阅读说明：本技术 一种碳化蚕丝光催化剂的制备方法及其应用 (preparation method and application of carbonized silkworm mercerization catalyst ) 是由 曾兴业 陈振雄 王寒露 张战军 吴世逵 于 2019-08-15 设计创作，主要内容包括：本发明公开了一种碳化蚕丝光催化剂的制备方法及其应用。这种碳化蚕丝光催化剂是由以下的制备方法制得：将天然蚕丝与活化剂浸泡于水中,取出浸泡后的蚕丝,干燥,再将干燥后的蚕丝在惰性气氛保护下焙烧制成。本发明还公开了一种燃油的光催化脱硫方法,是将待脱硫的燃油、萃取剂和碳化蚕丝光催化剂混合,以空气作为氧化剂,在光照下进行光催化反应,分离上层油相得到脱硫后的燃油。本发明的催化剂制备工艺简单,在UV光辐射下能有效地降低燃油中难以脱除的二苯并噻吩类硫化物；脱硫过程在室温下即可实现脱硫,反应条件温和；采用空气为氧化剂,无需加入易爆性过氧化物,降低了潜在的安全风险。本发明的催化剂在燃油脱硫方面具有良好的应用价值。(the invention discloses a preparation method and application of a carbonized silkworm mercerization catalyst. The carbonized silk photocatalyst is prepared by the following preparation method: soaking natural silk and an activating agent in water, taking out the soaked silk, drying, and roasting the dried silk under the protection of inert atmosphere. The invention also discloses a method for the photocatalytic desulfurization of fuel oil, which is to mix the fuel oil to be desulfurized, an extracting agent and a carbonized silk photocatalyst, take air as an oxidant, carry out photocatalytic reaction under illumination, and separate an upper oil phase to obtain the desulfurized fuel oil. The catalyst has simple preparation process, and can effectively reduce dibenzothiophene sulfides which are difficult to remove in fuel oil under the radiation of UV light; the desulfurization can be realized at room temperature in the desulfurization process, and the reaction condition is mild; air is used as an oxidant, explosive peroxide is not required to be added, and potential safety risks are reduced. The catalyst of the invention has good application value in the aspect of fuel oil desulfurization.)

1. A preparation method of a carbonized silkworm mercerization catalyst is characterized by comprising the following steps: the method comprises the following steps:

1) soaking natural silk and activating agent in water, taking out the soaked silk, and drying;

2) roasting the dried silk under the protection of inert atmosphere to obtain a carbonized silk photocatalyst;

In the step 1), the activating agent is one or more of oxalic acid, phosphotungstic acid, citric acid, lauric acid, boric acid and potassium chloride.

2. The method for preparing carbonized silkworm mercerization catalyst according to claim 1, characterized by comprising the following steps: in the step 1), the mass ratio of the natural silk to the activating agent is 1: (0.1-0.3).

3. The method for preparing carbonized silkworm mercerization catalyst according to claim 1, characterized by comprising the following steps: in the step 2), the roasting temperature is 450-900 ℃.

4. A photocatalyst for fuel oil desulfurization is characterized in that: is prepared by the preparation method of any one of claims 1 to 3.

5. A photocatalytic desulfurization method for fuel oil is characterized in that: the method comprises the following steps: mixing fuel oil to be desulfurized, an extracting agent and a carbonized silk photocatalyst, taking air as an oxidant, carrying out photocatalytic reaction under illumination, and separating an upper oil phase to obtain desulfurized fuel oil; the carbonized silkworm mercerization catalyst is prepared by the preparation method of any one of claims 1 to 3.

6. The photocatalytic desulfurization method according to claim 5, characterized in that: the volume ratio of the fuel oil to be desulfurized to the extracting agent is 1: (0.1 to 1); the dosage ratio of the fuel to be desulfurized to the photocatalyst is 1L: (0.3-1.5) g.

7. The photocatalytic desulfurization method according to claim 6, characterized in that: the sulfur content of the fuel to be desulfurized is 400 mg/L-1500 mg/L.

8. The photocatalytic desulfurization method according to claim 6, characterized in that: the extractant is selected from one or more of methanol, ethanol, ethylene glycol, N-methyl pyrrolidone, N-dimethylformamide, acetonitrile, sulfolane and dimethyl sulfoxide.

9. The photocatalytic desulfurization method according to claim 5, characterized in that: the radiation light source of the photocatalytic reaction is an ultraviolet lamp.

