Hydroprocessing Bulk Catalyst and Methods of Making Thereof

• US 20110124494A1
• Filed: 11/24/2009
• Published: 05/26/2011
• Est. Priority Date: 11/24/2009
• Status: Active Grant

• Current Assignee: Chevron USA Incorporated (Chevron Corp.)
• Original Assignee: Chevron USA Incorporated (Chevron Corp.)
• Inventors: Mironov, Oleg, Kuperman, Alexander E.
• Granted Patent: US 8,372,776 B2
• Time in Patent Office: Days
• US Class Current: 502/167
• 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 a solvent carrier.

Claims

1. A process for preparing a catalyst composition comprising:

i) providing at least two metal precursors of different “

d”

block element metals;

ii) combining the at least two metal precursors with a sulfiding agent, forming at least a sulfided catalyst precursor; and

iii) mixing the at least a sulfided catalyst precursor with a hydrocarbon compound to transform the sulfided catalyst precursor into a catalyst composition having 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.

3. The process of claim 1, wherein the sulfiding agent is selected from the group of elemental sulfur, ammonium sulfide, ammonium polysulfide ([(NH₄)₂S_x), ammonium thiosulfate ((NH₄)₂S₂O₃), sodium thiosulfate Na₂S₂O₃), thiourea CSN₂H₄, carbon disulfide, dimethyl disulfide (DMDS), dimethyl sulfide (DMS), tertiarybutyl polysulfide (PSTB), tertiarynonyl polysulfide (PSTN), mercaptanes, thioglycols, and mixtures thereof.

4. The process of claim 3, wherein the sulfiding agent is ammonium sulfide (NH₄)₂S and the metal precursors are sulfided for a period of time 5 minutes to 5 hours at a temperature from 20 to 100°

C. at a pressure from 0 to 100 psig.

5. The process of claim 1, wherein the at least a sulfur additive is added to the sulfiding step, wherein the sulfur additive is selected from the group of elemental sulfur, thiodiazoles, thio acids, thio amides, thiocyanates, thio esters, thiophenols, thiosemicarbazides, thioureas, mercapto alcohols, dialkyl sulfides, dihydroxyalkyl sulfides, diaryl sulfides, diaralkyl sulfides, dimethyl sulfoxides, diethanol disulfide, tert-nonylpolysulfides, dimethyl sulphide, dimethyl disulphide, 2,2-dithiobis ethanol, and mixtures thereof.

6. The process of claim 1, wherein the at least two metal precursors of different “

d”

block element metals are selected from iron(III) nitrate, zinc nitrate, ferric sulfide, ferrous sulfide, iron sulfide, zinc sulfide, ferric sulfate, ferric nitrate, ferric phosphate, nickel sulfate, nickel nitrate, nickel phosphate, nickel acetate, and mixtures thereof.

7. The process of claim 1, wherein a sufficient amount of metal precursors are provided for b/a to have a molar ratio ranging from 0.1 to 10.

8. The process of claim 1, wherein M is Fe and L is Zn and Fe and Zn have a molar ratio Fe:

Zn ranging from 1;

10 to about 10;

1.

9. The process of claim 1, wherein the sulfided catalyst precursor is transformed into a catalyst composition at a temperature of 100-400°

C. and a pressure of 0-1000 psig.

10. The process of claim 1, wherein the hydrocarbon compound is selected from the group of is naptha, decant oil, diesel, VGO (vacuum gas oil), light gas oil, MCO (medium cycle oil), light cycle oil (LCO), heavy cycle oil (HCO), aromatic solvents, and mixtures thereof.

11. The process of claim 1, wherein at least a surfactant is added to the hydrocarbon compound in forming the catalyst composition.

12. The process of claim 1, wherein at least a surfactant is added to the hydrocarbon compound in forming the catalyst composition.

13. The process of claim 1, wherein at least a sacrificial material is added to the hydrocarbon compound in forming the catalyst composition.

33. The process 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.

34. The process 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.

35. The process 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.

36. The process 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.

37. The process 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.

2. The process of claim 2, wherein the catalyst composition has an X-ray powder diffraction pattern with at least three diffraction peaks located at 2-θ

angles of greater than 25°

.

14. A process for preparing a catalyst composition comprising:

i) providing at least two metal precursors of different “

d”

block element metals, a first metal precursor and a second metal precursor;

ii) sulfiding the first metal precursor with a sulfiding agent forming a first sulfided catalyst precursor; and

iii) combining the first sulfided catalyst precursor and the second metal precursor with a hydrocarbon compound to transform the precursors into a catalyst composition having 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.

15. The process of claim 14, 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°

.

