Metals recovery from spent supported catalyst

Patent metadata

Field	Value
Publication number	US-2023257280-A1
Application number	US-202217744018-A
Country	US
Kind code	A1
Filing date	May 13, 2022
Priority date	Feb 14, 2022
Publication date	Aug 17, 2023
Grant date	—

Abstract

An improved method for recovering metals from spent supported catalysts, including spent supported hydroprocessing catalysts. The method and associated processes comprising the method are useful to recover spent supported catalyst metals used in the petroleum and chemical processing industries. The method generally involves a combination of a pyrometallurgical and a hydrometallurgical method and includes forming a potassium carbonate calcine from the spent supported catalyst containing Group VIIIB/Group VIB/Group VB metal compound(s) combined with potassium carbonate, and extracting and recovering soluble Group VIB metal and soluble Group VB metal compounds from the potassium carbonate calcine.

First claim

What is claimed is:

1 . A method for recovering metals from a deoiled spent supported catalyst, wherein the catalyst comprises a Group VIB metal, a Group VIIIB metal, a Group VB metal and a catalyst support material, the method comprising:
combining a deoiled spent supported catalyst comprising Group VIIIB, Group VIB, and Group VB metals with potassium carbonate to form a deoiled spent catalyst/potassium carbonate mixture; heating the deoiled spent supported catalyst/potassium carbonate mixture under oxidative conditions to reduce the levels of sulfur and carbon and to form a spent supported catalyst/potassium carbonate calcine comprising a water-soluble Group VIB metal compound, a water-soluble Group VB metal compound and a water-insoluble Group VIIIB metal compound; combining the spent supported catalyst/potassium carbonate calcine with water under slurry leach process conditions to form a spent supported catalyst/potassium carbonate calcine slurry and to leach the water-soluble Group VIB metal compound and the water-soluble Group VB metal compound from the spent supported catalyst/potassium carbonate calcine; separating and removing a filtrate and a solid residue from the spent supported catalyst/potassium carbonate calcine slurry, the filtrate comprising the water-soluble Group VIB metal compound and the water-soluble Group VB metal compound and the solid residue comprising the water-insoluble Group VIIIB metal compound; and recovering the water-soluble Group VIB metal compound and the water-soluble Group VB metal compound from the filtrate of the spent supported catalyst/potassium carbonate calcine slurry.

2 . The method of claim 1 , wherein the deoiled spent supported catalyst is substantially devoid of residual hydrocarbons, or is devoid of residual hydrocarbons, or comprises residual hydrocarbons in an amount of less than about 1000 ppm, or 500 ppm, or 100 ppm.

3 . The method of claim 1 , wherein the deoiled spent supported catalyst comprises residual hydrocarbons and the process further comprises heating the catalyst under optionally non-oxidative conditions sufficient to reduce the level of residual hydrocarbons via pyrolysis to an amount of less than about 1000 ppm, or 500 ppm, or 100 ppm.

4 . The method of claim 1 , wherein the oxidative conditions comprise a temperature in the range of about 575° C. to 600° C., or 600-625° C., or 625-650° C.

5 . The method of claim 1 , wherein the catalyst support material comprises alumina, silica, titania, or a combination thereof, or wherein a catalyst support material comprising alumina, silica, titania, or a combination thereof is used to prepare the catalyst.

6 . The method of claim 1 , wherein the spent supported catalyst does not comprise or is not a slurry catalyst.

7 . The method of claim 1 , wherein the spent supported catalyst is an ebullated bed or a fixed bed catalyst.

8 . The method of claim 1 , wherein the oxidative heating conditions comprise heating the deoiled spent supported catalyst at a first temperature in the presence of air, or a gas mixture comprising no more than about 20 vol. % oxygen.

9 . The method of claim 1 , wherein the levels of sulfur and carbon are individually, or both reduced to less than pre-selected amounts, as measured by CO 2 and SO 2 thermal oxidation product gas analysis, of less than about 1 wt. %, or about 0.8 wt. %, or about 0.5 wt. %, or about 0.2 wt. %, or about 0.1 wt. %.

10 . The method of claim 1 , wherein the heating of the spent supported deoiled catalyst/potassium carbonate mixture under oxidative conditions is at a temperature in the range of about 600° C. to 650° C., or about 610° C. to 650° C., or about 610° C. to 630° C., or is greater than about 600° C., or about 610° C., or about 620° C., or about 630° C., or about 640° C., or about 650° C.

