PROCESS FOR PREPARING HYDROPROCESSING BULK CATALYSTS

• US 20090107891A1
• Filed: 10/31/2007
• Published: 04/30/2009
• Est. Priority Date: 09/10/2004
• Status: Active Grant

• Current Assignee: Chevron USA Incorporated (Chevron Corp.)
• Original Assignee: Chevron USA Incorporated (Chevron Corp.)
• Inventors: Brait, Axel, Kuperman, Alexander E., Mironov, Oleg, Lopez, Jaime
• Granted Patent: US 7,754,645 B2
• Time in Patent Office: Days
• US Class Current: 208/216.R
• CPC Class Codes: B01J 27/049 with iron group metals or platinum group metals
• CPC Class Codes: B01J 27/0515 with iron group metals or platinum group metals
• CPC Class Codes: B01J 37/20 Sulfiding
• CPC Class Codes: C07F 11/005 compounds without a metal-carbon linkage
• CPC Class Codes: C07F 15/045 without a metal-carbon linkage
• CPC Class Codes: C10G 2300/1003 Waste materials
• CPC Class Codes: C10G 2300/1022 Fischer-Tropsch products
• CPC Class Codes: C10G 2300/1033 Oil well production fluids
• CPC Class Codes: C10G 2300/1074 Vacuum distillates
• CPC Class Codes: C10G 2300/207 Acid gases, e.g. H2S, COS, SO2, HCN
• CPC Class Codes: C10G 2300/703 Activation
• CPC Class Codes: C10G 45/04 characterised by the catalyst used
• CPC Class Codes: C10G 45/08 in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
• CPC Class Codes: C10G 45/16 suspended in the oil, e.g. slurries
• CPC Class Codes: C10G 47/26 suspended in the oil, e.g. slurries
• CPC Class Codes: C10G 49/02 characterised by the catalyst used
• CPC Class Codes: C10G 49/04 containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
• CPC Class Codes: C10G 49/12 suspended in the oil, e.g. slurries
• CPC Class Codes: Y10S 502/517 Sulfur or sulfur compound removal
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]

Abstract

A process to prepare hydroprocessing bulk catalysts is provided. The hydroprocessing catalyst has the formula (M^t)_a(X^u)_b(S^v)_d(C^w)_e(H^x)_f(O^y)_g(N^z)_h, wherein M is at least one group VIB metal; X is at least at least a metal compound selected from a non-noble Group VIII metal, a Group VIIIB metal, a Group VIB metal, a Group IVB metal, and a Group IIB metal (“Promoter Metal”); t, u, v, w, x, y, z representing the total charge for each of the components (M, X, S, C, H, O and N, respectively); ta+ub+vd+we+xf+yg+zh=0; and 0=<b/a=<5, (a+0.5b)<=d<=(5a+2b), 0<=e<=11(a+b), 0<=f<=7(a+b), 0<=g<=5(a+b), 0<=h<=0.5(a+b). In one embodiment, the process comprises the steps of: combining and reacting at least one Group VIB metal compound with at least one group VIII non-noble metal compound to obtain an intermediate mixture; sulfiding the intermediate mixture with a sulfiding agent forming a catalyst precursor; and mixing the catalyst precursor with a hydrocarbon compound to form the hydroprocessing catalyst composition.

Claims

1. A process for preparing a hydroprocessing catalyst composition, which process comprising the steps of:

i) combining and reacting at least one Group VIB metal compound (“

M”

) with at least a metal compound (“

Promoter Metal”

compound X) selected from a non-noble Group VIII metal, a Group VIIIB metal, a Group VIB metal, a Group IVB metal, and a Group IIB metal to obtain an intermediate mixture;

ii) sulfiding the intermediate mixture, with a sulfiding agent in solution forming a catalyst precursor; and

iii) mixing the catalyst precursor with-a hydrocarbon compound to form a hydroprocessing catalyst composition having formula

(M^t)_a(X^u)_b(S^v)_d(C^w)_r(H^x)_f(O^y)_g(N^z)_h,

wherein

subscripts a and b each are suitably greater than 0 such that 0≦

b/a≦

5, 0≦

f ≦

7 (a+b), 0≦

g≦

5(a+b), 0≦

h≦

0.5(a+h),

the molar ratio of the sulfiding agent to the at least one Group VIB metal compound M and the at least a Promoter Metal compound X is sufficient for subscript d to have a value of;

(a+0.5b) ≦

d≦

(5a+2b),

t, u, v, w, x, y, z, each representing total charge for each of;

M, X, S, C, H, O and N, respectively,

ta+ub+vd+we+xf+yg+zh+32 0; and

the catalyst precursor is mixed with a sufficient amount of hydrocarbon for subscript e to have a value of 0≦

e≦

11 (a+b).

