US4013547A
Expired / Lapsed
US
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Desulfurization of residual petroleum oils with a catalyst calcined at higher temperatures
Assignee: Union Oil Company of California
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Filing: 1976-01-22
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Granted: 1977-03-22
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Expires: 1996-01-22
Abstract
Abstract Residual oils comprising asphaltenes, metal compounds, and refractory sulfur compounds are hydrodesulfurized by contact with a unique type of cobalt-molybdenum-alumina catalyst characterized by certain critical physical properties of surface area, pore volume, pore size distribution, and by a specific type of active surface area, all resulting from a final calcining step carried out at temperatures between about 1250° and 1400° F for a sufficient time to give a pore size distribution such that at least about 40% of the total pore volume is in pores in the 75-100 angstrom diameter range.
Inventors
- 👤 Grant A. Mickelson
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 14:01
CPC Classifications
B; B01; B01J; B01J35/00; B01J35/60; B01J23/00; B01J23/70; B01J23/76; B01J23/84; B01J23/85; B01J23/88; B01J23/882; B01J35/61; B01J35/615; B01J35/63; B01J35/633; B01J35/635; B01J35/64; B01J35/647; C; C10; C10G; C10G2300/00; C10G2300/10; C10G2300/107
Claims Analysis
Total Claims: 15
Claim 1
Independent Claim
135 words
A process for the hydrodesulfurization of a residual petroleum feedstock, which comprises contacting said feedstock in admixture with added hydrogen at elevated desulfurization temperatures and pressures with a catalyst consisting essentially of a sulfided composite of about 1-7 weight-percent CoO and 8-16 weight-percent MoO 3 supported on a carrier consisting essentially of activated alumina, said catalyst being further characterized by: a. a total surface area between about 150 and 350 m 2 /g; b. a total pore volume between about 0.3 and 0.8 ml/g, at least about 40% of said pore volume being in pores of 75-100 A diameter; and c. a pore volume in pores about 100 A diameter of between about 0.01 and 0.1 ml/g; said catalyst having been calcined at a temperature between about 1250° and 1400° F prior to said contacting.
Claim 2
Dependent Claim
135 words
A process for the hydrodesulfurization of a residual petroleum feedstock, which comprises contacting said feedstock in admixture with added hydrogen at elevated desulfurization temperatures and pressures with a catalyst consisting essentially of a sulfided composite of about 1-7 weight-percent CoO and 8-16 weight-percent MoO 3 supported on a carrier consisting essentially of activated alumina, said catalyst being further characterized by: a. a total surface area between about 150 and 350 m 2 /g; b. a total pore volume between about 0.3 and 0.8 ml/g, at least about 40% of said pore volume being in pores of 75-100 A diameter; and c. a pore volume in pores about 100 A diameter of between about 0.01 and 0.1 ml/g; said catalyst having been calcined at a temperature between about 1250° and 1400° F prior to said contacting.
Claim 3
Dependent Claim
35 words
A process as defined in claim 1 wherein at least about 50% of said pore volume is in pores of 75-100 A diameter, and less than about 25% is in pores of 30-70 A diameter.
Claim 4
Dependent Claim
26 words
A process as defined in claim 2 wherein said catalyst was calcined for at least about 1 hour at temperatures between about 1325° and 1375° F.
Claim 5
Dependent Claim
33 words
A process as defined in claim 2 wherein said catalyst is in the form of consolidated particles having a ratio of external surface area to volume of between 70 and 160 reciprocal inches.
Claim 6
Dependent Claim
113 words
A process for the hydrodesulfurization of a residual petroleum feedstock containing 1-20 weight-percent asphaltenes and 10-500 ppm metals, which comprises contacting said feedstock in admixture with 500-8,000 SCF/B of hydrogen at a temperature of 650°-850° F and a pressure of 1000-3000 psig, with a catalyst consisting essentially of a sulfided composite of 1-7 weight-percent CoO and 8-16 weight-percent MoO 3 supported on a carrier consisting essentially of activated alumina, said catalyst being further characterized by: a. a total surface area between 150 and 350 m 2 /g; b. a total pore volume between about 0.3 and 0.8 ml/g, at least about 40% of said pore volume being in pores of 75-100 A diameter;
Claim 7
Dependent Claim
113 words
A process for the hydrodesulfurization of a residual petroleum feedstock containing 1-20 weight-percent asphaltenes and 10-500 ppm metals, which comprises contacting said feedstock in admixture with 500-8,000 SCF/B of hydrogen at a temperature of 650°-850° F and a pressure of 1000-3000 psig, with a catalyst consisting essentially of a sulfided composite of 1-7 weight-percent CoO and 8-16 weight-percent MoO 3 supported on a carrier consisting essentially of activated alumina, said catalyst being further characterized by: a. a total surface area between 150 and 350 m 2 /g; b. a total pore volume between about 0.3 and 0.8 ml/g, at least about 40% of said pore volume being in pores of 75-100 A diameter;
Claim 8
Dependent Claim
116 words
c. a pore volume in pores above 100 A diameter of between about 0.01 and 0.1 ml/g; and d. a particle-form shape having a ratio of external surface area to volume of between 70 and 160 reciprocal inches; said catalyst having been prepared by the steps of: 1. slurrying an alumina hydrogel in an aqueous solution of ammonium molybdate; 2. spray drying the resulting slurry to a water content of about 10-40 weight-percent; 3. mulling the spray-dried composite with water and sufficient acid to give a pH between 3.6 and 6.0; 4. extruding the mulled composite into extrudates having a maximum overall diameter between 0.03 and 0.06 inches and a length between 0.1 and 0.25 inches;
Claim 9
Dependent Claim
116 words
c. a pore volume in pores above 100 A diameter of between about 0.01 and 0.1 ml/g; and d. a particle-form shape having a ratio of external surface area to volume of between 70 and 160 reciprocal inches; said catalyst having been prepared by the steps of: 1. slurrying an alumina hydrogel in an aqueous solution of ammonium molybdate; 2. spray drying the resulting slurry to a water content of about 10-40 weight-percent; 3. mulling the spray-dried composite with water and sufficient acid to give a pH between 3.6 and 6.0; 4. extruding the mulled composite into extrudates having a maximum overall diameter between 0.03 and 0.06 inches and a length between 0.1 and 0.25 inches;
Claim 10
Dependent Claim
13 words
calcining the resulting extrudates at a temperature between about 900° and 1400° F;
Claim 11
Dependent Claim
13 words
calcining the resulting extrudates at a temperature between about 900° and 1400° F;
Claim 12
Dependent Claim
28 words
impregnating the calcined extrudates with an aqueous solution of a thermally decomposable cobalt compound; and 7. calcining the impregnated extrudates at a temperature between 1250° and 1400° F.
Claim 13
Dependent Claim
28 words
impregnating the calcined extrudates with an aqueous solution of a thermally decomposable cobalt compound; and 7. calcining the impregnated extrudates at a temperature between 1250° and 1400° F.
Claim 14
Dependent Claim
35 words
A process as defined in claim 5 wherein at least about 50% of said pore volume is in pores of 75-100 A diameter, and less than about 25% is in pores of 30-70 A diameter.
Claim 15
Dependent Claim
29 words
A process as defined in claim 6 wherein said catalyst is calcined for at least about 1 hour at temperatures between about 1325° and 1375° F in step (7).
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1980-03-21 | 1980-09-20 | 1981-03-22 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-03-21 | 1984-09-20 | 1985-03-22 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-03-21 | 1988-09-20 | 1989-03-22 | $7700.00 | Window Closed / Lapsed |