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Method for low-temperature oxidation desulfurization of fuel oil

A technology for oxidative desulfurization and fuel oil, which is applied in the fields of oil processing, refining, and refining in the petrochemical industry. It can solve the problems of extraction agent regeneration-cycle, difficult synthesis of ionic liquids, and complex processes, etc., to overcome short catalyst life, The effect of avoiding large-scale equipment investment

Inactive Publication Date: 2015-12-02
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Yu Guoxian, Lu Shanxiang et al. (Journal of Fuel Chemistry 2005, 2, 1, 73-78) reported a gasoline oxidative desulfurization system composed of hydrogen peroxide-formic acid-activated carbon, using thiophene as a simulated compound, and the initial content of thiophene was 2000ppm. hours, the sulfur removal rate is only 85%, and the final sulfur content is 300ppm, which is difficult to meet the needs of ultra-deep desulfurization
Zhu Wenshuai, Li Minghua etc. (GreenChemistry2009, 11, 810-815; GreenChemistry2009, 11, 1801-1807; CN102898474A; CN103740398A; CN103992814A) disclosed a series of extraction-oxidative desulfurization systems composed of hydrogen peroxide-ionic liquid-inorganic iron salt, the most Under optimal conditions, the sulfur in simulated gasoline can be reduced from 100ppm to below 3ppm, but the synthesis of ionic liquid is difficult, and there is the problem of extraction agent regeneration-cycle, and the process is more complicated

Method used

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  • Method for low-temperature oxidation desulfurization of fuel oil
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  • Method for low-temperature oxidation desulfurization of fuel oil

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Using n-octane (CAS: 111-65-9, purity >96%, purchased from Aladdin reagents) and thiophene (1-thia-2,4-cyclopentadiene, CAS: 110-02-1, purity >99.5%, purchased from Aladdin Reagent) to configure simulated gasoline, and add decane (CAS: 124-18-5, purity >98%, purchased from Aladdin Reagent) as an internal standard for analysis. Add 1g of thiophene and 1g of decane to 998g of n-octane to configure simulated gasoline, in which the sulfur content is 61.45ppm.

[0023] Pipette simulated oil 100g, and Au(1%wt) / TiO 2 (AUROlite, CAS: 7440-57-5, Stremproduct) catalyst 2g, H 2 o 2 (CAS: 7722-84-1, purity > 30wt%, purchased from Sinopharm Chemical Reagent Co., Ltd.) 3.33g was added to a closed three-necked flask. Set the rotation speed to 700rpm by mechanical stirring, and react at 30°C for 180min, and take ~1g of sample during the reaction.

[0024] Agilent7890A type chromatography was used for analysis, and the chromatography was configured with 30mHP-5 capillary column, hyd...

Embodiment 2

[0028] The configuration of the simulated oil is the same as in Example 1. Pipette simulated oil 100g, Au(1%wt) / TiO 2 (AUROlite, CAS:7440-57-5, Stremproduct), Au (1%wt) / C (self-made, prepared by modified ion exchange method), Au-Pd (1%wt) / C (self-made, prepared by sol deposition method) ) each catalyst 2g, H 2 o 2 (CAS: 7722-84-1, purity>30wt%, purchased from Sinopharm Chemical Reagent Co., Ltd.) 3.33g, the final pressure of oxygen was 30bar, the magnetic stirring was set at 700rpm, and the reaction was carried out at 60°C for 30min. Quantitative analysis of thiophene is the same as that described in Implementation 1. After 30min, C carrier, Au / TiO 2 , Au / C, Au-Pd / C desulfurization rates were 59.4%, 49.2%, 88.2% and 96.9%. Simulated gasoline treated with Au / C and Au-Pd / C can meet Euro V and China V standards.

Embodiment 3

[0030] The configuration of the simulated oil is the same as in Example 1. Pipette simulated oil 100g, and adopt Au(1wt%) / TiO prepared by impregnation method 2 (AUROlite, CAS: 7440-57-5, Stremproduct), Au (1wt%) / ZnO (AUROlite, CAS: 7440-57-5, Stremproduct), Au (1wt%) / C (self-made, modified ion exchange method Preparation) catalyst each 2g, H 2 o 2 (CAS: 7722-84-1, purity > 30wt%, purchased from Sinopharm Group Chemical Reagent Co., Ltd.) 3.33g, added together in a water-bath bottle with a sealed jacket, under the irradiation of a 300W high-pressure mercury lamp, using magnetic stirring, set Rotate at 700rpm, react at 60°C for 30min. The quantitative analysis of thiophene is the same as that shown in Implementation 1. After 30min, Au / TiO 2, Au / ZnO, Au / C desulfurization rates were 63.2%, 70.6% and 83.6%. Simulated gasoline treated with Au / C can meet Euro V and China V standards.

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Abstract

The invention relates to a method for oxidation desulfurization of fuel oil. According to the method, (1) peroxide or a mixture of peroxide and oxygen (air) and (2) a heterogeneous catalyst which has catalytic action and contains Pd, Pt, Ru, Au and Ag are involved, and under the effect of the catalyst, the peroxide is decomposed to generate high-oxidbillity free radicals to be used for oxidized removal of sulphur-containing substances in the fuel oil. The molar mass of the catalyst on a metal basis is 1 / 5000-1 / 2 that of sulfide, and the molar mass of an oxidizing agent is 1 / 2-100 / 1 that of the sulfide. Compared with a conventional method, the method has the advantages of being high in desulfurization efficiency, moderate in reaction condition and simple in process and having easiness in separation.

Description

technical field [0001] The invention relates to a method for low-temperature oxidative desulfurization of fuel oil, in particular to a method for decomposing peroxides under the action of a catalyst to generate highly oxidative free radicals to oxidize and remove sulfur-containing substances in fuel oil, which belongs to the oil product processing industry in the petrochemical industry. , Refining and refining fields. Background technique [0002] With the continuous increase of the number of automobiles in the world, the harm of the exhaust gas generated by the combustion of automobile fuel to the environment is becoming more and more serious. SOx, NOx and particulate matter (PM) in the exhaust gas can cause acid rain, damage the ozone layer and lead to the generation of atmospheric photochemical smog. Among them, SOx can obviously promote the production of NOx and particulate matter, and is the most harmful. Therefore, all countries have paid great attention to the low s...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G27/12
Inventor 杨雪晶李剑平朱刚利王金岭何林汪华林
Owner EAST CHINA UNIV OF SCI & TECH
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