Method for removing sulfur in diesel by photo catalytic oxidation

The method for using photochemical catalysis of removing gasoline and diesel oil the method of sulphur

technical field

The invention relates to any one of claims oxygen's oil product of catalytic oxidation is 7-10 by the direct transgression, and oil product organic carbon non-loss in the temperate photo-catalysis removal of gasoline and diesel oil the method of sulphur.

background technology

Use of the fuel oil to the gasoline, diesel fuel and heavy oil and administration of the kettle body of the combustion and energy-storage form, wherein the sulphide to dozens of a thousand ppm, preferably of the air and a acid and a concentration such. Use of each, and method for and fuel oil based on the is the sulphide, to hydrodesulfurizing of universal, use a catalyst that is constantly, administering is for the sulphur and oil product is H2S, wherein the oil product, and technical line is mature, the refining and MBR technology. A technology the deletion is the is formidable, hydrogen is more than 90% of heat by mass of the is unsaturated hydrocarbon, wherein Yuanzhi With large scale reducing, and to a and a sterically hindrance's the substitution diamido-2 and benzo thiophthene's reducing ability is low; the impossible to achieve the elastomer of the preceding claims wherein the <p> diphenyl: thiophtheneMechanism and producing the research of the intermediate (Yanke che, Wanhong, A Jincai, Zhao, et. a7. Photooxidation of dibenzothiophene and 4, 6-dimethyldibenzothiophene sensitized of N-methylquinolium: tetrafluoborate mechanism and intermediate investigation. The Z*/? ; A. C&w. S, 2005, 109, 8270-8276) and published the magazine 2006 to 110 巻 the 2942nd print of articles the visible light at 2 pairs of methoxy Benzyl-four, 6 - diphenyl pyranium salt photoactivate to thiophthene oxide and sulphide: Absence of electronic transmission mechanism for preparing of hydrocarbon (” Yanke Che Wanhong, A Jincai Zhao, wherein. Visual photooxidation of dibenzothiophenes sensitized of 2- (4-methoxyphenyl) - 4, 6-diphenylpyrylium: an electronic transfer mechanism (involvement of peroxide. Household//z, bearing C7^ million, 2006, 110, 2942-2948) and published at Europe A) 2004 to 10 巻 the 2277th print of articles and diesel oil with a desulfuration: A method for pedicoccus to any one of the emulsion according to recycle of the oxidizing process of catalyst (” Is Li, Zongxuan Ginger, High Jinbo, et. a7. Ultra-Deep DesulfUrization of Said: With a Recoverable Catalyst is Assembled Emulsion. CENTIGRADE/zem 0.5 ph /2004, 10, 2277-2280). A industrial paint according to Valero energy connecting the method further by to at least one of separating 50 in the Second Krotz refining/day diesel oil demonstration desulfuration device, for the organic sulphide is an organic peroxide, then of the extracting agent in the step of separating sulfoxide of polar material, hopes of reaching efficient and low and an. A is applied to the catalytic oxidation method, wherein a is the organic polymer the process of the oxidizing acid the foundation, wherein deletion is - steel according, and reaction is the organic of said claims, the mixing the solvent extraction, wherein of the material to the diamido-2 and so on. Of said claims, wherein at least of the maximal shortcoming of the flue has a, the sulfocompound can only oxidizing to the sulfone or the product sulfoxide, an organic polymer wherein the extract, the step of removing aldehyde is further loss of organic carbon. The preparation method of of the is the use of perquisite layer of the organic sulphur after oxide, for example Japanese claim JP200430588A the washing the photochemical catalysis reaction in perquisite using the heteropoly acid, an aqueous phase is the strong polar organic sulphur component of the antioxidant, wherein the reaction is finished, wherein said that and method for removing the oxidizing thiophthene benzene and organic sulphur of thiophthene group or substituted of the corresponding sulfone or sulphoxide, wherein the is wherein the original sulphide is the alkylation thiophthene benzene or thiophthene benzene, wherein the oxidization alkyl wherein the polar of carboxylic acid, and oxygen/oil phase/water phase at the surface of the; the oxidization efficiency is low, and enhanceThe oxygen outlet pressure the molar ratio, and temperature of the loss of organic components. An, wherein the oxidizing and push to a more economical meshes wherein the top of the possibilities of several, useful to (1) possibly with a step of catalytic oxidation and sulphide efficiently and highly-selective oxidation is 7-10 by or (S is not a shape of organic hydrocarbon, thereby avoiding the extraction ABR+OBR process, and) and (2), does not use the organic peroxide or H202, wherein the soluble macromolecule oxygen, (3) overcomes the cobalt-depleted electronic diamido-2 easily reduction by the problem by directly, and 100% transformed bithiophene-thieno the catalytic oxidation actions. The invention heteropoly acid excited state-based the special electron transport and oxygen and performance, realized by the molecular oxygen successfully from the solvent is 7-10 by the photo-catalysis oxidized desulfuration method, and in premise of the organic hydrocarbonized lost component and target.

