EP0565324A1 - Méthode de récupération d'un composé organique du soufre à partir d'une huile - Google Patents

Méthode de récupération d'un composé organique du soufre à partir d'une huile Download PDF

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Publication number
EP0565324A1
EP0565324A1 EP93302642A EP93302642A EP0565324A1 EP 0565324 A1 EP0565324 A1 EP 0565324A1 EP 93302642 A EP93302642 A EP 93302642A EP 93302642 A EP93302642 A EP 93302642A EP 0565324 A1 EP0565324 A1 EP 0565324A1
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Prior art keywords
organic sulfur
sulfur compound
liquid oil
oil
acid
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP93302642A
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German (de)
English (en)
Inventor
Tetsuo Aida
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Funakoshi Izumi
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Funakoshi Izumi
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen

Definitions

  • the present invention relates to a method of recovering organic sulfur compounds useful from the viewpoint of industry in the fields of production of medicines, agricultural chemicals, heat-resistant resins, etc., from mineral oils obtained from petroleum, oil sand, oil shale and coal, that is, liquid oils.
  • a technique for recovering an organic sulfur compound from an industrial gas, such as a waste gas, is disclosed in Japanese Patent Publication No. 26577/1978.
  • a waste gas containing an organic sulfur compound is absorbed into a mineral oil under pressure to recover the organic sulfur compound as a high concentration gas.
  • the method of recovering an organic sulfur compound comprises depressurizing the mineral oil, absorbing the industrial gas containing an organic sulfur compound, diffusing the organic sulfur compound by steam, circulating the industrial gas through an absorption column for reuse and, at the same time, condensing a vapor mixture comprising the diffused organic sulfur compound, the mineral oil and steam to separate the mixture into an oily layer and a watery layer, and contacting the gas generated by the depressurization with the oily layer to provide a gas containing the organic sulfur compound in a high concentration.
  • This method of recovering an organic sulfur compound is silent on the recovery of an organic sulfur compound from a mineral oil.
  • U.S. Patent 3,341,448 by Ford discloses a method of oxidizing a sulfur compound contained in a hydrocarbon, which comprises oxidizing a sulfur compound contained in a hydrocarbon with an oxidizing agent and then thermally decomposing the resultant oxide in the presence of a catalyst in a hydrogen atmosphere at high temperature.
  • the organic sulfur compound contained in a hydrocarbon is selectively oxidized and then decomposed at high temperature, so that the organic sulfur compound contained in a hydrocarbon is not recovered in such a state that the original chemical structure is maintained.
  • U.S. Patent 2,749,284 by Noble discloses a method which comprises oxidizing a sulfur compound contained in a hydrocarbon with an organic peroxide into an oxide such as a sulfoxide or a sulfone.
  • the organic peroxide disclosed in the Noble patent is poor in the oxidizing capability and the specific reactivity to the organic sulfur compound (selectivity for the reaction with the organic sulfur compound). Therefore, it acts only on particular functional groups contained in a relatively small amount in the liquid oil, for example, thiol and dialkyl sulfides, and scarcely acts on chemically stable functional groups present in a large amount in gas oil and heavy fuel oil, such as benzothiophene and dibenzothiophene derivatives.
  • U.S. Patent 4,830,733 by Nagji describes the use of an adsorbent for removing a sulfur compound from a fluid.
  • the Nagji patent is one relating to the recovery of a sulfur compound from a fluid with an adsorbent, it discloses, in essence, only the recovery of hydrogen sulfide from natural gas and does not relate to the adsorption of the oxidized fluid. Further, the substance adsorbed thereby is mainly hydrogen sulfide, and the use of a catalyst, maintenance, etc., are required of an apparatus for adsorbing the substance.
  • Amethod of separating and removing an organic sulfur compound which is mainly used for this purpose at the present time, comprises reacting a mineral oil with hydrogen gas under violent reaction conditions of a high temperature and a high pressure in the presence of a catalyst to convert the organic sulfur compound into harmful hydrogen sulfide and separating the hydrogen sulfide.
  • Such a hydrogenating desulfurization method cannot be applied when it is intended to isolate the organic sulfur compound from the mineral oil in such a state that the original chemical structure is maintained as much as possible to thereby utilizing the organic sulfur compound.
