Hydroconversion multi-metallic catalysts and method for making thereof

• US 9,266,098 B2
• Filed: 09/05/2013
• Issued: 02/23/2016
• Est. Priority Date: 09/05/2012
• Status: Active Grant

• Current Assignee: Chevron USA Incorporated (Chevron Corp.)
• Original Assignee: Chevron USA Incorporated (Chevron Corp.)
• Inventors: Han, Jinyi, Kuperman, Alexander E., Maesen, Theodorus Ludovicus Michael, Trevino, Horacio
• Primary Examiner(s): SWAIN, MELISSA STALDER
• Application Number:
  US14/019,421
• Publication Number:
  US 20140066297A1
• Time in Patent Office: 901 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: B01J 2235/00 Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
• CPC Class Codes: B01J 2235/15 X-ray diffraction
• CPC Class Codes: B01J 2235/30 Scanning electron microscopy; Transmission electron microscopy
• CPC Class Codes: B01J 27/043 with iron group metals or platinum group metals
• CPC Class Codes: B01J 27/047 with chromium, molybdenum, tungsten or polonium
• CPC Class Codes: B01J 27/049 with iron group metals or platinum group metals
• CPC Class Codes: B01J 27/051 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 35/613 10-100 m2/g
• CPC Class Codes: B01J 35/633 less than 0.5 ml/g
• CPC Class Codes: C10G 45/08 in combination with chromium, molybdenum, or tungsten metals, or compounds thereof

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.

Claims

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 Ni₉S₈ and Ni₃S₂ 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 Ni₉S₈ and Ni₃S₂ 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 MoS₂ phase and WS₂ 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 Ni₃S₂ 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 m²/g and a pore volume of at least 0.05 cm³/g.

20. The self-supported MMS catalyst of claim 19, wherein the catalyst has a BET surface area of at least 40 m²/g and a pore volume of at least 0.05 cm³/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).