The invention

A objective of the present invention presence of the claims, wherein the light catalyst, the catalyst ratio of the hydrogen of the preceding claims, sulphide is not of the sulphur and thoroughly, wherein the sulphur catalyst compound is from the aerobic and is 7-10 by inorganic transgression, a time and in the photo-catalysis removal of gasoline and diesel oil according to non-segregation of hydrocarbons component grains method of sulphur.

The invention relates to a mild conditions of photochemical catalysis of removing fuel oil the method for sulfocompound. Is characterised of: The catalyst is formed with a light emitting, wherein in the oil product sulfocompound's the molecular oxygen supplying oxidation of air is the sulphur dioxide, transgresses from the reaction solution, and removal of an. This invention claims a core is light - catalyst/agent to the molecular oxygen. Agent is methanol, ethanol or acetonitrile, catalyst is any mixture or derivative of phosphotungstic acid, phosphotungstate, phosphomolybdic acid, phosphomolybdate or a heteropoly acid.

The light is adjusted to wavelength is provided to the constituent photocatalyst or the complex contains cattail light or the sunlight; The molecular oxygen is as follows in the air the molecular oxygen or a pure oxygen and.

The catalyst dosage is 0.01 to -5 g/cu.cm of a fuel oil; The additive amount is 1-500 g/cu.cm of a fuel oil.

The oxidizing agent is the pure oxygen of molecular oxygen or ischemia and air, wherein the pressure is 0.02-1.0MPa .

Light source is xenon lamp and high pressure mercury lamp artificial light source or and sunshine. The photocatalysed catalytic oxidation method is adapted for removing the oil product according sulfocompounds, comprising diamido-2 and pharmaceutically, 2 of methyl bithiophene-thieno [ 3] is pharmaceutically, 2, 5 - thioxenes, 2, 3 - thioxenes and 2 - bithiophene-thieno, 2, 5) preparing a pharmaceutically and benzo thiophthenes), thioethers (meth sulphide, sodium and polyaryl thioether butyl or) thiol compound (ethylmercaptan, wherein mercaptan or (c2). Is suitable for the finished product fuel oil (gasoline and diesel oil) and semi-finished product fuel oil and. Is a normal temperature and pressure, a without, the concentration of ABR+OBR process in the post step, and a sulphur branches of the 7-10 by the form, without sulfone, thiosulfate thioether, and organic sulphur, wherein without loss of organic carbon, the oil product of greater than 99% are.

Brief description of the drawings

Heating the continuous. collecting a reaction device diagram.

Figure 2. the pharmaceutical composition according to claim 8 for diamido-2 and sulfocompounds of auxiliary/catalyst/light and/or molecular oxygen is transformed dynamics curve.

Figure 3. pharmaceutical composition according to claim 8 and/chromatography mass spectrum detection 7-10 by determined colour peak and mass spectrum heating.

Figure 4. in the pharmaceutical composition according to claim nines or 2 or pharmaceutically the catalytic oxidation actions has a method for the alkyl, and an aromatic and other hydrocarbon.

Figure 5. the pharmaceutical composition according to claim one wherein the photochemical catalysis system and test control to a combination of gasoline is samples and for and.

Specifically from the real-time device and compulsive of light of the herein described in detailed further explanation to the invention. The invention is performed by the steps.

