Method used for catalytic oxidation removing of dibenzothiophenes in oil products with zeolite molecular sieve loaded composite catalyst

A zeolite molecular sieve and composite catalyst technology, which is applied in the field of dibenzothiophene, can solve the problems of limiting the wide application of solid-phase supported catalysts, limiting the application of solid-phase supported catalysts, and the difficulty of successful loading of transition metals, and achieves fast, efficient and effective. Effects of conversion, good economic benefits and application prospects, high catalytic oxidation rate and catalytic oxidation efficiency

Active Publication Date: 2019-08-23
GUANGDONG UNIV OF PETROCHEMICAL TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the existing solid-phase supported catalysts still have problems such as high cost, insufficient catalytic oxidation performance, and poor regeneration performance when they are used for catalytic oxidation of petroleum, which severely limits the wide application of solid-phase supported catalysts.
In addition, most of the existing methods for the preparation of solid-phase supported catalysts have problems such as cumbersome preparation process and high preparation cost, and many transition metals are not easy to be successfully supported on the carrier, which also limits the practical application of solid-phase supported catalysts.
In order to successfully load the transition metals on the carrier, the existing synthesis methods choose to synthesize catalysts by hydrothermal reaction under high temperature and high pressure conditions, but these synthesis methods have disadvantages such as harsh conditions and high cost.
In addition, in the existing oxidative desulfurization technology, most researchers choose to add a certain amount of extractant to the oil that has undergone oxidation reaction to extract the oxidation product to achieve the purpose of removing sulfur-containing organic matter, but this separation of oxidation product and The extraction method of crude oil, on the one hand, will increase the cost of desulfurization technology, on the other hand, the extractant will extract some useful substances in crude oil

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  • Method used for catalytic oxidation removing of dibenzothiophenes in oil products with zeolite molecular sieve loaded composite catalyst
  • Method used for catalytic oxidation removing of dibenzothiophenes in oil products with zeolite molecular sieve loaded composite catalyst
  • Method used for catalytic oxidation removing of dibenzothiophenes in oil products with zeolite molecular sieve loaded composite catalyst

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Embodiment 1

[0046] A method for removing dibenzothiophene from oil by catalytic oxidation of zeolite molecular sieve supported composite catalyst, the process flow diagram is as follows figure 1 shown, including the following steps:

[0047] Take zeolite molecular sieve supported composite catalyst (A1, A2, A3, A4, A5), titanium dioxide / zeolite molecular sieve composite catalyst (B1), molybdenum trioxide / zeolite molecular sieve composite catalyst (B2), each 0.10g, add to 20mL, Add 280 μL of cyclohexanone peroxide (CYHPO / Oxidizing agent, O / S=2) solution, the temperature is 100 ℃ in the oil bath pot under magnetic stirring, carry out catalytic oxidation reaction 30min, wherein during the catalytic oxidation reaction process dibenzothiophene (DBT) is converted into dibenzothiophene sulfone (DBTO 2 ) crystals; after the reaction is completed, cool to room temperature, filter the product solution after the catalytic oxidation reaction, and filter and separate the catalyst in the product sol...

Embodiment 2

[0072] A method for removing dibenzothiophene in oil by catalytic oxidation of a zeolite molecular sieve supported composite catalyst, comprising the following steps:

[0073] Get 4 groups of zeolite molecular sieve supported composite catalysts (A1) prepared in Example 1, the quality is successively 0.05g, 0.10g, 0.15g, 0.20g, add to 20mL respectively, the dibenzothiophene with sulfur concentration of 500ppmw In (DBT)-n-octane solution (that is, simulated petroleum containing dibenzothiophene), the mixed solutions numbered C1, C2, C3, and C4 in turn; to the mixed solutions numbered C1, C2, C3, and C4 Add 140 μ L, 210 μ L, 280 μ L, 350 μ L of cyclohexanone peroxide solution in turn (the O / S in these solutions of cyclohexanone peroxide is 1, 1.5, 2, 2.5 in turn, and the mass fraction of cyclohexanone peroxide solution is 50 %), in an oil bath at a temperature of 100°C under magnetic stirring, the catalytic oxidation reaction was carried out for 15 minutes, wherein during the ca...

Embodiment 3

[0077] A method for removing dibenzothiophene in oil by catalytic oxidation of a zeolite molecular sieve supported composite catalyst, comprising the following steps:

[0078] Get 5 groups of zeolite molecular sieve supported composite catalysts (A1) prepared in Example 1, every group of 0.10g, add respectively to 20mL, dibenzothiophene (DBT)-n-octane solution (i.e. 280 μL of cyclohexanone peroxide (oxidizing agent, O / S=2) solution with a mass fraction of 50% was added to the simulated petroleum containing dibenzothiophene), respectively, at 40°C, 60°C, and 80°C , 100°C, 120°C in an oil bath under magnetic stirring for 30 minutes, wherein dibenzothiophene (DBT) is converted into dibenzothiophene sulfone (DBTO) during the catalytic oxidation reaction 2 ) crystals; after the reaction is completed, cool to room temperature, filter the product solution after the catalytic oxidation reaction, and filter and separate the catalyst in the product solution from the simulated petroleum,...

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Abstract

The invention discloses a method used for catalytic oxidation removing of dibenzothiophenes in oil products with a zeolite molecular sieve loaded composite catalyst. The method comprises following steps: the zeolite molecular sieve loaded composite catalyst is mixed with a petroleum product containing dibenzothiophenes, an oxidizing agent is added for catalytic oxidation reaction to remove dibenzothiophenes in the petroleum product; wherein zeolite molecular sieve is taken as the carrier of the zeolite molecular sieve loaded composite catalyst, and is loaded with molybdenum trioxide and titanium dioxide. The method is simple in technology, convenient in operation, low in cost, high in removing efficiency, and excellent in removing effect, is capable of realizing effective conversion of dibenzothiophenes in petroleum product with high efficiency, realizing ultra high efficiency and ultra deep oxidation desulphurization, possesses extremely excellent economic benefit, and is promising inapplication prospect.

Description

technical field [0001] The invention belongs to the technical field of petrochemical industry, and relates to a method for removing dibenzothiophene in oil by catalytic oxidation using a zeolite molecular sieve-loaded composite catalyst. Background technique [0002] In recent years, the emission of sulfur organic compounds in petroleum has seriously affected air quality, endangered human health and shortened the service life of various automobile engines. In response to these challenges, many countries have instituted new specifications for the sulfur content of fuel. For example, the EU standard: the concentration of sulfur in petroleum must not exceed 10ppmw. In the United States, sulfur concentrations in diesel and gasoline are limited to below 15 ppmw and 30 ppmw, respectively. Therefore, deep and rapid desulfurization is an urgent research problem for researchers. [0003] Oxidative desulfurization (ODS) has the advantages of mild operating conditions, simple operat...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G27/00B01J29/78
CPCB01J23/002B01J29/7876B01J2229/186C10G27/00C10G2300/202
Inventor 杨春平罗倩童梦滢林燕杜诚马寅江利梅钟袁元
Owner GUANGDONG UNIV OF PETROCHEMICAL TECH
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