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Process for the desulfurization of hydrocarbon oils with water vapor addition to the reaction zone

Assignee: Shell USA Inc
•
Filing: 1976-02-09
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Granted: 1977-10-04
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Expires: 1996-02-09
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Abstract

Abstract A hydrodesulfurization process for vanadium-containing ols and certain hydrogenative metal-containing supported catalysts, wherein after deposition of certain amount of vanadium on the catalyst in the absence of added water vapor, water vapor is added to the reaction zone resulting in long-lived, low-cost desulfurization.

Inventors

  • 👤 Karel M. A. Pronk

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-30 09:01
CPC Classifications
C; C10; C10G; C10G45/00; C10G45/02; C10G2300/00; C10G2300/10; C10G2300/107

Claims Analysis

Total Claims: 11
Claim 1
Independent Claim 183 words
A continuous process for the catalytic hydrodesulfurization of vanadium-containing heavy hydrocarbon oils which comprises (a) contacting in a reaction zone vanadium-containing heavy hydrocarbon oil at elevated temperature and pressure with hydrogen and with a catalyst which contains from about 0.5 to 20 parts by weight of nickel and/or cobalt and from about 2.5 to 60 parts by weight of molybdenum and/or tungsten per 100 parts by weight of a porous carrier selected from the group consisting of alumina, silica, magnesia, zirconia and mixtures thereof and in the absence of added water vapor until the average vanadium content of the catalyst has increased during said contacting by at least 5 parts by weight per 100 parts by weight of said catalyst and (b) adding and maintaining a quantity of water vapor to the reaction zone after said vanadium content of said catalyst has increased during said contacting by at least 5 parts by weight per 100 parts by weight of said catalyst, said quantity of water corresponding to a water vapor partial pressure in the range from 0.5 to 30 bar during the process.
Claim 2
Dependent Claim 183 words
A continuous process for the catalytic hydrodesulfurization of vanadium-containing heavy hydrocarbon oils which comprises (a) contacting in a reaction zone vanadium-containing heavy hydrocarbon oil at elevated temperature and pressure with hydrogen and with a catalyst which contains from about 0.5 to 20 parts by weight of nickel and/or cobalt and from about 2.5 to 60 parts by weight of molybdenum and/or tungsten per 100 parts by weight of a porous carrier selected from the group consisting of alumina, silica, magnesia, zirconia and mixtures thereof and in the absence of added water vapor until the average vanadium content of the catalyst has increased during said contacting by at least 5 parts by weight per 100 parts by weight of said catalyst and (b) adding and maintaining a quantity of water vapor to the reaction zone after said vanadium content of said catalyst has increased during said contacting by at least 5 parts by weight per 100 parts by weight of said catalyst, said quantity of water corresponding to a water vapor partial pressure in the range from 0.5 to 30 bar during the process.
Claim 3
Dependent Claim 37 words
A process as in claim 1, wherein the addition of water vapor to said hydrodesulfurization is started in said process after the average vanadium content of a catalyst has increased by at least 10 parts by weight.
Claim 4
Dependent Claim 30 words
A process as in claim 1, wherein the desulfurization temperature has been increased to approximately the maximum allowable value in said hydrodesulfurization prior to the addition of said water vapor.
Claim 5
Dependent Claim 35 words
A process as in claim 1, wherein said quantity of water vapor added to said desulfurization process corresponds to a water vapor partial pressure in the range from 1 to 15 bar during the process.
Claim 6
Dependent Claim 28 words
A process as in claim 1, wherein in the catalyst the atomic ratio of said nickel and/or cobalt to said molybdenum and/or tungsten is between 0.1 and 5.
Claim 7
Dependent Claim 26 words
A process as in claim 1, wherein said catalyst is in sulfide form and the carrier is selected from the group consisting of silica and silica-alumina.
Claim 8
Dependent Claim 65 words
A process as in claim 1, wherein the temperature is in the range of 300°-475° C, the hydrogen partial pressure is in the range of 30-200 bar, the space velocity is in the range of 0.1-10 parts by weight of oil per part by volume of catalyst per hour and the hydrogen/oil ratio is in the range of 150-2,000 Nl H 2 /kg of oil.
Claim 9
Dependent Claim 65 words
A process as in claim 7 wherein the temperature is in the range of 350°-450° C, the hydrogen partial pressure is in the range of 50-150 bar, the space velocity is in the range of 0.5-3 parts by weight of oil per part by volume of catalyst per hour and the hydrogen/oil ratio is in the range of 250-1,000 Nl H 2 /kg of oil.
Claim 10
Dependent Claim 22 words
A process as in claim 1, wherein the desulfurization step (a) is preceded by a demetallization treatment of the heavy hydrocarbon oil.
Claim 11
Dependent Claim 32 words
A process as in claim 9, wherein the desulfurization step (a) is preceded by a catalytic hydrodemetallization treatment of the heavy hydrocarbon oil over a nickel and vanadium on silica demetallization catalyst.

References Cited (Backward Citations)

US3116234A Cited
US3112257A Cited
US3471398A Cited
US3536607A Cited
US3501396A Cited
US3617481A Cited
US3753894A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1980-10-03 1981-04-04 1981-10-04 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1984-10-03 1985-04-04 1985-10-04 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1988-10-03 1989-04-04 1989-10-04 $7700.00 Window Closed / Lapsed

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