  • An aim of the present invention is to isolate an organic sulfur compound from a mineral oil in such a state that the original chemical structure thereof in the mineral oil, that is, liquid oil, is maintained as much as possible to thereby utilize the organic sulfur compound by providing a method which comprises oxidizing an organic sulfur compound with an oxidizing agent and recovering the oxidized organic sulfur compound from the system by separation means, such as distillation, in a simple and economical manner.
  • the present invention relates to a method of recovering an organic sulfur compound from a liquid oil, which comprises treating a liquid oil containing an organic sulfur compound obtained from petroleum, oil sand, oil shale or coal with an oxidizing agent, separating the oxidized sulfur compound by distillation, solvent extraction and/or adsorption means to isolate the oxidized organic sulfur compound from the liquid oil.
  • the organic sulfur compound recovered is preferably a sulfoxide compound and/or a sulfone compound.
  • the present invention relates to a method of recovering an organic sulfur compound from a liquid oil, comprising the steps of:
  • the liquid oil is preferably selected from among naphtha (b.p.: up to 30°C), gasoline (b.p.: 30 - 220 °C), kerosine (b.p.: 220 - 300 °C), gas oil (b.p.: 300 - 360 °C) and heavy fuel oil.
  • An embodiment of the present invention comprises reacting the liquid oil with a peracid oxidizing agent or a hypochlorous acid oxidizing agent at a temperature in the range of from 0 to 140°C while agitating, separating an oily phase from the reaction mixture after the reaction, adding an aqueous alkali solution to the oil to wash the same, further washing the oil with water, and recovering the resultant oxidized organic sulfur compound.
  • Another embodiment of the present invention comprises reacting the liquid oil with a gaseous oxidizing agent at a temperature in the range of -20 to 50 °C while bubbling the gaseous oxidizing agent, adding a reducing agent to the reaction mixture for washing the oil, further washing the oil with water, and recovering the resultant oxidized organic sulfur compound from the oil.
  • a further embodiment of the present invention comprises reacting the liquid oil with a gaseous oxidizing agent at a temperature in the range of -20 to 50 °C in the presence of a photosensitizer in such a manner that the gaseous oxidizing agent is bubbled while irradiating the reaction system with light, adding a reducing agent to the reaction mixture for washing the oil, further washing the oil with water, and recovering the resultant oxidized organic sulfur compound.
  • Afurther embodiment of the present invention comprises treating the liquid oil with an oxidizing agent and distilling the treated liquid oil in the boiling point range of the liquid oil before the treatment in a rectifier to recover the oxidized organic sulfur compound as a distillation residue.
  • a further, embodiment of the present invention comprises treating the liquid oil with an oxidizing agent, distilling the treated liquid oil in the boiling point range of the liquid oil before the treatment in a rectifier, and passing the distillate through a column packed with an adsorbent selected from among activated carbon, silica gel, alumina, and combinations of two or more of them to adsorb the oxidized organic sulfur compound on the adsorbent.
  • an adsorbent selected from among activated carbon, silica gel, alumina, and combinations of two or more of them to adsorb the oxidized organic sulfur compound on the adsorbent.
  • a further embodiment of the present invention comprises treating the liquid oil with an oxidizing agent, cooling the treated liquid oil to a temperature at which insoluble components deposit, allowing the oil to stand as such, separating an oily component from the system by means of a filter or a separator and distilling the oil in the boiling point range of the liquid oil before the treatment in a rectifier to recover the oxidized organic sulfur compound as a low-temperature insoluble and a distillation residue.
  • a further embodiment of the present invention comprises treating the liquid oil with an oxidizing agent, cooling the treated liquid oil to a temperature at which insoluble components deposit, allowing the oil to stand as such, separating an oily component from the system by means of a filter or a separator, distilling the oil in the boiling point range of the liquid oil before the treatment in a rectifier, and passing the distillate through a column packed with an adsorbent selected from among activated carbon, silica gel, alumina, and combinations of two or more of them to recover the oxidized organic sulfur compound remaining in the distillate.