11 . The method of claim 10 , wherein the heating under oxidative conditions comprises heating for a pre-selected time in the range of about 0.5 to 12 hr, or 1 to 8 hr, or 4 to 8 hr, or less than about 12 hr, or 10 hr or 8 hr.

12 . The method of claim 10 , wherein the heating comprises first heating under inert gas heating conditions at a temperature of less than about 600° C. or 550° C., or 500° C. or 450° C. for a pre-selected time in the range of about 0.5 to 4 hr, or 1 to 3 hr, or less than about 4 hr, or 2 hr.

13 . The method of claim 10 , wherein the heating under oxidative conditions produces gasses and is conducted so that the thermal oxidation product gas comprises at least about 20 wt. % O 2 , less than about 0.25 wt. % CO 2 and less than about 0.25 wt. % SO 2 .

14 . The method of claim 1 , wherein the gas flow conditions during heating of the deoiled spent supported catalyst/potassium carbonate mixture under oxidative conditions comprise air and are sufficient to remove any thermal oxidation product gas.

15 . The method of claim 1 , wherein the slurry leach process conditions comprise a leach temperature in the range of about 60 to 90° C., or 60 to 80° C., or 70 to 80° C., or wherein the leach temperature is greater than about 60° C. or 70° C.

16 . The method of claim 1 , wherein the slurry leach process conditions comprise a leach time in the range of about 1 to 5 hr, or about 2 to 5 hr, or about 2 to 4 hr.

17 . The method of claim 1 , wherein the slurry leach process conditions comprise a leach pH in the range of about 9.5 to 11, or about 10 to 11, or about 10 to 10.5.

18 . The method of claim 1 , wherein the slurry leach of the potassium carbonate calcine is conducted without pH modification.

19 . The method of claim 1 , wherein the filtrate comprises soluble molybdate or vanadate compounds, or a mixture thereof.

20 . The method of claim 1 , wherein the filtrate contains greater than about 70 wt. %, or 75 wt. %, or 80 wt. %, or 85 wt. %, or 90 wt. % of the Group VIB metal or greater than about 50 wt. %, or 60 wt. %, or 70 wt. %, or 80 wt. %, or 90 wt. % of the Group VB metal present in the deoiled spent supported catalyst, or both greater than about 70 wt. %, or 75 wt. %, or 80 wt. %, or 85 wt. %, or 90 wt. % of the Group VIB metal and greater than about 50 wt. %, or 60 wt. %, or 70 wt. %, or 80 wt. %, or 90 wt. % of the Group VB metal present in the deoiled spent supported catalyst.

21 . The method of claim 1 , wherein the solid residue comprises Group VB metal and/or Group VIB metal and/or Group VIIIB metal compound solids.

22 . The method of claim 1 , wherein the filtrate comprises potassium molybdate, potassium vanadate, or a mixture thereof.

23 . The method of claim 1 , wherein the extraction of the Group VB metal present in the deoiled spent supported catalyst is greater than about 80 wt. %, or about 85 wt. %, or about 90 wt. %.

24 . The method of claim 1 , wherein the extraction of the Group VIB metal present in the deoiled spent supported catalyst is greater than about 80 wt. %, or about 85 wt. %, or about 90 wt. %.

25 . The method of claim 1 , wherein the recovery of the water-soluble Group VIB metal compound and the water-soluble Group VB metal compound from the potassium carbonate calcine slurry filtrate is carried out by separately recovering the Group VIB and the Group VB metal compounds from the filtrate, the method comprising:
contacting the filtrate comprising the Group VIB and Group VB metal compounds with an ammonium salt to form a mixture under metathesis reaction conditions effective to convert the me

Assignees

• Chevron Usa Inc

Inventors

• Bhaduri Rahul Shankar
• Mironov Oleg A
• Kuperman Alexander E

Classifications

• C01G39/02 Primary

  Oxides; Hydroxides · CPC title

• C01G39/006

  Compounds containing molybdenum, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• C01G31/006

  Compounds containing vanadium, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• C22B7/009

  General processes for recovering metals or metallic compounds from spent catalysts (for recovering specific metals C22B11/00 - C22B61/00) · CPC title

• C22B3/14 Primary

  containing ammonia or ammonium salts · CPC title