(1) Are: reactingDissolving the solid catalyst in the auxiliary agent, and a processing oil product mixture, and pressure resistance is greater than the 0.5MPa sealed Pryxs glass or the quartz glass container. The compressed air is reaction, under stirring, shines the reaction with the xenon lamp or a high pressure mercury lamp and. After reacting, the sustained-release the air device, the GC/MS determined to the sample.

(2) Continuous-type reaction: Figure 1 to make the processing fuel oil suction 2 to distill in the reactor, of the compressed air (l) is guided in the reactor, the flow reaction under the ultraviolet source illuminations 3, wherein the residence time, the reaction solution is 22-57 the separation device, 6 branches of the oil in the region of the area 5 and assistant/catalyst according 7, wherein the oil product differentiates the standard oil product 4, aid catalyst to 7 and a reactor are.

The catalyst is 1 millilitre acetonitrile 3 to 30 ml of the reactor and 2 milligrams and procuress acid, and then heating the mixture of different content of any of the sulphur content is respectively

72mg/l, under 102mg/l,) is 9 ml; the mixing sequentially, sealed, and more than 02, and 02 of 0.08MPa, stirring, wherein the xenon lamp (500W), the ultraviolet rays, 10 hours after the reaction is stopped, 1-10% of divestment at rate is 45%, 65% and 75%.

The photochemical catalysis system and test control to a combination of gasoline is samples' and control of material, is represented by Figure 5.

The pharmaceutical composition according to claim 2 to 1 ethanol millilitre of 30 ml of reactor and 2 milligrams sodium phosphotungstate, then adding the sulphur content of the gasoline under 9 ml, mixing sequentially, sealed, and more than 02, and 02 of 0.05MPa, stirring, and high pressure mercury lamp (200W), the ultraviolet rays, 10 hours after the reaction is stopped, 1-10% of divestment rate of 35% is.

The pharmaceutical composition according to claim 3 is millilitre 1 and 3 to 30 ml of the reactor and 2 milligrams phosphomolybdic acid, and then heating the mixture of different content of any of the sulphur content of the 72mg/l, under 102mg/l,) is 9 ml; the mixing sequentially, sealed, and more than 02, and 02 of 0.08MPa, stirring, wherein the xenon lamp (500W), the ultraviolet rays, 10 hours after the reaction is stopped, 1-10% of divestment at rate is 22%, 35% and 47%.

The pharmaceutical composition according to claim 4 is 1 millilitre of acetonitrile 30 ml of reactor and 0. 4 milligrams phosphotungstic acid, then adding the sulphur content of the 400mg/l processing diesel oil 9 ml, mixing sequentially, sealed, and more than 02, and 02 of 0.05MPa, stirring, and high pressure mercury lamp (200W), the ultraviolet rays, wherein the 16-2 to the stopped reaction, diesel oil of divestment rate of 40% is.

The pharmaceutical composition according to claim 5 is 5 ml of acetonitrile in a 30 ml of reactor, 5 when slightly 2) bithiophene-thieno methyl, 2 milligrams phosphotungstic acid, mixing sequentially, sealed, and more than 02, and 02 of 0.08MPa, stirring, wherein the xenon lamp (500W), mixing, 1.5 hours after stopped reaction, 2 of methyl diamido-2 conversion speed, 100% to 65% of sulphur dioxide.

The pharmaceutical composition according to claim 6 is 5 ml of ethanol is 130 ml of reactor, 5 when slightly 2, 5 - thioxenes, 2 milligrams phosphotungstic acid, mixing sequentially, sealed, and more than 02, and 02 of 0.08MPa, shines with the sunshine, 1.5 hours after stopped reaction, 2, 5 - thioxene conversion speed 100%,.

The pharmaceutical composition according to claim 7 is 5 ml of acetonitrile in 130 ml of reactor, the milligram 16-2) thiophthene, 1 milligram phosphotungstic acid and preparation phosphomolybdic acid, mixing sequentially, sealed, and more than 02, and 02 of 0.04MPa, wherein the xenon lamp (500W), the ultraviolet rays, 1.5 hours after stopped reaction, benzene thiophthene conversion 80%.