  • the organic sulfur compound contained in the liquid oil is preferably a thiophene compound which has a divalent sulfur atom and is chemically stable.
  • the divalent sulfur atom of the thiophene compound is combined with oxygen by an oxidation reaction to convert the compound into a sulfoxide, a sulfone ora sulfonic acid containing a sulfur atom having a highervalency, and the formed sulfoxide, sulfone orsulfonic acid is recovered.
  • the recovery method of the present invention comprises pretreating a liquid oil, that is, a mineral oil with various oxidizing agents to convert an organic sulfur compound into an oxide with the original molecular skeleton thereof substantially maintained as such, and recovering the oxidized organic sulfur compound useful from the viewpoint of industry from the mineral oil in an efficient and simple manner at a low cost through the utilization of an accompanying change in the physical and chemical properties, such as the polarity, boiling point and melting point of the molecule.
  • an organic sulfur compound having a divalent sulfur atom and contained in a mineral oil is reacted with various oxidizing agents different from each other in the oxidizing capability to convert the organic sulfur compound into a sulfoxide compound and a sulfone compound successively and the reaction product is separated from other components and recovered through the utilization of a change in the physical and chemical properties of the reaction product caused by the chemical conversion.
  • the oxidized organic sulfur compound can be easily separated and recovered by distillation through the utilization of the fact that the boiling point of the oxidized organic sulfur compound is much higher than that of the organic sulfur compound in a nonoxidized state.
  • the oxidized organic sulfur compound can be selectively extracted and recovered through the utilization of a change in the solubility in various solvents based on an increase in the polarity of the molecule.
  • the change in the chemical properties remarkably improves also the adsorbability to adsorbents, such as silica gel or alumina, the adsorption, separation and purification with the use of an adosrbent can be easily conducted at a very high efficiency. Further, a combination of the above-described separation and recovery methods can provide more favorable results.
  • the method of recovering an organic sulfur compound according to the present invention enables only a particular group of organic sulfur compounds to be selectively isolated by conducting reactions while properly selecting the oxidizing agents through the utilization of the difference in the reactivity among the organic sulfur compounds per se in the mineral oil in the oxidation reaction.
  • an oxidizing agent capable of selectively oxidizing an organic sulfur compound containing a divalent sulfur atom into a sulfoxide compound alone the oxidized organic sulfur compound can be isolated as a sulfoxide.
  • an oxidizing agent having a capability of oxidizing the organic sulfur compound into a sulfone compound the oxidized organic sulfur compound can be isolated as a sulfone.
  • the mineral oil containing an organic sulfur compound is selected from among crude oil, oil shale, oil sand, coal tar, liquefied oil of coal, petroleum products obtained directly therefrom, that is, naphtha, gasoline, kerosine, gas oil, heavy fuel oil, pitch and indirect petroleum products obtained by chemical decomposition of the above-described mineral oils.
  • Examples of the oxidizing agent which may be used in the method of recovering an organic sulfur compound according to the present invention include oxygen gas, air, nitrogen tetraoxide gas, ozone gas, chlorine gas, bromine, sodium metaperiodate, potassium bichromate, potassium permanganate, anhydrous chromic acid, hypochlorous acid, hydrogen peroxide, peracetic acid, a mixture of hydrogen peroxide water with acetic acid, performic acid, a mixture of hydrogen peroxide water with formic acid, m-chloroperbenzoic acid, a mixture of hydrogen peroxide water with m-chlorobenzoic acid, perchloroacetic acid, a mixture of hydrogen peroxide water with chloroacetic acid, perdichloroacetic acid, a mixture of hydrogen peroxide water with dichloroacetic acid, pertrichloroacetic acid, a mixture of hydrogen peroxide water with trichloroacetic acid, pertrifluoroacetic acid, a mixture of hydrogen peroxide water
  • the method of recovering an organic sulfur compound according to the present invention comprises reacting a mineral oil with an organic peracid oxidizing agent or an inorganic oxidizing agent at a temperature in the range of from 0 to 100 °C with stirring, separating an oil component after the completion of the reaction, adding water to the oil component to wash the same, and recovering the resultant oxidized organic sulfur compound from the liquid oil.
