Reconstituted dehydrogenation catalyst showing slowed activity loss when compared with fresh catalyst

Patent metadata

Field	Value
Publication number	US-11951455-B2
Application number	US-202217671779-A
Country	US
Kind code	B2
Filing date	Feb 15, 2022
Priority date	Feb 20, 2012
Publication date	Apr 9, 2024
Grant date	Apr 9, 2024

Abstract

A process for dehydrogenating alkane or alkylaromatic compounds comprising contacting the given compound and a dehydrogenation catalyst in a fluidized bed. The dehydrogenation catalyst is prepared from an at least partially deactivated platinum/gallium catalyst on an alumina-based support that is reconstituted by impregnating it with a platinum salt solution, then calcining it at a temperature from 400° C. to 1000° C., under conditions such that it has a platinum content ranging from 1 to 500 ppm, based on weight of catalyst; a gallium content ranging from 0.2 to 2.0 wt %; and a platinum to gallium ratio ranging from 1:20,000 to 1:4. It also has a Pt retention that is equal to or greater than that of a fresh catalyst being used in a same or similar catalytic process.

First claim

What is claimed is:

1. A process for dehydrogenating alkane or alkylaromatic compounds comprising:
(1) reconstituting an at least partially deactivated dehydrogenation catalyst by
(a) obtaining a dehydrogenation catalyst comprising platinum and gallium on an alumina-based support, the dehydrogenation catalyst having been previously fresh but having become at least partially deactivated by the selective removal of platinum from the dehydrogenation catalyst, wherein the at least partially deactivated dehydrogenation catalyst has a ratio of platinum to gallium that is less than a ratio of platinum to gallium of the previously fresh dehydrogenation catalyst;
(b) impregnating the at least partially deactivated dehydrogenation catalyst with a solution consisting of a platinum salt in water to form an impregnated dehydrogenation catalyst, wherein the platinum salt comprises one or more of tetraamineplatinum (II) nitrate, platinum (II) nitrate, and platinum (II) acetylacetonate; and
(c) calcining the impregnated dehydrogenation catalyst at a temperature ranging from 400° C. to 1000° C.;
(b) and (c) being carried out under conditions suitable to form a reconstituted dehydrogenation catalyst having (i) a platinum content ranging from 1 part per million, based on weight of catalyst, to 500 parts per million, based on weight of catalyst; (ii) a gallium content ranging from 0.2 wt % to 2.0 wt %; and (iii) a ratio of platinum to gallium ranging from 1:20,000 to 1:4; and

(2) contacting, in a fluidized bed, an alkane compound or an alkylaromatic compound with at least a portion of the reconstituted dehydrogenation catalyst,
wherein the reconstituted dehydrogenation catalyst further exhibits a platinum retention greater than or equal to the platinum retention of a fresh dehydrogenation catalyst when each is used in the same or another, otherwise identical dehydrogenation process.

2. The process of claim 1 , wherein the platinum content of the reconstituted dehydrogenation catalyst ranges from 40 parts per million, based on weight of catalyst, to 400 parts per million, based on weight of catalyst, and the ratio of platinum to gallium content ranges from 1:500 to 1:5.

3. The process of claim 2 , wherein the platinum content of the reconstituted dehydrogenation catalyst ranges from 150 parts per million, based on weight of catalyst, to 300 parts per million, based on weight of catalyst, and the ratio of platinum to gallium content ranges from 3:400 to 3:80.

4. The process of claim 1 , wherein the reconstituted dehydrogenation catalyst exhibits a propane dehydrogenation activity that is at least 2% absolute propane conversion greater than that exhibited by the at least partially deactivated catalyst.

5. The process of claim 1 , further comprising the step of drying the impregnated dehydrogenation catalyst at a temperature ranging from 50° C. to 150° C. prior to calcining it.

6. The process of claim 1 , wherein the gallium lost from the at least partially deactivated dehydrogenation catalyst is minimized.

7. The process of claim 1 , wherein calcining the impregnated dehydrogenation catalyst comprises calcining the impregnated dehydrogenation at a temperature ranging from 600° C. to 800° C.

8. The process of claim 1 , wherein (b) and (c) result in adding from 108 ppm platinum to 500 ppm platinum to the least partially deactivated dehydrogenation catalyst.

9. The process of claim 1 , wherein (b) and (c) result in adding from 108 to 200 ppm platinum to the least partially deactivated dehydrogenation catalyst.

10. The process of claim 1 , wherein calcining the impregnated dehydrogenation catalyst converts the platinum salt to platinum oxide (PtO), platinum metal (Pt), or a combination thereof.

11. The process of claim 1 , wherein calcining the impregnated dehydrogenation catalyst occurs at a temperature from 600° C. to 800° C., for a time from 40 minutes to 360 minutes, under an atmosphere comprising air, wherein the calcining converts the platinum salt to platinum oxide (PtO), platinum metal (Pt), or a combination thereof.

12. The process of claim 1 , wherein impregnating the at least partially deactivated dehydrogenation catalyst comprises contacting the at least partially deactivated dehydrogenation catalyst with the solution consisting of a platinum salt in water at ambient temperature and pressure.

13. The process of claim 1 , wherein the process further comprises aging the impregnated dehydrogenation catalyst for a time from 4 hours to 16 hours.

Assignees

• Dow Global Technologies Llc

Inventors

• Luo Lin
• Rosenfeld Devon C
• Malek Andrzej M

Classifications

• B01J23/62 Primary

  with gallium, indium, thallium, germanium, tin or lead · CPC title

• B01J23/96

  of catalysts comprising metals, oxides or hydroxides of the noble metals · CPC title

• B01J38/485

  Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements · CPC title

• C07C5/322

  with metal oxides or metal sulfides · CPC title

• C07C5/3337

  of the platinum group · CPC title