Naphthene ring opening over self-supported multi-metallic catalysts

Patent metadata

Field	Value
Publication number	US-9919987-B1
Application number	US-201615358248-A
Country	US
Kind code	B1
Filing date	Nov 22, 2016
Priority date	Nov 22, 2016
Publication date	Mar 20, 2018
Grant date	Mar 20, 2018

Abstract

A process is disclosed for opening naphthenic rings of naphthenic ring-containing compounds. Naphthene ring opening is achieved using a self-supported mixed metal sulfide catalyst comprising nickel sulfide, molybdenum sulfide, tungsten sulfide and an organic complexing agent. The catalyst is characterized as having a composition of metal components, in terms of molar ratios; as follows: 0.25≤Ni/(Ni+Mo+W)≤0.80; 0<Mo/(Ni+Mo+W)≤0.25; 0.12≤W/(Ni+Mo+W)≤0.50; and 1.5≤W/Mo≤3.0.

First claim

The invention claimed is:

1. A process for selective opening naphthene rings of naphthene ring-containing compounds in a feed stream, the process comprising:
contacting a naphthene ring-containing feed stream under ring opening conditions with hydrogen and a self-supported mixed metal sulfide catalyst comprising nickel sulfide, molybdenum sulfide, tungsten sulfide and an organic complexing agent, thereby forming a ring-opened product having increased linear paraffin functionality relative to that of the naphthene ring-containing feed stream;
wherein the self-supported mixed metal sulfide catalyst is characterized as having a composition of metal components, in terms of molar ratios, as follows:
(a) 0.25≤Ni/(Ni+Mo+W)≤0.80;
(b) 0<Mo/(Ni+Mo+W)≤125;
(c) 0.12≤W/(Ni+Mo+W)≤0.50; and
(d) 1.5<W/Mo<3.0,
wherein the organic complexing agent is maleic acid.

2. The process of claim 1 , wherein the naphthene ring-containing feed stream has a nitrogen content of at least 50 wppm and a sulfur content of at least 100 wppm.

3. The process of claim 1 , wherein the ring opening conditions include a temperature of from 550° F. to 840° F. (288° C. to 449° C.); a hydrogen partial pressure of from 250 to 5000 psig (1.8 to 34.6 MPa); a liquid hourly space velocity of from 0.05 to 10 h −1 ; and a hydrogen treat gas rate of from 200 to 10,000 SCFB (35.6 to 1781 m 3 /m 3 ).

4. The process of claim 1 , further comprising recovering the ring-opened product.

5. The process of claim 4 , further comprising blending the ring-opened product with a petroleum stream having a boiling point from 175° C. to 600° C., wherein a blend of the ring-opened product and the petroleum stream has a cetane number of at least 40.

6. The process of claim 1 , wherein the self-supported mixed metal sulfide catalyst is binderless.

7. The process of claim 1 , wherein the self-supported mixed metal sulfide catalyst is non-calcined.

8. The process of claim 1 , wherein the W/Mo molar ratio is in a range of 2.0 to 2.8.

9. The process of claim 1 , wherein the self-supported mixed metal sulfide catalyst is characterized as having a molar ratio of metal components Ni, Mo and W in a range of:
(a) 1.08≤Ni/(Mo+W)≤2.03;
(b) 0<Mo/(Ni+W)≤0.18; and
(c) 0.20≤W/(Ni+Mo)≤0.72.

10. The process of claim 1 , wherein the self-supported mixed metal sulfide catalyst has a multi-phased structure comprising five phases: (1) a molybdenum sulfide phase; (2) a tungsten sulfide phase; (3) a molybdenum tungsten sulfide phase; (4) an active nickel phase; and (5) a nickel sulfide phase.

11. The process of claim 10 , 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) combinations thereof.

12. The process of claim 10 , wherein the active nickel phase comprises at least one of atomic nickel and reduced nickel substituted into the molybdenum tungsten sulfide phase.

13. The process of claim 10 , wherein the nickel sulfide phase comprises slabs of at least one of Ni 9 S 8 and Ni 3 S 2 crystals.

Assignees

• Chevron Usa Inc

Inventors

• Zhan Bi-Zeng
• Kuperman Alexander

Classifications

• B01J37/20

  Sulfiding · CPC title

• C07C5/2732

  Catalytic processes · CPC title

• B01J27/051

  Molybdenum · CPC title

• C07C2527/051

  Molybdenum · CPC title

• C10G2300/1037

  Hydrocarbon fractions · CPC title