2. The process of claim 1, wherein the hydroprocessing catalyst has an X-ray powder diffraction pattern with at least one broad diffraction peak at any of Bragg angles 8 to 180°

, 32 to 40, and 55 to 65°

(from 0 to 70°

2θ

scale).

3. The process of claim 2, wherein the at least one broad diffraction peak is greater than 2 degrees wide at ½

height.

4. The process of claim 2, wherein the catalyst has at least one broad diffraction peak at Bragg angle of 8 to 18°

(from 0 to 70°

2θ

scale).

5. The process of claim 4, wherein the broad diffraction peak at Bragg angle 8 to 18°

(from 0 to 70°

2θ

scale) is greater than 2 degrees wide at ½

height.

6. The process of claim 5, wherein the broad diffraction peak at Bragg angle 8 to 18°

(from 0 to 70°

2θ

scale) is greater than 5 degrees wide, at ½

height.

7. The process of claim 1, wherein the catalyst has a median particle size of 0.0005 to 1000 microns.

8. The process of claim 6, wherein the catalyst has an average particle size of 0.3 to 20 μ

m.

9. The process of claim 7, wherein the catalyst has a pore volume of 0.05-5 ml/g as determined by nitrogen adsorption.

10. The process of claim 1, wherein the intermediate mixture is a non-homogenous suspension.

11. The process of claim 1, wherein the catalytic precursor is a slurry.

12. The process of claim 1, wherein the sulfiding agent is ammonium sulfide in aqueous solution.

13. The process of claim 1, wherein the intermediate mixture is a clear homogenous solution.

14. The process of claim 1, wherein the intermediate mixture is a non-homogenous suspension.

15. The process of claim 1, wherein the reaction of the at least one Group VIB metal compound with the at least one Promoter Metal compound is at 0°

C. to 300°

C. and at a pressure ranging from 0 to 3000 psig.

16. The process of claim 1, wherein the at least one Group VIB metal is molybdenum and the at least one Promoter Metal is nickel.

17. The process of claim 1 ,wherein the at least one Group VIB metal compound is molybdenum, the at least one Promoter Metal compound is nickel, the weight ratio of nickel to molybdenum is about 1:

100 to about 1;

2.

18. The process of claim 1, wherein the intermediate mixture is sulfided with a sulfiding agent selected from the group of ammonium sulfide, ammonium polysulfide ([(NH₄)₂S_x), ammonlum thiosulfate ((NH₄)₂S₂O₃), sodium thiosulfate Na2S2O₃), thiourea CSN2H4, carbon disulfide, dimethyl disulfide (DMDS), dimethyl sulfide (DMS), tertiarybutyl polysulfide (PSTB)and tertiarynonyl polysulfide (PSTN), and mixtures thereof

19. The process of claim 1, wherein the intermediate mixture is sulfided with ammonium sulfide (NH₄)₂S for a period of time 5 minutes to 5 hours at a temperature from 20to 100°

C, and at 0-100 psig.

20. The processor claim 1, wherein the catalyst precursor is mixed with the hydrocarbon compound at a temperature of 100-300°

C. and at a pressure of 0 -25 1000 psig, forming the hydroprocessing catalyst of formula (M^t)_a(X^u)_b(S^v)_d(C^w)_t(H^x)_f(O^y)_g(N^z)_h.

22. The process of claim 1, further comprising the step of feeding the catalyst composition of the formula (M¹)_a(X^u)_b(S^v)_d(C^w)_e(H^x)_f(O^y)_g(N^z)_h with an oil feedstock in a hydroconversion process.

25. A catalyst composition prepared by the process of claim 1.

21. The process of claim l, wherein the step of combining and reacting the at least one of a Group VIB metal compound with the at least a Promoter Metal compound to obtain an intermediate mixture comprises:

mixing at least a Group VIB metal oxide and aqueous ammonia to form at least a Group VIB metal compound in aqueous solution;

reacting the at least a Group VIB metal compound in aqueous solution with the at least one Promoter Metal compound to form the intermediate mixture.

23. The process of claim 21, wherein the hydroconversion is at a temperature of 200 to 500°

C., a hydrogen pressure of from 5 to 300 bar, a liquid hourly space velocity of from 0.05 to 10 h<sup>−

1</sup> and at a hydrogen treat gas rate of from 35.6 to 1780 m³ /m³ (200 to 10000 SCF/B).

24. The process of claim 21, wherein the catalyst is added to the feedstock at a rate of 0.0.1 to 3 wt. %.

26. Use of the catalyst composition of claim 24, in hydroprocessing a hydrocarbon feedstock.