Dehydrogenation catalysts and methods for using them

Patent metadata

Field	Value
Publication number	US-2022016604-A1
Application number	US-202117367764-A
Country	US
Kind code	A1
Filing date	Jul 6, 2021
Priority date	Jul 20, 2020
Publication date	Jan 20, 2022
Grant date	—

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 the range of 0.5 wt. % to 20 wt. %, calculated as elemental metal on a calcined basis; Ce, present in the composition in an amount within the range of 0.2 wt. % to 20 wt. %, calculated as elemental metal on a calcined basis; Pt, present in the composition in an amount within the range of 1 ppm to 500 ppm, calculated as elemental metal on a calcined basis; optionally, 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 20 wt. %, calculated as elemental metal on a calcined basis; and a silica-alumina support S1, present in the composition in an amount within the range of 50 wt. % to 99 wt. %, calculated as oxide on a calcined basis, silica being present in S1 in an amount within the range of 1 wt. % to 30 wt. %, calculated as SiO 2 on a calcined basis.

2 . The catalyst composition of claim 1 , wherein Ga is present in the composition in an amount within the range of 1.5 wt. % to 10 wt. %, e.g., 1.5 wt. % to 8.5 wt. %, or 1.5 wt. % to 7 wt. %, or 1.5 wt. % to 5 wt. %, or 1.5 wt. % to 3 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 20 wt. %, e.g., 0.5 wt. % to 15 wt. %, or 0.5 wt. % to 10 wt. %, or 0.5 wt. % to 7 wt. %, or 0.5 wt. % to 5 wt. %, or 0.5 wt. % to 3 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 the range of 1 ppm to 400 ppm, e.g., 5 ppm to 400 ppm, or 25 ppm to 400 ppm, or 100 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 the 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 16 , wherein M2 includes one or more alkaline earth metals, present in the composition in a combined amount within the range of 0.2 wt. % to 10 wt. %.

8 . The catalyst composition of claim 1 , wherein silica is present in S1 in an amount within the range of 2 wt. % to 20 wt. % of 51.

9 . The catalyst composition of claim 1 , wherein alumina is present in S1 in an amount within the range of 70 wt. % to 99 wt. %, calculated as Al 2 O 3 on a calcined basis.

10 . The catalyst composition of claim 1 , wherein the support S1 is present in the composition in an amount within the range of 50 wt. % to 98 wt. %.

11 . 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 the range of 0.01 wt. % to 10 wt. %.

12 . The catalyst composition of any of claims 1 , 8 - 10 and 16 - 21 , 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

13 . The catalyst composition of claim 1 , wherein
Ga is present in the composition in an amount within the range of 1 wt. % to 5 wt. %, e.g., 2 wt. % to 5 wt. %; Ce is present in the composition in an amount within the range of 1 wt. % to 10 wt. %, e.g., 1 wt. % to 5 wt. %; Pt is present in the composition in an amount within the range of 10 ppm to 500 ppm, e.g., 10 ppm to 400 ppm; and S1 is present in the composition in an amount within the range of 80 wt. % to 99 wt. %.

14 . The catalyst composition of claim 13 , wherein silica is present in S1 in an amount within the range of 2 wt. % to 20 wt. %.

15 . The catalyst composition of claim 13 , wherein M2 is K, present in the composition in an amount within the range of 0.2 wt. % to 2.5 wt. %.

16 . The catalyst composition of claim 13 , comprising one or more of La, Mn, Ti, Fe, Cu, Sn, and Zn, present in the composition in a combined amount within the range of 0.01 wt. % to 10 wt. %.

17 . The catalyst composition of claim 1 , wherein
Ga is present in the composition in an amount within the range of 2 wt. % to 5 wt. %, e.g., 3 wt. % to 5 wt. %; Ce is present in the composition in an amount within the range of 1 wt. % to 5 wt. %; Pt is present in the composition in an amount within the range of 100 ppm to 500 ppm, e.g., 100 ppm to 400 ppm; M2 is a mixture of K and Ba, present in the composition in a combined amount within the range of 0.5 wt. % to 5 wt. %; S1 is present in the composition in an amount within the range of 90 wt. % to 99 wt. %; and silica is present in S1 in an amount within the range of 2 wt. % to 20 wt. %.

18 . The catalyst composition of claim 1 , wherein the total amount of Ga, Ce, Pt, M2 and 51 is at least 80 wt. %, e.g., at least 85 wt. %, or at least 87 wt. %, or at least 90 wt. % of the composition.

19 . A method for preparing a 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
optionally, an M2 source; and
calcining the impregnated silica-alumina support S1.

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

Assignees

• Clariant Int Ltd

Inventors

• Xing Rong
• Fridman Vladimir

Classifications

• C07C5/3337

  of the platinum group · CPC title

• B01J21/12 Primary

  Silica and alumina · CPC title

• C07C2523/63

  with rare earths or actinides · CPC title

• B01J23/63

  with rare earths or actinides · CPC title

• B01J37/088

  Decomposition of a metal salt · CPC title