Hydroprocessing bulk catalyst and methods of making thereof

• US 8,389,433 B2
• Filed: 11/24/2009
• Issued: 03/05/2013
• Est. Priority Date: 11/24/2009
• Status: Active Grant

• Current Assignee: Chevron USA Incorporated (Chevron Corp.)
• Original Assignee: Chevron Corp.
• Inventors: Mironov, Oleg, Kuperman, Alexander E., Han, Jinyi
• Primary Examiner(s): WOOD, ELIZABETH D
• Application Number:
  US12/625,368
• Publication Number:
  US 20110124493A1
• Time in Patent Office: 1,197 Days
• Field of Search: 502/200, 502/219, 502/220, 502/221, 502/222, 502/223, 502/167, 502/168
• US Class Current: 502/200
• CPC Class Codes: B01J 23/80 with zinc, cadmium or mercury
• CPC Class Codes: B01J 27/043 with iron group metals or platinum group metals
• CPC Class Codes: B01J 27/049 with iron group metals or platinum group metals
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/40 characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: B01J 37/20 Sulfiding
• CPC Class Codes: C10G 49/02 characterised by the catalyst used

Abstract

A hydroprocessing bulk catalyst is provided. A process to prepare hydroprocessing bulk catalysts is also provided. The hydroprocessing catalyst has the formula (R^p)_i(M^t)_a(L^u)_b(S^v)_d(C^w)_e(H^x)_f(O^y)_g(N^z)_h, wherein M is at least at least a “d” block element metal; L is also at least a “d” block element metal, but different from M; t, u, v, w, x, y, z representing the total charge for each of the components (M, L, S, C, H, O and N, respectively); R is optional and in one embodiment, R is a lanthanoid element metal; 0<=i<=1; pi+ta+ub+vd+we+xf+yg+zh=0; 0<b; 0<b/a=<5; 0.5(a+b)<=d<=5(a+b); 0<e<=11(a+b); 0<f<=7(a+b); 0<g<=5(a+b); 0<h<=2(a+b). The catalyst has an X-ray powder diffraction pattern with at least three diffractions peak located at 2-θ angles of greater than 25°. In one embodiment, the catalyst is prepared by forming at least a sulfided catalyst precursors from at least two “d” block element metals; and mixing the catalyst precursor with a hydrocarbon compound to form the hydroprocessing catalyst composition. In another embodiment, the catalyst is prepared by the thermal decomposition of an oil dispersible sulfur containing organic metal precursor upon contact with a hydrocarbon oil, generating a slurry catalyst. In yet another embodiment, the catalyst is prepared from an in-situ or ex-situ sulfidation of “d block element metal precursors in solvent carrier.

Claims

1. A catalyst composition having a formula

(R^p)_i(M^t)_a(L^u)_b(S^v)_d(C^w)_e(H^x)_f(O^y)_g(N^z)_h, wherein

R is optional, R is at least a lanthanoid element metal or an alkaline earth metal;

M is at least a “

d”

block element metal;

L is at least a “

d”

block element metal different from the “

d”

block element metal M;

0<

=i<

=1;

0<

b/a=<

5,

0.5(a+b)<

=d<

=5(a+b),

0<

e<

=11(a+b),

0<

f<

=7(a+b),

0<

g<

=5(a+b),

0<

h<

=2(a+b),

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

M, L, S, C, H, O and N, respectively, wherein pi+ta+ub+vd+we+xf+yg+zh=0; and

wherein the “

d”

block element is selected from the group consisting of iron, zinc titanium, nickel, copper, cobalt, chromium, and manganese; and

wherein the catalyst has an X-ray powder diffraction pattern with at least three diffraction peaks located at 2-θ

angles of greater than 25°

.

2. The catalyst composition of claim 1, wherein the at least three diffraction peaks are respectively located at Bragg angles:

25°

to 30°

, 45°

to 50° and

52°

to 60°

(from 0 to 70°

2-θ

scale).

3. The catalyst composition of claim 1, wherein the catalyst has an average particle size of 0.0005 to 1000 microns.

4. The catalyst composition of claim 1, wherein the catalyst has an average particle size of 0.3 to 20 μ

m.

5. The catalyst composition of claim 1, wherein the catalyst comprises clusters of colloidal sized particles of less than 100 nm in size.

