WO2021027491A1 - 一种碳化蚕丝光催化剂的制备方法及其应用 - Google Patents

一种碳化蚕丝光催化剂的制备方法及其应用 Download PDF

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WO2021027491A1
WO2021027491A1 PCT/CN2020/102830 CN2020102830W WO2021027491A1 WO 2021027491 A1 WO2021027491 A1 WO 2021027491A1 CN 2020102830 W CN2020102830 W CN 2020102830W WO 2021027491 A1 WO2021027491 A1 WO 2021027491A1
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silk
photocatalyst
desulfurization
fuel
photocatalytic
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PCT/CN2020/102830
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English (en)
French (fr)
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曾兴业
陈振雄
王寒露
张战军
吴世逵
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广东石油化工学院
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Priority to US17/635,402 priority Critical patent/US20220288575A1/en
Publication of WO2021027491A1 publication Critical patent/WO2021027491A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0205—Oxygen-containing compounds comprising carbonyl groups or oxygen-containing derivatives, e.g. acetals, ketals, cyclic peroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
    • C10G32/04—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms by particle radiation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C10G2300/703—Activation

Definitions

  • the invention relates to a fuel desulfurization catalyst material, in particular to a preparation method and application of a carbonized silk photocatalyst.
  • Non-hydrodesulfurization technologies mainly include oxidative desulfurization, extractive desulfurization, adsorption desulfurization and photocatalytic desulfurization.
  • photocatalytic desulfurization technology is a new type of desulfurization technology with great potential due to its advantages of green environmental protection, carbon neutrality and sustainable production.
  • the photocatalytic desulfurization technology is mainly based on the photocatalytic desulfurization method of semiconductor photocatalyst.
  • Han Na et al. reported the photocatalytic desulfurization method of BiVO 4 supported on SBA-15 molecular sieve (Han Na, Chen Zhengli, Su Wei, etc., the preparation of BiVO 4 /SBA-15 catalyst and its photocatalytic oxidative desulfurization performance [J]. Journal of Fuel Chemistry and Technology, 2019, 47(02): 191-198); Liu Bui et al. introduced a TiO 2 /La 3+ method for removing sulfide in model gasoline.
  • the desulfurization rate can reach 91.5% ( Liu Bui, Zhang Gai, Gao Min etc., Preparation of La 3+ /TiO 2 hollow microspheres and photocatalytic oxidation desulfurization performance of model gasoline[J]. Environmental Engineering Journal, 2018, 12(12): 3371-3378). Although semiconductor photocatalysts show good desulfurization performance, the reserves of semiconductor materials and their wide application limit their prices.
  • CN109650374A discloses a method for preparing a type of graphene 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.
  • CN109626370A discloses a biomass-based porous carbon material in the seeds of Platanus acerifolia. The activator used is mainly a solid strong base.
  • CN109626357A introduces an ultrafine carbon nanotube and its preparation method.
  • the photocatalysts of these carbon materials are mainly based on carbon materials such as graphene and graphene oxide, carbon nanotubes and porous carbon, and no attempt has been made to be used for photocatalytic desulfurization research. Moreover, these carbonized materials are difficult to meet the needs of modern industrial production because of their high cost or long reaction time. In the huge family of carbon materials, there is also a type of biomass carbon materials. Biomass carbon materials have the advantages of green and sustainable, many miscellaneous elements and low prices.
  • Silk is a natural high molecular weight fibrin, containing carbon, nitrogen, oxygen, hydrogen and other elements.
  • high-temperature carbonization is directly performed on silk, because during the high-temperature process, as the deoxygenation and dehydrogenation reaction occurs, the resulting carbonized material is dense and has fewer active functional groups and low photocatalytic activity.
  • Technical difficulties are the use of silk to make a photocatalyst with good performance and apply it to fuel desulfurization treatment, so as to expand the use of silk, a traditional material, and provide new carbon materials for fuel photocatalytic desulfurization, which has become a problem for researchers in this field.
  • the purpose of the present invention is to provide a preparation method of carbonized silk photocatalyst and its application in fuel photocatalytic desulfurization.
