Method for preparing supported molybdenum-oxide-based and tungsten-oxide-based oxidation desulfurization catalysts

Abstract

The invention discloses a method for preparing supported molybdenum-oxide-based and tungsten-oxide-based oxidation desulfurization catalysts, belonging to the technical fields of coal processing, petroleum processing and petrochemical industry and relating to a method for preparing catalysts for removing thiophene-type heteroaromatic sulfide-containing solids from distillate oil and chemical materials by oxidation. The method is characterized by preparing the catalysts in a way of implementing plasma treatment on the molybdenum-oxide-based or the tungsten-oxide-based catalyst supported by a porous supporter under a hydrogen or inert gas atmosphere. The method has the effect and the benefit of remarkably enhancing the oxidation desulfurization activity of the supported molybdenum-oxide-based and tungsten-oxide-based catalysts, and has wide application prospect in the field of deep desulfurization.

Description

technical field

[0001] The invention belongs to the technical fields of coal processing, petroleum processing and petrochemical industry, and relates to a supported molybdenum-based and tungsten-based molybdenum-based and tungsten-based materials mainly used for oxidative removal of thiophene aromatic heterocyclic sulfides in gasoline, kerosene and diesel fraction oil and chemical raw materials Preparation method of solid catalyst. Background technique

[0002] Organic sulfur compounds in fuel burn to form SO x , is one of the main sources of air pollution. In recent years, with the intensification of the trend of crude oil becoming heavier and inferior, the content of organic sulfur compounds in fuel oil has gradually increased, but environmental protection requirements have become increasingly stringent. A common problem with sulfur content.

[0003] In refineries, the removal of organic sulfur compounds in oil is mainly achieved through hydrodesulfurization (HDS) proce...

Examples

Embodiment 1

[0018] Example 1: Under Ar gas atmosphere, MoO 3 / SiO 2 and WO 3 / SiO 2 Catalyst preparation

[0019] Preparation of Supported MoO by Equal Volume Impregnation Method 3 / SiO 2 and WO 3 / SiO 2 Catalyst: Weigh 0.920g of ammonium molybdate or 0.852g of ammonium metatungstate and dissolve it in 9ml of deionized water to make a solution, add it dropwise to 3g of white carbon black, stir well, let stand at room temperature for 12h, and dry at 120°C for 4h , the temperature was raised to 500°C at a rate of 2°C / min, and SiO was prepared after calcination for 5 hours. 2 Loaded MoO 3 or WO 3 Catalyst, denoted as MoO 3 / SiO 2 or WO 3 / SiO 2 , where MoO 3 or WO 3 The loading amount of is 20% by mass fraction (based on the total mass of the catalyst).

[0020] Under Ar gas atmosphere, MoO was treated with plasma 3 / SiO 2 catalyst. reaction in a dielectric barrier discharge plasma reactor ( figure 1 ) in. The catalyst filling volume is 2mL; the inlet Ar gas flow rate is...

Embodiment 2

[0021] Example 2: In H 2 Atmosphere, MoO 3 / SiO 2 and WO 3 / SiO 2 Catalyst preparation

[0022] Preparation of Supported MoO by Equal Volume Impregnation Method 3 / SiO 2 and WO 3 / SiO 2 Catalyst: Weigh 0.920g of ammonium molybdate or 0.852g of ammonium metatungstate and dissolve it in 9ml of deionized water to make a solution, add it dropwise to 3g of white carbon black, stir well, let stand at room temperature for 12h, and dry at 120°C for 4h , the temperature was raised to 500°C at a rate of 2°C / min, and SiO was prepared after calcination for 5 hours. 2 Loaded MoO 3 or WO 3 Catalyst, denoted as MoO 3 / SiO 2 or WO 3 / SiO 2 , where MoO 3 or WO 3 The loading amount of is 20% by mass fraction (based on the total mass of the catalyst).

[0023] in H 2 Under gas atmosphere, MoO was treated with plasma 3 / SiO 2 and WO 3 / SiO 2 catalyst. reaction in a dielectric barrier discharge plasma reactor ( figure 1 ) in. Catalyst filling volume 2mL; inlet H 2 The gas...