  • Another embodiment of the method of recovering an organic sulfur compound according to the present invention comprises treating a liquid oil with an oxidizing agent and then with an extractant selected from among acetonitrile, propionitrile, butyronitrile, nitromethane, nitroethane, nitropropane, nitrobenzene, dimethyl sulfoxide, N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methylpyrrolidinone, trimethyl phosphate, triethyl phosphate, hexamethylphosphoric amide, phosphorane, and mixtures thereof with water in a concentration of from 0 to 50 % to recover the resultant oxidized organic sulfur compound from the liquid oil.
  • an extractant selected from among acetonitrile, propionitrile, butyronitrile, nitromethane, nitroethane, nitropropane, nitrobenzene, dimethyl sulfoxide, N,N'-dimethylformamide, N,
  • a further embodiment of the method of recovering an organic sulfur compound according to the present invention comprises treating the liquid oil with an oxidizing agent, passing the treated liquid oil through an adsorption column packed with an adsorbent selected from among activated clay, silica gel, alumina, and mixtures thereof to adsorb the formed organic sulfur oxide on the activated clay, and desorbing and separating the adsorbed organic sulfur oxide with a solvent selected from among methanol, ethanol, propanol, butanol, acetone, acetonitrile, nitromethane, and mixtures thereof to recoverthe oxidized organic sulfur compound from the liquid oil.
  • an oxidizing agent passing the treated liquid oil through an adsorption column packed with an adsorbent selected from among activated clay, silica gel, alumina, and mixtures thereof to adsorb the formed organic sulfur oxide on the activated clay, and desorbing and separating the adsorbed organic sulfur oxide with a solvent selected from among methanol, ethanol, propanol,
  • Astill furtherembodimentofthe method of recovering an organic sulfur compound according to the present invention comprises reacting a liquid oil fractoin obtained by distillation in the boiling point range as narrow as possible in a rectifying column with an oxidizing agent, separating an oil component, washing the oil component with water, and redistilling the oil component in the same boiling point range as that in the distillation of the liquid oil before the treatment with the oxidizing agent to concentrate and recover the resultant oxidized organic sulfur compound in the distillation residue.
  • a gas oil (b.p. range: 300 - 360 °C; combustible sulfur content: 0.53 % by weight) was cooled to 0 °C in a 200-ml hard glass round-bottomed flask equipped with a homogenizer agitator, a reflux condenser and a gas blow tube and agitated for one hour while passing air containing ozone (about 1.0 %) into the gas oil. After the supply of ozone was stopped, only air was further passed into the gas oil for additional one hour, and agitation was continued for additional one hour while gradually raising the temperature of the flask to 20 °C.
  • the gas oil layer was distilled in a rectifier to provide 92 ml of a fraction having a boiling point in the range of from 300 to 360 °C and 8 ml of a distillation residue.
  • the distillation fraction had a sulfur content of 0.32 % and was mainly composed of benzothiophene and dibenzothiophene derivatives.
  • the recovery of the organic sulfur compound in the distillation residue and the tar was 72 % in terms of sulfur, and the oxidation product was mainly composed of a sulfone compound.
  • the reaction mixture was cooled to 0 °C and allowed to stand to separate tar and a gas oil layer followed by washing with a 2 N aqueous sodium sulfite solution and further with water.
  • the gas oil layer was distilled in a rectifier to provide 86 ml of a fraction having a boiling point in the range of from 300 to 360 °C and 12 ml of a distillation residue.
  • the distillation fraction had a sulfur content of 0.04 % and was mainly composed of benzothiophene and dibenzothiophene derivatives.
  • the recovery of the organic sulfur compound in the distillation residue and the tar was 97 % in terms of sulfur, and the oxidation product was mainly composed of a sulfone compound.
  • the reaction mixture was cooled to 0 °C and allowed to stand to separate tar and a gas oil layer followed by washing with a 2 N aqueous sodium sulfite solution and further with water.
  • the gas oil layer was again separated, and 10 ml of nitromethane was added thereto.
  • the mixture was vigorously stirred for one hour and allowed to stand, and the gas oil layer and the nitromethane layer were separated from each other.
