US3876530A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Multiple stage hydrodesulfurization with greater sulfur and metal removal in initial stage
Assignee: Gulf Research and Development Co
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Filing: 1973-08-22
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Granted: 1975-04-08
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Expires: 1993-08-22
Abstract
Abstract A multiple stage process is described for the catalytic hydrodesulfurization and hydrodemetallization of a residual petroleum oil boiling above the gasoline range. The product of the process comprises essentially material boiling above the gasoline range and comprises little material boiling below the initial boiling point of the residual oil feed. The hydrodesulfurization-demetallization process comprises an initial stage involving relatively high hydrogen pressure in the presence of a catalyst comprising a relatively low proportion of catalytically active hydrogenation metals in which demetallization activity is high with an unaged catalyst but diminishes as the catalyst becomes aged. The process employs a final stage in series having a relatively lower hydrogen pressure and a catalyst comprising a relatively higher proportion of hydrogenation metals in which the demetallization activity is lower with an unaged catalyst but increases as the catalyst becomes aged. The stream entering the final stage contains an amount up to 10, 20 or even 25 weight percent of the asphaltene content of the charge to the first stage while the effluent from the final stage is essentially free of asphaltenes.
Inventors
- 👤 James A Frayer
- 👤 Daniel Y Ko
- 👤 John A Paraskos
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 16:04
CPC Classifications
C; C10; C10G; C10G45/00; C10G45/02; C10G45/04; C10G45/06; C10G45/08; C10G2300/00; C10G2300/10; C10G2300/107
Claims Analysis
Total Claims: 15
Claim 1
Independent Claim
178 words
A PROCESS FOR HYDRODESULFURIZING A FEED RESIDUAL PETROLEUM OIL CONTAINING ASPHALTENES, METALS AND SULFUR IN A PLURALITY OF STAGES IN SERIES INCLUDING AN INITIAL STAGE AND A FINAL STAGE EACH OPERATING AT A HYDROGEN PRESSURE ABOVE 1,000 PSI AND AT A TEMPERATURE BETWEEN ABOUT 650* TO 800*F., EACH STAGE EMPOLYING A CATALYST COMPRISING GROUP VI AND GROUP VIII METALS ON ALUMINA THE CATALYST IN SAID FINAL STAGE COMPRISING A HIGHER WEIGHT PERCENT OF GROUP VI AND GROUP VIII METALS THAN THE CATALYST IN SAID INITIAL STAGE, INCREASING THE TEMPERATURE IN EACH STAGE WITH INCREASING CATALYST AGE TO COMPENSATE FOOR CATALYST ACTIVITY AGING LOSS, MAINTAINING A LOWER HYDROGEN PRESSURE IN SAID FINAL STAGE IN SAID INITIAL STAGE, REMOVING ASPHALTENES, METALS AND SULFUR FROM THE FEED OIL IN SAID INITIAL AND SAID FINAL STAGE SAID PROCESS PRODUCING HYDRODESULFURIZED EFFLUENT WITH A SMALLER TOTAL AMOUNT OF CATALYST THAN IF SAID INITIAL AND FINAL STAGES OPERATED AT THE SAME HYDROGEN PRESSURE AND WITH CATALYST HAVING THE SAME PERCENT OF GROUP VI AND GROUP VIII METALS TO ACHIEVE THE SAME AMOUNT OF DESULFURIZTION.
