Hydroconversion multi-metallic catalyst and method for making thereof

• US 8,586,500 B2
• Filed: 10/18/2011
• Issued: 11/19/2013
• Est. Priority Date: 11/11/2010
• Status: Active Grant

• Current Assignee: Chevron USA Incorporated (Chevron Corp.)
• Original Assignee: Chevron USA Incorporated (Chevron Corp.)
• Inventors: Kuperman, Alexander E., Maesen, Theodorus, Dykstra, Dennis
• Primary Examiner(s): Zimmer, Anthony J
• Application Number:
  US13/275,557
• Publication Number:
  US 20120122655A1
• Time in Patent Office: 763 Days
• Field of Search: 502305-310, 502/313, 502/315, 502/316, 502/321
• US Class Current: 502/305
• CPC Class Codes: B01J 23/002 Mixed oxides other than spinels, e.g. perovskite
• CPC Class Codes: B01J 23/8885 containing also molybdenum
• CPC Class Codes: B01J 2523/00 Constitutive chemical elements of heterogeneous catalysts
• CPC Class Codes: B01J 2523/68 Molybdenum
• CPC Class Codes: B01J 2523/69 Tungsten
• CPC Class Codes: B01J 2523/847 Nickel
• CPC Class Codes: B01J 37/009 Preparation by separation, e.g. by filtration, decantation, screening
• CPC Class Codes: B01J 37/03 Precipitation; Co-precipitation
• CPC Class Codes: B01J 37/036 to form a gel or a cogel
• CPC Class Codes: B01J 37/20 Sulfiding
• CPC Class Codes: B01J 37/341 making use of electric or magnetic fields, wave energy or particle radiation use of flames, plasma or lasers B01J37/349
• CPC Class Codes: B01J 37/348 Electrochemical processes, e.g. electrochemical deposition or anodisation
• CPC Class Codes: C10G 2300/1033 Oil well production fluids
• CPC Class Codes: C10G 45/08 in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
• CPC Class Codes: C10G 47/04 Oxides
• CPC Class Codes: C10G 49/04 containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof

Abstract

In a process for forming a bulk hydroprocessing catalyst by sulfiding a catalyst precursor made in a co-precipitation reaction, up to 60% of the metal precursor feeds do not react to form catalyst precursor and end up in the supernatant. In the present disclosure, the metals can be recovered via any of chemical precipitation, ion exchange, electro-coagulation, and combinations thereof to generate an effluent stream containing less than 50 mole % of metal ions in at least one of the metal residuals, and for at least one of the metal residuals is recovered as a metal precursor feed, which can be recycled for use in the co-precipitation reaction. An effluent stream from the process to waste treatment contains less than 50 ppm metal ions.

Claims

1. A process for forming a bulk hydroprocessing catalyst with minimal amount of metals to waste treatment, the method comprising:

co-precipitating at reaction conditions at least one of a Group VIB metal precursor feed and at least a Promoter metal precursor feed selected from Group VIII, Group IIB, Group IIA, Group IVA and combinations thereof, to form a mixture comprising a catalyst precursor, wherein the reaction conditions comprise a temperature between 25-350°

C. and a pressure between 0 to 3000 psig and a pH of 0-12;

isolating the catalyst precursor from the mixture, forming a supernatant containing at least a Promoter metal residual and at least a Group VIB metal residual in an amount of at least 10 mole % of the metal precursor feeds;

treating the supernatant by any of chemical precipitation, ion exchange, electro-coagulation, and combinations thereof to generate at least a metal precursor feed and a first effluent stream containing less than 50 mole % of metal ions in at least one of the metal residuals;

treating the first effluent stream to recover at least 80 mol % of the metal ions in the first effluent stream to form at least a metal precursor feed;

recycling the at least a metal precursor feed formed by treating the first effluent stream to the co-precipitating step; and

sulfiding the catalyst precursor forming the bulk catalyst,

wherein an effluent stream from the process to waste treatment contains less than 50 ppm metal ions.

2. The process of claim 1, further comprising drying the catalyst precursors at a temperature of at least 150°

C. before the sulfidation step.

3. The process of claim 2, wherein the catalyst precursor is dried at a temperature of at least 300°

C. before the sulfidation step.

4. The process of claim 2, wherein the catalyst precursor is dried at a temperature of at least 325°

C. for the catalyst precursor to have the formula (X)_b(Mo)_c(W)_dO_z;

wherein X is Ni or Co, the molar ratio of b;

(c+d) is 0.5/1 to 3/1, the molar ratio of c;

d is >

0.01/1, and z=[2b+6 (c+d)]/2.

