Hydroconversion multi-metallic catalysts and method for making thereof

Patent metadata

Field	Value
Publication number	US-9266098-B2
Application number	US-201314019421-A
Country	US
Kind code	B2
Filing date	Sep 5, 2013
Priority date	Sep 5, 2012
Publication date	Feb 23, 2016
Grant date	Feb 23, 2016

Abstract

The invention relates to a self-supported mixed metal sulfide (MMS) catalyst for hydrotreating hydrocarbon feedstock and to a method for preparing the catalyst. The MMS catalyst is characterized as having a multi-phased structure comprising five phases: a molybdenum sulfide phase, a tungsten sulfide phase, a molybdenum tungsten sulfide phase, an active nickel phase, and a nickel sulfide phase.

First claim

The invention claimed is:

1. A mixed metal sulfide (MMS) catalyst, comprising:
molybdenum sulfide, nickel sulfide, and tungsten sulfide, wherein the catalyst is characterized as having a multi-phased structure comprising five phases: a molybdenum sulfide phase, a tungsten sulfide phase, a molybdenum tungsten sulfide phase, an active nickel phase, and a nickel sulfide phase;
wherein the catalyst is characterized as having molar ratios of metal components Ni:Mo:W in a region defined by five points ABCDE of a ternary phase diagram, and wherein the five points ABCDE are defined as: A (Ni=0.72, Mo=0.00, W=0.28), B (Ni=0.25, Mo=0.00, W=0.75), C (Ni=0.25, Mo=0.25, W=0.50), D (Ni=0.60, Mo=0.25, W=0.15), E (Ni=0.72, Mo=0.13, W=0.15); and
wherein the mixed metal sulfide catalyst is self-supported.

2. The self-supported MMS catalyst of claim 1 , wherein the molybdenum tungsten sulfide phase comprising at least a layer, wherein the at least a layer contains at least one of: a) molybdenum sulfide and tungsten sulfide; b) tungsten isomorphously substituted into molybdenum sulfide as individual atoms or as tungsten sulfide domains; c) molybdenum isomorphously substituted into tungsten sulfide as individual atoms or as molybdenum sulfide domains; and d) mixtures thereof.

3. The self-supported MMS catalyst of claim 2 , wherein the molybdenum sulfide and tungsten sulfide phase comprises 1 to 6 layers.

4. The self-supported MMS catalyst of claim 2 , wherein the at least a layer comprises tungsten isomorphously substituted into molybdenum sulfide as individual atoms forming an intralayer atomic mixture.

5. The self-supported MMS catalyst of claim 2 , wherein the at least a layer comprises tungsten isomorphously substituted into molybdenum sulfide as tungsten domains.

6. The self-supported MMS catalyst of claim 2 , wherein the at least a layer comprises molybdenum isomorphously substituted into tungsten sulfide as individual atoms forming an intralayer atomic mixture.

7. The self-supported MMS catalyst of claim 2 , wherein the at least a layer comprises molybdenum isomorphously substituted into tungsten sulfide as molybdenum domains.

8. The self-supported MMS catalyst of claim 2 , wherein the molybdenum tungsten sulfide phase comprises inter-layer mixtures of tungsten sulfide and molybdenum sulfide.

9. The self-supported MMS catalyst of claim 2 , wherein the at least a layer comprises mixtures of individual domains of tungsten sulfide and molybdenum sulfide.

10. The self-supported MMS catalyst of claim 1 , wherein the active nickel phase comprises at least one of atomic nickel and reduced nickel substituted into the molybdenum tungsten sulfide phase.

11. The self-supported MMS catalyst of claim 1 , wherein the active nickel phase comprises NiS x nanoparticles.

12. The self-supported MMS catalyst of claim 1 , wherein the nickel sulfide phase comprises slabs of Ni 9 S 8 and Ni 3 S 2 layers.

13. The self-supported MMS catalyst of claim 1 , wherein the nickel sulfide phase serves as support for the molybdenum tungsten sulfide phase.

14. The self-supported MMS catalyst of claim 12 , wherein the molybdenum tungsten sulfide phase envelopes the slabs of Ni 9 S 8 and Ni 3 S 2 layers.

15. The self-supported MMS catalyst of claim 1 , wherein the nickel sulfide phase stabilizes dispersion of the active nickel phase onto the molybdenum tungsten sulfide phase.