The pharmaceutical composition according to claim 8 is 5 ml of acetonitrile in a 30 ml of reactor, 1 slightly pipe (3) bithiophene-thieno, the pipe slightly the diamido-2, the pipe slightly 2, 5 of the compound, pharmaceutically the pipe slightly 2 - bithiophene-thieno, the pipe slightly 2, 3 - thioxenes, 2 milligrams phosphotungstic acid, mixing sequentially, sealed, and more than 02, and 02 of 0.08MPa, stirring, wherein the xenon lamp (500W), the ultraviolet rays, 5 hours after the reaction is stopped, 3 of methyl bithiophene-thieno and pharmaceutically 2 and 5, 3,3,3-trifluoropropene bithiophene-thieno and 2 - bithiophene-thieno, 2, 3 - thioxene conversion speed of 100%.

The diamido-2 and sulfocompounds/catalyst/light and/or molecular oxygen is 02 to 5 hours is 100% of transforming agent, the finished product is 7-10 by, gas chromatography/mass spectrum detection adding 7-10 is represented by Figure 2 and 3 of examples 9 to adding 5 ml of acetonitrile in 130 ml of reactor comprises (2 milligrams phosphotungstic acid), then adding 1 to increase slightly 2 of methyl) bithiophene-thieno and 10 pipe the slightly, toluene, normal hexane and Process Thereof, 2 of methyl - 2 - 3-butene-1-alcohol, the butylenes, mixing sequentially, sealed, and more than 02, and 02 of 0.08MPa, stirring, wherein the xenon lamp (500W), the ultraviolet rays, 1.5 hours after stopped reaction, the gas phaseThe result and FORMULA, 2 of methyl diamido-2 conversion speed is 95%, and component a conversion <p> photochemical catalysis system according to one of alkyl, and an aromatic and other hydrocarbon the catalytic oxidation influences (and comparisons of 2 of methyl) bithiophene-thieno, gas chromatography/mass spectrum test result represented in the reaction time is no to change. Is represented by Figure 4 of the catalyst to adding 5 ml of acetonitrile in a 30 ml of reactor and usual, 5 when slightly 2) bithiophene-thieno methyl, 2 milligrams phosphotungstic acid, the mixing the average, sealed, and then drying to obtain high-purity helium, stirring, wherein the xenon lamp (500W), the ultraviolet rays, 1.5 hours after the reaction is stopped, 2 of methyl diamido-2 conversion <p> to 2 adding 5 ml of acetonitrile in a 30 ml of reactor and usual, 5 when slightly 2) bithiophene-thieno methyl, 2 milligrams phosphotungstic acid, the mixing the average, sealed, and more than 02, and 02 of 0.08MPa, stirring,

The heating to 80 degrees CENTIGRADE, does not use the ultraviolet rays to conduct the dark reaction, 1.5 hours after the reaction is stopped, 2 of methyl diamido-2 conversion <p> to 3 adding 5 ml of gasoline in a 30 ml of reactor and usual (sulphur under content), wherein the added auxiliary agent are added 2 milligrams phosphotungstic acid, and mixing sequentially, sealed, and more than 02, and 02 of 0.08MPa, stirring, the ultraviolet rays of the reaction, 1.5 hours after the reaction is stopped, percentage of desulfurization <p> to 4 adding 5 ml of gasoline in a 30 ml of reactor and usual (sulphur under content), wherein the added assistant adding 5 ml water to be 2 milligrams phosphotungstic acid, mixing sequentially, sealed, and more 02nd, And 02 of 0.08MPa, stirring, the ultraviolet rays of the reaction, 1.5 hours after the reaction is stopped, percentage of desulfurization <p> to 5 adding 5 ml of acetonitrile in a 30 ml of reactor and usual, 5 when slightly 2) bithiophene-thieno methyl, 2 milligrams silicotungstic acid, mixing sequentially, sealed, and more than 02, and 02 of 0.08MPa, the 氤 the lamp (500W), the ultraviolet rays, 1.5 hours after stopped reaction, 2 of methyl diamido-2 conversion speed 9%.