Catalysts for the oxidative dehydrogenation of alkanes

Patent metadata

Field	Value
Publication number	US-11230512-B2
Application number	US-201916515105-A
Country	US
Kind code	B2
Filing date	Jul 18, 2019
Priority date	Jul 19, 2018
Publication date	Jan 25, 2022
Grant date	Jan 25, 2022

Abstract

This document relates to oxidative dehydrogenation catalysts that include molybdenum, vanadium, and oxygen.

First claim

What is claimed is:

1. An oxidative dehydrogenation catalyst comprising molybdenum, vanadium, and oxygen, wherein:
the molar ratio of molybdenum to vanadium in the catalyst is from 1:0.15 to 1:0.75, as determined by inductively coupled plasma mass spectrometry (ICP-MS),
oxygen is present in the catalyst at least in an amount to satisfy the valency of any present metal oxides, and
the amorphous phase of the catalyst is from 55 wt. % to 80 wt. %, as determined by X-ray diffraction (XRD).

2. The oxidative dehydrogenation catalyst of claim 1 , wherein the amorphous phase is from 55 wt. % to 75 wt. %, as determined by XRD.

3. The oxidative dehydrogenation catalyst of claim 1 , wherein the catalyst has a 35% conversion temperature from about 300° C. to about 400° C.

4. The oxidative dehydrogenation catalyst of claim 1 , wherein the catalyst has a selectivity to ethylene from 65% to 99%.

5. The oxidative dehydrogenation catalyst of claim 1 , wherein the catalyst is prepared by a method comprising:
providing an aqueous mixture comprising molybdenum and vanadium,
hydrothermally reacting the mixture to form a precalcined catalyst, and
calcining the precalcined catalyst to form the catalyst.

6. The oxidative dehydrogenation catalyst of claim 5 , wherein providing the aqueous mixture comprising molybdenum and vanadium comprises combining an aqueous mixture comprising molybdenum and an aqueous mixture comprising vanadium.

7. The oxidative dehydrogenation catalyst of claim 6 , wherein the aqueous mixture comprising molybdenum is prepared from a first composition comprising (NH 4 ) 6 Mo 7 O 24 .4H 2 O and a first water.

8. The oxidative dehydrogenation catalyst of claim 6 , wherein the aqueous mixture comprising vanadium is prepared from a second composition comprising VOSO 4 XH 2 O and a second water.

9. An oxidative dehydrogenation catalyst comprising molybdenum, vanadium, and oxygen, wherein:
the molar ratio of molybdenum to vanadium in the catalyst is from 1:0.20 to 1:0.60, as determined by ICP-MS,
oxygen is present in the catalyst at least in amount to satisfy the valency of any present metal oxides, and
the amorphous phase of the catalyst is greater than 55 wt. %, as determined by XRD.

10. The oxidative dehydrogenation catalyst of claim 9 , wherein the molar ratio of molybdenum to vanadium in the catalyst is from 1:0.24 to 1:0.58, as determined by ICP-MS.

11. The oxidative dehydrogenation catalyst of claim 9 , wherein the amorphous phase of the catalyst is from 55 wt. % to 75 wt. %, as determined by XRD.

12. The oxidative dehydrogenation catalyst of claim 9 , wherein the catalyst characterized by having XRD diffraction peaks (2θ degrees) at least at 23.5±0.5, 25.6±0.5, and 27.1±0.7, wherein the XRD is obtained using CuKα radiation.

13. The oxidative dehydrogenation catalyst of claim 9 , wherein the catalyst has a 35% conversion temperature from about 300° C. to about 425° C.

14. The oxidative dehydrogenation catalyst of claim 9 , wherein the catalyst has a selectivity to ethylene from 65% to 95%.

15. The oxidative dehydrogenation catalyst of claim 9 , wherein the catalyst is prepared by a method comprising:
providing an aqueous mixture comprising molybdenum and vanadium,
hydrothermally reacting the mixture to form a precalcined catalyst, and
calcining the precalcined catalyst in the presence of air to form the catalyst.

16. An oxidative dehydrogenation catalyst comprising molybdenum, vanadium, and oxygen, wherein:
the molar ratio of molybdenum to vanadium in the catalyst is from 1:0.20 to 1:0.50, as determined by ICP-MS,
oxygen is present in the catalyst at least in amount to satisfy the valency of any present metal oxides, and
the amorphous phase of the catalyst is greater than 55 wt. %, as determined by XRD.