16. The self-supported MMS catalyst of claim 1 , wherein the catalyst is further characterized by an X-ray diffraction pattern showing peaks corresponding to MoS 2 phase and WS 2 phase.

17. The self-supported MMS catalyst of claim 1 , wherein the catalyst is further characterized by an X-ray diffraction pattern showing peaks corresponding to Ni 3 S 2 phase.

18. The self-supported MMS catalyst of claim 1 , wherein the catalyst is further characterized by TEM image showing lattice fringes on nickel sulfide of 4.60±0.5 Å and 2.87±0.5 Å.

19. The self-supported MMS catalyst of claim 1 , wherein the catalyst has a BET surface area of at least 20 m 2 /g and a pore volume of at least 0.05 cm 3 /g.

20. The self-supported MMS catalyst of claim 19 , wherein the catalyst has a BET surface area of at least 40 m 2 /g and a pore volume of at least 0.05 cm 3 /g.

21. The self-supported MMS catalyst of claim 1 , wherein the catalyst after hydrotreating a heavy coker gas oil for at least 0.5 hrs. has a surface area reduction of less than 80%.

22. The self-supported MMS catalyst of claim 1 , wherein the catalyst is further characterized by a Ni surface concentration/Ni bulk concentration ratio of greater than 0.4 as characterized by XPS.

23. The self-supported MMS catalyst of claim 22 , wherein the catalyst is further characterized by a Ni surface concentration/Ni bulk concentration ratio of greater than 0.5 as characterized by XPS.

24. The self-supported MMS catalyst of claim 1 , wherein the catalyst is further characterized by a W surface concentration/W bulk concentration ratio of greater than 0.3 as characterized by XPS.

25. The self-supported MMS catalyst of claim 24 , wherein the catalyst is further characterized by a W surface concentration/W bulk concentration ratio of greater than 0.4 as characterized by XPS.

26. The self-supported MMS catalyst of claim 1 , wherein the catalyst is characterized by having a molar ratio of metal components Ni:Mo:W in a range of: 0.33≦Ni/(Mo+W)≦2.57, a range of Mo/(Ni+W) molar ratios of 0.00≦Mo/(Ni+W)≦0.33, and a range of W/(Ni+Mo) molar ratios of 0.18≦W/(Ni+Mo)≦3.00.

27. The self-supported MMS catalyst of claim 1 , wherein the catalyst is characterized as having molar ratios of metal components Ni:Mo:W in a region defined by six points ABCDEF of a ternary phase diagram, and wherein the six points ABCDEF are defined as: A (Ni=0.67, Mo=0.00, W=0.33), B (Ni=0.67, Mo=0.10, W=0.23), C (Ni=0.60, Mo=0.15, W=0.25), D (Ni=0.52, Mo=0.15, W=0.33), E (Ni=0.52, Mo=0.06, W=0.42), F (Ni=0.58, Mo=0.0, W=0.42).

28. The self-supported MMS catalyst of claim 1 , wherein the catalyst is characterized as having a molar ratio of metal components Ni:Mo:W in a range of:
1.08<=Ni/(Mo+W)<=2.03
0<=Mo/(Ni+W)<=0.18; and
0.33<=W/(Mo+Ni))<=0.72.

29. The self-supported MMS catalyst of claim 1 , wherein the catalyst is characterized as having molar ratios of metal components Ni:Mo:W in a region defined by four points ABCD of a ternary phase diagram, and wherein the four points ABCD are defined as: A(Ni=0.67, Mo=0.00, W=0.33), B(Ni=0.58, Mo=0.0, W=0.42), C(Ni=0.52, Mo=0.15, W=0.33), D(Ni=0.60, Mo=0.15, W=0.25).

Assignees

• Han Jinyi
• Kuperman Alexander E
• Maesen Theodorus Ludovicus Michael
• Trevino Horacio
• Chevron Usa Inc

Inventors

• Han Jinyi
• Kuperman Alexander E
• Maesen Theodorus Ludovicus Michael
• Trevino Horacio

Classifications

• C10G45/08

  in combination with chromium, molybdenum, or tungsten metals, or compounds thereof · CPC title

• B01J27/047

  with chromium, molybdenum, tungsten or polonium · CPC title

• B01J27/043

  with iron group metals or platinum group metals · CPC title

• B01J27/0515 Primary

  with iron group metals or platinum group metals · CPC title

• B01J27/051

  Molybdenum · CPC title