Hydroconversion multi-metallic catalyst and method for making thereof

• US 8,575,062 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:
  US13/275,597
• Publication Number:
  US 20120122656A1
• 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 2523/845 Cobalt
• 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 in a co-precipitation reaction, up to 60% of the metal precursor feeds do not react to form catalyst precursor and stay in the supernatant. In one embodiment, at least a precipitant is added to the product mixture at a molar ratio of precipitant to metal residuals in the supernatant ranging from 1.5:1 to 20:1 to precipitate at least 50 mole % of metal ions in the residuals forming additional catalyst precursor. The remaining metal residuals 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 at least one of the metal residuals. In one embodiment, at least one of the metal residuals is recovered and recycled for use as a metal precursor feed in the co-precipitation reaction.

Claims

1. A process for forming a bulk hydroprocessing catalyst, 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 product mixture comprising a first catalyst precursor and a first 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, 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;

adding at least a precipitant to the product mixture at a molar ratio of precipitant to metal residuals ranging from 1.5;

1 to 20;

1 to precipitate at least 50 mole % of metal ions in the residuals forming additional catalyst precursor;

isolating the catalyst precursors from the product mixture, forming a second supernatant containing less than 5000 ppm of metal ions in the metal residuals; and

sulfiding the catalyst precursors forming the bulk catalyst.

2. The process of claim 1, further comprising drying the first and additional catalyst precursors at a temperature of 150 to 300°

C. before the sulfidation step.

3. The process of claim 2, wherein the drying is at a temperature of 200°

C. or less.

4. The process of claim 1, further comprising calcining the first and second catalyst precursors at a temperature of at least 300°

C. before the sulfidation step.

5. The process of claim 4, wherein the calcination is at a temperature of at least 325°

C. to form at least one catalyst precursor having 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.

6. The process of claim 3, wherein the drying is at a temperature of 200°

C. or less, forming at least a catalyst precursor having 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.

7. The process of claim 6, wherein M^P is at least a Group VIII metal.

8. The process of claim 1, wherein the isolation of the first and additional catalyst precursors is via at least one of filtering, decanting, centrifuging, and combinations thereof.

9. The process of claim 1, prior to the addition of the precipitant, further comprising adjusting the pH of the mixture to a pre-selected pH to facilitate the formation of the additional catalyst precursor.

10. The process of claim 1, prior to the isolation of the first and additional catalyst precursors, further comprising adjusting the pH of the mixture to a pre-selected pH to facilitate the isolation of the first and additional catalyst precursors.

11. The process of claim 9, wherein the pH of the mixture is adjusted by adding at least an acid or a base.

12. The process of claim 10, wherein the pH of the mixture is adjusted by adding nitric acid.

13. The process of claim 12, wherein the pH of the mixture is adjusted to about 5 to 6.5.

14. The process of claim 1, wherein the precipitant is selected from compounds of metals exhibiting amphoteric behavior.

15. The process of claim 14, wherein the precipitant is selected from compounds of Ni, Zn, Al, Sn, and Nb.

16. The process of claim 15, wherein the precipitant is selected from aluminium nitrate, aluminium sulphate, zinc nitrate, ammonium aluminate, ammonium zincate, niobium pentoxide, zirconium oxide, and mixtures thereof.

17. The process of claim 15, wherein the precipitant is ammonium aluminate.

18. The process of claim 1, wherein the precipitant is selected from the group of alumina, alumina silica, titanates, silicates and mixtures thereof.

19. The process of claim 1, further comprising:

supplying the second supernatant to a reactor vessel having a plurality of electrodes having a positive or a negative charge provided by a power supply, forming a slurry containing insoluble metal compounds;

recovering the insoluble metal compounds, forming a first effluent stream containing less than 100 ppm metals.

20. The process of claim 1, further comprising:

providing at least an exchange resin;

contacting the second supernatant with the ion exchange resin for at least 50% of metal ions in at least one of the metal residuals in the second supernatant to be bound onto the resin, forming an effluent stream containing less than 100 ppm metals.

21. The process of claim 1, further comprising:

treating the second supernatant with at least an additive selected from the group of acids, sulfide-containing compound, bases, and mixtures thereof under mixing conditions for a sufficient amount of time to precipitate at a pre-selected pH at least a portion of the first and second metal residuals, forming an effluent stream containing less than 100 ppm metals.

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