US20040154959A1 - Method for desulphurizing a hydrocarbon mixture - Google Patents
Method for desulphurizing a hydrocarbon mixture Download PDFInfo
- Publication number
- US20040154959A1 US20040154959A1 US10/468,912 US46891204A US2004154959A1 US 20040154959 A1 US20040154959 A1 US 20040154959A1 US 46891204 A US46891204 A US 46891204A US 2004154959 A1 US2004154959 A1 US 2004154959A1
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- Prior art keywords
- acid
- process according
- equal
- acid catalyst
- solid
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- LLNCIAMOTREUEZ-UHFFFAOYSA-N CC1=CC=CC(C2=CC=CC(C)=C2S(=O)(=O)O)=C1 Chemical compound CC1=CC=CC(C2=CC=CC(C)=C2S(=O)(=O)O)=C1 LLNCIAMOTREUEZ-UHFFFAOYSA-N 0.000 description 2
- OKCLFLHPYRKCHJ-UHFFFAOYSA-N CC1=CC=CC2=C1S(=O)(=O)C1=C2C=CC=C1C Chemical compound CC1=CC=CC2=C1S(=O)(=O)C1=C2C=CC=C1C OKCLFLHPYRKCHJ-UHFFFAOYSA-N 0.000 description 1
- FFRCCJRZCKJGMS-UHFFFAOYSA-N CC1=CC=CC2=C1S(=O)C1=C2C=CC=C1C Chemical compound CC1=CC=CC2=C1S(=O)C1=C2C=CC=C1C FFRCCJRZCKJGMS-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
Definitions
- the present invention relates to a process for the desulphurization of a mixture of hydrocarbons containing sulphur compounds, comprising at least one oxidation step, in which there are used, as oxidizing agent, hydrogen peroxide, acetic acid and an acid catalyst, so as to oxidize the sulphur compounds.
- RSR′ represents an aliphatic or aromatic sulphur compound.
- the present invention aims to avoid the abovementioned disadvantages and to provide a novel process for removing sulphur from mixtures of hydrocarbons which makes it possible to significantly reduce their sulphur content.
- the invention therefore relates to a process for the desulphurization of a mixture of hydrocarbons containing sulphur compounds, comprising a step of oxidation by means of hydrogen peroxide, acetic acid and an acid catalyst in order to oxidize the sulphur compounds, in which the acid catalyst contains an acid solid chosen from cation-exchange resins having a pKa of less than or equal to 4, from solids based on silicon oxide additionally containing a trivalent metal, and from particles of inorganic solid on which acidic organic groups are grafted such that the particles thus grafted have a pKa of less than or equal to 4.
- the acid catalyst contains an acid solid chosen from cation-exchange resins having a pKa of less than or equal to 4, from solids based on silicon oxide additionally containing a trivalent metal, and from particles of inorganic solid on which acidic organic groups are grafted such that the particles thus grafted have a pKa of less than or equal to 4.
- Ka is the dissociation constant of the acid in aqueous medium at 25° C.
- the acid catalyst is necessary to accelerate the formation of peracetic acid starting with hydrogen peroxide and acetic acid by the reaction [1]
- the peracetic acid thus formed is the substance which oxidizes the sulphur compounds, in particular to corresponding sulphones, according to the reaction [2]
- reaction medium for oxidation it is possible to distinguish at least two phases: an organic phase essentially consisting of the mixture of hydrocarbons and which may optionally contain part of the acetic acid and part of the peracetic acid, and an aqueous phase essentially containing water, hydrogen peroxide, part of the acetic acid and part of the peracetic acid.
- One of the characteristic aspects of the invention lies in the use of a solid as catalyst to accelerate the formation of the peracetic acid.
- the solid catalyst may be in contact with the aqueous and organic phases in a three-phase medium, the third phase being solid and consisting of the solid catalyst.
- the catalyst may for example be used in suspension in the reaction medium or in the form of a fixed bed. In both cases, the fact that a solid is used has the advantage that the catalyst can be easily separated from the reaction medium and in particular from the organic phase, for example by filtration when the catalyst is in suspension. Because of this, contamination of the organic phase with the catalyst is avoided.
