Hydroconversion multi-metallic catalysts and method for making thereof

• US 9,504,993 B2
• Filed: 09/05/2013
• Issued: 11/29/2016
• 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.
• Primary Examiner(s): SWAIN, MELISSA STALDER
• Application Number:
  US14/019,360
• Publication Number:
  US 20140066294A1
• Time in Patent Office: 1,181 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 self-supported MMS catalyst consists essentially of molybdenum sulfide and tungsten sulfide, wherein the catalyst contains at least 0.1 mol % of Mo and at least 0.1 mol % of W, on a transition metal basis.

Claims

1. A mixed metal sulfide (MMS) catalyst consisting of molybdenum sulfide and tungsten sulfide, wherein the catalyst contains at least 0.1 mol % of Mo and at least 0.1 mol % of W;

and wherein the mixed metal sulfide catalyst is self-supported.

2. The self-supported MMS catalyst of claim 1, wherein the catalyst is characterized as having a molybdenum sulfide and tungsten sulfide phase comprising at least a layer containing 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 catalyst is characterized as having a molybdenum sulfide and tungsten sulfide phase comprising at least two layers, and wherein the at least two layers comprise 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 catalyst is prepared by sulfiding a molybdenum metal precursor and a tungsten metal precursor in an amount sufficient for the catalyst to contain at least 0.1 mol % of Mo and 0.1 mol % of W.

11. The self-supported MMS catalyst of claim 10, 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.

12. The self-supported MMS catalyst of claim 10, 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.

13. The self-supported MMS catalyst of claim 10, wherein the catalyst is prepared by sulfiding a molybdenum metal precursor and a tungsten metal precursor under a H₂-containing gas pressure with at least a sulfiding agent at a temperature ranging from 25°

C. to 500°

C. from 10 minutes to 15 days.

14. The self-supported MMS catalyst of claim 1, wherein the molybdenum sulfide is MoS_2+e and the tungsten sulfide is WS_2+e, and wherein e has a value between 0 and 1.