Claims
- 1. A process for removing sulfur from organic sulfur compounds of a feed hydrocarbon stream comprising the steps of:
contacting the hydrocarbon stream with a sufficient amount of an oxidizing agent at oxidation conditions to oxidize the organic sulfur compounds in the feed hydrocarbon stream; contacting the feed hydrocarbon stream containing oxidized organic sulfur compounds with sufficient amounts of hydrogen at hydrodesulfurization conditions over a hydrodesulfurization catalyst to produce hydrocarbon stream with substantially lower sulfur content and a gas stream containing hydrogen sulfide; and recovering the hydrocarbon stream containing substantially less sulfur than the feed hydrocarbon.
- 2. The process of claim 1, wherein oxidizing the organic sulfur compounds to produce substantially oxidized organic sulfur compounds comprises the steps of:
contacting the hydrocarbon stream with an aqueous oxidizing agent for oxidizing organic sulfur compounds comprising:
from about 0.5% to about 4.5% hydrogen peroxide; from about 75 wt % to about 92 wt % of a C1 to C4 carboxylic acid; and water in an amount not to exceed about 25 wt %; and extracting at least part of the oxidized organic sulfur compounds from the hydrocarbon stream into the aqueous oxidizer composition; and separating the aqueous oxidizing agent from the hydrocarbon stream prior to the hydrodesulfurization step.
- 3. The process of claim 1 which comprises contacting the hydrocarbon containing oxidized sulfur compounds in the presence of a hydrotreating catalyst at a temperature greater than about 100° C., at a pressure greater than about 100 psig, at a liquid hourly space velocity of from about 0.2 to about 10.0, and at a gas flow rate of from about 100 to about 5,000 standard cubic feet per barrel having at least about 70% hydrogen.
- 4. The process of claim 3, wherein the temperature is from about 100° C. to about 400° C. and the pressure is from about 100 psig to about 1000 psig.
- 5. The process of claim 1, wherein the hydrocarbon stream with substantially lowered sulfur content which is recovered contains less than about 50 ppm by weight of sulfur.
- 6. A process for removing sulfur from a hydrocarbon stream boiling in the diesel full range comprising the steps of:
contacting the hydrocarbon stream containing organic sulfur compounds at a temperature of from about 90° C. to about 105° C. for a period of time up to about 15 minutes with an oxidizing agent comprising:
from about 79 wt % to about 89 wt % formic acid, from about 2 wt % to about 3 wt % hydrogen peroxide, and from about 8 wt % to about 14 wt % water: in an amount such that the molar ratio of formic acid to hydrogen peroxide is from about 12:1 to about 60:1, wherein the amount of oxidizing agent added is such that there is a stoichiometric excess of hydrogen peroxide over that which is necessary to oxidize the sulfur present in the hydrocarbon creating an aqueous phase and a hydrocarbon phase; separating the aqueous phase and recovering the hydrocarbon phase containing oxidized sulfur compounds; contacting the recovered hydrocarbon stream containing the oxidized sulfur compounds with a hydrodesulfurization catalyst at a temperature of from about 100° C. to about 400° C., at a pressure of from about 100psig to about 1,000 psig, at a liquid hourly space velocity of from about 0.2 to about 10.0, and at a gas flow rate of from about 100 to about 5,000 standard cubic feet per barrel having at least 70% hydrogen to produce a diesel product stream containing less than about 5 ppm sulfur and a gas stream containing hydrogen sulfide; and recovering the diesel product.
- 7. A process for reducing the sulfur content of a hydrocarbon stream which comprises the steps of:
contacting the hydrocarbon stream containing the organic sulfur compounds with an effective amount of an alkaline earth metal peroxide stream which, upon activation, produces hydrogen peroxide in situ to form a reaction mixture in which the organic sulfur can be oxidized; and an effective, activating amount of an acid which reacts with the peroxide to generate hydrogen peroxide in situ, which reacts with the organic sulfur present in the hydrocarbon stream to form organic sulfones and sulfoxides corresponding to the sulfur compounds in the hydrocarbon stream; recovering a hydrocarbon stream having substantially all sulfur as oxidized sulfur compounds from the reaction mixture; hydrotreating the hydrocarbon stream having substantially all sulfur as oxidized sulfur compounds to produce a hydrogen sulfide stream and a substantially sulfur free hydrocarbon product; and recovering the substantially sulfur free hydrocarbon product.
- 8. A process for removing sulfur from a hydrocarbon stream containing organic oxidized sulfur compounds comprising the steps of:
contacting the hydrocarbon stream containing up to about 6 wt % total sulfur as organic sulfones or sulfoxides with a hydrodesulfurization catalyst at hydrodesulfurization conditions with a gas stream containing at least about 70% hydrogen to form a gas stream containing substantial amounts of hydrogen sulfide and a hydrocarbon stream substantially free of sulfur.
- 9. The process of claim 8 wherein hydrodesulfurization conditions comprises contacting the hydrocarbon containing oxidized sulfur compounds with a hydrotreating catalyst at a temperature from about 100° C. to about 400° C., at a pressure greater than about 100 psig, at a liquid hourly space velocity of from about 0.2 to about 10.0, and at a gas flow rate of from about 100 to about 5,000 standard cubic feet per barrel.