- the catalyst may be in contact with the aqueous phase alone, in a separate tank, for example in the form of a suspension, a fixed bed or a fluid bed.
- This second configuration has an additional advantage of avoiding side reactions between the catalyst and the organic phase, and in particular the acid-base reactions mentioned above.
- mixture of hydrocarbons is understood to mean any product predominantly containing combustible hydrocarbons such as paraffins, olefins, naphthenic compounds and aromatic compounds. This may be crude oil or a petroleum derivative obtained by any known refining, treatment.
- the mixture of hydrocarbons may be chosen from vehicle fuels such as petrol or diesel, and from domestic fuels such as, for example, heating fuel oil.
- sulphur compounds denotes all the compounds present in the mixture of hydrocarbons which contain sulphur. They are in particular benzothiophene, dibenzothiophene and their mono- or polysubstituted derivatives, more specifically 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene.
- the sulphur compounds may be oxidized for example to corresponding sulphoxides, sulphones and sulphonic acids.
- sulphoxides 4,6-dimethyldibenzothiophene
- the corresponding sulphoxide has the following structure
- the corresponding sulphone has the following structure
- the acid catalyst contains a cation exchange resin having a pKa of less than or equal to 4.
- the pKa is advantageously less than or equal to 3, in particular 2, preferably 0 and most particularly less than or equal to ⁇ 1.74.
- the resin may be chosen from fluorinated resins, where the hydrogen atoms of the hydrocarbon backbone have been partially or completely substituted with fluorine atoms. Completely fluorinated resins are preferred.
- the resins preferably further contain acid groups.
- the acid groups may be chosen from phenol, arsonic, phosphonic, phosphinic, seleninic, selenonic, sulphinic, sulphonic and carboxylic groups. Sulphonic and/or carboxylic groups are preferred. Fluorinated resins containing sulphonic groups give good results. Typical structures of fluorinated resins carrying sulphonic groups are described in the publication by M. A. Harmer et al., J.
- the acid catalyst may consist of the resin alone or it may consist of a matrix in which the resin is dispersed in the form of particles.
- the matrix is preferably inorganic. It most often contains silica, alumina, zirconium or titanium oxide. Pure silica is preferred.
- NAFION® SAC 13 marketed by ALDRICH, the synthesis of which is described in the publication by M. A. Harmer et al., J. Am. Chem. Soc. 1996, 118, 7708-7715.
- the quantity of acid catalyst used in the first variant of the process of the invention should be sufficient to allow rapid formation of peracetic acid. It depends on the content of acid sites of the solid acid catalyst and the nitrogen peroxide and acetic acid concentrations of the aqueous phase.
- the quantity of acid catalyst is such that the number of mol of protons from the acid groups such as the carboxylic and/or sulphonic groups, per kg of aqueous phase with which the catalyst is in contact, is generally greater than or equal to 0.001, in particular 0.005 and most particularly 0.01.
- the quantity of acid catalyst is most often such that the number of mol of protons per kg of aqueous phase is less than or equal to 0.8, in particular 0.5 and most particularly 0.2. Quantities of acid catalyst which lead to a number of mol of protons per kg of aqueous phase greater than or equal to 0.08 and less than or equal to 0.1 give good results.
- the acid catalyst contains a solid based on silicon oxide which additionally contains a trivalent metal.
- the silicon/trivalent metal molar ratio in the solid is generally greater than or equal to 3, in particular 10. This ratio is usually less than or equal to 200, in particular 175. Values greater than or equal to 12 and less than or equal to 150 give good results.
- the trivalent metal may be chosen from boron, aluminium, gallium and iron. Aluminium is preferred.
- the solid is most often chosen from zeolites, clays and amorphous solids based on silicon oxide additionally containing a trivalent metal, in particular aluminium. The protonated forms of these solids are preferred.
- Zeolites of the H-ZSM-5, H-MOR, H-Beta and H-Y type gave good results.
- the zeolites H-ZSM-5 and H-MOR are preferred.
- titanium-containing zeolites give poor results. Consequently, the solid based on silicon oxide used in this variant of the process according to the invention is preferably free of titanium.
