Hydroconversion multi-metallic catalyst and method for making thereof

• US 9,327,274 B2
• Filed: 09/05/2013
• Issued: 05/03/2016
• 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:
  US14/019,319
• Publication Number:
  US 20140066293A1
• Time in Patent Office: 971 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 contains Ni:W in a mole ratio of 1:3 to 4:1, on a transition metal basis. The self supported MMS catalyst is characterized as having an HYD reaction rate constant of at least 15% higher than that of a catalyst comprising nickel sulfide alone or a catalyst comprising tungsten sulfide alone, when compared on same metal molar basis in hydrotreating of benzene as a feedstock at identical process conditions.

Claims

1. A mixed metal sulfide catalyst, comprising:

Ni₉S₈, Ni₃S₂, tungsten sulfide and an active nickel phase;

wherein the mixed metal sulfide catalyst is self-supported.

2. The mixed metal sulfide catalyst of claim 1, wherein the mixed metal sulfide catalyst has a Ni:

W mole ratio of 1;

3 to 4;

1.

3. The mixed metal sulfide catalyst of claim 1, wherein the active nickel phase comprises:

a) at least one of atomic nickel and reduced nickel; and

b) NiS_x nanoparticles, wherein 0≦

x≦

1.

4. The mixed metal sulfide catalyst of claim 1, further comprising a metal promoter selected from the group consisting of Mo, Nb, Ti, and mixtures thereof.

5. The mixed metal sulfide catalyst of claim 1, wherein the mixed metal sulfide catalyst is prepared by sulfiding a nickel metal precursor and a tungsten metal precursor in an amount sufficient for the mixed metal sulfide catalyst having a Ni:

W mole ratio of 1;

3 to 4;

1.

6. The mixed metal sulfide catalyst of claim 5, wherein the nickel metal precursor is selected from the group consisting of 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.

7. The mixed metal sulfide catalyst of claim 6, wherein the tungsten metal precursor is selected from the group consisting of 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.

8. The mixed metal sulfide catalyst of claim 5, wherein the tungsten metal precursor is selected from the group consisting of 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.