  • 96 ml of the resultant gas oil layer had a sulfur content of 0.03 % and was mainly composed of benzothiophene and dibenzothiophene derivatives.
  • the recovery of the organic sulfur compound in the nitromethane solution and the tar was 97 % in terms of sulfur, and the oxidation product was mainly composed of a sulfone compound.
  • the heavy fuel oil layer was again separated and 50 ml of an aqueous N,N'-dimethylformamide solution containing 10 % of water was added thereto.
  • the mixture was vigorously stirred at room temperature for one hour and allowed to stand, and the heavy fuel oil layer and the N,N'-dimethylformamide layer containing 10 % of water were separated from each other.
  • 93 ml of the resultant heavy fuel oil layer had a sulfur content of 0.21 % and was mainly composed of benzothiophene and dibenzothiophene derivatives.
  • the recovery of the organic sulfur compound in the N,N'-dimethylformamide solution and the tar was 89 % in terms of sulfur, and the oxidation product was mainly composed of a sulfone compound.
  • the mixture was vigorously stirred at room temperature for 2 hours and then allowed to stand to separate the mixture into a mineral layer and a layer of trimethyl phosphate containing 10 % of water.
  • 92 ml of the resultant heavy fuel oil layer had a sulfur content of 0.35 % and was mainly composed of benzothiophene and dibenzothiophene derivatives.
  • the recovery of the organic sulfur compound in the trimethyl phasophate solution was 83 % in terms of sulfur, and the oxidation product thereof was mainly composed of a sulfoxide compound.
  • coal tar combustible sulfur content: 0.67 % by weight
  • 10 ml of benzene as a viscosity depressant
  • 5 ml of hydrogen peroxide water (30 %) and 10 ml of formic acid were added thereto to conduct a reaction at 40 °C for 3 hours.
  • the coal tar layer was separated and washed with a 2 N aqueous sodium sulfite solution, and the coal tar layer was again separated.
  • a typical example was as follows: To 100m1 of diesel fuel 0.2 moles of t-butylhydroperoxide was added, and the mixture was vigorously stirred for one hour at room temperature and then one more hours at 80 °C. After the reaction, the mixture was washed with aqueous Na 2 SO 3 solution and fresh water. The separated diesel fuel layer was dried over anhydrous MgS0 4 . The organic sulfur components in the resulted diesel fuel was separated by the DMF-extraction and the silica-gel column chromatography. Results of these experiments are shown in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
EP93302642A 1992-04-06 1993-04-05 Méthode de récupération d'un composé organique du soufre à partir d'une huile Withdrawn EP0565324A1 (fr)

Applications Claiming Priority (2)

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JP112350/92 1992-04-06
JP11235092A JP3227521B2 (ja) 1992-04-06 1992-04-06 液状油中から有機硫黄化合物を回収する方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997020015A1 (fr) * 1995-11-27 1997-06-05 Deck Global Limited Procede et materiel de traitement d'hydrocarbures
US5958224A (en) * 1998-08-14 1999-09-28 Exxon Research And Engineering Co Process for deep desulfurization using combined hydrotreating-oxidation
US6160193A (en) * 1997-11-20 2000-12-12 Gore; Walter Method of desulfurization of hydrocarbons
US6171478B1 (en) 1998-07-15 2001-01-09 Uop Llc Process for the desulfurization of a hydrocarbonaceous oil
WO2001042397A1 (fr) * 1999-12-13 2001-06-14 Ds2 Tech, Inc. Procede de desulfuration de distillats de petrole
FR2802939A1 (fr) * 1999-12-28 2001-06-29 Elf Antar France Procede de desulfuration des derives du thiophene contenus dans les carburants