- the acid catalyst may consist of the solid alone or it may consist of the solid further containing organic functionalities. These may be chosen from sulphonic and carboxylic organic acid groups and from mixtures thereof.
- the quantity of acid catalyst used in the second variant of the process of the invention should be sufficient to allow rapid formation of peracetic acid. It depends on the content of acid sites of the solid acid catalyst and the hydrogen peroxide and acetic acid concentrations of the aqueous phase.
- the quantity of acid catalyst is generally such that the number of mol of trivalent metal per kg of aqueous phase with which the catalyst is in contact is greater than or equal to 0.001, in particular 0.005 and most particularly 0.01.
- the quantity of acid catalyst is usually such that the number of mol of trivalent metal per kg of aqueous phase is less than or equal to 0.8 in particular 0.5 and most particularly 0.2. Quantities of acid catalyst which lead to a number of mol of trivalent metal per kg of aqueous phase greater than or equal to 0.08 and less than or equal to 0.1 give good results.
- the acid catalyst contains inorganic solid particles on which acid organic groups have been grafted such that the particles thus grafted have a pKa of less than or equal 4.
- the pKa is advantageously less than or equal to 3, in particular 2, preferably 0 and most particularly less than or equal to ⁇ 1.74.
- the inorganic solid may be chosen from silicon, aluminium, zirconium and titanium oxide. Silicon oxide is preferred.
- the acid organic groups may be chosen from aliphatic, alicyclic, heterocyclic or aromatic groups containing an acid functionality.
- the acid functionalities may be chosen from phenol, arsonic, phosphonic, phosphinic, seleninic, selenonic, sulphinic, sulphonic and carboxylic functionalities. Sulphonic and/or carboxylic functionalities are preferred. These groups may contain up to 18 carbon atoms, in particular up to 12 carbon atoms, preferably up to 6. They may additionally contain one or more heteroatoms such as oxygen and/or fluorine.
- the acid organic groups may be grafted on the inorganic solid particles by any suitable known means, such as for example by the process described in the publication by J. H. Clark et al., C. R. Acad. Sci. Paris, Series IIc, Chimie/Chemistry 3 (2000) 399-404.
- the quantity of acid catalyst used in the third variant of the process of the invention should be sufficient to allow rapid formation of peracetic acid. It depends on the content of acid sites in the catalyst and the hydrogen peroxide and acetic acid concentrations of the aqueous phase.
- the quantity of acid catalyst is generally such that the number of mol of protons from the acid organic groups per kg of aqueous phase with which the catalyst is in contact is greater than or equal to 0.001, in particular 0.005 and most particularly 0.01.
- the quantity of acid catalyst is usually such that the number of mol of protons per kg of aqueous phase is less than or equal to 0.8, in particular 0.5 and most particularly 0.2. Quantities of acid catalyst which give a number of mol of protons per kg of aqueous phase greater than or equal to 0.08 and less than or equal to 0.1 give good results.
- the catalyst is generally used in the form of particles which may be obtained by any known process.
- the most diverse forms of particles come to mind, such as in particular powders, beads, pellets, extrudates or honeycomb structures.
- the average size of these particles depends on the type of use.
- the average size of the particles is generally greater than or equal to 5 ⁇ m, more particularly 10 ⁇ m and most particularly 50 ⁇ m.
- the average size of the particles is usually less than or equal to 500 ⁇ m, more particularly 250 ⁇ m and most particularly 150 ⁇ m. Average sizes greater than or equal to 100 ⁇ m and less than or equal to 125 ⁇ m are particularly suitable.
- the average size of the particles is generally greater than or equal to 0.5 mm, more particularly 1 mm and most particularly 2 mm.
- the average size of the particles is commonly less than or equal to 100 mm, more particularly 75 mm and most particularly 50 mm. Average sizes greater than or equal to 5 mm and less than or equal to 30 mm are particularly suitable.
- the oxidation is generally carried out at a temperature greater than or equal to 0° C., particularly 10° C. and preferably 20° C.
