Desulfurization method by catalytic oxidation for fuel oil

A technology for catalytic oxidative desulfurization and fuel oil, applied in chemical instruments and methods, refining with oxygenated compounds, catalysts for physical/chemical processes, etc. problems, to achieve good application prospects, reduce metal pollution, and low operating costs.

Inactive Publication Date: 2013-05-01
SHAANXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But there are some problems: (1) The catalyst is difficult to recycle, the catalyst life is short, and the stability is not ideal, so it is difficult to be applied in actual industrial production (Chem.Eng.Jpn.2002,35(12)Catal.Today 2010 ,150:37–41)
Although the desulfurization effect is ideal, the oxidative desulfurization reaction using air oxygen as the oxidant at a higher temperature inevitably occurs side reactions such as aromatic hydrocarbon oxidation
(3) The problem that the extraction agent reduces the quality of the oil product
The oxidative desulfurization method often uses extractant to remove oxidation products. In the extraction method, the addition of solvent as the extractant phase causes the quality of the oil to decline to a certain extent.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0012] Taking 10.0 mL of fuel oil with a sulfur content of 1000 μg / g as an example as a raw material, the method for catalytic oxidation desulfurization of it is realized by the following steps:

[0013] Measure 10.0 mL of fuel oil with a sulfur content of 1000 μg / g, add 0.0193 g of solid-supported double-layer ionic liquid-phosphotungstate catalyst, 1 mL of methanol, and 0.44 mL of peroxide with a concentration of 30% by mass Hydrogen, the molar ratio of sulfur in fuel oil to catalyst and hydrogen peroxide is 1:0.025:20, the volume ratio of fuel oil to methanol is 1:0.1, stir and react at 70°C for 10 hours, let stand and separate, the upper layer is For desulfurized fuel oil, the lower layer is the mixture of extractant and catalyst, which can be further extracted to separate the catalyst, which can be reused.

[0014] The above-mentioned immobilized double-layer ionic liquid-phosphotungstate catalyst is prepared by the following method:

[0015] Stir 1.8g of tetrabutylammon...

Embodiment 2

[0023] Taking 10.0 mL of fuel oil with a sulfur content of 1000 μg / g as an example as a raw material, the method for catalytic oxidation desulfurization of it is realized by the following steps:

[0024] Measure 10.0 mL of fuel oil with a sulfur content of 1000 μg / g, add 0.0154 g of solid-supported double-layer ionic liquid-phosphotungstate catalyst, 0.5 mL of methanol, and 0.22 mL of 30% superfluidic acid to it. Hydrogen oxide, the molar ratio of sulfur in fuel oil to catalyst and hydrogen peroxide is 1:0.02:10, the volume ratio of fuel oil to extractant is 1:0.05, stirred and reacted at 70°C for 10 hours, allowed to stand and separate into layers, The upper layer is desulfurized fuel oil, and the lower layer is the mixture of extractant and catalyst, which can be further extracted to separate the catalyst and can be reused.

[0025] The preparation method of the above-mentioned immobilized double-layer ionic liquid-phosphotungstate catalyst is the same as that of Example 1. ...

Embodiment 3

[0027] Taking 10.0 mL of fuel oil with a sulfur content of 1000 μg / g as an example as a raw material, the method for catalytic oxidation desulfurization of it is realized by the following steps:

[0028] Measure 10.0 mL of fuel oil with a sulfur content of 1000 μg / g, add 0.0231 g of solid-supported double-layer ionic liquid-phosphotungstate catalyst, 2 mL of methanol, and 0.55 mL of peroxide with a concentration of 30% by mass The molar ratio of hydrogen, sulfur in fuel oil to catalyst, methanol, and hydrogen peroxide is 1:0.03:25, and the volume ratio of fuel oil to extractant is 1:0.4. Stir and react at 70°C for 10 hours, let stand and separate , the upper layer is desulfurized fuel oil, and the lower layer is the mixture of extractant and catalyst, which can be further extracted to separate the catalyst and can be reused.

[0029] The preparation method of the above-mentioned immobilized double-layer ionic liquid-phosphotungstate catalyst is the same as that of Example 1. ...

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PUM

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Abstract

The invention provides a desulfurization method by catalytic oxidation for fuel oil. The method comprises the steps of taking low-concentration, non-toxic, cheap and readily accessible hydrogen peroxide as an oxidizer, taking immobilized double-layer ionic liquid-phosphotungstate as a catalyst, and separating desulfurized fuel oil by catalytic oxidation extraction. The method can effectively reduce metal contamination in an oil product, is good in desulfurization effect, high in oil product recovery and mild in reaction condition, and can particularly realize deep desulfurization of benzothiophene (BT) sulfide or dibenzothiophene (DBT) and a derivative of BT sulfide or DBT; and the catalyst is simple in preparation method, small in use amount and high in activity, and can be recycled after being filtered and washed simply, so that the material cost is lowered. The method is simple in technology, readily accessible in raw material, low in operating cost, mild in reaction condition, few in byproduct, small in environmental contamination, suitable for industrial application, and good in application prospect.

Description

technical field [0001] The invention belongs to the technical field of oxidation desulfurization, and in particular relates to a method for catalytic oxidation desulfurization of fuel oil through a catalytic oxidation-extraction method. Background technique [0002] The direct and indirect pollution and damage caused by the combustion of sulfur compounds in fuel oil to the environment are irreversible. For this reason, countries around the world have formulated fuel standards that strictly limit the sulfur content. At the same time, most countries have proposed measures to fundamentally solve automobile exhaust pollution from the source, that is, adopt new technologies and processes to reduce the sulfur content of fuel and produce clean fuels. Traditional hydrodesulfurization is the main desulfurization method that has been industrialized, but the desulfurization effect on benzothiophene (BT) sulfides, especially diphenylthiophene (DBT) and its derivatives is relatively poo...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G27/12C10G21/16C10G21/20B01J31/02
Inventor 石先莹马文娟偶辉魏俊发
Owner SHAANXI NORMAL UNIV
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