Methods of Regenerating Aromatization Catalysts with A Decoking Step Between Chlorine and Fluorine Addition

Patent metadata

Field	Value
Publication number	US-2019247833-A1
Application number	US-201916391385-A
Country	US
Kind code	A1
Filing date	Apr 23, 2019
Priority date	May 17, 2017
Publication date	Aug 15, 2019
Grant date	—

Abstract

Methods for regenerating a spent catalyst are disclosed. Such methods may employ a step of chlorinating the spent catalyst in the gas phase, followed by decoking the chlorinated spent catalyst, and then fluorinating the de-coked catalyst in a fluorine-containing solution of a fluorine-containing compound.

First claim

1 - 22 . (canceled)

23 . A method for regenerating a chlorinated spent catalyst comprising a transition metal and a catalyst support, the method comprising:
(i) contacting the chlorinated spent catalyst with a decoking gas stream comprising oxygen to produce a de-coked chlorinated catalyst, wherein the chlorinated spent catalyst comprises from about 0.5 wt. % to about 3 wt. % of chlorine; and (ii) contacting the de-coked chlorinated catalyst with a fluorine-containing solution comprising a fluorine-containing compound in the liquid phase to produce a fluorinated catalyst; wherein: the transition metal comprises a Group 8-11 transition metal; and the catalyst support comprises a large pore zeolite having an average pore diameter in a range of from about 7 Å to about 12 Å.

24 . The method of claim 23 , wherein the chlorinated spent catalyst further comprises fluorine.

25 . The method of claim 23 , wherein the chlorinated spent catalyst comprises at least about 1 wt. % carbon.

26 . The method of claim 23 , wherein the de-coked chlorinated catalyst comprises less than about 0.5 wt. % carbon.

27 . The method of claim 23 , wherein:
step (i) is conducted at a peak decoking temperature in a range from about 300° C. to about 500° C.; the decoking gas stream comprises an inert gas and oxygen; and the decoking gas stream is substantially free of halogen-containing compounds.

28 . The method of claim 23 , wherein an amount of the fluorine-containing compound in the fluorine-containing solution provides from about 0.1 to about 10 wt. % of fluorine (F) in the fluorine-containing solution.

29 . The method of claim 23 , wherein:
step (ii) is conducted at a fluorination temperature in a range from about 20° C. to about 50° C.; and the fluorine-containing solution comprises water and at least one of ammonium fluoride and tetramethylammonium fluoride.

30 . The method of claim 23 , further comprising a drying step, a calcination step, or both a drying step and a calcination step, after step (ii).

31 . The method of claim 23 , wherein:
the transition metal comprises platinum; and the catalyst support comprises a KL-zeolite and a binder comprising alumina, silica, a mixed oxide thereof, or a mixture thereof.

32 . The method of claim 31 , wherein:
the de-coked chlorinated catalyst comprises less than about 0.2 wt. % carbon; and the fluorinated catalyst comprises from about 0.5 wt. % to about 3 wt. % of fluorine.

33 . The method of claim 32 , wherein the fluorinated catalyst comprises from about 0.3 wt. % to about 3 wt. % of platinum.

34 . The method of claim 33 , wherein:
the decoking gas stream comprises nitrogen and oxygen; and the fluorine-containing solution comprises water and at least one of ammonium fluoride and tetramethylammonium fluoride.

35 . A method for regenerating a de-coked chlorinated catalyst comprising a transition metal and a catalyst support, the method comprising:
contacting the de-coked chlorinated catalyst with a fluorine-containing solution comprising a fluorine-containing compound in the liquid phase to produce a fluorinated catalyst; wherein: the de-coked chlorinated catalyst comprises from about 0.5 wt. % to about 3 wt. % of chlorine; the de-coked chlorinated catalyst comprises less than about 0.5 wt. % carbon; the transition metal comprises a Group 8-11 transition metal; and the catalyst support comprises a large pore zeolite having an average pore diameter in a range of from about 7 Å to about 12 Å.

36 . The method of claim 35 , wherein the de-coked chlorinated catalyst further comprises fluorine.

37 . The method of claim 36 , wherein the fluorinated catalyst comprises from about 0.5 wt. % to about 3 wt. % of fluorine.

38 . The method of claim 35 , wherein the de-coked chlorinated catalyst comprises less than about 0.2 wt. % carbon.

39 . The method of claim 35 , wherein an amount of the fluorine-containing compound in the fluorine-containing solution provides from about 0.1 to about 10 wt. % of fluorine (F) in the fluorine-containing solution.

40 . The method of claim 35 , wherein:
the de-coked chlorinated catalyst is contacted with the fluorine-containing solution at a fluorination temperature in a range from about 20° C. to about 50° C.; and the fluorine-containing solution comprises water and at least one of ammonium fluoride and tetramethylammonium fluoride.

41 . The method of claim 35 , further comprising a step of drying the fluorinated catalyst, a step of calcining the fluorinated catalyst, or both drying and calcining the fluorinated catalyst.

42 . The method of claim 35 , wherein:
the transition metal comprises platinum; and the catalyst support comprises a KL-zeolite and a binder comprising alumina, silica, a mixed oxide thereof, or a mixture thereof.

43 . The method of claim 42 , wherein:
the de-coked chlorinated catalyst comprises less than about 0.2 wt. % carbon; the de-coked chlorinated catalyst further comprises fluorine; the fluorinated catalyst comprises from about 0.5 wt. % to about 3 wt. % of fluorine; and the fluorinated catalyst comprises from about 0.3 wt. % to about 3 wt. % of platinum.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Snell Ryan W
• Alvez-Manoli Gabriela D

Classifications

• B01J38/12

  Treating with free oxygen-containing gas · CPC title

• C07C2529/62

  Noble metals · CPC title

• B01J29/90

  Regeneration or reactivation · CPC title

• B01J38/42 Primary

  using halogen-containing material · CPC title

• C10G35/095

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