Embodiment 3

[0024] Example 3: MoO 3 / SiO 2 -Ar and MoO 3 / SiO 2 Activity Evaluation of -H Catalyst

[0025] 0.2g of MoO 3 / SiO 2 -Ar or MoO 3 / SiO 2 The -H catalyst was packed in a fixed-bed reactor with an inner diameter of 8 mm, and the toluene solution of dibenzothiophene with a mass fraction of 0.2% was used as a simulated oil product, and cumene peroxide was used as an oxidant to carry out continuous oxidative desulfurization reaction. Other reaction conditions are: O / S molar ratio=4, normal pressure, reaction temperature 50°C, WHSV=32h -1 . Depend on figure 2 It can be seen that under the same conditions, the oxidative desulfurization activity of the plasma-treated catalyst is higher than that of MoO 3 / SiO 2 There is a significant improvement.

technical field

[0001] The invention belongs to the technical fields of coal processing, petroleum processing and petrochemical industry, and relates to a supported molybdenum-based and tungsten-based molybdenum-based and tungsten-based materials mainly used for oxidative removal of thiophene aromatic heterocyclic sulfides in gasoline, kerosene and diesel fraction oil and chemical raw materials Preparation method of solid catalyst. Background technique

[0002] Organic sulfur compounds in fuel burn to form SO x , is one of the main sources of air pollution. In recent years, with the intensification of the trend of crude oil becoming heavier and inferior, the content of organic sulfur compounds in fuel oil has gradually increased, but environmental protection requirements have become increasingly stringent. A common problem with sulfur content.

[0003] In refineries, the removal of organic sulfur compounds in oil is mainly achieved through hydrodesulfurization (HDS) proce...

Examples

Embodiment 1

[0018] Example 1: Under Ar gas atmosphere, MoO 3 / SiO 2 and WO 3 / SiO 2 Catalyst preparation

[0019] Preparation of Supported MoO by Equal Volume Impregnation Method 3 / SiO 2 and WO 3 / SiO 2 Catalyst: Weigh 0.920g of ammonium molybdate or 0.852g of ammonium metatungstate and dissolve it in 9ml of deionized water to make a solution, add it dropwise to 3g of white carbon black, stir well, let stand at room temperature for 12h, and dry at 120°C for 4h , the temperature was raised to 500°C at a rate of 2°C / min, and SiO was prepared after calcination for 5 hours. 2 Loaded MoO 3 or WO 3 Catalyst, denoted as MoO 3 / SiO 2 or WO 3 / SiO 2 , where MoO 3 or WO 3 The loading amount of is 20% by mass fraction (based on the total mass of the catalyst).

[0020] Under Ar gas atmosphere, MoO was treated with plasma 3 / SiO 2 catalyst. reaction in a dielectric barrier discharge plasma reactor ( figure 1 ) in. The catalyst filling volume is 2mL; the inlet Ar gas flow rate is...

Embodiment 2

[0021] Example 2: In H 2 Atmosphere, MoO 3 / SiO 2 and WO 3 / SiO 2 Catalyst preparation

[0022] Preparation of Supported MoO by Equal Volume Impregnation Method 3 / SiO 2 and WO 3 / SiO 2 Catalyst: Weigh 0.920g of ammonium molybdate or 0.852g of ammonium metatungstate and dissolve it in 9ml of deionized water to make a solution, add it dropwise to 3g of white carbon black, stir well, let stand at room temperature for 12h, and dry at 120°C for 4h , the temperature was raised to 500°C at a rate of 2°C / min, and SiO was prepared after calcination for 5 hours. 2 Loaded MoO 3 or WO 3 Catalyst, denoted as MoO 3 / SiO 2 or WO 3 / SiO 2 , where MoO 3 or WO 3 The loading amount of is 20% by mass fraction (based on the total mass of the catalyst).

[0023] in H 2 Under gas atmosphere, MoO was treated with plasma 3 / SiO 2 and WO 3 / SiO 2 catalyst. reaction in a dielectric barrier discharge plasma reactor ( figure 1 ) in. Catalyst filling volume 2mL; inlet H 2 The gas...

Embodiment 3

[0024] Example 3: MoO 3 / SiO 2 -Ar and MoO 3 / SiO 2 Activity Evaluation of -H Catalyst

[0025] 0.2g of MoO 3 / SiO 2 -Ar or MoO 3 / SiO 2 The -H catalyst was packed in a fixed-bed reactor with an inner diameter of 8 mm, and the toluene solution of dibenzothiophene with a mass fraction of 0.2% was used as a simulated oil product, and cumene peroxide was used as an oxidant to carry out continuous oxidative desulfurization reaction. Other reaction conditions are: O / S molar ratio=4, normal pressure, reaction temperature 50°C, WHSV=32h -1 . Depend on figure 2 It can be seen that under the same conditions, the oxidative desulfurization activity of the plasma-treated catalyst is higher than that of MoO 3 / SiO 2 There is a significant improvement.

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