10. the photocatalytic desulfurization method according to claim 5, characterized in that: the temperature of the photocatalytic reaction is 20-30 ℃; the time of the photocatalytic reaction is 120min to 180 min.

Technical Field

The invention relates to a fuel oil desulfurization catalyst material, in particular to a preparation method and application of a carbonized silk photocatalyst.

Background

With the popularization of automobiles, the production and life of people are seriously affected by the problem of environmental pollution caused by automobile exhaust, so that China is increasingly revised and provides a clean fuel standard with higher requirements. The national V fuel standard is started to be executed nationwide in 2017, and the maximum sulfur content in the fuel is regulated to be not more than 10 mg/kg. Since 2019, more stringent "national VIA" standards are being investigated to continue to drive air quality improvement. The current fuel oil desulfurization technologies are mainly divided into two categories: hydrodesulfurization technology and non-hydrodesulfurization technology are mostly adopted in industry at present, but the technology has the defects of poor effect of removing thiophene compounds, large equipment investment, high requirement, high operation cost and the like. The non-hydrodesulfurization technology mainly comprises oxidative desulfurization, extractive desulfurization, adsorption desulfurization, photocatalytic desulfurization and the like. The photocatalytic desulfurization technology has the advantages of environmental protection, neutral carbon and sustainable production, and is a novel desulfurization technology with great potential.

The existing photocatalytic desulfurization technology is mainly based on a photocatalytic desulfurization method of a semiconductor photocatalyst. BiVO loaded with SBA-15 molecular sieves is reported as Hanna et al₄The photocatalytic desulfurization method (Hanna, Chenpolitical, Suwe et al, BiVO)₄Preparation of SBA-15 catalyst and photocatalytic oxygen thereofChemical desulfurization Performance [ J]Fuel chemist, 2019,47(02): 191-198); liu Bu Li et al introduce TiO₂/La³⁺The method for removing the sulfide in the model gasoline has the desulfurization rate of 91.5 percent (La, Labulein, Zhang Qian, high sensitivity and the like) after the light radiation for 210min³⁺/TiO₂Preparation of hollow microsphere and photocatalytic oxidation desulfurization performance of model gasoline [ J]The journal of environmental engineering, 2018,12(12): 3371-3378). Although semiconductor photocatalysts exhibit better desulfurization performance, the reserves of semiconductor materials and their widespread use then limit their prices.

In recent years, carbon materials have been emerging as photocatalysts. For example, CN109650374A discloses a method for preparing graphene-like carbon material, which is mainly based on the result of high temperature carbonization of bacteria and culture medium, and the obtained carbon material is rich in phosphorus, oxygen, nitrogen and sulfur elements. CN109626370A discloses a biomass-based porous carbon material from sycamore seed, in which the activator is mainly solid strong base. CN109626357A discloses an ultra-fine carbon nanotube and a preparation method thereof. The photocatalysts of these carbon materials are mainly based on carbon materials such as graphene and graphene oxide, carbon nanotubes, and porous carbon, and have not been attempted to be used for photocatalytic desulfurization research. And the carbonized materials are difficult to meet the requirements of modern industrial production because of higher cost or longer reaction time. Within the large family of carbon materials, there is also a class of biomass carbon materials. The biomass carbon material has the advantages of green and sustainable property, more impurity elements, low price and the like.

Silk is a natural high molecular weight fibrin containing carbon, nitrogen, oxygen, hydrogen, etc. Generally, silk is directly carbonized at high temperature, because the carbonized material generated is compact and has less active functional groups and low photocatalytic activity along with the occurrence of deoxidation and dehydrogenation reactions in the high-temperature process. At present, no report on the application of silk in preparing a fuel oil desulfurization photocatalyst is disclosed. How to utilize silk to make a good performance photocatalyst to be applied to in the fuel desulfurization treatment, thereby expand the use of this traditional material of silk, provide novel carbon material for fuel photocatalytic desulfurization, become the technical problem that the researcher in the field need solve.

Disclosure of Invention

In order to overcome the problems in the prior art, the invention aims to provide a preparation method of a carbonized silkworm mercerizing catalyst and application of the carbonized silkworm mercerizing catalyst in photocatalytic desulfurization of fuel oil.