6. The catalyst composition of claim 1, wherein the catalyst has a pore volume of 0.05-5 ml/g as determined by nitrogen adsorption.

7. The catalyst composition of claim 1, wherein the catalyst has a pore volume of 0.1-4 ml/g as determined by nitrogen adsorption.

8. The catalyst composition of claim 1, wherein the catalyst has a surface area of at least 5 m²/g.

9. The catalyst composition of claim 1, wherein M is selected from zinc and iron and mixtures thereof and L is selected from zinc and iron and mixtures thereof.

10. The catalyst composition of claim 1, wherein M is iron and L is zinc or vice versa.

11. The catalyst composition of claim 10, wherein M is Fe and L is Zn and the weight ratio of Fe to Zn ranges from 1:

9 to about 9;

1.

12. The catalyst composition of claim 10, wherein M is Fe and L is Zn and the weight ratio of Fe to Zn ranges from 1:

2 to about 2;

1.

13. The catalyst composition of claim 10, wherein M is Fe and L is Zn and the weight ratio of Fe to Zn is about 1:

1.

14. The catalyst composition of claim 10, wherein M is Fe and L is Zn and the weight ratio of Fe to Zn ranges from 40 to 60%.

15. The catalyst composition of claim 1, wherein M and L am derived from metal precursors selected from the group of iron(III) dimethyldithiocarbamate (Fe-DTC), zinc diethyldithio-carbamate (Zn-DTC), and zinc diispropyldithiophosphate.

16. The catalyst composition of claim 1, wherein at least one of M and L is derived from a metal precursor selected from the group of sulfates, nitrates, carbonates, sulfides, oxysulfides, oxides and hydrated oxides, ammonium salts and heteropoly acids of “

d”

element metals.

17. The catalyst composition of claim 1, wherein at least one of M and L is derived from a metal precursor selected from the group of sulfates, nitrates, carbonates, sulfides, oxysulfides, oxides and hydrated oxides, ammonium salts and heteropoly acids of “

d”

element metals.

18. The catalyst composition of claim 1, wherein at least one of M and L is derived from a metal precursor selected from the group of “

d”

block element metal salts of organic acids.

19. The catalyst composition of claim 1, wherein at least one of M and L is derived from a metal precursor selected from the group of “

d”

element metal salts of acyclic acids, alicyclic aliphatic acids, carboxylic acids containing two or more carbon atoms, and mixtures thereof.

20. The catalyst composition of claim 1, wherein at least one of M and L is derived from a metal precursor selected from the group of acetates, oxylates, citrates, napthanates and octoates of “

d”

block element metals.

21. The catalyst composition of claim 1, wherein b/a has a molar ratio ranging from 0.1 to 10.

22. The catalyst composition of claim 1, wherein at least one of M and L is derived from a sulfide of “

d”

block element metals.

23. The catalyst composition of claim 1, wherein at least one of M and L is derived from a mineral of “

d”

block element metals.

24. The catalyst composition of claim 1, wherein the catalyst further comprises a refractory oxide material which comprises 50 wt. % or more titania, on oxide basis.

25. The catalyst composition of claim 1, wherein the catalyst is used for hydrogenation and added to a heavy oil feedstock at a catalyst to oil ratio of 0.25 to 4 wt. %.

26. The catalyst composition of claim 1, wherein the catalyst is added to a heavy oil feedstock in an amount sufficient to provide 1000 to 12,000 ppm of active “

d”

block element metals.

27. The catalyst composition of claim 1, wherein M is selected from iron and nickel and mixtures thereof, L is selected from nickel and iron and mixtures thereof, and M is different from L.

28. The catalyst composition of claim 1, wherein M is selected from copper and iron and mixtures thereof, L is selected from copper and iron and mixtures thereof, and M is different from L.

29. The catalyst composition of claim 1, wherein M is selected from cobalt and iron and mixtures thereof, L is selected from cobalt and iron and mixtures thereof, and M is different from L.

30. The catalyst composition of claim 1, wherein M is selected from chromium and iron and mixtures thereof, L is selected from chromium and iron and mixtures thereof, and M is different from L.

31. The catalyst composition of claim 1, wherein M is selected from titanium and iron and mixtures thereof;

L is selected from titanium and iron and mixtures thereof, and M is different from L.