US6277271B1 (en) 1998-07-15 2001-08-21 Uop Llc Process for the desulfurization of a hydrocarbonaceoous oil
WO2002018518A1 (fr) * 2000-09-01 2002-03-07 Unipure Corporation Procede servant a extraire de faibles quantites de soufre organique de combustibles hydrocarbures
WO2002062925A2 (fr) * 2001-02-08 2002-08-15 Bp Corporation North America Inc. Preparation integree de composants de melange destinee a des carburants de transport de raffinerie
WO2002081597A1 (fr) * 2001-03-30 2002-10-17 Ohtix Inc. Procede et dispositif pour la separation de compose sulfurique dans l'huile
FR2829771A1 (fr) * 2001-09-17 2003-03-21 Solvay Procede de desulfuration et/ou de desazotation d'un melange d'hydrocarbures
US6544409B2 (en) 2001-05-16 2003-04-08 Petroleo Brasileiro S.A. - Petrobras Process for the catalytic oxidation of sulfur, nitrogen and unsaturated compounds from hydrocarbon streams
FR2839307A1 (fr) * 2002-05-03 2003-11-07 Solvay Procede de desulfuration d'un melange d'hydrocarbures
US6673230B2 (en) 2001-02-08 2004-01-06 Bp Corporation North America Inc. Process for oxygenation of components for refinery blending of transportation fuels
WO2005012458A1 (fr) * 2003-08-01 2005-02-10 Bp Corporation North America Inc. Preparation de composants pour melange de raffinerie de carburants de transport
US6872231B2 (en) 2001-02-08 2005-03-29 Bp Corporation North America Inc. Transportation fuels
US6881325B2 (en) 2001-02-08 2005-04-19 Bp Corporation North America Inc. Preparation of components for transportation fuels
WO2005061675A1 (fr) * 2003-12-23 2005-07-07 Universita' Degli Studi Di Roma 'la Sapienza' Processus de desulfuration oxydative de fractions d'hydrocarbures et installation associee
WO2006060147A1 (fr) * 2004-11-23 2006-06-08 Chinese Petroleum Corporation Desulfuration oxydative et deazotation d'huiles de petrole
EP1674158A1 (fr) 2004-12-21 2006-06-28 Petroleo Brasileiro S.A. - PETROBAS Procédé d'oxidation extractive de polluants de fuels catalysé par des oxides de fer.
US7128829B1 (en) 2003-05-29 2006-10-31 Uop Llc Removal of impurities from liquid hydrocarbon streams
US7175755B2 (en) 2003-05-06 2007-02-13 Petroleo Brasileiro S.A.-Petrobras Process for the extractive oxidation of contaminants from raw hydrocarbon streams
CN1309805C (zh) * 2005-07-12 2007-04-11 中国石油化工集团公司 一种燃料油氧化脱硫工艺
WO2007078728A2 (fr) * 2005-12-16 2007-07-12 Exxonmobil Research And Engineering Company Extraction de charges de pétrole traitées au peroxyde
CN1331987C (zh) * 2004-07-09 2007-08-15 石油大学(北京) 石油油品氧化脱硫的方法
EP1957118A2 (fr) * 2005-10-28 2008-08-20 Indian Oil Corporation Limited Procede de desulfurisation bio-oxydative de combustibles a hydrocarbures liquides et produit ainsi obtenu
US20100300938A1 (en) * 2005-09-08 2010-12-02 Martinie Gary D Process for oxidative conversion of organosulfur compounds in liquid hydrocarbon mixtures
US8016999B2 (en) 2004-05-31 2011-09-13 Agency For Science, Technology And Research Process for removing sulfur from fuels
US20120018350A1 (en) * 2010-07-20 2012-01-26 Hsin Tung Lin Mixing-assisted oxidative desulfurization of diesel fuel using quaternary ammonium salt and portable unit thereof
CN102703111A (zh) * 2012-07-03 2012-10-03 山东大学 一种基于超声辅助臭氧氧化脱硫的方法
WO2013049177A1 (fr) * 2011-09-27 2013-04-04 Saudi Arabian Oil Company Extraction liquide-liquide sélective de produits de réaction de désulfuration oxydante
US8663459B2 (en) 2006-03-03 2014-03-04 Saudi Arabian Oil Company Catalytic process for deep oxidative desulfurization of liquid transportation fuels