The method adopts natural silkworm cocoons and an activating agent to carry out carbonization after soaking, and prepares the photocatalyst which is low in price and high in activity. Not only expands the application of the silk which is a traditional material, but also provides a novel carbon material for the photocatalytic desulfurization of fuel oil.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

The invention provides a preparation method of a carbonized silkworm mercerization catalyst. The preparation method of the carbonized silkworm mercerization catalyst comprises the following steps:

1) Soaking natural silk and activating agent in water, taking out the soaked silk, and drying;

2) Roasting the dried silk under the protection of inert atmosphere to obtain a carbonized silk photocatalyst;

In the step 1), the activating agent is one or more of oxalic acid, phosphotungstic acid, citric acid, lauric acid, boric acid and potassium chloride.

Preferably, in the step 1) of the preparation method of the carbonized silkworm mercerization catalyst, the mass ratio of the natural silk to the activating agent is 1: (0.1 to 0.3); further preferably, the mass ratio of the natural silk to the activating agent is 1: (0.15 to 0.25); most preferably, the mass ratio of the natural silk to the activating agent is 1: 0.2.

Preferably, in step 1) of the preparation method of the carbonized silkworm mercerization catalyst, the natural silk is prepared by the following treatment methods: washing natural silk cocoon with water, and cutting cleaned silk cocoon into pieces to obtain sheet silk. The purpose of the water washing is to wash away impurities on the surface of the cocoons. The area of the chips is preferably 1cm²(1 cm. times.1 cm). The flake silk is used as a raw material for preparing the carbonized silk photocatalyst.

preferably, in the step 1) of the preparation method of the carbonized silkworm mercerization catalyst, the dosage ratio of the natural silks to the water for soaking is 1 g: (50-200) mL; further preferably, the dosage ratio of the natural silk to the water for soaking is 1 g: (80-120) mL.

preferably, in the step 1) of the preparation method of the carbonized silkworm mercerization catalyst, the soaking time is 12-24 h.

Preferably, in the step 1) of the preparation method of the carbonized silkworm mercerization catalyst, the water used for soaking is deionized water.

Preferably, in the step 1) of the preparation method of the carbonized silkworm mercerization catalyst, the drying is carried out for 20 to 30 hours under the vacuum drying condition at the temperature of between 35 and 50 ℃; more preferably, the drying is carried out for 22 to 26 hours under vacuum at 38 to 42 ℃.

Preferably, in the step 2) of the preparation method of the carbonized silkworm mercerization catalyst, the inert atmosphere is one or more of nitrogen, helium, neon and argon; further preferably, the inert atmosphere is a helium or argon atmosphere.

Preferably, in the step 2) of the preparation method of the carbonized silkworm mercerization catalyst, the gas flow of the inert atmosphere is 3 mL/min-12 mL/min; more preferably, the gas flow rate of the inert atmosphere is 5mL/min to 10 mL/min.

Preferably, in the step 2) of the preparation method of the carbonized silkworm mercerization catalyst, the roasting temperature is 450-900 ℃; further preferably, the temperature of the calcination is 500 to 700 ℃.

Preferably, in the step 2) of the preparation method of the carbonized silkworm mercerization catalyst, the roasting is specifically carried out for 3-5 h after the temperature is raised to the roasting temperature from room temperature at 4-6 ℃/min; more preferably, the calcination is carried out by heating the mixture from room temperature to the calcination temperature at a rate of 5 ℃/min and then maintaining the temperature for 3.5 to 4.5 hours.

Preferably, the preparation method of the carbonized silk mercerization catalyst in step 2) further comprises a step of washing the carbonized silk product after roasting, wherein the washing is specifically washing with water and alcohol, and the purpose of washing is to remove the residual activating agent on the surface of the carbonized silk product.

The invention provides an application of the carbonized silk photocatalyst, in particular to an application of the carbonized silk photocatalyst in photocatalytic desulfurization of fuel oil.

The photocatalyst for fuel oil desulfurization is prepared by the preparation method of the carbonized silkworm mercerized catalyst.

The invention also provides a specific application method of the photocatalyst, namely a photocatalytic desulfurization method of fuel oil.

a method for photocatalytic desulfurization of fuel oil comprises the following steps: mixing fuel oil to be desulfurized, an extracting agent and a carbonized silk photocatalyst, taking air as an oxidant, carrying out photocatalytic reaction under illumination, and separating an upper oil phase to obtain desulfurized fuel oil; wherein, the carbonized silkworm mercerization catalyst is prepared by the preparation method.

