Patent US3919402A successfully refreshed from Google Patents.
US3919402A
Expired / Lapsed
US
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Petroleum oil desulfurization process
Assignee: KVB Inc
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Filing: 1973-08-06
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Granted: 1975-11-11
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Expires: 1993-08-06
Abstract
Abstract A method of the removal of sulfur from petroleum oils in which the sulfur in the oils is oxidized in part with an oxide of nitrogen to form gaseous sulfur compounds (e.g., SO2, SO3). The sulfur containing gas can then be further used by condensing and absorbing the sulfur trioxide in concentraded sulfuric acid. Water is then added to the resulting solution of SO3 and concentrated sulfuric acid (oleum) to form additional sulfuric acid as a product. The remaining sulfur compounds in the oil may be simultaneously oxidized by a suitable oxide of nitrogen to form sulfoxides which, if desired, can be removed to further reduce the sulfur content by mixing the oxidized oil with a selective solvent, such as methanol, which is immiscible in the oil and in which the oxidized sulfur compounds will dissolve. Separation of the oil from the methanol-sulfur oxidized compound solution can be accomplished in a gravity separator or the like. The oxidizing gas is regenerated by the addition of oxygen in the feed gas or in the make-up gas and recirculated to oxidize further feeds of petroleum oils. If required, certain pretreatment steps may be used before oxidizing the oil to reduce polymerization and other side reactions such as cracking.
Inventors
- 👤 Eugene Daniel Guth
- 👤 Norman L Helgeson
- 👤 Kenneth W Arledge
- 👤 Anthony R Brienza
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 14:50
CPC Classifications
C; C01; C01B; C01B17/00; C01B17/69; C01B17/74; C10; C10G; C10G27/00; C10G27/04
Claims Analysis
Total Claims: 17
Claim 1
Independent Claim
153 words
A METHOD OF REMOVING SULFUR FROM LIQUID PETROLEUM OIL WHICH HAS BEEN FRACTIONATED TO REMOVE COMPONENTS WHICH VOLTALIZE AT THE OPERATION TEMPERATURE OF SAID METHOD, COMPRISING THE STEPS OF: A. OXIDIZING THE SULFUR COMPOUNDS IN SAID LIQUID PETROLEUM OIL AT A TEMPERATURE OF ABOUT 50* TO 350*F WITH AN OXIDIZING GAS CONTAINING (I) A TOTAL OF ABOUT 0.5 TO 15% VOLUME % OF ONE OR MORE OF THE OXIDES OF NITROGEN SELECTED FROM THE GROUP CONSISTING OF NO2, N2O3, N2O4 AND N2O5; (II) ABOUT 1-30 VOLUME % OF OXYGEN AND (III) A REMAINING VOLUME % OF GAS WHICH IS INERT IN THE OXIDATION AND SERVES AS A DILUENT OT PREVENT THE FORMATION OF AN EXPLOSIVE MIXTURE, TO DIRECTLY FORM GASEOUS SULFUR OXIDE COMPOUNDS INCLUDING GASEOUS SO3 AS A CONSTITUENT IN THE GAS PRODUCED, THEREBY REDUCING THE SULFUR CONTENT OF SAID PETROLEUM OIL; AND B. TREATING SAID SO3 GAS TO PRODUCE CONCENTRATED SULFURIC ACID.
