Oxidative dehydrogenation of hydrocarbons using catalysts with trace promoter metal loading

• US 20040068148A1
• Filed: 10/08/2002
• Published: 04/08/2004
• Est. Priority Date: 10/08/2002
• Status: Abandoned Application

• Current Assignee: Conoco Incorporated (ConocoPhillips)
• Original Assignee: Conoco Incorporated (ConocoPhillips)
• Inventors: McDonald, Steve R., Ramani, Sriram, Chen, Zhen, Allison, Joe D., Gaffney, Anne, Chen, Shang Y., Carmichael, Lisa M.
• Application Number:
  US10/266,404
• Publication Number:
  US 20040068148A1
• Time in Patent Office: Days
• US Class Current: 585/16
• CPC Class Codes: B01J 23/42 Platinum
• CPC Class Codes: B01J 23/44 Palladium
• CPC Class Codes: B01J 23/56 Platinum group metals
• CPC Class Codes: C07C 11/02 Alkenes
• CPC Class Codes: C07C 2523/26 Chromium
• CPC Class Codes: C07C 2523/42 Platinum
• CPC Class Codes: C07C 2523/44 Palladium
• CPC Class Codes: C07C 2523/745 Iron
• CPC Class Codes: C07C 5/48 with oxygen as an acceptor

Abstract

Catalysts and methods useful for the production of olefins from alkanes via oxidative dehydrogenation (ODH) are disclosed. The ODH catalysts are comprised of a Group VIII promoter metal present at trace levels. The Group VIII promoter metal is preferably platinum, palladium or a combination thereof and is preferably present at a promoter metal loading of between about 0.005 and about 0.1 weight percent. Optionally, the ODH catalysts include a base metal, metal oxide, or combination thereof. The optional base metal is selected from the group consisting of Group IB-IIB metals, Group IVB-VIIB metals, Group IIA-VA metals, scandium, yttrium, actinium, iron, cobalt, nickel, their oxides, and combinations thereof. The base metal is more preferably selected from the group consisting copper, tin, chromium, gold, manganese and their respective oxides and any combinations thereof. The base metal loading is preferably between about 0.5 and about 10 weight percent. Optionally, the promoter metal can be supported on a refractory material. The refractory support is preferably comprised of a material selected from group consisting of zirconia, stabilized zirconias, alumina, stabilized aluminas, and combinations thereof.

Claims

1. An oxidative dehydrogenation catalyst comprising a promoter metal selected from the group consisting of Group VIII metals and present at a promoter metal loading between about 0.005 and about 0.1 weight percent.

2. The oxidative dehydrogenation catalyst of claim 1 wherein the promoter metal is present at a promoter metal loading between about 0.005 and about 0.05 weight percent.

3. The oxidative dehydrogenation catalyst of claim 1 further comprising a base metal selected from the group consisting of Group IB-IIB metals, Group IVB-VIIB metals, Group IIA-VA metals, scandium, yttrium, actinium, iron, cobalt, nickel, their oxides and combinations thereof.

4. The oxidative dehydrogenation catalyst of claim 1 further comprising a base metal selected from the group consisting of manganese, chromium, tin, copper, gold, their corresponding oxides and combinations thereof.

5. The oxidative dehydrogenation catalyst of claim 1 further comprising a refractory support.

6. The oxidative dehydrogenation catalyst of claim 5 wherein the refractory support is comprised of a material selected from group consisting of zirconia, magnesium stabilized zirconia, zirconia stabilized alumina, yttrium stabilized zirconia, calcium stabilized zirconia, alumina, cordierite, titania, silica, magnesia, niobia, vanadia, nitrides, silicon nitride, cordierite, cordierite-alpha alumina, zircon mullite, spodumene, alumina-silica magnesia, zircon silicate, sillimanite, magnesium silicates, zircin, petalite, carbon black, calcium oxide, barium sulfate, silica-alumina, alumina-zirconia, alumina-chromia, alumina-ceria, and combinations thereof.

7. The oxidative dehydrogenation catalyst of claim 5 wherein the refractory support is comprised of a material selected from the group consisting of zirconia, stabilized zirconias, alumina, stabilized aluminas, and combinations thereof.

8. The oxidative dehydrogenation catalyst of claim 6 further comprising a base metal selected from the group consisting of Group IB-IIB metals, Group IVB-VIIB metals, Group IIA-VA metals, scandium, yttrium, actinium, iron, cobalt, nickel, their corresponding oxides, and combinations thereof.

9. The oxidative dehydrogenation catalyst of claim 6 further comprising a base metal selected from the group consisting of manganese, chromium, tin, copper, gold, their corresponding oxides and combinations thereof.

10. The oxidative dehydrogenation catalyst of claim 9 wherein the base metal is present at a base metal loading between about 0.5 and about 20 weight percent.

11. The oxidative dehydrogenation catalyst of claim 9 wherein the base metal is present at a base metal loading between about 2 and about 6 weight percent.

12. The oxidative dehydrogenation catalyst of claim 9 having a molar ratio of base metal to promoter metal of about 10 or more.

13. The oxidative dehydrogenation catalyst of claim 1 wherein the promoter metal comprises platinum, palladium, or a combination thereof.