- the temperature is usually less than or equal to 100° C., in particular 90° C. and most particularly 80° C. Temperatures of 25 to 70° C. are suitable.
- the hydrogen peroxide is generally used in the oxidation reaction in the form of an aqueous solution. Before mixing with the acetic acid, this solution most often has a hydrogen peroxide concentration greater than or equal to 1% by weight, in particular 10% by weight.
- the hydrogen peroxide concentration is commonly less than or equal to 80%, in particular 70%.
- a concentration of 30 to 60% by weight is suitable.
- the quantity of hydrogen peroxide present in the oxidation reaction medium depends on the quantity of sulphur present in the mixture of hydrocarbons.
- the molar ratio between the hydrogen peroxide and the sulphur is generally greater than or equal to 1, in particular 2. This ratio is often less than or equal to 5 000, in particular 3 000. Ratios of 3 to 1 500 are particularly suitable.
- the acetic acid is generally used in the oxidation reaction in the form of an aqueous solution.
- the molar ratio between the acetic acid and the hydrogen peroxide used in the oxidation reaction medium is generally greater than or equal to 0.01, in particular 0.1 and most particularly 0.25. This ratio is often less than or equal to 4, in particular 2. Ratios of 0.5 to 1.5 are particularly suitable.
- the aqueous phase entering into contact with the mixture of hydrocarbons is used in a volume such that the ratio of the volumes of this aqueous phase and of the mixture of hydrocarbons ensures optimum dispersion of the phases.
- This ratio is generally less than or equal to 0.5, in particular 0.3. It is usually greater than or equal to 0.01, in particular 0.05. Values greater than or equal to 0.1 and less than or equal to 0.25 are preferred.
- the oxidation may be carried out at atmospheric pressure or at supra-atmospheric pressure. It is preferable to work at atmospheric pressure.
- the oxidation may be preceded by one or more hydrodesulphurization steps. It may also be followed by one or more steps for separating the oxidized sulphur compounds. These separations may be carried out in various ways: distillation, extraction by means of solvents, adsorption onto solids, pyrrolysis, acid or base hydrolysis and precipitation.
- the process according to the invention may be carried out continuously or batchwise.
- the process is carried out continuously using the plant schematically represented in the figure.
- the oxidation reaction is carried out in the tank 1 which is fed with a mixture of hydrocarbons at the bottom of the tank by the pipe 2 and with hydrogen peroxide and peracetic acid solution at the top of the tank by the pipe 3.
- the tank 1 two phases are distinguishable: an organic phase essentially consisting of the mixture of hydrocarbons, and an aqueous phase containing in particular hydrogen peroxide and peracetic acid.
- the oxidized organic phase which is less dense than the aqueous phase is removed at the top of the tank 1 by the pipe 4 and it may be transferred to a unit for separating the oxidized sulphur compounds.
- the aqueous phase containing in particular the hydrogen peroxide and the acetic acid leaves the tank 1 by the pipe 5 and is transferred into the tank 6, in which the solid acid catalyst is present. The latter remains inside the tank 6.
- the hydrogen peroxide reacts with the acetic acid under the action of the solid acid catalyst to reform peracetic acid.
- An aqueous solution containing the peracetic acid thus reformed leaves the tank 6 by the pipe 3 and again joins the tank 1.
- the system is fed with fresh hydrogen peroxide and optionally with fresh acetic acid via the pipe 7.
- the system may be purged via the pipe 8.
- a synthetic solution of benzothiophene (BT) and dibenzothiophene (DBT) in toluene is used to simulate a mixture of hydrocarbons containing sulphur-containing derivatives.
- the benzo- and dibenzothiophene type compounds are difficult to remove by hydrodesulphurization and predominantly contribute to the S content of certain petroleum products.
- the BT and DBT contents are determined by gas chromatography after 5 h.
- the residual BT and DBT contents correspond to an S content of 1 211 ppm weight.
- Example 1 The conditions of Example 1 are, reproduced except that 0.21 g of H 2 SO 4 at 97% is introduced.
- the residual BT and DBT contents correspond to an S content of 14 ppm weight.
