Dehydrogenation catalysts and methods for preparing and using them

Patent metadata

Field	Value
Publication number	US-11021419-B2
Application number	US-201916246682-A
Country	US
Kind code	B2
Filing date	Jan 14, 2019
Priority date	Jan 14, 2019
Publication date	Jun 1, 2021
Grant date	Jun 1, 2021

Abstract

This disclosure relates to catalysts comprising gallium, cerium, and a mixed oxide support useful in the dehydrogenation of hydrocarbons, to methods for making such catalysts, and to methods for dehydrogenating hydrocarbons with such catalysts. For example, in one embodiment, a catalyst composition includes gallium oxide, present in the composition in an amount within the range of about 0.1 wt. % to about 30 wt. %, cerium oxide, present in the composition in an amount within the range of about 0.1 wt. % to about 15 wt. %, a promoter, M1, selected from Pt, Ir, La, or a mixture thereof, present in the composition in an amount within the range of about 0.005 wt. % to about 4 wt. %, a promoter, M2, selected from the group 1 elements (e.g., Li, Na, K, Cs), present in the composition in an amount within the range of about 0.05 wt. % to about 3 wt. %, and a support, S1, selected from alumina, silica, zirconia, titania, or a mixture thereof, present in the composition in an amount within the range of about 60 wt. % to about 99 wt. %.

First claim

What is claimed is:

1. A calcined dehydrogenation catalyst composition comprising
gallium oxide, present in the composition in an amount within the range of about 1 wt. % to about 20 wt. %, calculated as Ga 2 O 3 on a calcined basis;
cerium oxide, present in the composition in an amount within the range of about 0.1 wt. % to about 10 wt. %, calculated as CeO 2 on a calcined basis;
a promoter M1 selected from platinum, iridium, lanthanum, or a mixture thereof, present in the composition in an amount within the range of about 0.01 wt. % to about 2 wt. %, calculated as oxide on a calcined basis;
a promoter M2 selected from the group 1 elements, present in the composition in an amount within the range of about 0.05 wt. % to about 3 wt. %, calculated as oxide on a calcined basis; and
a support S1 selected from alumina, silica, zirconia, titania, or a mixture thereof, present in the composition in an amount within the range of about 60 wt. % to about 99 wt. %, calculated as oxide on a calcined basis.

2. The catalyst composition of claim 1 , wherein M1 includes Ir.

3. The catalyst composition of claim 1 , wherein M1 is present in the composition in an amount within the range of about 0.01 wt. % to about 1 wt. %, calculated as oxide on a calcined basis.

4. The catalyst composition of claim 1 , wherein M2 is selected from Li, Na, K, and Cs.

5. The catalyst composition of claim 1 , wherein M2 is present in the composition in an amount within the range of about 0.05 wt. % to about 2 wt. %, calculated as oxide on a calcined basis.

6. The catalyst composition of claim 1 , further comprising a promoter M1-B selected from Sn and Pd, present in the composition in an amount within the range of about 0.005 wt. % to about 0.5 wt. %, calculated as SnO 2 or PdO, respectively, on a calcined basis.

7. The catalyst composition of claim 1 , further comprising a promoter M3 selected from Mg, Ca, Sr, Ba, Fe, Co, and Ni, present in the composition in an amount within the range of about 0.05 wt. % to about 10 wt. %, calculated as oxide on a calcined basis.

8. The catalyst composition of claim 7 , wherein M3 is selected from Mg and Ca, and is present in the composition in an amount within the range of about 0.05 wt. % to about 7 wt. %.

9. The catalyst composition of claim 1 , wherein
gallium oxide is present in the composition in an amount within the range of about 2 wt. % to about 15 wt. %, calculated as Ga 2 O 3 on a calcined basis;
cerium oxide is present in the composition in an amount within the range of about 0.1 wt. % to about 3 wt. %, calculated as CeO 2 on a calcined basis;
M1 is present in the composition in an amount within the range of about 0.01 wt. % to about 1 wt. %, calculated as oxide on a calcined basis; and
M2 is K, present in the composition in an amount within the range of about 0.05 wt. % to about 1 wt. %, calculated as K 2 O on a calcined basis.

10. The catalyst composition of claim 9 , further comprising M3, wherein M3 is selected from Mg, Ca, Sr, Ba, and Fe, present in an amount within the range of about 0.05 wt. % to about 7 wt. %, calculated as oxide on a calcined basis.

11. The catalyst composition of claim 9 , wherein M1 includes Ir.

12. The catalyst composition of claim 1 , wherein S1 is a mixture of alumina and silica, a mixture of alumina and zirconia, or a mixture of alumina and titania.

13. The catalyst composition of claim 1 , wherein
S1 is a mixture of alumina, silica, and zirconia;
alumina and silica are present in a weight ratio within the range of about 0.5:1 to about 25:1; and
alumina and zirconia are present in a weight ratio within the range of about 90:1 to about 40:1.

14. The catalyst composition of claim 1 , wherein S1 is present in the composition in an amount within the range of about 70 wt. % to about 99 wt. %.

15. The catalyst composition of claim 1 , wherein the composition comprises
none of or less than 1 wt. % of the lanthanides other than lanthanum and cerium; and
none of or less than 0.5 wt. % of chromium.

16. The catalyst composition of claim 1 , optionally including a promoter M1-B selected from Sn and Pd, and optionally including a promoter M3 selected from Mg, Ca, Sr, Ba, and Fe, wherein the total amount of gallium oxide, cerium oxide, M1, M1-B, M2, M3, and S1 is at least about 97.5 wt. % of the catalyst composition.

17. A method for preparing a dehydrogenation catalyst composition according to claim 1 , comprising
providing an aqueous solution comprising
a gallium source;
a cerium source;
an M1 source;
an M2 source; and
an S1 source;
forming a solid from the solution; and
calcining the solid so formed.

18. A method for dehydrogenating hydrocarbon, the method comprising contacting a hydrocarbon feed with the catalyst composition of claim 1 .

19. The catalyst composition of claim 1 , wherein S1 is a mixture of alumina and silica, present in a weight ratio of alumina to silica within the range of about 0.5:1 to about 25:1.

20. The catalyst composition of claim 1 , wherein S1 is a mixture of alumina and zirconia, present in a weight ratio of alumina to zirconia within the range of about 1:1 to about 25:1.

Assignees

• Clariant Int Ltd

Inventors

• Xing Rong
• Fridman Vladimir

Classifications

• B01J23/002

  Mixed oxides other than spinels, e.g. perovskite · CPC title

• C07C2523/89

  combined with noble metals · CPC title

• C07C5/3332

  with metal oxides or metal sulfides · CPC title

• B01J21/12

  Silica and alumina · CPC title

• B01J23/6562

  Manganese · CPC title