Dehydrogenation catalysts and methods for using them

Patent metadata

Field	Value
Publication number	US-11701643-B2
Application number	US-202117367764-A
Country	US
Kind code	B2
Filing date	Jul 6, 2021
Priority date	Jul 20, 2020
Publication date	Jul 18, 2023
Grant date	Jul 18, 2023

Abstract

The present disclosure relates to gallium-based dehydrogenation catalysts that further include additional metal components, and to methods for dehydrogenating hydrocarbons using such catalysts. One aspect of the disclosure provides a calcined dehydrogenation catalyst that includes a gallium species, a cerium species, a platinum promoter, and a silica-alumina support. Optionally, the composition can include a promoter selected from the alkali metals and alkaline earth metals.

First claim

What is claimed is:

1. A dehydrogenation catalyst composition comprising
Ga, present in the composition in an amount within a range of 2 wt. % to 20 wt. %, calculated as elemental metal on a calcined basis;
Ce, present in the composition in an amount within a range of 0.5 wt. % to 10 wt. %, calculated as elemental metal on a calcined basis;
Pt, present in the composition in an amount within a range of 1 ppm to 500 ppm, calculated as elemental metal on a calcined basis;
a promoter M2 selected from the alkali metals, the alkaline earth metals, and any mixture thereof, present in the composition in an amount of up to 7.5 wt. %, calculated as elemental metal on a calcined basis; and
a silica-alumina support S1, present in the composition in an amount within a range of 50 wt. % to 97.5 wt. % of the composition, calculated as oxide on a calcined basis, silica being present in S1 in an amount within a range of 5 wt. % to 30 wt. % of the mass of S1, calculated as SiO 2 on a calcined basis,
wherein amounts of Ga, Ce, Pt, and promoter M2, are provided on the basis of the amount of the support S1 being 100 wt %.

2. The catalyst composition of claim 1 , wherein Ga is present in the composition in an amount within a range of 2 wt. % to 10 wt. % calculated as elemental metal on a calcined basis.

3. The catalyst composition of claim 1 , wherein Ce is present in the composition in an amount of 0.5 wt. % to 7 wt. % calculated as elemental metal on a calcined basis.

4. The catalyst composition of claim 1 , wherein Pt is present in the composition in an amount within a range of 1 ppm to 400 ppm, calculated as elemental metal on a calcined basis.

5. The catalyst composition of claim 1 , wherein M2 includes one or more alkali metals, present in the composition in a combined amount within a range of 0.2 wt. % to 2.5 wt. %.

6. The catalyst composition of claim 1 , wherein M2 includes K.

7. The catalyst composition of claim 1 , wherein alumina is present in S1 in an amount within a range of 70 wt. % to 95 wt. %, calculated as Al 2 O 3 on a calcined basis.

8. The catalyst composition of any claim 1 , further comprising one or more of La, Mn, Ti, Fe, Cu, Sn, W, Y, and Zn, present in the composition in a combined amount within a range of 0.01 wt. % to 10 wt. %.

9. The catalyst composition of claim 1 , wherein Ga is present in an amount of 2 to 10 wt. %, and Pt is present in an amount of 5 ppm to 400 ppm.

10. The catalyst composition of claim 1 , wherein
Ga is present in the composition in an amount within a range of 2 wt. % to 5 wt. %;
Ce is present in the composition in an amount within a range of 1 wt. % to 10 wt. %; and
Pt is present in the composition in an amount within a range of 10 ppm to 500 ppm.

11. The catalyst composition of claim 10 , wherein M2 is K, present in the composition in an amount within a range of 0.2 wt. % to 2.5 wt. %.

12. The catalyst composition of claim 10 , comprising one or more of La, Mn, Ti, Fe, Cu, Sn, and Zn, present in the composition in a combined amount within a range of 0.01 wt. % to 10 wt. %.

13. The catalyst composition of claim 12 , wherein M2 includes one or more alkaline earth metals, present in the composition in a combined amount within a range of 0.2 wt. % to 7.5 wt. %.

14. The catalyst composition of claim 1 , wherein
Ga is present in the composition in an amount within a range of 2 wt. % to 5 wt. %;
Ce is present in the composition in an amount within a range of 1 wt. % to 5 wt. %;
Pt is present in the composition in an amount within a range of 100 ppm to 500 ppm;
M2 is a mixture of K and Ba, present in the composition in a combined amount within a range of 0.5 wt. % to 5 wt. %.

15. The catalyst composition of claim 1 , wherein the total amount of Ga, Ce, Pt, M2 and S1 and any of La, Mn, Ti, Fe, Cu, Zn, W, Y and Zn is at least 98 wt. % of the composition.

16. The catalyst composition of claim 1 , wherein M2 is present in an amount in a range of 0.2 wt. % to 7.5 wt. %.

17. A method for preparing the dehydrogenation catalyst composition according to claim 1 , comprising
providing a silica-alumina support S1, optionally impregnated with one or more of Ga, Ce, Pt, and M2;
impregnating the silica-alumina support S1 with an impregnation solution comprising one or more of
a Ga source;
a Ce source;
a Pt source; and
an M2 source; and

calcining the impregnated silica-alumina support S1 to obtain the dehydrogenation catalyst composition.

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

19. The method of claim 18 , carried out at a temperature in a range of 400° C. to 850° C.

20. The method of claim 19 , operated at a conversion in a range of 25-70 wt. % and a selectivity of at least 80 wt. %.

Assignees

• Clariant Int Ltd

Inventors

• Xing Rong
• Fridman Vladimir

Classifications

• B01J23/896 Primary

  with gallium, indium or thallium · CPC title

• B01J21/12 Primary

  Silica and alumina · CPC title

• B01J23/63

  with rare earths or actinides · CPC title

• B01J23/6562

  Manganese · CPC title

• B01J37/024

  Multiple impregnation or coating · CPC title