Preferably, in the method for the photocatalytic desulfurization of the fuel oil, the volume ratio of the fuel oil to be desulfurized to the extracting agent is 1: (0.1 to 1); further preferably, the volume ratio of the fuel oil to be desulfurized to the extracting agent is 1: (0.15 to 0.8); still further preferably, the volume ratio of the fuel oil to be desulfurized to the extracting agent is 1: (0.16-0.5).

Preferably, in the method for the photocatalytic desulfurization of fuel oil, the dosage ratio of the fuel oil to be desulfurized to the photocatalyst is 1L: (0.3-1.5) g; further preferably, the dosage ratio of the fuel to be desulfurized to the photocatalyst is 1L: (0.33-1.33) g.

Preferably, in the method for the photocatalytic desulfurization of the fuel oil, air is introduced to participate in the photocatalytic reaction, and the flow rate of the air is 0mL/min to 50 mL/min; more preferably, the flow rate of the air is 0mL/min to 40 mL/min. When the air flow is 0mL/min, namely air is not blown into the reaction system by adopting an air pipe, and oxygen of the reaction system comes from dissolved oxygen contacting with the air on the surface of the reaction liquid; when having air current, reaction system adopts the trachea to drum the air into reaction liquid bottom, and the air current is broken up and is escaped in reaction liquid under the effect of stirring, makes oxygen sufficient like this, and the contact is also more abundant to the velocity of flow of air is blown in the external flowmeter control of accessible.

Preferably, in the method for the photocatalytic desulfurization of the fuel, the sulfur content of the fuel to be desulfurized is 400 mg/L-1500 mg/L; further preferably, the sulfur content of the fuel to be desulfurized is 500 mg/L-1400 mg/L.

Preferably, in the method for photocatalytic desulfurization of fuel oil, the extractant is selected from one or more of methanol, ethanol, ethylene glycol, N-methylpyrrolidone, N-dimethylformamide, acetonitrile, sulfolane and dimethyl sulfoxide; further preferably, the extractant is selected from one or more of methanol, N-methyl pyrrolidone and acetonitrile; most preferably, the extractant is acetonitrile.

Preferably, in the method for photocatalytic desulfurization of fuel oil, the radiation light source of the photocatalytic reaction is an ultraviolet lamp (UV light source); further preferably, the radiation source for the photocatalytic reaction is a high-pressure mercury lamp having a dominant wavelength of 365 nm.

Preferably, in the method for the photocatalytic desulfurization of the fuel oil, the temperature of the photocatalytic reaction is 20-30 ℃; further preferably, the temperature of the photocatalytic reaction is 22 to 25 ℃.

Preferably, in the method for the photocatalytic desulfurization of the fuel oil, the time of photocatalytic reaction is 120-180 min; more preferably, the time of the photocatalytic reaction is 130min to 150 min.

Preferably, in the method for photocatalytic desulfurization of fuel oil, the method for separating the upper oil phase is standing; specifically, after the photocatalytic reaction, standing and layering are carried out, and the obtained upper oil phase is the desulfurized fuel oil.

The invention has the beneficial effects that:

The catalyst has simple preparation process, and can effectively reduce dibenzothiophene sulfides which are difficult to remove in fuel oil under the radiation of UV light; the desulfurization can be realized at room temperature in the desulfurization process, and the reaction condition is mild; air is used as an oxidant, explosive peroxide is not required to be added, and potential safety risks are reduced. The catalyst of the invention has good application value in the aspect of fuel oil desulfurization.

Drawings

FIG. 1 is a schematic diagram of a silk carbonization mechanism;

FIG. 2 is a schematic diagram of the mechanism of photocatalytic desulfurization of silk carbonized material;

FIG. 3 is a scanning electron microscope image of a silk carbonized material subjected to phosphotungstic acid activation treatment in the invention;

FIG. 4 is a scanning electron microscope image of a silk carbonized material co-activated by potassium chloride and oxalic acid according to the present invention;

FIG. 5 is a scanning electron microscope image of boric acid-activated silk carbonized material of the present invention;

FIG. 6 is a scanning electron microscope image of the silk carbonized material without activator treatment of the present invention.