  • natural silkworm cocoons are soaked in an activator and then carbonized to prepare a low-cost photocatalyst with high activity. It not only expands the use of silk, a traditional material, but also provides a new type of carbon material for fuel photocatalytic desulfurization.
  • the invention provides a method for preparing a carbonized silk photocatalyst.
  • the preparation method of this carbonized silk photocatalyst includes the following steps:
  • the activator is one or more of oxalic acid, phosphotungstic acid, citric acid, lauric acid, boric acid, and potassium chloride.
  • the mass ratio of natural silk to activator is 1:(0.1-0.3); more preferably, the mass ratio of natural silk to activator is 1:( 0.15-0.25); most preferably, the mass ratio of natural silk to activator is 1:0.2.
  • step 1) of the preparation method of this carbonized silk photocatalyst natural silk is prepared by the following treatment method: washing natural cocoons with water, and then cutting the washed cocoons into fragments to obtain sheet-like silk.
  • the purpose of washing with water is to wash away impurities on the surface of the cocoons.
  • the area of the fragments is preferably 1 cm 2 (1 cm ⁇ 1 cm).
  • the flaky silk is used as a raw material to prepare a carbonized silk photocatalyst.
  • the ratio of the amount of natural silk to the water used for soaking is 1g: (50-200) mL; further preferably, the ratio of the amount of natural silk to the water used for soaking is 1g: (80 ⁇ 120) mL.
  • the soaking time is 12h-24h.
  • the water used for soaking is deionized water.
  • the drying is vacuum drying at 35°C to 50°C for 20h-30h; more preferably, drying is vacuum drying at 38°C to 42°C for 22h to 26h .
  • the inert atmosphere is one or more of nitrogen, helium, neon, and argon; further preferably, the inert atmosphere is helium or argon. Gas atmosphere.
  • the gas flow rate of the inert atmosphere is 3mL/min-12mL/min; further preferably, the gas flow rate of the inert atmosphere is 5mL/min-10mL/min.
  • the calcination temperature is 450°C to 900°C; more preferably, the calcination temperature is 500°C to 700°C.
  • step 2) of the preparation method of this carbonized silk photocatalyst the calcination is specifically heated from room temperature to the above calcination temperature at a rate of 4°C/min-6°C/min, and then held for 3h-5h; more preferably, calcination Specifically, after the temperature is raised from room temperature to the above-mentioned calcination temperature at 5°C/min, the temperature is maintained for 3.5h to 4.5h.
  • step 2) of the preparation method of this carbonized silk photocatalyst after roasting, it also includes a step of washing the carbonized silk product.
  • the washing specifically involves washing with water and alcohol, and the purpose of washing is to remove the residue on the surface of the carbonized silk product. Activator.
  • the present invention provides the application of the carbonized silk photocatalyst mentioned above, specifically it is applied to the photocatalytic desulfurization of fuel oil.
  • a photocatalyst for desulfurization of fuel oil which is prepared by the above preparation method of carbonized silk photocatalyst.
  • the invention also provides a specific application method of the photocatalyst, that is, a photocatalytic desulfurization method of fuel oil.
  • a method for photocatalytic desulfurization of fuel oil including the following steps: mixing fuel to be desulfurized, extractant, and carbonized silk photocatalyst, using air as oxidant, performing photocatalytic reaction under light, and separating the upper oil phase to obtain desulfurized fuel ; Among them, the carbonized silk photocatalyst is prepared by the above-mentioned preparation method.
  • the volume ratio of the fuel to be desulfurized to the extractant is 1:(0.1-1); further preferably, the volume ratio of the fuel to be desulfurized to the extractant is 1:( 0.15-0.8); It is further preferred that the volume ratio of the fuel to be desulfurized to the extractant is 1:(0.16-0.5).
  • the ratio of the amount of fuel to be desulfurized to the photocatalyst is 1L: (0.3 ⁇ 1.5) g; further preferably, the ratio of the amount of fuel to be desulfurized to the photocatalyst is 1L: (0.33 ⁇ 1.33)g.