- Example 1 The conditions of Example 1 are reproduced except that 2.25 g of Nafion® NR 50 (beads 7-9 mesh, Aldrich) are introduced.
- the residual BT and DBT contents correspond to an S content of 107 ppm weight.
- the residual BT and DBT contents correspond to an S content of 910 ppm weight.
- Example 1 The conditions of Example 1 are reproduced except that 0.41 g of Dowex® 50 W X 8 (beads 20-50 mesh, H + -form, Fluka) is introduced.
- Example 1 The conditions of Example 1 are reproduced except that 2.25 g of particles of an inorganic solid (silica) grafted with organic acid groups, which is obtained according to the procedure described in the publication by J. H. Clark et al., C.R. Acad. Sci. Paris, Series IIc, Chimie/Chemistry 2000, 3, 399-404, are introduced.
- the oxidation step was carried out on hydrotreated transport diesel fuel, the sulphur content of which is 39 ppm by weight measured by X-ray fluorescence. Analysis by gas chromatography with specific detection of sulphur by atomic emission (AED) shows that the sulphur compounds present are substituted dibenzothiophenes, and more particularly 4,6-dimethyldibenzothiophene.
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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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0102688 | 2001-02-26 | ||
FR0102688A FR2821350B1 (fr) | 2001-02-26 | 2001-02-26 | Procede de desulfuration d'un melange d'hydrocarbures |
PCT/EP2002/001956 WO2002068567A1 (fr) | 2001-02-26 | 2002-02-22 | Procédé de désulfuration d'un mélange d'hydrocarbures |
Publications (1)
Publication Number | Publication Date |
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US20040154959A1 true US20040154959A1 (en) | 2004-08-12 |
Family
ID=8860522
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/468,912 Abandoned US20040154959A1 (en) | 2001-02-26 | 2002-02-22 | Method for desulphurizing a hydrocarbon mixture |
Country Status (6)
Country | Link |
---|---|
US (1) | US20040154959A1 (fr) |
EP (1) | EP1377652A1 (fr) |
JP (1) | JP2004528416A (fr) |
CA (1) | CA2439162A1 (fr) |
FR (1) | FR2821350B1 (fr) |
WO (1) | WO2002068567A1 (fr) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060000750A1 (en) * | 2002-05-03 | 2006-01-05 | Chantal Louis | Method of desulphurising a mixture of hydrocarbons |
US20100025665A1 (en) * | 2006-05-25 | 2010-02-04 | Barry Rand | Organic photosensitive devices using subphthalocyanine compounds |
US7744749B2 (en) | 2005-09-08 | 2010-06-29 | Saudi Arabian Oil Company | Diesel oil desulfurization by oxidation and extraction |
US20100300938A1 (en) * | 2005-09-08 | 2010-12-02 | Martinie Gary D | Process for oxidative conversion of organosulfur compounds in liquid hydrocarbon mixtures |
US7880027B2 (en) | 2007-08-23 | 2011-02-01 | Rohm And Haas Company | Method for producing unsaturated carboxylic acids and nitriles |
US20110220547A1 (en) * | 2010-03-15 | 2011-09-15 | Abdennour Bourane | Targeted desulfurization process and apparatus integrating oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds |
US20110220550A1 (en) * | 2010-03-15 | 2011-09-15 | Abdennour Bourane | Mild hydrodesulfurization integrating targeted oxidative desulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds |
US20110233110A1 (en) * | 2010-03-29 | 2011-09-29 | Omer Refa Koseoglu | Integrated hydrotreating and oxidative desulfurization process |
US20120138449A1 (en) * | 2012-02-12 | 2012-06-07 | King Abdulaziz City for Science and Technology (KACST) | Method of removing sulfur from crude oil and diesel using ionizing radiation |
US20140284251A1 (en) * | 2012-02-06 | 2014-09-25 | Shun-Sheng Cheng | Fuel Desulfurization Method |