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WO2014138810A1 (fr) * 2013-03-15 2014-09-18 Ultraclean Pty Ltd Procédé d'élimination de composés soufrés à partir d'hydrocarbures
US8936719B2 (en) 2006-03-22 2015-01-20 Ultraclean Fuel Pty Ltd. Process for removing sulphur from liquid hydrocarbons
US9290712B2 (en) 2010-09-03 2016-03-22 Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources Canada Production of high-cetane diesel product
US9441169B2 (en) 2013-03-15 2016-09-13 Ultraclean Fuel Pty Ltd Process for removing sulphur compounds from hydrocarbons
US10125319B2 (en) 2011-07-31 2018-11-13 Saudi Arabian Oil Company Integrated process to produce asphalt and desulfurized oil
USRE48674E1 (en) 2010-07-07 2021-08-10 Finchimica S.P.A. Method for the synthesis of 5-amino-1-phenyl-3-cyano-4-trifluoromethyl sulfinyl

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Publication number Priority date Publication date Assignee Title
JP2002322482A (ja) * 2001-04-24 2002-11-08 Idemitsu Kosan Co Ltd 有機硫黄化合物含有液状油の脱硫方法
JP2002322483A (ja) * 2001-04-24 2002-11-08 Idemitsu Kosan Co Ltd 有機硫黄化合物含有液状油の脱硫方法
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JP2004055483A (ja) * 2002-07-24 2004-02-19 Idemitsu Kosan Co Ltd 燃料電池用水素の製造方法
US7074375B2 (en) * 2002-12-03 2006-07-11 Engelhard Corporation Method of desulfurizing a hydrocarbon gas by selective partial oxidation and adsorption
JP4520808B2 (ja) * 2004-10-01 2010-08-11 電源開発株式会社 有機硫黄酸化物の製造方法
US20120059204A1 (en) * 2009-05-12 2012-03-08 Wako Pure Chemical Industries, Ltd. Method for purifying organic solvent
WO2013035200A1 (fr) * 2011-09-09 2013-03-14 Aida Tetsuo Procédé pour la production de mazout à très faible teneur en soufre

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2749284A (en) * 1950-11-15 1956-06-05 British Petroleum Co Treatment of sulphur-containing mineral oils with kerosene peroxides
FR1472280A (fr) * 1965-02-23 1967-03-10 Exxon Research Engineering Co Procédé de désulfuration d'un mélange d'hydrocarbures
US3551328A (en) * 1968-11-26 1970-12-29 Texaco Inc Desulfurization of a heavy hydrocarbon fraction

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2749284A (en) * 1950-11-15 1956-06-05 British Petroleum Co Treatment of sulphur-containing mineral oils with kerosene peroxides
FR1472280A (fr) * 1965-02-23 1967-03-10 Exxon Research Engineering Co Procédé de désulfuration d'un mélange d'hydrocarbures
US3551328A (en) * 1968-11-26 1970-12-29 Texaco Inc Desulfurization of a heavy hydrocarbon fraction

Cited By (62)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997020015A1 (fr) * 1995-11-27 1997-06-05 Deck Global Limited Procede et materiel de traitement d'hydrocarbures
US6274785B1 (en) * 1997-11-20 2001-08-14 Walter Gore Method of desulfurization of hydrocarbons
US6160193A (en) * 1997-11-20 2000-12-12 Gore; Walter Method of desulfurization of hydrocarbons
US6277271B1 (en) 1998-07-15 2001-08-21 Uop Llc Process for the desulfurization of a hydrocarbonaceoous oil
US6171478B1 (en) 1998-07-15 2001-01-09 Uop Llc Process for the desulfurization of a hydrocarbonaceous oil
US5958224A (en) * 1998-08-14 1999-09-28 Exxon Research And Engineering Co Process for deep desulfurization using combined hydrotreating-oxidation
WO2001042397A1 (fr) * 1999-12-13 2001-06-14 Ds2 Tech, Inc. Procede de desulfuration de distillats de petrole
US6565741B2 (en) 1999-12-13 2003-05-20 William Wismann Process for desulfurization of petroleum distillates
FR2802939A1 (fr) * 1999-12-28 2001-06-29 Elf Antar France Procede de desulfuration des derives du thiophene contenus dans les carburants
WO2001048119A1 (fr) * 1999-12-28 2001-07-05 Elf Antar France Procede de desulfuration des derives du thiophene contenus dans des carburants
