阅读说明：本技术 一种基于二氧化硅纳米球负载型氧化钼量子点催化剂的含硫燃料油脱硫方法 (Sulfur-containing fuel oil desulfurization method based on silica nanosphere supported molybdenum oxide quantum dot catalyst ) 是由 崔佳伟 王光辉 田永胜 柯萍 刘巍 马志江 徐浩伦 于 2019-11-07 设计创作，主要内容包括：本发明提供了一种基于二氧化硅纳米球负载型氧化钼量子点催化剂的含硫燃料油脱硫方法,包括如下步骤：向含硫燃料油中添加二氧化硅纳米球负载型氧化钼量子点催化剂和氧化剂,在常压下反应完全后,取上层有机相即为脱硫后的燃料油。本发明以二氧化硅纳米球负载型氧化钼量子点作为催化剂,对油品进行脱硫。对苯并噻吩、二苯并噻吩、4,6-二甲基二苯并噻吩氧化有良好的催化性能。(The invention provides a sulfur-containing fuel oil desulfurization method based on a silica nanosphere supported molybdenum oxide quantum dot catalyst, which comprises the following steps: adding a silicon dioxide nanosphere supported molybdenum oxide quantum dot catalyst and an oxidant into sulfur-containing fuel oil, and taking an upper layer organic phase as desulfurized fuel oil after the reaction is completed under normal pressure. The invention takes the silicon dioxide nanosphere loaded molybdenum oxide quantum dots as a catalyst to desulfurize oil products. Has good catalytic performance for oxidizing benzo thiophene, dibenzothiophene and 4, 6-dimethyl dibenzothiophene.)

1. A sulfur-containing fuel oil desulfurization method based on a silica nanosphere supported molybdenum oxide quantum dot catalyst is characterized in that the silica nanosphere supported molybdenum oxide quantum dot catalyst and an oxidant are added into sulfur-containing fuel oil, after complete reaction at normal pressure, the mixture is stood, and then an upper layer organic phase is taken as desulfurized fuel oil.

2. The desulfurization method of sulfur-containing fuel oil based on silica nanosphere supported molybdenum oxide quantum dot catalyst according to claim 1, characterized in that: the sulfur-containing fuel oil is simulated gasoline or straight-run gasoline.

3. The desulfurization method of sulfur-containing fuel oil based on silica nanosphere supported molybdenum oxide quantum dot catalyst according to claim 2, characterized in that: the simulated gasoline is n-octane containing benzothiophene, dibenzothiophene or 4, 6-dimethyldibenzothiophene, and the sulfur content of the simulated gasoline is 400 ppm.

4. The desulfurization method of sulfur-containing fuel oil based on silica nanosphere supported molybdenum oxide quantum dot catalyst according to claim 1, characterized in that: the adding amount of the silicon dioxide nanosphere supported molybdenum oxide quantum dot catalyst is 0.2-1.4% of the mass of the sulfur-containing fuel oil.

5. The desulfurization method of sulfur-containing fuel oil based on silica nanosphere supported molybdenum oxide quantum dot catalyst according to claim 1, characterized in that: the oxidant is 30% of hydrogen peroxide by mass fraction, and the addition amount of the oxidant is 0.1-0.5% of the volume of the sulfur-containing fuel oil.

6. The desulfurization method of sulfur-containing fuel oil based on silica nanosphere supported molybdenum oxide quantum dot catalyst according to claim 1, characterized in that: the reaction temperature is 45-70 ℃ and the reaction time is 5-25 min.

7. The desulfurization method of sulfur-containing fuel oil based on silica nanosphere supported molybdenum oxide quantum dot catalyst according to claim 6, characterized in that: the reaction temperature is 60 ℃, and the reaction time is 10 min.

8. According toThe desulfurization method for sulfur-containing fuel oil based on silica nanosphere supported molybdenum oxide quantum dot catalyst of any one of claims 1-7, characterized in that, the silica nanosphere supported molybdenum oxide quantum dot catalyst is prepared by the following method: mixing MoS₂Adding the powder and the silicon dioxide nanospheres into deionized water, stirring until the powder and the silicon dioxide nanospheres are uniformly mixed, adding hydrogen peroxide, adjusting the solution to be neutral by using a sodium hydroxide aqueous solution after the reaction is completed, and then carrying out solid-liquid separation to obtain a solid part, namely the silicon dioxide nanosphere supported molybdenum oxide quantum dot catalyst.

9. The method for desulfurizing sulfur-containing fuel oil based on silica nanosphere-supported molybdenum oxide quantum dot catalyst according to claim 8, wherein said MoS is₂The using amount of the powder and the silicon dioxide nanospheres is 0.05-0.15 by mass: 1; the concentration of the hydrogen peroxide is 30 wt%, the dosage of the silicon dioxide nanospheres and the volume of the hydrogen peroxide are 0.25g/mL in a solid-to-liquid ratio, and the dosage of the hydrogen peroxide and the deionized water is 2: 3; the concentration of the sodium hydroxide aqueous solution is 10 mol/L.