16. The process of claim 14, wherein the sulfiding agent is selected from the group of elemental sulfur, ammonium sulfide, ammonium polysulfide ([(NH₄)₂S_x), ammonium thiosulfate ((NH₄)₂S₂O₃), sodium thiosulfate Na₂S₂O₃), thiourea CSN₂H₄, carbon disulfide, dimethyl disulfide (DMDS), dimethyl sulfide (DMS), tertiarybutyl polysulfide (PSTB), tertiarynonyl polysulfide (PSTN), mercaptanes, thioglycols, and mixtures thereof.

17. The process of claim 14, wherein the sulfiding agent is ammonium sulfide (NH₄)₂S.

18. The process of claim 14, wherein the at least a sulfur additive is added to the sulfiding step, wherein the sulfur additive is selected from the group of elemental sulfur, thiodiazoles, thio acids, thio amides, thiocyanates, thio esters, thiophenols, thiosemicarbazides, thioureas, mercapto alcohols, dialkyl sulfides, dihydroxyalkyl sulfides, diaryl sulfides, diaralkyl sulfides, dimethyl sulfoxides, diethanol disulfide, tert-nonylpolysulfides, dimethyl sulphide, dimethyl disulphide, 2,2-dithiobis ethanol, and mixtures thereof.

19. The process of claim 14, wherein M is Fe and L is Zn and Fe:

Zn has a molar ratio ranging from 1;

10 to 10;

1.

20. The process of claim 14, wherein the first sulfided catalyst precursor and the second metal precursor are transformed to a catalyst composition at a temperature of 100-400°

C. and at a pressure of 0-1000 psig.

21. The process of claim 14, wherein the at least two metal precursors of different “

d”

block element metals are selected from iron(III) nitrate, zinc nitrate, ferric sulfide, ferrous sulfide, iron sulfide, zinc sulfide, ferric sulfate, ferric nitrate, ferric phosphate, nickel sulfate, nickel nitrate, nickel phosphate, nickel acetate, and mixtures thereof.

22. A process for preparing a catalyst composition comprising:

i) providing at least two metal precursors of different “

d”

block element metals;

ii) sulfiding a first metal precursor with a sulfiding agent forming a first sulfided catalyst precursor;

ii) sulfiding a second metal precursor with a sulfiding agent forming a second sulfided catalyst precursor; and

iii) combining the first sulfided catalyst precursor and the second sulfided metal precursor with a hydrocarbon compound to transform the precursors into a catalyst composition having 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.

23. The process of claim 22, 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°

.

24. The process of claim 22, wherein the sulfiding agent is selected from the group of elemental sulfur, ammonium sulfide, ammonium polysulfide ([(NH₄/₂S_x), ammonium thiosulfate ((NH₄)₂S₂O₃), sodium thiosulfate Na₂S₂O₃), thiourea CSN₂H₄, carbon disulfide, dimethyl disulfide (DMDS), dimethyl sulfide (DMS), tertiarybutyl polysulfide (PSTB), tertiarynonyl polysulfide (PSTN), mercaptanes, thioglycols, and mixtures thereof.

25. The process of claim 22, wherein the sulfided metal precursors are transformed into a catalyst composition at a temperature of 100-400°

C. and at a pressure of 0 to 1000 psig.

26. The process of claim 22, wherein the at least two metal precursors of different “

d”

block element metals are selected from iron(III) nitrate, zinc nitrate, ferric sulfide, ferrous sulfide, iron sulfide, zinc sulfide, ferric sulfate, ferric nitrate, ferric phosphate, nickel sulfate, nickel nitrate, nickel phosphate, nickel acetate, and mixtures thereof.

28. The process of claim 22, wherein the at least a sulfur additive is added to the sulfiding step, wherein the sulfur additive is selected from the group of elemental sulfur, thiodiazoles, thio acids, thio amides, thiocyanates, thio esters, thiophenols, thiosemicarbazides, thioureas, mercapto alcohols, dialkyl sulfides, dihydroxyalkyl sulfides, diaryl sulfides, diaralkyl sulfides, dimethyl sulfoxides, diethanol disulfide, tert-nonylpolysulfides, dimethyl sulphide, dimethyl disulphide, 2,2-dithiobis ethanol, and mixtures thereof.

29. The process of claim 22, wherein M is Fe and L is Zn having a molar ratio Fe:

Zn ranging from 1;

2 to about 2;

1.

30. The process of claim 22, wherein the hydrocarbon compound is selected from the group of is naptha, decant oil, diesel, VGO (vacuum gas oil), light gas oil, MCO (medium cycle oil), light cycle oil (LCO), heavy cycle oil (HCO), aromatic solvents, and mixtures thereof.

31. The process of claim 22, wherein at least a surfactant is added to the hydrocarbon compound in forming the catalyst composition.

32. The process of claim 22, wherein at least a surfactant is added to the hydrocarbon compound in forming the catalyst composition.