Aromatization catalyst and methods of making and using same

Patent metadata

Field	Value
Publication number	US-11311863-B2
Application number	US-202016923324-A
Country	US
Kind code	B2
Filing date	Jul 8, 2020
Priority date	May 7, 2018
Publication date	Apr 26, 2022
Grant date	Apr 26, 2022

Abstract

A process of making an aromatization catalyst comprising: (a) mixing a zeolite, a binder, and water to form a mixture; (b) extruding the mixture to form a green extrudate; (c) drying the green extrudate to form a dried green extrudate; (d) calcining the dried green extrudate to form a support, wherein calcining the dried green extrudate is the only calcination step in the process; (e) washing the support to form a washed support; (f) drying the washed support to form a dried washed support; (g) impregnating the dried washed support with a Group 8-10 transition metal compound and at least one halide-containing compound to form a metalized-halided material; and (h) vacuum drying the metalized-halided material to form a dried metalized-halided material which is the aromatization catalyst.

First claim

What is claimed is:

1. A process comprising:
(a) mixing an KL-zeolite, a binder, and water to form a mixture;
(b) extruding the mixture to form a green extrudate;
(c) drying the green extrudate to form a dried green extrudate;
(d) calcining the dried green extrudate to form a support, wherein calcining the dried green extrudate is the first of only two calcination steps in the process;
(e) washing the support to form a washed support;
(f) drying the washed support to form a dried washed support;
(g) impregnating the dried washed support with a Group 8-10 transition metal compound and at least two halide-containing compounds to form a metalized-halided material;
(h) vacuum drying the metalized-halided material to form a dried metalized-halided material; and
(i) calcining the dried metalized-halided material to form an aromatization catalyst, wherein calcining the dried metalized-halided material is the second of only two calcination steps in the process.

2. The process of claim 1 wherein the Group 8-10 transition metal compound comprises a metal selected from the group consisting of platinum, palladium, rhodium, iridium, ruthenium, osmium, and any combination thereof.

3. The process of claim 1 wherein the Group 8-10 transition metal compound comprises platinum.

4. The process of claim 3 wherein the Group 8-10 transition metal compound comprises ammonium tetrachloroplatinate, diammineplatinum (II) nitrite, bis-(ethylenediamine)platinum (II) chloride, dichlorodiammine platinum, tetraammineplatinum (II) hydroxide, tetraammineplatinum chloride, tetraammineplatinum (II) nitrate, or a combination thereof.

5. The process of claim 1 wherein the at least two halide-containing compounds comprise a fluoride-containing compound, a chloride-containing compound, or a combination thereof.

6. The process of claim 1 wherein the aromatization catalyst comprises the Group 8-10 transition metal in an amount of from about 0.1 wt. % to about 5 wt. % based on the total weight of the aromatization catalyst.

7. The process of claim 1 wherein the aromatization catalyst has a micropore volume of from about 0.04 cc/g to about 0.10 cc/g.

8. The process of claim 1 wherein the aromatization catalyst has a crush strength of from about 4.5 lbs. (2.0 Kg) to about 15 lbs. (6.8 Kg).

9. The process of claim 1 wherein the KL-zeolite has a mole ratio of silicon to aluminum ranging from about 1.0 to about 3.5.

10. The process of claim 1 wherein the KL-zeolite has an effective pore diameter ranging from about 6 Angstroms to about 15 Angstroms.

11. The process of claim 1 wherein the KL-zeolite has a mean particle size of less than about 6 microns.

12. The process of claim 1 wherein the at least two halide-containing compounds comprise one or more compounds represented by the formula N(R)4X, where X is a halide and where R represents a hydrogen or a substituted or unsubstituted carbon chain molecule having 1-20 carbon atoms and wherein each R may be the same or different.

13. The process of claim 12 wherein R is selected from the group consisting of methyl, ethyl, propyl, butyl, and a combination thereof.

14. The process of claim 1 wherein the at least two halide-containing compounds comprise ammonium chloride, tetramethylammonium chloride (TMAC), tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, or a combination thereof.

15. The process of claim 1 wherein the at least two halide-containing compounds comprise ammonium fluoride, tetramethylammonium fluoride (TMAF), tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, methyltriethylammonium fluoride, or a combination thereof.

16. The process of claim 14 wherein the at least two halide-containing compounds are present in an amount of from about 0.1 wt. % to about 5 wt. % based on the total weight of the aromatization catalyst.

17. The process of claim 14 wherein the Group 8-10 transition metal compound comprises platinum and an atomic ratio of platinum to chloride is from about 1.0:0.1 to about 1.0:10.

18. The process of claim 15 wherein the at least two halide-containing compounds are present in an amount of from about 0.1 wt. % to about 1 wt. % based on the total weight of the aromatization catalyst.

19. The process of claim 15 wherein the Group 8-10 transition metal compound comprises platinum and an atomic ratio of platinum to fluoride is from about 1.0:0.1 to about 1.0:20.

20. The process of claim 1 wherein the calcination temperature ranges from about 500° F. (260° C.) to about 1500° F. (816° C.).

21. The process of claim 1 wherein washing comprises contacting with water having a pH of from about 5 to about 9.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Snell Ryan W
• Alvez-Manoli Gabriela

Classifications

• B01J29/62

  Noble metals · CPC title

• B01J37/26

  Fluorinating · CPC title

• B01J29/7469

  MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3 · CPC title

• C10G35/095 Primary

  containing crystalline alumino-silicates, e.g. molecular sieves {(C10G35/065 takes precedence)} · CPC title

• B01J37/0201

  Impregnation · CPC title