17. The oxidative dehydrogenation catalyst of claim 16 , wherein the molar ratio of molybdenum to vanadium in the catalyst is from 1:0.25 to 1:0.45, as determined by ICP-MS.

18. The oxidative dehydrogenation catalyst of claim 16 , wherein the amorphous phase of the catalyst is from 55 wt. % to 85 wt. %, as determined by XRD.

19. The oxidative dehydrogenation catalyst of claim 16 , wherein the catalyst is characterized by having XRD diffraction peaks (2θ degrees) at least at 23.5±0.5, 25.6±0.5, and 27.1±0.7, wherein the XRD is obtained using CuKα radiation.

20. The oxidative dehydrogenation catalyst of claim 16 , wherein the catalyst has a 35% conversion temperature from about 320° C. to about 400° C.

21. The oxidative dehydrogenation catalyst of claim 16 , wherein the catalyst has a selectivity to ethylene from 70% to 95%.

22. The oxidative dehydrogenation catalyst of claim 16 , wherein the catalyst is prepared by a method comprising:
providing an aqueous mixture comprising molybdenum and vanadium,
hydrothermally reacting the mixture to form a precalcined catalyst,
air calcining the precalcined catalyst to form the catalyst, and
washing the catalyst with an acid solution.

23. The oxidative dehydrogenation catalyst of claim 22 , wherein the acid solution comprises oxalic acid.

24. The oxidative dehydrogenation catalyst of claim 23 , wherein the concentration of oxalic acid is from about 0.05 M to about 0.5 M.

25. An oxidative dehydrogenation catalyst comprising molybdenum, vanadium, and oxygen, wherein:
the molar ratio of molybdenum to vanadium in the catalyst is from 1:0.35 to 1:0.65, as determined by ICP-MS,
oxygen is present in the catalyst at least in amount to satisfy the valency of any present metal oxides, and
the amorphous phase of the catalyst is greater than 55 wt. %, as determined by XRD.

26. The oxidative dehydrogenation catalyst of claim 25 , wherein the amorphous phase of the catalyst is from 55 wt. % to 75 wt. %, as determined by XRD.

27. The oxidative dehydrogenation catalyst of claim 25 , wherein the amorphous phase of the catalyst is from 56 wt. % to 66 wt. %, as determined by XRD.

28. The oxidative dehydrogenation catalyst of claim 25 , wherein the catalyst is characterized by having XRD diffraction peaks (2θ degrees) at least at 26.3±0.3 and 29.4±0.3, wherein the XRD is obtained using CuKα radiation.

29. The oxidative dehydrogenation catalyst of claim 25 , wherein the catalyst has a 35% conversion temperature from about 300° C. to about 425° C.

30. The oxidative dehydrogenation catalyst of claim 25 , wherein the catalyst has a selectivity to ethylene from 65% to 95%.

31. The oxidative dehydrogenation catalyst of claim 25 , wherein the catalyst is prepared by a method comprising:
providing an aqueous mixture comprising molybdenum and vanadium,
hydrothermally reacting the mixture to form a precalcined catalyst, and
calcining the precalcined catalyst under a nitrogen atmosphere to form the catalyst.

32. An oxidative dehydrogenation catalyst comprising molybdenum, vanadium, and oxygen, wherein:
the molar ratio of molybdenum to vanadium in the catalyst is from 1:0.30 to 1:0.50, as determined by ICP-MS,
oxygen is present in the catalyst at least in amount to satisfy the valency of any present metal oxides, and
the amorphous phase of the catalyst is greater than 45 wt. %, as determined by XRD; and
wherein the catalyst is prepared by a method comprising:
providing an aqueous mixture comprising molybdenum and vanadium,
hydroth

Assignees

• Nova Chem Int Sa

Inventors

• Gao Xiaoliang
• Barnes Marie
• Simanzhenkov Vasily
• Sebastiao Elena
• Sullivan David
• Kim Yoonhee

Classifications

• B01J35/30

  characterised by their physical properties · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J35/80

  characterised by their amorphous structures · CPC title

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title

• B01J2235/15

  X-ray diffraction · CPC title