Hydrotreating catalyst composition and processes therefor and therewith

• US 6,090,274 A
• Filed: 12/29/1998
• Issued: 07/18/2000
• Est. Priority Date: 12/29/1998
• Status: Expired due to Fees

• Current Assignee: Phillips Petroleum Company (ConocoPhillips)
• Original Assignee: Phillips Petroleum Company (ConocoPhillips)
• Inventors: Drake, Charles A., Wu, An-hsiang
• Primary Examiner(s): Griffin, Steven P.
• Assistant Examiner(s): Ildebrando, Christina
• Application Number:
  US09/221,814
• Time in Patent Office: 567 Days
• Field of Search: 502/64, 502/71, 502/77, 208/216 R, 208/209, 208/251 H, 208/254 H, 208/143
• US Class Current: 208/216.00R
• CPC Class Codes: B01J 29/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• CPC Class Codes: B01J 29/48 containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• CPC Class Codes: C10G 45/12 containing crystalline alumino-silicates, e.g. molecular sieves

Abstract

A nitrided calcined modified zeolite composition having incorporated therein a molybdenum promoter and a co-promoter. A carburized nitrided calcined modified zeolite composition having incorporated therein a molybdenum promoter and a co-promoter. Producing the composition by incorporating a molybdenum promoter compound and a co-promoter compound into the zeolite followed by thermal treatment of the resulting zeolite with a nitriding agent and, optionally, further thermally treating the resulting zeolite with a hydrocarbon, preferably in the presence of hydrogen. A hydrotreating process that contacts a hydrocarbon-containing fluid with the nitrided, optionally carburized, calcined modified zeolite composition under a condition sufficient to effect the reduction of sulfur content in the hydrocarbon-containing fluid.

Claims

1. A composition comprising a ZSM-5 zeolite having incorporated therein a nitrided promoter incorporating molybdenum in combination with a co-promoter chosen from among the group consisting of boron, magnesium, phosphorus, sulfur, tin, titanium and zirconium thereby providing a nitrided co-promoted ZSM-5 zeolite.

2. A composition according to claim 1 wherein the nitrided co-promoted ZSM-5 zeolite is a carburized nitrided co-promoted ZSM-5 zeolite.

3. A composition according to claim 1 wherein the weight ratio of said promoter to said zeolite is in the range of from about 0.0001:

1 to about 1;

1.

4. A composition according to claim 2 wherein the weight ratio of said promoter to said zeolite is in the range of from about 0.0001:

1 to about 1;

1.

5. A composition according to claim 1 wherein the weight ratio of said promoter to said zeolite is in the range of from 0.005:

1 to 0.75;

1.

6. A composition according to claim 2 wherein the weight ratio of said promoter to said zeolite is in the range of from 0.005:

1 to 0.75;

1.

7. A composition according to claim 2 wherein at least one promoter is a metal carbide and the weight ratio of carbon to said metal is in the range of from about 0.01:

1 to about 50;

1.

8. A composition according to claim 2 wherein at least one promoter is a metal carbide and the weight ratio of carbon to said metal is in the range of from 0.1:

1 to 10;

1.

9. A composition according to claim 7 wherein the weight ratio of carbon to said metal is in the range of from 0.1:

1 to 10;

1.

10. A composition comprising a ZSM-5 zeolite having impregnated thereon a promoter comprising nitrogen, molybdenum and at least one co-promoter selected from the group consisting of boron, magnesium, phosphorus, sulfur, tin, titanium and zirconium.

11. A composition according to claim 10 wherein the promoter further comprises carbon.

12. A process for producing a zeolite composition comprising

(1) contacting a ZSM-5 zeolite with (a) at least one molybdenum compound and (b) at least one compound comprising boron, magnesium, phosphorus, sulfur, tin, titanium and zirconium under a condition sufficient to incorporate said (a) and (b) compounds into said zeolite to form a modified zeolite;

(2) calcining said modified zeolite to produce a calcined modified zeolite; and

(3) contacting said calcined modified zeolite under nitriding conditions with a nitriding agent to provide a nitrided calcined modified zeolite.

13. A process according to claim 12 wherein the nitriding agent is ammonia.

14. A process according to claim 13 wherein said nitrided calcined modified zeolite is contacted with a carburizing agent under carburizing conditions.

15. A process according to claim 14 wherein the carburizing agent is a hydrocarbon.

16. A process according to claim 15 wherein the hydrocarbon is chosen from among lower alkanes.

17. A process according to claim 16 wherein the lower alkane is methane.

18. A process comprising contacting a first hydrocarbon-containing fluid, which comprises at least one saturated hydrocarbon, with a catalyst composition to produce a second hydrocarbon-containing fluid wherein said catalyst composition comprises a ZSM-5 zeolite having incorporated therein a promoter comprising at least molybdenum nitride and a nitride of a co-promoter selected from the group consisting of boron, magnesium, phosphorus, sulfur, tin, titanium and zirconium.

19. A process according to claim 18 wherein the weight ratio of said promoters to said zeolite is in the range of from 0.005:

1 to 0.75;

1.

20. A process according to claim 18 wherein at least one promoter is a metal carbide and the weight ratio of carbon to metal is in the range of from 0.1:

1 to 10;

1.

21. A process according to claim 20 wherein said catalyst composition consists essentially of a ZSM-5 zeolite having impregnated thereon nitrogen and carbon and at least an oxide of molybdenum and an oxide of a co-promoter wherein the weight ratio of said promoter to said zeolite is in the range of from about 0.0001:

1 to about 1;

1 and the weight ratio of carbon to metal is in the range of from about 0.01;

1 to about 50;

1.

22. A process according to claim 21 wherein the weight ratio of said promoter to said zeolite is in the range of from 0.005:

1 to 0.75;

1 and the weight ratio of carbon to metal is in the range of from 0.1;

1 to 10;

1.

23. A process according to claim 18 wherein said first hydrocarbon-containing fluid comprises at least one sulfur compound and said contacting is carried out in the presence of a hydrogen-containing fluid.

24. A process according to claim 21 wherein said first hydrocarbon-containing fluid comprises at least one sulfur compound and said contacting is carried out in the presence of a hydrogen-containing fluid.

25. A hydrotreating process comprising contacting, in the presence of a hydrogen-containing fluid, a hydrocarbon fluid comprising at least one saturated hydrocarbon and at least one sulfur compound with a catalyst composition under a condition sufficient to reduce the sulfur compound content in said fluid wherein said catalyst composition is prepared by the steps comprising:

(1) contacting a ZSM-5 zeolite with a molybdenum compound and a co-promoting compound selected from the group consisting of boron, magnesium, phosphorus, sulfur, tin, titanium and zirconium under a condition sufficient to incorporate said promoters onto said zeolite to form a modified zeolite;

(2) calcining said modified zeolite to produce a calcined modified zeolite; and

(3) contacting said calcined modified zeolite with ammonia under nitriding conditions to provide a nitrided calcined modified zeolite.

26. A process according to claim 25 wherein said nitrided calcined modified zeolite is further contacted with a carburizing agent under carburizing conditions to provide a carburized nitrided calcined modified zeolite.

27. A process according to claim 25 wherein said hydrocarbon fluid is selected to form the group consisting of naphthas, coker naphtha, catalytically cracked gasolines, pyrolysis gasolines, and combinations of two or more thereof.

28. A process according to claim 26 wherein said hydrocarbon fluid is selected to form the group consisting of naphthas, coker naphtha, catalytically cracked gasolines, pyrolysis gasolines, and combinations of two or more thereof.