Hydroconversion multi-metallic catalysts and method for making thereof

• US 9,205,413 B2
• Filed: 09/05/2013
• Issued: 12/08/2015
• 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:
  US14/019,457
• Publication Number:
  US 20140066298A1
• Time in Patent Office: 824 Days
• Field of Search: None
• US Class Current: 1/1
• 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 method for preparing a self-supported mixed metal sulfide (MMS) catalyst for hydrotreating hydrocarbon feedstock. The method comprises mixing a sufficient amount of a nickel (Ni) metal precursor, a sufficient amount of a molybdenum (Mo) metal precursor, and a sufficient amount of a tungsten (W) metal precursor to produce a catalyst precursor having a molar ratio Ni:Mo:W in relative proportions defined by a region of a ternary phase diagram showing transition metal elemental composition in terms of nickel, molybdenum, and tungsten mol-%, wherein the region is defined by five points ABCDE and wherein the five points are: A (Ni=0.72, Mo=0.00, W=0.28), B (Ni=0.55, Mo=0.00, W=0.45), C (Ni=0.48, Mo=0.14, W=0.38), D (Ni=0.48, Mo=0.20, W=0.33), E (Ni=0.62, Mo=0.14, W=0.24); and sulfiding the catalyst precursor under conditions sufficient to convert the catalyst precursor into a sulfide catalyst.

Claims

1. A process for making a self-supported mixed metal sulfide (MMS) catalyst comprising molybdenum sulfide, nickel sulfide, and tungsten sulfide, the process comprising:

mixing a sufficient amount of a nickel (Ni) metal precursor, a sufficient amount of a molybdenum (Mo) metal precursor, and a sufficient amount of a tungsten (W) metal precursor to produce a catalyst precursor having a molar ratio of metal components Ni;

Mo;

W in relative proportions defined by a region of a ternary phase diagram showing transition metal elemental composition in terms of nickel, molybdenum, and tungsten mol-%, wherein the region is defined by five points ABCDE and wherein the five points are;

A in which Ni=0.72, Mo=0.00, W=0.28;

B in which Ni=0.55, Mo=0.00, W=0.45;

C in which Ni=0.48, Mo=0.14, W=0.38;

D in which Ni=0.48, Mo=0.20, W=0.33; and

E in which Ni=0.62, Mo=0.14, W=0.24; and

sulfiding the catalyst precursor under conditions sufficient to convert the catalyst precursor into a sulfide catalyst.

2. The process of claim 1, wherein the amounts of a Ni metal precursor, a Mo metal precursor, and a W metal precursor are sufficient for the catalyst precursor to have 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.

3. The process of claim 1, wherein the amounts of a Ni metal precursor, a Mo metal precursor, and a W metal precursor are sufficient for the catalyst to have 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.

4. The process of claim 1, further comprising:

calcining the catalyst precursor to a temperature of at least 300°

C. prior to sulfiding the catalyst precursor.

5. The process of claim 1, further comprising:

heating the catalyst precursor to a temperature of at least 150°

C. prior to sulfiding the catalyst precursor.

6. The process of claim 1, wherein after sulfiding, the catalyst has a BET surface area of at least 20 m²/g and a pore volume of at least 0.05 cm³/g.

7. The process of claim 1, wherein after sulfiding, the catalyst has a BET surface area of at least 40 m²/g and a pore volume of at least 0.05 cm³/g.

8. The process of claim 1, wherein after sulfiding, the catalyst has a Ni surface concentration/Ni bulk concentration ratio of greater than 0.4 as characterized by XPS.

9. The process of claim 1, wherein after sulfiding, the catalyst has a Ni surface concentration/Ni bulk concentration ratio of greater than 0.5 as characterized by XPS.

10. The process of claim 1, wherein after sulfiding, the catalyst has a W surface concentration/W bulk concentration ratio of greater than 0.3 as characterized by XPS.

11. The process of claim 10, wherein after sulfiding, the catalyst has a W surface concentration/W bulk concentration ratio of greater than 0.4 as characterized by XPS.

12. The process of claim 1, wherein after sulfiding, the catalyst shows 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.

13. The process of claim 12, wherein the molybdenum tungsten sulfide phase comprises at least a layer and 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.

14. The process of claim 12, wherein the active nickel phase comprises at least one of atomic nickel and reduced nickel substituted into edge of the molybdenum tungsten sulfide phase.

15. The process of claim 12, wherein the active nickel phase comprises NiS_x nanoparticles dispersed onto the molybdenum tungsten sulfide phase or edge of the molybdenum tungsten sulfide phase.

16. The process of claim 12, wherein the nickel sulfide phase comprises slabs of Ni₉S₈ and Ni₃S₂ layers.

17. The process of claim 1, wherein the molybdenum metal precursor is selected from molybdenum metal, alkali metal molybdates, ammonium metallates of molybdenum, molybdenum sulphate, molybdenum phosphate, molybdenum silicate, molybdenum borate, molybdenum naphthenate, pentacyclodienyl molybdate, cyclopentadienyl Mo tricarbonyl dimer, ammonium salts of phosphomolybdic acids, phosphomolybdic acid, molybdenum oxide, Mo—

P heteropolyanion compounds, Mo—

Si heteropolyanion compounds, inorganic metal sulfides of molybdenum, sulfur-containing inorganic compounds of molybdenum, sulfur-containing organic compounds of molybdenum, and mixtures thereof.

18. The process of claim 1, wherein the tungsten metal precursor is selected from alkali metal tungstates, ammonium metallates of tungsten, inorganic tungsten compounds, tungsten naphthenate, pentacyclodienyl tungsten dihydride, tungsten oxide, W—

P heteropolyanion compounds, W—

Si heteropolyanion compounds, sulfur-containing inorganic compounds of tungsten, sulfur-containing organic compounds of tungsten, and mixtures thereof.

19. The process of claim 1, wherein the nickel metal precursor is selected from inorganic metal sulfides of nickel, sulfur-containing inorganic compounds of nickel, sulfur-containing organic compounds of nickel, nickel carbonate, nickel hydroxide, nickel phosphate, nickel phosphite, nickel formate, nickel fumarate, nickel molybdate, nickel tungstate, nickel oxide, nickel alloys, cyclopentadienyl nickel, nickel naphthenate, and mixtures thereof.