Claim 2
Independent Claim
153 words
A METHOD OF REMOVING SULFUR FROM LIQUID PETROLEUM OIL WHICH HAS BEEN FRACTIONATED TO REMOVE COMPONENTS WHICH VOLTALIZE AT THE OPERATION TEMPERATURE OF SAID METHOD, COMPRISING THE STEPS OF: A. OXIDIZING THE SULFUR COMPOUNDS IN SAID LIQUID PETROLEUM OIL AT A TEMPERATURE OF ABOUT 50* TO 350*F WITH AN OXIDIZING GAS CONTAINING (I) A TOTAL OF ABOUT 0.5 TO 15% VOLUME % OF ONE OR MORE OF THE OXIDES OF NITROGEN SELECTED FROM THE GROUP CONSISTING OF NO2, N2O3, N2O4 AND N2O5; (II) ABOUT 1-30 VOLUME % OF OXYGEN AND (III) A REMAINING VOLUME % OF GAS WHICH IS INERT IN THE OXIDATION AND SERVES AS A DILUENT OT PREVENT THE FORMATION OF AN EXPLOSIVE MIXTURE, TO DIRECTLY FORM GASEOUS SULFUR OXIDE COMPOUNDS INCLUDING GASEOUS SO3 AS A CONSTITUENT IN THE GAS PRODUCED, THEREBY REDUCING THE SULFUR CONTENT OF SAID PETROLEUM OIL; AND B. TREATING SAID SO3 GAS TO PRODUCE CONCENTRATED SULFURIC ACID.
Claim 3
Dependent Claim
38 words
The method of claim 1 in which after treating said SO3 gas to form sulfuric acid a remaining portion of said gas produced is mixed with a make-up gas containing oxygen and recycled to serve said oxidizing gas.
Claim 4
Dependent Claim
38 words
The method of claim 1 in which said petroleum oil is pretreated prior to oxidation by thermal soaking the oil at a temperature of about 450*F for up to 6 hours, to minimize unwanted side reactions during oxidation.
Claim 5
Dependent Claim
42 words
The method of claim 1 in which said petroleum oil is pretreated by reacting any active groups in said petroleum oil with a reactant selected from the group consisting of water, hydrogen and ammonia to reduce such active groups prior to oxidation.
Claim 6
Dependent Claim
33 words
The method of claim 1 in which said petroleum oil is pretreated prior to oxidation by topping said petroleum oil by heating said petroleum oil at temperatures up to 800*F at atmospheric pressure.
Claim 7
Dependent Claim
28 words
The method of claim 1 in which said petroleum oil is pretreated prior to oxidation by heating said petroleum oil at temperatures up to 1000*F in a vacuum.
Claim 8
Dependent Claim
60 words
The method of claim 1 in which said oxidation takes place in a packed tower reactor and said liquid petroleum oil is fed into said reactor at a rate of about 0.5 to 25 gals/min/sq.ft. of reactor area; and said oxidizing gas is fed into said reactor at a flow rate of about 1 to 125 lbs/min/sq.ft. of reactor area.
Claim 9
Dependent Claim
25 words
The method of claim 1 in which during the oxidation of said liquid petroleum oil sulfoxides and sulfonic acids are formed in said petroleum oil.
Claim 10
Dependent Claim
12 words
The method of claim 1 in which said inert gas is nitrogen.
Claim 11
Dependent Claim
19 words
The method of claim 1 in which the oxidation occurs at a pressure of about 0.5 to 50 atmospheres.
Claim 12
Dependent Claim
23 words
The method of claim 1 in which the liquid petroleum oil is oxidized for a time period of about 10 to 1500 minutes.
Claim 13
Dependent Claim
28 words
The method of claim 1 in which said inert gas comprises a gas selected from the group consisting of nitrogen, argon, CO, CO2, water vapor and mixtures thereof.
Claim 14
Dependent Claim
27 words
The method of claim 1 in which NO2 is present and at least part of the NO2 used is formed by the reaction of NO and oxygen.
Claim 15
Dependent Claim
26 words
The method of claim 13 in which said oxidizing gas contains about 1-9% NO, about 1-9% NO2, about 1-19% O2 and said inert gas is nitrogen.
Claim 16
Dependent Claim
18 words
The method of claim 1 wherein step (b) is performed by absorbing said SO3 gas in sulfuric acid.
Claim 17
Dependent Claim
19 words
The method of claim 15 wherein said concentrated sulfuric acid is diluted with water and is withdrawn as required.
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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) | 1978-11-10 | 1979-05-12 | 1979-11-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-11-10 | 1983-05-12 | 1983-11-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-11-10 | 1987-05-12 | 1987-11-11 | $7700.00 | Window Closed / Lapsed |