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

A tungsten oxide-based, oxidative desulfurization technology, used in coal processing, petroleum processing and petrochemical fields, can solve the problems of loss of oil, difficult to completely separate oil and water, and immiscibility of oil and water, and achieve the effect of improving activity.

Inactive Publication Date: 2013-08-14
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there are two problems in this catalytic system: (1) There is a large amount of water in the reaction system. Since oil and water are difficult to completely separate, not only will part of the oil be lost, but also a large amount of oily wastewater will be produced, causing environmental pollution
(2) Oil and water are immiscible, and the reaction mainly occurs at the two-phase interface, making the mass transfer efficiency of the reaction system very low
The reported catalysts mainly include supported NiMo, CoMo, NiCoMo, MoO 3 , CrO 3 、WO 3 , Nb 2 o 5 , V 2 o 5 and ZrO 2 and other transition metal oxides, supported by Al 2 o 3 、TiO 2 , SiO 2 -Al 2 o 3 and zeolite molecular sieves, among which supported molybdenum oxide-based and tungsten oxide-based catalysts are the most commonly used catalysts, but their activity and stability need to be further improved

Method used

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

Examples

Experimental program
Comparison scheme
Effect test

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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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...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/28B01J23/30
Inventor 李翔王孟艳王安杰赵璐
Owner DALIAN UNIV OF TECH
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