Catalytic hydrodesulfurization of organic compounds employing alumina promoted with zinc titanate, cobalt and molybdenum as the catalytic agent

• US 4,287,050 A
• Filed: 02/28/1980
• Issued: 09/01/1981
• Est. Priority Date: 02/28/1980
• Status: Expired due to Term

• Current Assignee: Phillips Petroleum Company (ConocoPhillips)
• Original Assignee: Phillips Petroleum Company (ConocoPhillips)
• Inventors: Eastman, Alan D., Gardner, Lloyd E.
• Primary Examiner(s): Hearn, Brian E.
• Application Number:
  US06/125,437
• Time in Patent Office: 551 Days
• Field of Search: 208/213, 208/215, 208/216 R, 208/217
• US Class Current: 208/215
• CPC Class Codes: B01J 23/8873 Zinc, cadmium or mercury
• CPC Class Codes: C10G 45/08 in combination with chromium, molybdenum, or tungsten metals, or compounds thereof

Abstract

The catalytic hydrodesulfurization and/or hydrodenitrogenation of an organic sulfur compound and/or an organic nitrogen compound is carried out in the presence of a catalyst composition comprising catalytic grade alumina, titanium, cobalt, zinc and molybdenum.

Claims

1. A process for the catalytic hydrodesulfurization of an organic sulfur compound comprising the step of contacting said organic sulfur compound under suitable hydrodesulfurization conditions with a catalyst composition comprising catalytic grade alumina, zinc titanate, cobalt, and molybdenum.

2. A process in accordance with claim 1 wherein said organic sulfur compound is selected from the group consisting of sulfides, disulfides, mercaptans, thiophenes, benzothiophenes, dibenzothiophenes and the like and mixtures of any two or more thereof.

3. A process in accordance with claim 1 wherein said catalyst composition is prepared by calcining a mixture of zinc oxide and titanium dioxide in the presence of free oxygen at a temperature in the range of about 650°

C. to about 1050°

C. to form zinc titanate, adding the thus formed zinc titanate to the catalytic grade alumina, adding cobalt and molybdenum to the catalytic grade alumina, and calcining the catalytic grade alumina to which zinc titanate, cobalt and molybdenum have been added in the presence of free oxygen at a temperature in the range of about 500°

to about 650°

C., said cobalt and molybdenum being present in said catalyst composition in the oxide form after the calcining step.

4. A process in accordance with claim 1 wherein the total concentration of the oxides of titanium, cobalt, zinc and molybdenum is in the range of about 3 to about 35 weight percent based on the total weight of the catalyst composition.

5. A process in accordance with claim 4 wherein the concentration of the oxide of titanium plus the concentration of the oxide of zinc is in the range of about 2 to about 25 weight percent based on the weight of the total catalyst composition and the concentration of the cobalt oxide plus the concentration of the molybdenum oxide is in the range of about 2 to about 25 weight percent based on the weight of the total catalyst composition.

6. A process in accordance with claim 4 wherein the concentration of the oxide of titanium plus the concentration of the oxide of zinc is in the range of about 5 to about 15 weight percent based on the weight of the total catalyst composition and the concentration of the cobalt oxide plus the concentration of the molybdenum oxide is in the range of about 10 to about 20 weight percent based on the weight of the total catalyst composition.

7. A process in accordance with claim 1 wherein the atomic ratio of zinc to titanium in said catalyst composition is in the range of about 1:

1 to about 3;

1 and the atomic ratio of cobalt to molybdenum in said catalyst composition is in the range of about 0.1;

1 to about 3;

1.

8. A process in accordance with claim 1 wherein the atomic ratio of zinc to titanium in said catalyst composition is in the range of about 1.8:

1 to about 2.2;

1 and the atomic ratio of cobalt to molybdenum in said catalyst composition is in the range of about 0.6;

1 to about 0.7;

1.

9. A process in accordance with claim 1 wherein said organic sulfur compound is contained in a fluid feed stream.

10. A process in accordance with claim 9 wherein said fluid feed stream contains aromatic hydrocarbons.

11. A process in accordance with claim 9 wherein said suitable hydrodesulfurization conditions comprise a temperature in the range of about 205°

C. to about 538°

C., a total system pressure in the range of 200 psig to about 3000 psig, a hydrogen flow rate in the range of about 100 to about 10,000 SCF/bbl and a residence time for said fluid feed stream in the presence of said catalyst composition in the range of about 0.1 to about 20 liquid volumes of said fluid feed stream per volume of said catalyst composition per hour.

12. A process in accordance with claim 9 wherein said suitable hydrodesulfurization conditions comprise a temperature in the range of about 316°

C. to about 427°

C., a total system pressure in the range of 400 psig to about 1000 psig, a hydrogen flow rate in the range of about 500 to about 3000 SCF/bbl and a residence time for said fluid feed stream in the presence of said catalyst composition in the range of about 1 to about 5 liquid volumes of said fluid feed stream per volume of said catalyst composition per hour.

13. A process in accordance with claim 9 additionally comprising the steps of:

discontinuing the flow of said fluid feed stream over said catalyst composition; and

contacting said catalyst composition, after the flow of said fluid feed stream is discontinued, with a free oxygen-containing fluid under suitable regeneration conditions to thereby regenerate said catalyst composition.

14. A process in accordance with claim 13 wherein said suitable regeneration conditions comprise a feed rate of said free oxygen-containing fluid suitable to remove substantially all of the carbonaceous deposits from said catalyst composition, a temperature in the range of about 425°

C. to about 650°

C., and a pressure in the range of about 400 to about 1000 psig.

15. A process in accordance with claim 13 additionally comprising the step of purging said catalyst composition with an inert fluid after the step of terminating the flow of said fluid feed stream and before the step of regenerating said catalyst composition.

16. A process in accordance with claim 13 additionally comprising the steps of:

terminating the flow of said free oxygen-containing fluid over said catalyst composition after said catalyst composition is substantially regenerated;

purging said catalyst composition with an inert fluid after the flow of said free oxygen-containing fluid is terminated;

terminating the flow of said inert fluid over said catalyst composition after said free oxygen-containing fluid is substantially purged from said catalyst composition; and

recontacting said catalyst composition with said fluid feed stream after the flow of said inert fluid terminated.

17. A process in accordance with claim 1 wherein said catalyst composition is completely sulfided prior to the step of contacting said organic sulfur compound with said catalyst composition.

18. A process in accordance with claim 17 wherein said catalyst composition is completely sulfided by contacting a substantially unsulfided catalyst composition with hydrogen sulfide at a temperature in the range of about 175°

C. to about 225°

C. until hydrogen sulfide is detected in the effluent flowing from said catalyst composition and then contacting said catalyst composition with hydrogen sulfide at a temperature in the range of about 350°

C. to about 400°

C. until hydrogen sulfide is detected in the effluent flowing from said catalyst composition.