- 10. A process for removing sulfur from a hydrocarbon stream comprising the steps of:
oxidizing the sulfur compounds in the hydrocarbon stream to produce organic oxidized sulfur compounds comprising the steps of: contacting the hydrocarbon stream with an oxidizer composition for oxidizing organic sulfur compounds comprising from about 0.5% to about 4.5% hydrogen peroxide, from about 75 wt % to about 92 wt % of a C1-C4 carboxylic acid, water in an amount not to exceed about 25 wt %, and during such oxidation, extracting at least part of the oxidized organic sulfur compounds from hydrocarbon in an aqueous spent oxidizer phase; and recovering the hydrocarbon containing the oxidized sulfur compounds from the aqueous spent oxidizer; and contacting the hydrocarbon containing oxidized sulfur compounds with a hydrotreating catalyst at a temperature greater than about 100° C., at a pressure greater than about 100 psig, at a liquid hourly space velocity of from about 0.2 to about 10.0, and at a gas flow rate of from about 100 to about 5,000 standard cubic feet per barrel having at least about 70% hydrogen to form hydrogen sulfide gas and a hydrocarbon stream substantially free of sulfur; and recovering the hydrocarbon stream having a sulfur content of from about 0.0001% to about 1 wt %.
- 11. A process for removing sulfur from a sulfur containing cracked naphtha without substantially hydrogenating the olefins of the cracked naphtha comprising the steps of:
oxidizing the sulfur compounds in the cracked naphtha to produce oxidized organic sulfur compounds; and then hydrodesulfurizing the oxidized organic sulfur compounds to produce a hydrogen sulfide stream and a substantially sulfur free naphtha product.
- 12. The process of claim 11, wherein oxidizing the sulfur compounds to produce oxidized organic sulfur compounds comprises the steps of: contacting the sulfur containing cracked naphtha with an effective amount of an aqueous oxidizer composition comprising:
from about 0.5% to about 4.5% hydrogen peroxide; from about 75 wt % to about 92 wt % of a C1-C4 carboxylic acid; and water in an amount not to exceed about 25 wt %; and during such oxidation, extracting at least some of the oxidized organic sulfur compounds from the cracked naphtha into the aqueous oxidizer composition.
- 13. The process of claim 11 wherein hydrotreating the naphtha comprises contacting the naphtha containing oxidized sulfur compounds with a hydrotreating catalyst at a temperature from about 100° C. to about 400° C., at a pressure greater than about 100 psig, at a liquid hourly space velocity of from about 0.2 to about 10.0, and at a gas flow rate of from about 100 to about 5,000 standard cubic feet per barrel having at least about 70% hydrogen.
- 14. The process of claim 13, wherein oxidizing the sulfur compounds in the naphtha to produce an oxidized organic naphtha stream comprises the steps of:
contacting the sulfur containing naphtha with an effective amount of an aqueous oxidizer composition comprising: from about 0.5% to about 4.5% hydrogen peroxide; from about 75 wt % to about 92 wt % of a C1-C4 carboxylic acid; and water in an amount not to exceed about 25 wt %; and during such oxidation, extracting at least some of the oxidized organic sulfur compounds from the cracked naphtha into the aqueous oxidizer.
- 15. A process for removing organic sulfur from crude oil comprising;
oxidizing the organic sulfur in the crude oil stream containing organic sulfur compounds to produce an oxidized sulfur containing crude stream; distilling the oxidized sulfur containing crude stream containing the oxidized sulfur to produce a light distillate, a medium distillate, a heavy distillate and a reduced crude; hydrotreating the light distillate to produce low sulfur gasoline and a hydrogen sulfide gas stream; hydrotreating the medium distillate to produce desulfurized diesel and heating oil and a hydrogen sulfide gas stream; and hydrotreating the heavy distillate to produce a desulfurized reduced crude feed stream to a fluid catalytic cracker feed and a hydrogen sulfide gas stream; separating the hydrogen sulfide gas stream from the desulfurized gasoline, diesel, and heating oil; and cracking the reduced crude feed stream to produce low sulfur gasoline and low sulfur diesel and heating oil.
- 16. A process for removing sulfur from a crude oil stream to form low sulfur hydrocarbon products comprising the steps of;
distilling the crude stream to produce a light distillate, a medium distillate, a heavy distillate and a reduced crude; cracking the heavy distillate to produce a cracked naphtha stream; oxidizing the light distillate, medium distillate and cracked naphtha to produce an oxidized product stream; separating the oxidized product stream to produce a gasoline stream and diesel stream; hydrotreating the gasoline to produce low sulfur gasoline and a gas stream containing hydrogen sulfide; hydrotreating the diesel stream to produce low sulfur diesel and heating oil and a gas stream containing hydrogen sulfide; and recovering the gasoline, diesel and heating oil as low sulfur product streams.
- 17. A process for refining a crude oil stream containing sulfur to produce low sulfur hydrocarbon products comprising the steps of;
distilling the crude stream to produce a light distillate, a medium distillate, a heavy distillate and a reduced crude the sulfur in the; oxidizing the sulfur containing compounds in the light distillate, the medium distillate, and the heavy distillate to produce an oxidized gasoline, an oxidized diesel and heating oil; and an oxidized feed stream, respectively; hydrotreating the oxidized gasoline to produce low sulfur gasoline; hydrotreating the oxidized diesel and heating oil to produce low sulfur diesel and heating oil; hydrotreating the oxidized feed stream to a feed stream; and cracking and separating the feed stream into a low sulfur gasoline and a low sulfur diesel/heating oil.
PRIOR RELATED APPLICATIONS
[0001] This application claims priority to U. S. Provisional Application No. 60/311,646 filed on Aug. 10, 2001, which is incorporated in its entirety by reference herein.
Provisional Applications (1)
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Number |
Date |
Country |
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60311646 |
Aug 2001 |
US |