Hydroconversion multi-metallic catalyst and method for making thereof

• US 8,575,061 B2
• Filed: 10/18/2011
• Issued: 11/05/2013
• 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:
  US13/275,459
• Publication Number:
  US 20120122658A1
• Time in Patent Office: 749 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 metal ions in at least one of the metal precursor feeds do not react to form catalyst precursor and end up in the supernatant as metal residuals. In the present disclosure, the metals can be recovered via ion-exchange, wherein an exchange resin is provided for a portion of the metal ions in the supernatant to be exchanged and bound onto the resin. The previously resin-bound metals can be subsequently recovered, or the effluent stream for the exchange resin column can also be recovered, forming at least a metal precursor feed which can be used in the co-precipitation reaction.

Claims

1. A process for forming a hydroprocessing catalyst composition, the method comprises:

co-precipitating at reaction conditions at least 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 a total amount of at least 10 mole % of metal ions in the metal precursor feeds;

contacting the supernatant with an ion exchange resin for a sufficient amount of time for at least 50 mole % of metal ions in the metal residuals to be bound onto the resin, forming a first effluent stream containing unbound metal residuals;

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

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

recycling the metal precursor feed to the co-precipitating step; and

sulfiding the catalyst precursor forming the bulk catalyst.

2. The process of claim 1, wherein the supernatant is contacted with the ion exchange resin for a sufficient amount of time for at least 80 mole % of the metal ions in at least one of the metal residuals in the supernatant to be bound onto the resin.

3. The process of claim 1, wherein at least a cation exchange resin is provided to bind at least 80% of metal ions in the Promoter metal residual.

4. The process of claim 3, 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 bound onto the resin.

5. The process of claim 1, wherein the resin is eluted with at least an acid to form an eluate.

6. The process of claim 5, wherein the Promoter metal residual comprises a nickel compound and wherein the resin is eluted with at least one of sulphuric acid and nitric acid to a pH of less than 3, forming a nickel salt for use in the co-precipitation step as a Promoter metal precursor feed.

7. The process of claim 1, further comprising treating the first effluent stream by chemical precipitation to recover the unbound metal residuals as a Group VIB metal precursor feed.

8. The process of claim 7, wherein the first effluent 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 unbound metal residuals.

9. The process of claim 8, further comprising isolating and recovering the precipitate, forming a second effluent stream comprising less than 25 mole % of the Group VIB metal residual.

10. The process of claim 9, further comprising adding at least a calcium compound to the second effluent stream under mixing conditions forming at least a calcium salt.

11. The process of claim 10, wherein the molar ratio of added calcium compound to the Group VIB metal residual ranges from 2:

1 to 50;

1.

12. The process of claim 10, wherein the Group VIB metal residual comprises at least a molybdenum compound and a tungsten compound and the calcium salt comprises at least one of CaMoO₄ and CaWO₄.

13. The process of claim 9, further comprising acidifying the second effluent stream to a pH of less than 7.

14. The process of claim 9, wherein the Group VIB metal residual comprises at least a molybdenum compound and a tungsten compound and the precipitate comprises molybdate, tungstate and combinations thereof.

15. The process of claim 14, further comprising dissolving the precipitate comprising molybdate, tungstate and combinations thereof in an aqueous ammonium hydroxide solution, forming ammonium heptamolybdate, ammonium heptatungstate and combinations thereof.

16. The process of claim 1, wherein at least an anion exchange resin is provided to bind at least 80% of the metal ions in the Group VIB metal residual.

17. The process of claim 1, wherein the resin is eluted with a hydroxide based to form an eluate.

18. The process of claim 1, wherein at least a cation chelating resin is provided to bind at least 80% of the metal ions in the Group VIB metal residual.

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

20. The process of claim 1, further comprising calcining the catalyst precursor at a temperature of at least 300°

C. before the sulfidation step.

21. The process of claim 20, wherein the calcination is 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.

22. The process of claim 1, further comprising drying the catalyst precursor at a temperature of 200°

C. or less before the sulfidation step for a catalyst precursor with 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 a 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.

27. The process of claim 1, wherein the supernatant is brought into contact with a chelated ion exchange resin having at least one substituent selected from hydroxy, ether, amine, quaternary amine, a divalent sulfur substituent, amine oxide and hydroxy amine.

28. The process of claim 1, wherein the first effluent stream or the eluate stream is treated generating an effluent to waste treatment containing less than 50 ppm of Group VIB and Promoter metals.

23. In a process for forming a bulk hydroprocessing catalyst, the process comprising:

co-precipitating at reaction conditions at least 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 metal ions in the metal precursor feeds;

calcining the catalyst precursor to form a catalyst precursor of 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; and

sulfiding the catalyst precursor forming the bulk catalyst, wherein the improvement comprising;

contacting the supernatant with an ion 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;

eluting the resin to produce an eluate stream containing metals ions previously bound onto the resin; and

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

24. A process for forming a hydroprocessing catalyst composition, the method comprises:

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% of the metal precursor feeds;

treating the supernatant with at least an acid at a pre-selected pH to precipitate at least a Promoter metal residual and a Group VIB metal residual, forming a first effluent stream containing less than 50% of at least one of Promoter metal residual and a Group VIB metal residual;

providing at least an exchange resin;

contacting the supernatant with the ion exchange resin for a sufficient amount of time for at least 50 mole % 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;

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

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

recycling the metal precursor feed to the co-precipitating step; and

sulfiding the catalyst precursor forming the bulk catalyst.

25. The process of claim 24, 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.

26. The process of claim 25, wherein the cation chelating resin contains an amine functionality group.