Claim 2
Dependent Claim
178 words
A PROCESS FOR HYDRODESULFURIZING A FEED RESIDUAL PETROLEUM OIL CONTAINING ASPHALTENES, METALS AND SULFUR IN A PLURALITY OF STAGES IN SERIES INCLUDING AN INITIAL STAGE AND A FINAL STAGE EACH OPERATING AT A HYDROGEN PRESSURE ABOVE 1,000 PSI AND AT A TEMPERATURE BETWEEN ABOUT 650* TO 800*F., EACH STAGE EMPOLYING A CATALYST COMPRISING GROUP VI AND GROUP VIII METALS ON ALUMINA THE CATALYST IN SAID FINAL STAGE COMPRISING A HIGHER WEIGHT PERCENT OF GROUP VI AND GROUP VIII METALS THAN THE CATALYST IN SAID INITIAL STAGE, INCREASING THE TEMPERATURE IN EACH STAGE WITH INCREASING CATALYST AGE TO COMPENSATE FOOR CATALYST ACTIVITY AGING LOSS, MAINTAINING A LOWER HYDROGEN PRESSURE IN SAID FINAL STAGE IN SAID INITIAL STAGE, REMOVING ASPHALTENES, METALS AND SULFUR FROM THE FEED OIL IN SAID INITIAL AND SAID FINAL STAGE SAID PROCESS PRODUCING HYDRODESULFURIZED EFFLUENT WITH A SMALLER TOTAL AMOUNT OF CATALYST THAN IF SAID INITIAL AND FINAL STAGES OPERATED AT THE SAME HYDROGEN PRESSURE AND WITH CATALYST HAVING THE SAME PERCENT OF GROUP VI AND GROUP VIII METALS TO ACHIEVE THE SAME AMOUNT OF DESULFURIZTION.
Claim 3
Dependent Claim
30 words
The process of claim 1 wherein the final temperature in said initial and final stage is about the same and is reached at about the same time in process operation.
Claim 4
Dependent Claim
23 words
The process of claim 1 wherein the hydrodesulfurized effluent comprises more than 90 volume percent boiling above the gasoline range based on feed.
Claim 5
Dependent Claim
23 words
The process of claim 1 wherein the hydrodesulfurized effluent comprises more than 95 volume percent boiling above the gasoline range based on feed.
Claim 6
Dependent Claim
23 words
The process of claim 1 wherein the hydrodesulfurized effluent comprises more than 98 volume percent boiling above the gasoline range based on feed.
Claim 7
Dependent Claim
35 words
The process of claim 1 wherein the initial stage catalyst deactivation is due primarily to saturative metals-loading on the catalyst and the final stage catalyst deactivation is due primarily to coke formation on the catalyst.
Claim 8
Dependent Claim
38 words
The process of claim 6 wherein said saturative metals-loading occurs when the most saturated portion of the catalyst contains 40 to 50 weight percent of Group VI plus Group VIII metals plus metals deposited from the feed oil.
Claim 9
Dependent Claim
25 words
The process of claim 1 wherein the termination catalyst age is at least 6 barrels of feed oil per pound of catalyst in a stage.
Claim 10
Dependent Claim
25 words
The process of claim 1 wherein the termination catalyst age is at least 10 barrels of feed oil per pound of catalyst in a stage.
Claim 11
Dependent Claim
25 words
The process of claim 1 wherein the termination catalyst age is at least 12 barrels of feed oil per pound of catalyst in a stage.
Claim 12
Dependent Claim
33 words
The process of claim 1 wherein the hydrogen pressure in the final stage is in the range 1400 to 1600 psi and the hydrogen pressure in the initial stage is above this range.
Claim 13
Dependent Claim
30 words
The process of claim 1 wherein the hydrogen pressure in the final stage is 1400 to 1700 psi and the hydrogen pressure in the initial stage is above this range.
Claim 14
Dependent Claim
28 words
In the process of claim 1, passing said feed oil through said process while the feed oil demetallization/desulfurization ratio decreases in said initial stage with increasing catalyst age.
Claim 15
Dependent Claim
15 words
The process of claim 1, including a hydrodesulfurization stage between said initial and final stages.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1978-04-07 | 1978-10-07 | 1979-04-08 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-04-07 | 1982-10-07 | 1983-04-08 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-04-07 | 1986-10-07 | 1987-04-08 | $7700.00 | Window Closed / Lapsed |