Detailed Description

FIG. 1 is a schematic diagram of a mechanism of silk carbonization. With reference to FIG. 1, the preparation mechanism of the carbonized silkworm mercerization catalyst of the present invention is illustrated as follows: after natural silk is soaked in an activating agent solution for a certain time, a certain amount of activating agent is adsorbed. Under the protection of inert atmosphere, the deoxidation and denitrification reaction is carried out under the high temperature condition. Due to the existence of the activating agent, certain hydrogen atoms can be provided, so that dehydration reaction in the carbonization process is facilitated, and the carbonized silk forms a highly graphitized material.

FIG. 2 is a schematic diagram of the mechanism of photocatalytic desulfurization of silk carbonized material. With reference to fig. 2, the mechanism of the photocatalytic desulfurization of fuel oil according to the present invention is illustrated as follows: the sulfides are present in the oil phase, while the carbonized silk is present in the extracted phase. Sulfide in oil phase is transferred to extraction phase by extraction, and carbonized silk generates HO & O under light radiation₂ ^-And the like. The generated active oxygen oxidizes the sulfide and converts the sulfide into high-polarity sulfide, and the high-polarity sulfide is remained in the extraction phase. As the oxidation reaction proceeds, the sulfides in the oil phase are continuously transferred to the extract phase and removed, thereby obtaining an oil phase with low sulfur content.

The present invention will be described in further detail with reference to specific examples. The starting materials used in the examples are, unless otherwise specified, commercially available from conventional sources.

Preparation of example 1

washing natural silkworm cocoon with deionized water for 3 times to remove impurities on the surface of silkworm cocoon. Then shearing the cleaned silkworm cocoon into 1cm area²(1 cm. times.1 cm). Soaking 1g of flaky silk and 0.1g of phosphotungstic acid in 100mL of deionized water for 24h, taking out the soaked silk, and drying the silk in a vacuum drying oven at 40 ℃ for 24 h. After continuing to dryThe silk is placed in a tubular furnace, argon is introduced into the tubular furnace, and the flow of the argon is 5 mL/min. And (3) heating the mixture to 700 ℃ from room temperature at a speed of 5 ℃/min in a tubular furnace, roasting the mixture for 4 hours at the temperature of 700 ℃, and naturally cooling the mixture to room temperature to obtain the phosphotungstic acid activated carbonized silk. Finally, the surface of the sample was washed 3 times with distilled water and ethanol to remove the remaining activator, and the sample was named LWS-700.

The characterization and analysis of the catalyst product prepared in this example are carried out, and the scanning electron microscope image of the silk carbonized material (LWS-700) activated by phosphotungstic acid is shown in figure 3.

preparation of example 2

Washing natural silkworm cocoon with deionized water for 3 times to remove impurities on the surface of silkworm cocoon. Then shearing the cleaned silkworm cocoon into 1cm area²(1 cm. times.1 cm). 1g of flaky silk, 0.1g of potassium chloride and 0.2g of oxalic acid are soaked in 100mL of deionized water for 18h, and the soaked silk is taken out and placed in a vacuum drying oven at 40 ℃ for drying for 24 h. And continuously placing the dried silk in a tubular furnace, and introducing argon into the tubular furnace, wherein the flow of the argon is 10 mL/min. And (3) heating the mixture to 500 ℃ from room temperature by a tubular furnace at a speed of 5 ℃/min, roasting the mixture for 4 hours at the temperature of 500 ℃, and naturally cooling the mixture to room temperature to obtain the carbonized silk co-activated by potassium chloride and oxalic acid. Finally, the surface of the sample was washed 3 times with distilled water and ethanol to remove the remaining activator, and the sample was named KCS-500.

The characterization analysis of the catalyst product prepared in this example is carried out, and the scanning electron microscope image of the silk carbonized material (KCS-500) co-activated by potassium chloride and oxalic acid is shown in figure 4.

Preparation of example 3

Washing natural silkworm cocoon with deionized water for 3 times to remove impurities on the surface of silkworm cocoon. Then shearing the cleaned silkworm cocoon into 1cm area²(1 cm. times.1 cm). Soaking 1g of flaky silk and 0.2g of boric acid in 100mL of deionized water for 24h, taking out the soaked silk, and drying the silk in a vacuum drying oven at 40 ℃ for 24 h. And continuously placing the dried silk in a tubular furnace, and introducing argon into the tubular furnace, wherein the flow of the argon is 5 mL/min. And (3) heating the mixture to 500 ℃ from room temperature at a speed of 5 ℃/min in a tube furnace, roasting the mixture for 4 hours at the temperature of 500 ℃, and naturally cooling the mixture to room temperature to obtain the boric acid activated carbonized silk. Washing with distilled water and ethanol for 3 times, and removingThe activator remaining on the surface, sample was designated PS-500.