US7179368B2 (en) * 1999-12-28 2007-02-20 Elf Antar France Method for desulfurizing thiophene derivatives contained in fuels
WO2002018518A1 (fr) * 2000-09-01 2002-03-07 Unipure Corporation Procede servant a extraire de faibles quantites de soufre organique de combustibles hydrocarbures
US6402940B1 (en) 2000-09-01 2002-06-11 Unipure Corporation Process for removing low amounts of organic sulfur from hydrocarbon fuels
US6406616B1 (en) 2000-09-01 2002-06-18 Unipure Corporation Process for removing low amounts of organic sulfur from hydrocarbon fuels
AU2001279318B2 (en) * 2000-09-01 2006-03-30 Quadrant Management, Inc. Process for removing low amounts of organic sulfur from hydrocarbon fuels
KR100815598B1 (ko) 2000-09-01 2008-03-24 유니퓨어 코퍼레이션 탄화수소 연료에서 미량의 유기황 제거방법
WO2002062925A2 (fr) * 2001-02-08 2002-08-15 Bp Corporation North America Inc. Preparation integree de composants de melange destinee a des carburants de transport de raffinerie
WO2002062925A3 (fr) * 2001-02-08 2003-11-20 Bp Corp North America Inc Preparation integree de composants de melange destinee a des carburants de transport de raffinerie
US6673230B2 (en) 2001-02-08 2004-01-06 Bp Corporation North America Inc. Process for oxygenation of components for refinery blending of transportation fuels
US6872231B2 (en) 2001-02-08 2005-03-29 Bp Corporation North America Inc. Transportation fuels
US6881325B2 (en) 2001-02-08 2005-04-19 Bp Corporation North America Inc. Preparation of components for transportation fuels
WO2002081597A1 (fr) * 2001-03-30 2002-10-17 Ohtix Inc. Procede et dispositif pour la separation de compose sulfurique dans l'huile
US6544409B2 (en) 2001-05-16 2003-04-08 Petroleo Brasileiro S.A. - Petrobras Process for the catalytic oxidation of sulfur, nitrogen and unsaturated compounds from hydrocarbon streams
WO2003025097A1 (fr) * 2001-09-17 2003-03-27 Solvay (Société Anonyme) Procede de desulfuration et/ou de desazotation d'un melange d'hydrocarbures
FR2829771A1 (fr) * 2001-09-17 2003-03-21 Solvay Procede de desulfuration et/ou de desazotation d'un melange d'hydrocarbures
FR2839307A1 (fr) * 2002-05-03 2003-11-07 Solvay Procede de desulfuration d'un melange d'hydrocarbures
WO2003093203A1 (fr) * 2002-05-03 2003-11-13 Solvay (Societe Anonyme) Procédé de désulfuration d'un mélange d'hydrocarbures
US7175755B2 (en) 2003-05-06 2007-02-13 Petroleo Brasileiro S.A.-Petrobras Process for the extractive oxidation of contaminants from raw hydrocarbon streams
US7128829B1 (en) 2003-05-29 2006-10-31 Uop Llc Removal of impurities from liquid hydrocarbon streams
WO2005012458A1 (fr) * 2003-08-01 2005-02-10 Bp Corporation North America Inc. Preparation de composants pour melange de raffinerie de carburants de transport
WO2005061675A1 (fr) * 2003-12-23 2005-07-07 Universita' Degli Studi Di Roma 'la Sapienza' Processus de desulfuration oxydative de fractions d'hydrocarbures et installation associee
US8016999B2 (en) 2004-05-31 2011-09-13 Agency For Science, Technology And Research Process for removing sulfur from fuels
CN1331987C (zh) * 2004-07-09 2007-08-15 石油大学(北京) 石油油品氧化脱硫的方法
WO2006060147A1 (fr) * 2004-11-23 2006-06-08 Chinese Petroleum Corporation Desulfuration oxydative et deazotation d'huiles de petrole
US7276152B2 (en) 2004-11-23 2007-10-02 Cpc Corporation, Taiwan Oxidative desulfurization and denitrogenation of petroleum oils
EP1674158A1 (fr) 2004-12-21 2006-06-28 Petroleo Brasileiro S.A. - PETROBAS Procédé d'oxidation extractive de polluants de fuels catalysé par des oxides de fer.
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