10. The desulfurization method for sulfur-containing fuel oil based on silica nanosphere supported molybdenum oxide quantum dot catalyst according to claim 8, wherein the reaction temperature for preparing the silica nanosphere supported molybdenum oxide quantum dot catalyst is room temperature, and the reaction time is 5-30 min; and the solid-liquid separation refers to centrifuging the mixed solution, taking a precipitate, washing and drying in vacuum to obtain a solid part.

Technical Field

The invention belongs to the technical field of deep desulfurization of oil products, and particularly relates to a sulfur-containing fuel oil desulfurization method based on a silica nanosphere supported molybdenum oxide quantum dot catalyst.

Background

The combustion of organic sulfur-containing compounds in fuel oils produces large amounts of Sulfur Oxides (SO)_x) And sulfate particles, which can cause acid rain and the like to have serious effects on the environment. Moreover, the combustion of sulfur-containing organic compounds in fuel oils can also corrode automobile engines, while SO_xThe existence of the catalyst can poison the three-way catalyst of the automobile exhaust converter and reduce NO_xConversion efficiency of incompletely combusted hydrocarbons, particulate matter, etc. China, the united states, and the european union, etc. have consequently developed a series of stricter laws and regulations on the organic sulfur content standards in fuel oils. Researchers in various places have also developed various production technologies for ultra-low sulfur fuel oil.

Oxidative desulfurization was first developed by Unipure corporation in 2001 and was later considered to be one of the most promising processes for producing ultra-low sulfur fuel oils. The oxidative desulfurization can be carried out under the mild reaction conditions of normal temperature and normal pressure and the presence of a proper catalyst, and the selectivity of the thiophene organic sulfur-containing compounds which are difficult to remove by hydrodesulfurization is high.

The molybdenum-based catalyst has the advantages of high valence, small ionic radius, polyhedral oxide structure, different valence under different conditions and the like, so that the molybdenum-based catalyst plays an important role in petrochemical industry and other industries and has wide application prospect in the field of catalysis. Jia and colleagues found in MoO₃As catalyst, H₂O₂The oxidant can effectively remove the organic sulfur compounds in the fuel oil under mild reaction conditions. Meanwhile, the silicon dioxide can be used as an excellent catalyst carrier due to high chemical stability and thermal stability, large specific surface area and good compatibility with other materials. In addition, the silica shows B acidity which is beneficial for the catalytic reaction, and the rich hydroxyl on the surface of the silica is beneficial for the adsorption of oxidation products. Albeit now in MoO_xThere are many reports on catalysts, but it is common to report MoO_xThe research of the molybdenum oxide particle size on the modification of the molybdenum oxide has been stopped, and the research on the influence of the molybdenum oxide particle size on the catalytic effect is rarely reported. The surface effect of the molybdenum oxide quantum dots enables the surfaces of the quantum dots to have a plurality of holes and defects, and the quantum dots have large surface energy and high activity. The application of the high-activity molybdenum oxide quantum dots to the catalytic oxidation desulfurization of the fuel oil is of great significance.

Disclosure of Invention

The invention explores the catalytic performance of the silica nanosphere supported molybdenum oxide quantum dot catalyst, and finds that the catalyst has good catalytic performance on oxidation of benzo thiophene, dibenzothiophene and 4, 6-dimethyl dibenzothiophene. Therefore, the invention provides a desulfurization method based on silica nanosphere supported molybdenum oxide quantum dots, which takes the silica nanosphere supported molybdenum oxide quantum dots as a catalyst to desulfurize oil products.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a sulfur-containing fuel oil desulfurization method based on a silica nanosphere supported molybdenum oxide quantum dot catalyst comprises the following steps:

adding a silicon dioxide nanosphere supported molybdenum oxide quantum dot catalyst and an oxidant into sulfur-containing fuel oil, reacting completely under normal pressure, standing, and taking an upper layer organic phase, namely the desulfurized fuel oil.

On the basis of the technical scheme, the invention can further have the following specific selection or optimized selection.

Specifically, the sulfur-containing fuel oil is simulated gasoline or straight-run gasoline. Wherein the simulated gasoline is n-octane containing benzothiophene, dibenzothiophene or 4, 6-dimethyldibenzothiophene, and the sulfur content of the simulated gasoline is 400 ppm.

Specifically, the adding amount of the silica nanosphere supported molybdenum oxide quantum dot catalyst is 0.2-1.4% of the mass of the sulfur-containing fuel oil, and the adding amount of the oxidant is 0.1-0.5% of the volume of the sulfur-containing fuel oil.

