized, activated alumina support, the steps which comprise combining a finely divided, solid alumina support with said platinum group metal component and said base metal oxide to provide a composite thereof by contacting said support with a liquid containing therein at least one compound of a platinum group metal, essentially including a compound of platinum, in an amount such that platinum is the major amount of platinum group metal, heating said alumina support, after the aforesaid contacting with said liquid containing therein said at least one compound, at a temperature sufficiently high to provide thereon said platinum group metal component, admixing finely divided solid particles of said base metal oxide with said finely divided solid particles of said alumina support and forming in air dispersed particles of an aqueous mixture containing said composite of said alumina support, said platinum group metal compound and base metal oxide, and contacting the dispersed particles with a compact bed of said macrosize, solid carrier particles having a surface area of at least about 75 square meters per gram, and drying resulting particulate carrier coated with the solids of said dispersed particles.

19. A method of claim 18 in which said dispersed particles are an aqueous, comminuted mixture in which said base metal component is in finely-divided, solid form.

20. A method of claim 19 in which said platinum group metal comprises one or both of platinum and palladium, and one or more of rhodium, ruthenium and iridium.

21. A method of claim 20 in which said platinum group metal comprises rhodium and platinum.

30. The method of claim 18 wherein said heating and said drying of said support are carried out after the contacting of said support with said liquid containing said compound of a platinum group metal and the depositing of the resultant contacted support and said solid finely divided base metal component on said carrier.

31. The method of claim 30 wherein said heating is carried out at a temperature of at least about 250°

C.