Asphaltene hydrodesulfurization with small catalyst particles utilizing a hydrogen quench for the reaction

Abstract

The hydrodesulfurization of a crude oil or a reduced crude containing the asphaltene fraction proceeds at unexpectedly low temperatures by utilizing a catalyst comprising a Group VI and Group VIII metal on alumina when the catalyst particles are very small and have a diameter between about 1/20 and 1/10 inch and the reaction is quenched with hydrogen.

We claim: 
     
       1. A process for the hydrodesulfurization of a crude oil or a reduced crude containing the asphaltene fraction of the crude comprising passing a mixture of hydrogen and said oil through a compact bed of catalyst particles comprising a Group VI metal and Group VIII metal on alumina, the hydrogen partial pressure being .[˜]. 1000 to 5000 pounds per square inch, .[.and.]. said particles in said bed being between 1/20 and 1/40 inch in diameter .Iadd.and a throughput of at least 127 volumes of oil per volume of catalyst is continued for at least 10 days. .Iaddend. 
     
     
       2. The process of claim 1 wherein the particles in said bed are between about 1/25 and 1/36 inch in diameter. 
     
     
       3. The process of claim 1 wherein the particles in said bed are between about 1/29 and 1/34 inch in diameter. 
     
     
       4. The process of claim 1 wherein the catalyst comprises nickel-cobalt-molybdenum on alumina. 
     
     
       5. The process of claim 1 including the step of applying a hydrogen quench to said bed to control the temperature thereof. 
     
     
       6. A process for the hydrodesulfurization of a crude oil or a reduced crude containing the asphaltene fraction of the crude comprising passing a mixture of hydrogen and said oil through a compact bed of catalyst particles comprising a Group VI metal and Group VIII metal on alumina, the hydrogen partial pressure being .[˜]. 1000 to 5000 pounds per square inch, said particles in said bed being between about 1/20 and 1/40 inch in diameter, .[.and.]. applying a hydrogen quench to said bed .Iadd.and a throughput of at least 127 volumes of oil per volume of catalyst is continued for at least 10 days. 
     
     
       7. The process of claim 6 wherein the particles in said bed are between about 1/25 and 1/36 inch in diameter. 
     
     
       8. The process of claim 6 wherein the particles in said bed are between about 1/29 and 1/34 inch in diameter. 
     
     
       9. The process of claim 6 wherein the catalyst comprises nickel-cobalt-molybdenum on alumina. 
     
     
       10. The process of claim 6 wherein the charge oil contains between about 0.002 and 0.03 weight percent of nickel and vanadium. 
     
     
       11. A process for the hydrodesulfurization of a crude oil or a reduced crude oil containing the asphaltene fraction of the crude comprising passing a mixture of hydrogen and said oil through catalyst particles comprising a Group VI metal and Group VIII metal, said particles being divided into a plurality of compact beds in series, the hydrogen partial pressure being about 1000 to 5000 pounds per square inch, said catalyst particles in said beds being between about 1/20 and 1/40 inch in diameter, applying a hydrogen quench to said catalyst beds, and continuing said process for at least 10 days and a throughout of at least 127 volumes of oil per volume of catalyst. 
     
     
       12. The process of claim 11 wherein the particles in said beds are between about 1/25 and 1/36 inch in diameter. 
     
     
       13. The process of claim 11 wherein the particles in said beds are between about 1/25 and 1/34 inch in diameter. 
     
     
       14. The process of claim 11 wherein the catalyst comprises nickel-cobalt-molybdenum on alumina. 
     
     
       15. The process of claim 11 wherein the charge oil contains between about 0.002 and 0.03 weight percent of nickel and vanadium. 
     
     
       16. The process of claim 1 wherein the hydrogen partial pressure is 1000 to 3000 pounds per square inch. 
     
     
       17. The process of claim 1 wherein the hydrogen partial pressure is 1500 to 2500 pounds per square inch.  .[.18. The process of claim 1 wherein throughput is continued for at least 10 days and 127 volumes of oil per 
     
     
        volume of catalyst..]. 19. The process of claim 6 wherein the hydrogen 
     
     
        partial pressure is 1000 to 3000 pounds per square inch. 20. The process of claim 6 wherein the hydrogen partial pressure is 1500 to 2500 pounds per square inch.  .[.21. The process of claim 6 wherein throughput is continued for at least 10 days and 127 volumes of oil per volume of 
     
     
        catalyst..]. 22. The process of claim 11 wherein the hydrogen partial 
     
     
        pressure is 1000 to 3000 pounds per square inch. 23. The process of claim 11 wherein the hydrogen partial pressure is 1500 to 2500 pounds per square inch. .Iadd. 24. Claim 1 wherein a throughput of at least 1,293 volumes of oil per volume of catalyst is continued for at least 97.6 days. .Iaddend..Iadd. 25. Claim 6 wherein a throughput of at least 1,293 volumes of oil per volume of catalyst is continued for at least 97.6 days. .Iaddend..Iadd. 26. Claim 11 wherein a throughput of at least 1,293 volumes of oil per volume of catalyst is continued for at least 97.6 days. .Iaddend.