The characterization analysis of the catalyst product prepared in this example is carried out, and the scanning electron micrograph of the boric acid activated silk carbonized material (PS-500) is shown in figure 5.

Preparation of comparative example

washing natural silkworm cocoon with deionized water for 3 times to remove impurities on the surface of silkworm cocoon. Then shearing the cleaned silkworm cocoon into 1cm area²(1 cm. times.1 cm). 1g of flaky silk is soaked in 100mL of deionized water for 12h, and then the soaked silk is taken out and placed in a vacuum drying oven at 40 ℃ for drying for 24 h. And continuously placing the dried silk in a tubular furnace, and introducing argon into the tubular furnace, wherein the flow of the argon is 5 mL/min. Raising the temperature from room temperature to 500 ℃ at a speed of 5 ℃/min in a tube furnace, roasting for 4h at 500 ℃, and naturally cooling to room temperature to obtain the unactivated carbonized silk, named WH-500.

The characterization analysis of the catalyst product prepared in this example was carried out, and the scanning electron micrograph of the silk carbonized material (WH-500) without the activator treatment is shown in FIG. 6.

Application tests were carried out on the catalysts prepared in preparation examples 1 to 3 and comparative preparation examples. For illustration, the fuel tested by the invention is a simulated fuel consisting of normal paraffins; furthermore, the fuel oil is simulated fuel oil consisting of n-decane and tetradecane, and the sulfur content of the simulated fuel oil is 500ppm to 1400 ppm. The sulfur source of the fuel oil is selected from Dibenzothiophene (DBT).

The application method specifically comprises the following steps:

Preparing simulated fuel oil: dibenzothiophene is added into n-decane and n-tetradecane to prepare the simulated fuel oil with the sulfur content of 500 mg/L-1400 mg/L. For example, a simulated fuel having a sulfur content of 500mg/L was formulated by adding 1.439g of dibenzothiophene to 500mL of n-decane and n-tetradecane.

The test method comprises the following steps: the photocatalyst was added to a jacketed quartz bottle equipped with magnetic stirring and cooling circulating water, followed by the addition of simulated fuel oil and acetonitrile. Air is blown into the simulated oil through an air pump, or air is not blown into the simulated oil. When air is not blown in, oxygen in the reaction system is dissolved by oxygen contacting with air from the surface of the reaction liquid during the experiment. The chilled circulating water was maintained at 22 ℃. Firstly stirring the mixture without illumination, then reacting the mixture under the radiation of a high-pressure mercury lamp with the main wavelength of 365nm, standing the mixture, layering the mixture, extracting an upper layer oil product, measuring the sulfur content by a gas chromatograph, and calculating the desulfurization rate. The calculation formula of the desulfurization rate is as follows:

desulfurization rate ═ C₀-C_t)/C₀×100％ (1)

In formula (1):

C₀-initial concentration of sulphide in the fuel, in: mg/L;

C_t-concentration of sulphide reaction time t in fuel, unit: mg/L.

The following further describes the application test of the catalysts prepared in preparation examples 1 to 3 and comparative preparation examples, respectively.

Application example 1

0.01g of LWS-700 prepared in preparation example 1 was added to 15mL of DBT-containing simulated fuel with a sulfur content of 500mg/L, 7.5mL of acetonitrile was added, and the air flow was 20 mL/min. Firstly, stirring for 20min without illumination, then radiating for 140min under UV light to extract the upper layer oil, measuring the sulfur content and calculating the desulfurization rate to be 99.5%.

Application example 2

0.005g of LWS-700 prepared in preparation example 1 was added to 15mL of DBT-containing simulated fuel with a sulfur content of 500mg/L, 5mL of acetonitrile was added, and the air flow was 10 mL/min. Firstly, stirring for 20min without illumination, then radiating for 140min under UV light to extract the upper layer oil, measuring the sulfur content and calculating the desulfurization rate to be 96.7%.

Application example 3

0.008g of KCS-500 prepared in preparation example 2 was added to 15mL of a simulated fuel containing DBT with a sulfur content of 500mg/L, 2.5mL of acetonitrile was added, and the air flow rate was 40 mL/min. Firstly, stirring for 20min without illumination, then radiating for 140min under UV light to extract the upper layer oil, measuring the sulfur content and calculating the desulfurization rate to be 97.7%.

