Hydroprocessing bulk catalyst and uses thereof

• US 7,947,623 B2
• Filed: 05/26/2010
• Issued: 05/24/2011
• Est. Priority Date: 09/10/2004
• Status: Active Grant

• Current Assignee: Chevron USA Incorporated (Chevron Corp.)
• Original Assignee: Chevron USA Incorporated (Chevron Corp.)
• Inventors: Chen, Kaidong, Lopez, Jaime, Brait, Axel, Reynolds, Bruce, Kuperman, Alexander E., Mironov, Oleg
• Primary Examiner(s): Wood; Elizabeth D
• Application Number:
  US12/787,855
• Publication Number:
  US 20100234212A1
• Time in Patent Office: 363 Days
• Field of Search: 502/3, 502/167, 502/168, 502/219, 502/220, 502/221, 502/222, 502/223, 502/517
• US Class Current: 502/219
• CPC Class Codes: B01J 23/24 Chromium, molybdenum or tungsten
• CPC Class Codes: B01J 23/28 Molybdenum
• CPC Class Codes: B01J 23/85 Chromium, molybdenum or tungsten
• CPC Class Codes: B01J 23/882 and cobalt
• CPC Class Codes: B01J 23/883 and nickel
• CPC Class Codes: B01J 23/8885 containing also molybdenum
• CPC Class Codes: B01J 27/0515 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 35/612 less than 10 m2/g
• CPC Class Codes: B01J 35/613 10-100 m2/g
• CPC Class Codes: B01J 35/635 0.5-1.0 ml/g
• CPC Class Codes: B01J 35/638 more than 1.0 ml/g
• CPC Class Codes: B01J 37/0236 Drying, e.g. preparing a suspension, adding a soluble salt and drying
• CPC Class Codes: B01J 37/031 Precipitation
• CPC Class Codes: B01J 37/038 to form slurries or suspensions, e.g. a washcoat
• CPC Class Codes: B01J 37/04 Mixing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/16 Reducing
• CPC Class Codes: B01J 37/20 Sulfiding
• CPC Class Codes: B01J 37/343 of ultrasonic wave energy
• CPC Class Codes: C10G 2300/107 : Atmospheric residues having a boiling point of at least about 538 °C
• CPC Class Codes: C10G 2300/1077 : Vacuum residues
• CPC Class Codes: C10G 47/04 : Oxides
• CPC Class Codes: C10G 47/06 : Sulfides
• CPC Class Codes: C10G 49/04 : containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
• CPC Class Codes: Y10S 502/517 : Sulfur or sulfur compound removal

Abstract

A hydroprocessing bulk catalyst is provided. A process to prepare hydroprocessing bulk catalysts is also provided. The hydroprocessing catalyst has the formula (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 one group VIB metal; promoter metal L is optional and if present, L is at least one Group VIII non-noble metal; 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); ta+ub+vd+we+xf+yg+zh=0; 0=<b; 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). The catalyst has an X-ray powder diffraction pattern with at least one broad diffraction peak at any of Bragg angles: 8 to 18°, 32 to 40°, and 55 to 65° (from 0 to 70° 2-θ scale). In one embodiment, the catalyst is prepared by sulfiding at least one Group VIB metal compound and optionally at least one group VIII metal compound 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 catalyst composition, comprising the steps:

reacting at least one Group VIB metal compound (“

M”

) with at least a promoter metal compound L 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;

sulfiding the intermediate mixture with a sulfiding agent forming a catalyst precursor; and

mixing the catalyst precursor with a hydrocarbon compound to form a hydroprocessing catalyst composition having formula (M^t)_a(L^u)_b(S^v)_d(C^w)_e(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,

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 L is sufficient for subscript d to have a value of

(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),

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

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

ta+ub+vd+we+xf+yg+zh=0;

and wherein the catalyst has an X-ray powder diffraction pattern with at least one broad diffraction peak at any of Bragg angles;

8 to 18°

, 32 to 40°

, and 55 to 65°

(from 0 to 70°

2θ

scale).

2. The process of claim 1, wherein the sulfiding agent is selected from the group of H₂S, 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) and tertiarynonyl polysulfide (PSTN), and mixtures thereof.

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

C., and at 0-100 psig.

4. The process of claim 1, wherein the mixing of catalyst precursor with the hydrocarbon compound is at a temperature of 100-300°

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

5. The process of claim 1, wherein at least a surfactant is added to at least one of the process steps.

6. The process of claim 1, wherein at least a surfactant is mixed with the catalyst precursor and the hydrocarbon compound in forming the hydroprocessing catalyst composition.

7. The process of claim 1, wherein a surfactant is mixed with the sulfiding agent prior to sulfiding the intermediate mixture.

8. The process of claim 7, wherein the surfactant is selected from N-containing organic additives, P-containing organic additives, and mixtures thereof.

9. The process of claim 8, wherein the surfactant is selected from the group of aromatic amines, cyclic aliphatic amines, polycyclic aliphatic amines, carboxylic acids, and mixtures thereof.

10. The process of claim 7, wherein the surfactant is selected from the group of hexamethylenediamine, monoethanolamine, diethanolamine, triethanolamine, N,N-dimethyl-N′

-ethylethylenediamine;

amino alcohols, amino alkoxy-silanes, and mixtures thereof.

11. The process of claim 10, herein the surfactant is water-soluble cationic amine selected from the group of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dodecyl trimethyl ammonium amine, nonyl trimethyl ammonium chloride and dodecyl phenol quaternary amine soaps.

12. The process of claim 11, wherein at least a sulfur additive is added to the sulfiding step.

13. The process of claim 11, wherein the at least a 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.

14. The process of claim 12, wherein the at least a sulfur additive is dimethyl disulphide in formic acid.

15. The process of claim 12, wherein the at least a sulfur additive is in powder form mixed with at least another sulphur compound.

16. The process of claim 1, wherein

M is selected from molybdenum, tungsten, and mixtures thereof, and

L is selected from nickel, cobalt, and mixture thereof.

17. A process for preparing a catalyst composition, which process comprising:

sulfiding at least one Group VIB metal compound (“

M”

) with a sulfiding agent forming a sulfided Group VIB metal compound;

combining and reacting the sulfided Group VIB metal compound with at least a promoter metal compound L 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 form a catalyst precursor;

mixing the catalyst precursor with a hydrocarbon compound to form a hydroprocessing catalyst composition having formula (M^t)_a(L^u)_b(S^v)_d(C^w)_e(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+b),

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 L 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=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).

18. The process of claim 17, wherein

M is selected from molybdenum, tungsten, and mixtures thereof, and

L is selected from nickel, cobalt, and mixture thereof.

19. A process for preparing a catalyst composition, which process comprising:

sulfiding at least one Group VIB metal compound (“

M”

) with a sulfiding agent forming a sulfided Group VIB metal compound;

sulfiding at least a promoter metal compound L 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 with a sulfiding agent to form a sulfided promoter metal compound;

combining and reacting the sulfided Group VIB metal compound with the sulfided promoter metal compound to form a catalyst precursor;

mixing the catalyst precursor with a hydrocarbon compound to form a hydroprocessing catalyst composition having formula (M^t)_a(L^u)_b(S^v)_d(C^w)_e(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+b),

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 L 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=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).

20. The process of claim 19, wherein

M is selected from molybdenum, tungsten, and mixtures thereof, and

L is selected from nickel, cobalt, and mixture thereof.