Desulfurization catalyst for hydrocarbon oils, its preparation, and use thereof

Patent metadata

Field	Value
Publication number	US-10717939-B2
Application number	US-201715789813-A
Country	US
Kind code	B2
Filing date	Oct 20, 2017
Priority date	Oct 21, 2016
Publication date	Jul 21, 2020
Grant date	Jul 21, 2020

Abstract

Disclosed is a desulfurization catalyst for hydrocarbon oils, comprising a support and at least one metal promoter selected from the group consisting of cobalt, nickel, iron and manganese, the support comprising at least one metal oxide selected from the group consisting of oxides of Group IIB, Group VB and Group VIB metals and a refractory inorganic oxide, wherein the support further comprises at least about 5% by weight of vanadium carbide, based on the total weight of the desulfurization catalyst for hydrocarbon oils. The desulfurization catalyst for hydrocarbon oils shows a good stability, a high desulfurization activity, an excellent abrasion resistance, and a long service life. Also disclosed is a process for preparing the desulfurization catalyst for hydrocarbon oils, and use of the catalyst in the desulfurization of sulfur-containing hydrocarbon oils.

First claim

The invention claimed is:

1. A desulfurization catalyst for hydrocarbon oils, comprising a support and at least one metal promoter selected from the group consisting of cobalt, nickel, iron and manganese, wherein the support comprises (1) at least one metal oxide selected from the group consisting of oxides of Group IIB, Group VB and Group VIB metals, and (2) a refractory inorganic oxide, wherein the support further comprises at least about 5% by weight of vanadium carbide, based on a total weight of the desulfurization catalyst.

2. The desulfurization catalyst for hydrocarbon oils according to claim 1 , wherein the desulfurization catalyst is substantially free of silica.

3. The desulfurization catalyst for hydrocarbon oils according to claim 1 , wherein the desulfurization catalyst comprises:
1) about 10-80% by weight of the metal oxide;
2) about 3-35% by weight of the refractory inorganic oxide;
3) about 5-40% by weight of the vanadium carbide; and
4) about 5-30% by weight of the metal promoter,
based on the total weight of the desulfurization catalyst.

4. The desulfurization catalyst for hydrocarbon oils according to claim 1 , wherein the desulfurization catalyst comprises:
1) about 40-60% by weight of the metal oxide;
2) about 8-15% by weight of the refractory inorganic oxide;
3) about 12-25% by weight of the vanadium carbide; and
4) about 12-20% by weight of the metal promoter,
based on the total weight of the desulfurization catalyst.

5. The desulfurization catalyst for hydrocarbon oils according to claim 1 , wherein the metal oxide is at least one of zinc oxide, molybdenum oxide, and vanadium oxide.

6. The desulfurization catalyst for hydrocarbon oils according to claim 1 , wherein the refractory inorganic oxide is at least one of alumina, titanium oxide, zirconium dioxide, and tin dioxide.

7. The desulfurization catalyst for hydrocarbon oils according to claim 1 , wherein the vanadium carbide has a face-centered cubic crystal structure.

8. A process for preparing the desulfurization catalyst for hydrocarbon oils according to claim 1 , comprising the steps of:
(i) preparing a support comprising at least one metal oxide selected from the group consisting of oxides of Group JIB, Group VB, and Group VIB metals, a refractory inorganic oxide, and vanadium carbide, and
(ii) loading on the support at least one metal promoter selected from the group consisting of cobalt, nickel, iron, and manganese.

9. The process according to claim 8 , wherein the step (i) further comprises the steps of:
(1a) combining vanadium carbide, a binder, water, and a liquid acid to form a slurry, and mixing the slurry with at least one metal oxide selected from the group consisting of oxides of Group JIB, Group VB, and Group VIB metals, to produce a support slurry; or
(1b) combining a binder, water, and a liquid acid to form a slurry, and mixing the slurry with at least one metal oxide selected from the group consisting of oxides of Group IIB, Group VB, and Group VIB metals, and vanadium carbide, to produce a support slurry; and
(2) subjecting the support slurry to shaping, drying, and calcination to produce a support.

10. The process according to claim 9 , wherein the binder is at least one selected from the group consisting of an aluminium binder, a titanium binder, a zirconium binder, and a tin binder; the aluminium binder being at least one selected from the group consisting of alumina hydrate powder, hydrated alumina, aluminium sol, boehmite monohydrate, pseudo-boehmite monohydrate, alumina trihydrate, and amorphous aluminium hydroxide; the titanium binder being at least one selected from the group consisting of titanium tetrachloride, ethyl titanate, isopropyl titanate, titanium acetate, hydrous titanium oxide, and anatase-type titania; the zirconium binder being at least one selected from the group consisting of zirconium tetrachloride, zirconium oxychloride, zirconium acetate, hydrous zirconium oxide, and amorphous zirconium dioxide; and the tin binder being at least one selected from the group consisting of tin tetrachloride, tin tetra-isopropoxide, tin acetate, hydrous tin oxide, and tin dioxide.

11. The process according to claim 9 , wherein the support slurry has a pH of about 1-5, and the liquid acid is an acid or an aqueous solution of an acid, and wherein the acid is selected from the group consisting of water soluble inorganic acids, organic acids, and mixtures thereof.

12. The process according to claim 8 , wherein step (ii) further comprises the steps of:
(3) incorporating a precursor of the metal promoter into the support, followed by drying and calcination to produce a catalyst precursor; and
(4) reducing the catalyst precursor under a hydrogen-containing atmosphere, to produce the desulfurization catalyst for hydrocarbon oils.

13. The process according to claim 12 , wherein the precursor of the metal promoter is at least one selected from the group consisting of acetates, carbonates, nitrates, sulfates, thiocyanates, and oxides of the metal promoter.

14. The process according to claim 8 , wherein vanadium carbide has a face-centered cubic crystal structure.

15. The process according to claim 8 , wherein the vanadium carbide has a particle size of about 2-30 μm and the vanadium carbide particles have a specific surface area of from about 10 m 2 /g to 50 m 2 /g.

16. A desulfurization catalyst for hydrocarbon oils produced by the process according to claim 8 .

17. A method for the desulfurization of sulfur-containing hydrocarbon oils, comprising the step of contacting a sulfur-containing hydrocarbon oil with a desulfurization catalyst for hydrocarbon oils according to claim 1 in the presence of hydrogen.

18. The method according to claim 17 , wherein the contacting is carried out at a temperature of about 350-500° C. under a pressure of about 0.5-4 MPa.

Assignees

• China Petroleum & Chem Corp
• Sinopec Res Inst Petroleum

Inventors

• Lin Wei
• Song Ye
• Tian Huiping
• Wang Lei
• Liu Jun

Classifications

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• B01J2235/15

  X-ray diffraction · CPC title

• B01J35/38

  Abrasion or attrition resistance · CPC title

• C10G45/04

  characterised by the catalyst used · CPC title

• B01J37/18

  with gases containing free hydrogen · CPC title