Application example 4

0.02g of PS-500 prepared in preparation example 3 was added to 15mL of a simulated fuel containing DBT with a sulfur content of 500mg/L, 7.5mL of acetonitrile was added, and no air was blown. Firstly, stirring for 20min without illumination, then radiating for 140min under UV light to extract the upper layer oil, measuring the sulfur content and calculating the desulfurization rate to be 93.7%.

Application example 5

0.005g of LWS-700 prepared in preparation example 1 was added to 15mL of DBT-containing simulated fuel with a sulfur content of 500mg/L, 7.5mL of acetonitrile was added, and the air flow was 5 mL/min. Firstly, stirring for 20min without illumination, then radiating for 140min under UV light to extract the upper layer oil, measuring the sulfur content and calculating the desulfurization rate to be 96.5%.

Application example 6

0.005g of LWS-700 prepared in preparation example 1 was added to 15mL of DBT-containing simulated fuel with a sulfur content of 800mg/L, 7.5mL of acetonitrile was added, and the air flow was 20 mL/min. Firstly, stirring for 20min without illumination, then radiating for 140min under UV light to extract the upper layer oil, measuring the sulfur content and calculating the desulfurization rate to be 98.5%.

Application example 7

0.005g of LWS-700 prepared in preparation example 1 was added to 15mL of DBT-containing simulated fuel with a sulfur content of 1400mg/L, 7.5mL of acetonitrile was added, and the air flow was 20 mL/min. Firstly, stirring for 20min without illumination, then radiating for 140min under UV light to extract the upper layer oil, measuring the sulfur content and calculating the desulfurization rate to be 96.9%.

Application example 8

0.005g of LWS-700 prepared in preparation example 1 was added to 15mL of DBT-containing simulated fuel with a sulfur content of 500mg/L, 7.5mL of acetonitrile was added, and the air flow was 20 mL/min. Firstly, stirring for 20min without illumination, then radiating for 140min under UV light to extract the upper layer oil, measuring the sulfur content and calculating the desulfurization rate to be 98.9%.

Application comparative example 1

0.005g of WH-500 prepared in comparative example was added to 15mL of DBT-containing simulated fuel oil with a sulfur content of 500mg/L, 7.5mL of acetonitrile was added, and the air flow rate was 20 mL/min. Firstly, stirring for 20min without illumination, then radiating for 140min under UV light to extract the upper layer oil, measuring the sulfur content and calculating the desulfurization rate to be 63.7%.

Comparative application example 2

The same experiment was carried out using graphene oxide as a desulfurization catalyst, as disclosed in Deep desulfurization of liquid fuels with molecular oxygen through graphene photocatalysis (Zeng X., Xiao X., Li Y., et al., Applied Catalysis B: Environmental,2017,209(15): 98-109). Graphene oxide is prepared by a modified Hummers method, strong acid and strong oxidant are needed in the preparation process, explosive potential safety hazards exist in the preparation process, a large amount of acid-containing wastewater is generated in the cleaning process after the reaction is finished, and an additional wastewater treatment unit is needed. Formic acid is additionally added in the desulfurization process, and a small amount of acid dissolved in oil products can cause the quality reduction of the oil products. Although the graphene oxide has a good desulfurization effect, the preparation of the graphene oxide is complex, the production cost is high, and the graphene oxide is difficult to separate from an oil product after desulfurization, so that the graphene oxide is not suitable for practical popularization and application.

The results of the desulfurization test in application examples 1 to 8 and application comparative examples 1 to 2 are shown in Table 1.

Table 1 test results of application tests

The test results show that the catalyst can simulate the desulfurization of dibenzothiophene sulfides in fuel oil to 93.7-99.5% in 140min under the irradiation of UV light, and can effectively remove the dibenzothiophene sulfides in the fuel oil. The desulfurization process can be realized at room temperature, high temperature and high pressure are not needed, the reaction condition is mild, and the operation cost and the equipment maintenance cost are reduced; air is used as an oxidant, explosive peroxides (such as hydrogen peroxide) are not required to be added, and potential safety hazards are reduced. Compared with the existing catalyst, the catalyst of the invention has simple preparation process, does not generate a large amount of industrial wastewater in the preparation process, can utilize biomass operation raw materials, has low cost and has good application value in the aspect of fuel oil desulfurization.

the above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.