US8906227B2 (en) | 2012-02-02 | 2014-12-09 | Suadi Arabian Oil Company | Mild hydrodesulfurization integrating gas phase catalytic oxidation to produce fuels having an ultra-low level of organosulfur compounds |
US8920635B2 (en) | 2013-01-14 | 2014-12-30 | Saudi Arabian Oil Company | Targeted desulfurization process and apparatus integrating gas phase oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds |
US10947461B2 (en) | 2011-09-27 | 2021-03-16 | Saudi Arabian Oil Company | Selective liquid-liquid extraction of oxidative desulfurization reaction products |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US20040245116A1 (en) * | 2003-03-31 | 2004-12-09 | Permelec Electrode Ltd. | Method for the electrolytic synthesis of peracetic acid and sterilizing-cleaning method and apparatus |
US20050040078A1 (en) * | 2003-08-20 | 2005-02-24 | Zinnen Herman A. | Process for the desulfurization of hydrocarbonacecus oil |
ITRM20030598A1 (it) * | 2003-12-23 | 2005-06-24 | Univ Roma | Processo e relativo impianto per la desolforazione |
US9453798B2 (en) | 2010-12-01 | 2016-09-27 | Nalco Company | Method for determination of system parameters for reducing crude unit corrosion |
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US5114434A (en) * | 1989-02-03 | 1992-05-19 | Atochem | Viscoreduced diesel fuels having improved cetane numbers |
US5512260A (en) * | 1994-03-04 | 1996-04-30 | Mobil Oil Corporation | Reduction of sulfur content in a gaseous stream |
US5824622A (en) * | 1994-01-12 | 1998-10-20 | E. I. Du Pont De Nemours And Company | Porous microcomposite of perfluorinated ion-exchange polymer and metal oxide, a network of silica, or a network of metal oxide and silica derived via a sol-gel process |
US6171478B1 (en) * | 1998-07-15 | 2001-01-09 | Uop Llc | Process for the desulfurization of a hydrocarbonaceous oil |
US6231755B1 (en) * | 1998-01-30 | 2001-05-15 | E. I. Du Pont De Nemours And Company | Desulfurization of petroleum products |
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GB1132875A (en) * | 1965-02-23 | 1968-11-06 | Exxon Research Engineering Co | A desulfurization process |
GB9925971D0 (en) * | 1999-11-03 | 1999-12-29 | Exxon Chemical Patents Inc | Reduced particulate froming distillate fuels |
-
2001
- 2001-02-26 FR FR0102688A patent/FR2821350B1/fr not_active Expired - Fee Related
-
2002
- 2002-02-22 WO PCT/EP2002/001956 patent/WO2002068567A1/fr not_active Application Discontinuation
- 2002-02-22 EP EP02744899A patent/EP1377652A1/fr not_active Withdrawn
- 2002-02-22 CA CA002439162A patent/CA2439162A1/fr not_active Abandoned
- 2002-02-22 JP JP2002568664A patent/JP2004528416A/ja active Pending
- 2002-02-22 US US10/468,912 patent/US20040154959A1/en not_active Abandoned
Patent Citations (5)
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US5114434A (en) * | 1989-02-03 | 1992-05-19 | Atochem | Viscoreduced diesel fuels having improved cetane numbers |
US5824622A (en) * | 1994-01-12 | 1998-10-20 | E. I. Du Pont De Nemours And Company | Porous microcomposite of perfluorinated ion-exchange polymer and metal oxide, a network of silica, or a network of metal oxide and silica derived via a sol-gel process |
US5512260A (en) * | 1994-03-04 | 1996-04-30 | Mobil Oil Corporation | Reduction of sulfur content in a gaseous stream |
US6231755B1 (en) * | 1998-01-30 | 2001-05-15 | E. I. Du Pont De Nemours And Company | Desulfurization of petroleum products |
US6171478B1 (en) * | 1998-07-15 | 2001-01-09 | Uop Llc | Process for the desulfurization of a hydrocarbonaceous oil |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060000750A1 (en) * | 2002-05-03 | 2006-01-05 | Chantal Louis | Method of desulphurising a mixture of hydrocarbons |