5. The process of claim 2, wherein the catalyst precursor is dried at a temperature of at most 200°

C. for the catalyst precursor to have the formula A_v[(M^P)(OH)_x(L)ⁿ_y]_z(M^VIBO₄), wherein

A is at least one of an alkali metal cation, an ammonium, an organic ammonium and a phosphonium cation, M^P is selected from the group of Group VIII, Group IIB, Group IIA, Group IVA and combinations thereof, P is oxidation state with M^P having an oxidation state of either +2 or +4 depending on the selection of M^P,

L is at least a ligating agent L having an charge n<

=0;

M^VIB is at least a Group VIB metal having an oxidation state of +6,

M^P;

M^VIB has an atomic ratio of 100;

1 to 1;

100;

v−

2+(P*z)−

(x*z)+(n*y*z)=0; and

0<

y≦

−

P/n;

0<

x≦

P;

0<

v≦

2;

0<

z.

6. The process of claim 1, wherein the sulfiding of the catalyst precursor forming the bulk catalyst is either before or after loading the catalyst precursor into a hydroprocessing reactor.

7. The process of claim 1, wherein

the supernatant is treated in a reactor vessel having a plurality of electrodes having a positive or a negative charge provided by a power supply, and wherein the electrodes react with at least one of the metal residuals, forming a slurry containing insoluble metal compounds.

8. The process of claim 1, further comprising:

recovering the insoluble metal compound from the slurry, forming an effluent stream containing less than 20 mole % of at least one of the metal residuals in the supernatant.

9. The process of claim 8, further comprising:

adding to the effluent stream at least one of an acid, a sulfide-containing compound, a base, and combinations thereof, under mixing conditions at a temperature from ambient to 90°

C. for a sufficient amount of time to precipitate at a first pre-selected pH at least a portion of at least one of the metal residuals.

10. The process of claim 9, further comprising:

isolating and recovering the precipitate comprising at least a portion of the metal residuals, generating a third effluent stream containing less than 1000 ppm of at least one of the metal residuals.

11. The process of claim 1, wherein:

the supernatant is brought in contact with an exchange resin for a sufficient amount of time for at least 50% of metal ions in at least one of the metal residuals in the supernatant to be bound onto the resin, forming a first effluent stream containing unbound metal residuals.

12. The process of claim 1, further comprising:

treating the first effluent in a reactor vessel having a plurality of electrodes having a positive or a negative charge provided by a power supply, and wherein the electrodes react with at least one of the metal residuals, forming a slurry containing at least a precipitate;

isolating the precipitate from the slurry to recover a second effluent containing less than 2000 ppm metals.

13. The process of claim 12, further comprising:

adding to the second effluent stream at least an additive selected from the group of an acid, a sulfide-containing compound, a base, and combinations thereof, under mixing conditions at a temperature from 50°

C. to 90°

C. for a sufficient amount of time to precipitate at a first pre-selected pH at least a portion of the metal residuals, generating a third effluent stream containing less than 1000 ppm metals.

14. The process of claim 11, further comprising:

eluting the resin to produce an eluate containing the metal ions previously bound onto the resin;

recovering at least 80 mole % of the unbound metal residuals in the first effluent stream or at least 80 mole % of the metal ions in the eluate to form the at least a metal precursor feed.

15. The process of claim 11, wherein at least a cation exchange resin is provided to exchange and bind the metal ions.

16. The process of claim 11, wherein at least an ion exchange resin is provided to exchange and bind the metal ions.

17. The process of claim 11, wherein at least a cation chelating resin is provided to exchange and bind at least 50 mole % of metal ions in the Group VIB metal residual.

18. The process of claim 17, wherein the cation chelating resin contains an amine functionality group.

19. The process of claim 1, wherein the sulfiding of the catalyst precursor forming the bulk catalyst is either before or after loading the catalyst precursor into a hydroprocessing reactor.

20. The process of claim 11, wherein the Promoter metal residual comprises a nickel compound, the first effluent stream contains less than 50 ppm Ni, and at least 80% of the nickel is exchanged and bound onto the resin.

21. The process of claim 11, wherein the resin is eluted with at least an acid to form an eluate.

22. The process of claim 11, wherein the Promoter metal residual comprises a nickel compound and wherein the resin is eluted with sulfuric acid to a pH of less than 3, forming Ni(NO₃)₂ for use in the co-precipitation step as a Promoter metal precursor feed.

23. The process of claim 11, further comprising treating the first effluent stream by chemical precipitation to recover the Group VIB metal residual as a Group VIB metal precursor feed.

24. The process of claim 23, wherein the first effluent stream is treated by adding at least an acid under mixing conditions at a temperature from 50°

C. to 90°

C. for a sufficient amount of time to precipitate at a first pre-selected pH at least a portion of the Group VIB metal residual.

25. The process of claim 24, further comprising isolating and recovering the precipitate, forming a second effluent stream comprising less than 25 mole % of the Group VIB metal residual.

26. The process of claim 25, further comprising adding at least a calcium compound to the second effluent stream under mixing conditions at a temperature from 50°

C. to 90°

C. forming at least a calcium salt.

27. The process of claim 26, wherein the molar ratio of added calcium compound to the Group VIB metal residual ranges from 2:

1 to 50;

1.