Specifically, the oxidant is 30% of hydrogen peroxide by mass fraction.

Preferably, the reaction temperature is 60 ℃ and the reaction time is 10 min.

Specifically, the reaction temperature is 45-70 ℃ and the reaction time is 5-25 min.

Specifically, the silicon dioxide nanosphere supported molybdenum oxide quantum dot catalyst is prepared by the following method: mixing MoS₂Adding the powder and the silicon dioxide nanospheres into deionized water, stirring until the powder and the silicon dioxide nanospheres are uniformly mixed, adding hydrogen peroxide, adjusting the solution to be neutral by using a sodium hydroxide aqueous solution after the reaction is completed, and then carrying out solid-liquid separation to obtain a solid part, namely the silicon dioxide nanosphere supported molybdenum oxide quantum dot catalyst.

Wherein the MoS₂The using amount of the powder and the silicon dioxide nanospheres is 0.05-0.15 by mass: 1. the dosage of the silicon dioxide nanospheres and the volume of hydrogen peroxide are calculated by the solid-liquid ratio of 1: 4(g/mL), wherein the dosage of the hydrogen peroxide and the deionized water is 2: 3. the concentration of the hydrogen peroxide is 30 wt%, and the concentration of the sodium hydroxide aqueous solution is 10 mol/L. The preparation reaction temperature of the silicon dioxide nanosphere supported molybdenum oxide quantum dot catalyst is room temperature (20-30 ℃), and the reaction time is 5-30 min. The room temperature mainly means that the reaction can be directly carried out without heating. And the solid-liquid separation refers to centrifuging the mixed solution, taking a precipitate, washing and drying in vacuum to obtain a solid part. Specifically, the mixture was centrifuged at 8000rpm for 10min, the precipitate was washed with deionized water, centrifuged at 8000rpm for 10min, repeated for 3 more times, and finally vacuum dried at 60 ℃. The chemical formula of the molybdenum oxide is MoO_3-xWherein X is an arbitrary number within the range of 0 to 0.5.

The aqueous NaOH solution adjusted the solution to a neutral pH of about 7.0. The silica nanospheres are prepared by the prior art. And standing for about 10-30min until water and oil are separated. When the desulfurization rate of the silica nanosphere supported molybdenum oxide quantum dot catalyst is measured in a laboratory, a subsequent product needs to be cooled, subjected to constant volume and centrifugal separation, and an upper organic phase is taken as a desulfurized oil product. Wherein, the cooling, constant volume and centrifugal separation specifically comprises centrifuging the product at 8000rpm for 10min, collecting precipitate, washing with deionized water, centrifuging at 8000rpm for 10min, repeating the above operation for more than 3 times, and vacuum drying at 60 deg.C.

Compared with the prior art, the invention has the beneficial effects that:

(1) the invention applies the silicon dioxide nanosphere loaded molybdenum oxide quantum dots to the catalytic oxidation process of oil products, and has high desulfurization rate;

(2) the catalyst is a catalytic oxidation system for oil products containing sulfides, which is composed of the catalyst and an oxidant hydrogen peroxide, the catalyst can be recycled, the reusability is good, and solid and liquid are easy to separate;

(3) after the desulfurization reaction is finished, clean oil with extremely low sulfur content can be obtained by a simple method, and basically no loss is caused;

(4) the reacted oil product contains a large amount of sulfone substances which are oxidation products of sulfides in the oil product, but an extracting agent is not required to be added, the sulfone substances can be adsorbed by the silicon dioxide nanospheres, and then the regenerated catalyst can be obtained by regenerating the catalyst at high temperature.

Drawings

FIG. 1 is a Fourier transform-infrared spectrum of silica nanosphere-loaded molybdenum oxide quantum dots;

FIG. 2 is N of silica nanosphere supported molybdenum oxide quantum dots₂An adsorption-desorption curve;

FIG. 3 is an X-ray photoelectron spectrum of silica nanosphere-supported molybdenum oxide quantum dots;

FIG. 4 is a particle size distribution diagram and SEM image of silica nanosphere-supported molybdenum oxide quantum dots of example 1;

fig. 5 is a diagram of the catalytic oxidation removal effect of silica nanosphere-loaded molybdenum oxide quantum dots on different sulfur-containing organic compounds.

Detailed Description

For a better understanding of the present invention, the following further illustrates the present invention with reference to the accompanying drawings and specific examples, but the present invention is not limited to the following examples.

The following reagents were used: benzothiophene (Acros, USA), dibenzothiophene (Acros, USA), 4, 6-dimethyldibenzothiophene (Chemicals, Inc., national drug group), n-octane (Chemicals, Inc., national drug group), 30 wt% hydrogen peroxide (Chemicals, Inc., national drug group), and the like.