14. The oxidative dehydrogenation catalyst of claim 13 wherein the promoter metal is present at a promoter metal loading between about 0.005 and about 0.05 weight percent.

15. The oxidative dehydrogenation catalyst of claim 13 further comprising a base metal selected from the group consisting of Group IB-IIB metals, Group IVB-VIIB metals, Group IIA-VA metals, scandium, yttrium, actinium, iron, cobalt, nickel, their corresponding oxides and combinations thereof.

16. The oxidative dehydrogenation catalyst of claim 13 further comprising a base metal selected from the group consisting of manganese, chromium, tin, copper, gold, their corresponding oxides and combinations thereof.

17. The oxidative dehydrogenation catalyst of claim 13 further comprising a refractory support.

18. The oxidative dehydrogenation catalyst of claim 17 wherein the refractory support is comprised of a material selected from group consisting of zirconia, stabilized zirconias, alumina, stabilized aluminas, and combinations thereof.

19. A method for oxidative dehydrogenation comprising

a) providing a reactant mixture comprising one or more hydrocarbons and an oxidant;

b) providing an ODH catalyst comprising a promoter metal selected from the group consisting of Group VIII metals and present at a promoter metal loading between about 0.005 and about 0.1 weight percent;

c) exposing the reactant mixture to the ODH catalyst in a reactor under reaction promoting conditions; and

d) oxidatively dehydrogenating at least a fraction of the one or more hydrocarbons in the reactant mixture.

20. The method of claim 19 wherein the reactor is a short contact time reactor operated at a GHSV between about 20,000 hr⁻

1 and about 200,000,000 hr<sup>−

1</sup>.

21. The method of claim 19 wherein the reactor is a short contact time reactor operated at a GHSV between about 50,000 hr⁻

1 and about 50,000,000 hr<sup>−

1</sup>.

22. The method of claim 19 wherein the oxidant comprises a molecular oxygen-containing gas and the one or more hydrocarbons comprise one or more alkanes.

23. The method of claim 22 wherein the one or more alkanes comprise one or more paraffins with between 2 and 10 carbon atoms.

24. The method of claim 22 wherein the one or more alkanes comprise one or more paraffins with between 2 and 5 carbon atoms.

25. The method of claim 22 further comprising the step of preheating the reactant mixture to about 600°

C. or less.

26. The method of claim 22 further comprising the step of preheating the reactant mixture to about 300°

C. or less.

27. The method of claim 22 wherein the atomic oxygen-to-carbon ratio is between about 0.05:

1 and about 5;

1

28. The method of claim 22 wherein the alkane conversion is at least about 40 percent and the alkene selectivity is at least about 35 percent.

29. The method of claim 22 wherein the alkane conversion is at least about 85 percent and the alkene selectivity is at least about 60 percent.

30. The method of claim 19 wherein the ODH catalyst further comprises a base metal selected from the group consisting of Group IB-IIB metals, Group IVB-VIIB metals, Group IIA-VA metals, scandium, yttrium, actinium, iron, cobalt, nickel, their oxides and combinations thereof.

31. The method of claim 19 wherein the ODH catalyst further comprises a base metal selected from the group consisting of manganese, chromium, tin, copper, gold, their corresponding oxides and combinations thereof.

32. The method of claim 19 wherein the ODH catalyst further comprises a refractory support.

33. The method of claim 32 wherein the refractory support is comprised of a material selected from group consisting of zirconia, stabilized zirconias, alumina, stabilized aluminas, and combinations thereof.

34. The method of claim 32 wherein the ODH catalyst further comprises a base metal.

35. The method of claim 34 wherein the base metal is present at a base metal loading between about 0.5 and about 20 weight percent.

36. The method of claim 34 wherein the base metal is present at a base metal loading between about 2 and about 6 weight percent.

37. The method of claim 34 wherein the ODH catalyst has a molar ratio of the base metal to the promoter metal of about 10 or more.

38. The method of claim 19 wherein the promoter metal comprises platinum, palladium, or a combination thereof.

39. An alkene produced from an oxidative dehydrogenation (ODH) process using an ODH catalyst wherein the ODH catalyst comprises a promoter metal selected from the group consisting of Group VIII metals and present at a promoter metal loading between about 0.005 and about 0.1 weight percent.

40. The alkene of claim 39 wherein the ODH catalyst further comprises a base metal selected from the group consisting of Group IB-IIB metals, Group IVB-VIIB metals, Group IIA-VA metals, scandium, yttrium, actinium, iron, cobalt, nickel, their oxides and combinations thereof.

41. The alkene of claim 39 wherein the ODH catalyst further comprises a base metal selected from the group consisting of manganese, chromium, tin, copper, gold, their corresponding oxides and combinations thereof.

42. The alkene of claim 40 wherein the base metal is present at a base metal loading between about 0.5 and about 20 weight percent.

43. The alkene of claim 40 wherein the ODH catalyst has a molar ratio of base metal to promoter metal of about 10 or more.

44. The alkene of claim 39 wherein the ODH catalyst further comprises a refractory support.

45. The alkene of claim 39 wherein the promoter metal comprises platinum, palladium, or a combination thereof.