US9499751B2 (en) | 2005-09-08 | 2016-11-22 | Saudi Arabian Oil Company | Process for oxidative conversion of organosulfur compounds in liquid hydrocarbon mixtures |
US7744749B2 (en) | 2005-09-08 | 2010-06-29 | Saudi Arabian Oil Company | Diesel oil desulfurization by oxidation and extraction |
US20100300938A1 (en) * | 2005-09-08 | 2010-12-02 | Martinie Gary D | Process for oxidative conversion of organosulfur compounds in liquid hydrocarbon mixtures |
US8715489B2 (en) | 2005-09-08 | 2014-05-06 | Saudi Arabian Oil Company | Process for oxidative conversion of organosulfur compounds in liquid hydrocarbon mixtures |
US8242493B2 (en) | 2006-05-25 | 2012-08-14 | The Trustees Of Princeton University | Organic photosensitive devices using subphthalocyanine compounds |
US7973307B2 (en) * | 2006-05-25 | 2011-07-05 | The Trustees Of Princeton University | Organic photosensitive devices using subphthalocyanine compounds |
US20100025665A1 (en) * | 2006-05-25 | 2010-02-04 | Barry Rand | Organic photosensitive devices using subphthalocyanine compounds |
KR101387254B1 (ko) | 2006-05-25 | 2014-04-18 | 더 트러스티즈 오브 프린스턴 유니버시티 | 서브프탈로시아닌 화합물을 사용한 유기 감광성 소자 |
US7880027B2 (en) | 2007-08-23 | 2011-02-01 | Rohm And Haas Company | Method for producing unsaturated carboxylic acids and nitriles |
US9296960B2 (en) | 2010-03-15 | 2016-03-29 | Saudi Arabian Oil Company | Targeted desulfurization process and apparatus integrating oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds |
US20110220547A1 (en) * | 2010-03-15 | 2011-09-15 | Abdennour Bourane | Targeted desulfurization process and apparatus integrating oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds |
US20110220550A1 (en) * | 2010-03-15 | 2011-09-15 | Abdennour Bourane | Mild hydrodesulfurization integrating targeted oxidative desulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds |
US9644156B2 (en) | 2010-03-15 | 2017-05-09 | Saudi Arabian Oil Company | Targeted desulfurization apparatus integrating oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds |
US8658027B2 (en) | 2010-03-29 | 2014-02-25 | Saudi Arabian Oil Company | Integrated hydrotreating and oxidative desulfurization process |
US20110233110A1 (en) * | 2010-03-29 | 2011-09-29 | Omer Refa Koseoglu | Integrated hydrotreating and oxidative desulfurization process |
US9464241B2 (en) | 2010-03-29 | 2016-10-11 | Saudi Arabian Oil Company | Hydrotreating unit with integrated oxidative desulfurization |
US10947461B2 (en) | 2011-09-27 | 2021-03-16 | Saudi Arabian Oil Company | Selective liquid-liquid extraction of oxidative desulfurization reaction products |
US8906227B2 (en) | 2012-02-02 | 2014-12-09 | Suadi Arabian Oil Company | Mild hydrodesulfurization integrating gas phase catalytic oxidation to produce fuels having an ultra-low level of organosulfur compounds |
US20140284251A1 (en) * | 2012-02-06 | 2014-09-25 | Shun-Sheng Cheng | Fuel Desulfurization Method |
US9127214B2 (en) * | 2012-02-06 | 2015-09-08 | Shun-Sheng Cheng | Fuel desulfurization method |
US20120138449A1 (en) * | 2012-02-12 | 2012-06-07 | King Abdulaziz City for Science and Technology (KACST) | Method of removing sulfur from crude oil and diesel using ionizing radiation |
US8920635B2 (en) | 2013-01-14 | 2014-12-30 | Saudi Arabian Oil Company | Targeted desulfurization process and apparatus integrating gas phase oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds |
Also Published As
Publication number | Publication date |
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CA2439162A1 (fr) | 2002-09-06 |
WO2002068567A1 (fr) | 2002-09-06 |
EP1377652A1 (fr) | 2004-01-07 |
FR2821350A1 (fr) | 2002-08-30 |
JP2004528416A (ja) | 2004-09-16 |
FR2821350B1 (fr) | 2004-12-10 |
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