  • air is introduced to participate in the photocatalytic reaction, and the air flow rate is 0 mL/min-50 mL/min; further preferably, the air flow rate is 0 mL/min-40 mL/min.
  • the air flow rate is 0mL/min, that is, the reaction system does not use a gas pipe to blow air, and the oxygen in the reaction system comes from the dissolved oxygen contacting the air on the surface of the reaction liquid; when there is air flow, the reaction system uses a gas pipe to blow air into the bottom of the reaction liquid. Under the action of stirring, the air flow is dispersed in the reaction liquid and escapes, so that oxygen is sufficient and the contact is more sufficient, and the flow rate of the blown air can be controlled by an external flow meter.
  • the sulfur content of the fuel to be desulfurized is 400 mg/L to 1500 mg/L; further preferably, the sulfur content of the fuel to be desulfurized is 500 mg/L to 1400 mg/L.
  • the extractant is selected from methanol, ethanol, ethylene glycol, N-methylpyrrolidone, N,N-dimethylformamide, acetonitrile, sulfolane, dimethyl sulfoxide More preferably, the extractant is selected from one or more of methanol, N-methylpyrrolidone and acetonitrile; most preferably, the extractant is acetonitrile.
  • the radiation source of the photocatalytic reaction is an ultraviolet lamp (UV light source); more preferably, the radiation source of the photocatalytic reaction is a high-pressure mercury lamp with a main wavelength of 365 nm.
  • UV light source ultraviolet lamp
  • the radiation source of the photocatalytic reaction is a high-pressure mercury lamp with a main wavelength of 365 nm.
  • the temperature of the photocatalytic reaction is 20°C to 30°C; more preferably, the temperature of the photocatalytic reaction is 22°C to 25°C.
  • the photocatalytic reaction time is 120 min to 180 min; further preferably, the photocatalytic reaction time is 130 min to 150 min.
  • the method for separating the upper oil phase is standing; specifically, after the photocatalytic reaction, the upper oil phase obtained is the desulfurized fuel after standing for stratification.
  • the catalyst of the present invention has a simple preparation process, and can effectively reduce dibenzothiophene sulfides that are difficult to remove from fuel under UV light radiation; the desulfurization process can achieve desulfurization at room temperature, and the reaction conditions are mild; air is used as the oxidant. No need to add explosive peroxides, reducing potential safety risks.
  • the catalyst of the invention has good application value in fuel desulfurization.
  • Figure 1 is a schematic diagram of the carbonization mechanism of silk
  • Figure 2 is a schematic diagram of the photocatalytic desulfurization mechanism of silk carbonized materials
  • Figure 3 is a scanning electron micrograph of the silk carbonized material activated by phosphotungstic acid of the present invention.
  • Figure 4 is a scanning electron micrograph of the silk carbonized material co-activated with potassium chloride and oxalic acid of the present invention
  • Figure 5 is a scanning electron micrograph of the silk carbonized material activated by boric acid of the present invention.
  • Fig. 6 is a scanning electron micrograph of a carbonized silk material treated with no activator according to the present invention.
  • FIG. 1 is a schematic diagram of the carbonization mechanism of silk.
  • the preparation mechanism of the carbonized silk photocatalyst of the present invention is illustrated as follows: After natural silk is soaked in the activator solution for a certain period of time, a certain amount of activator is adsorbed. Under the protection of an inert atmosphere, deoxygenation and denitrification reactions occur under high temperature conditions. Due to the presence of the activator, a certain amount of hydrogen atoms can be provided to facilitate the dehydration reaction in the carbonization process. After carbonization, the silk forms a highly graphitized material.
  • FIG. 2 is a schematic diagram of the photocatalytic desulfurization mechanism of silk carbonized material.
  • the mechanism of the fuel photocatalytic desulfurization of the present invention is illustrated as follows: sulfide exists in the oil phase, and carbonized silk is in the extraction phase. Transferring the oil phase sulfide to extract phase by extraction, silk carbonized under light irradiation, and generates a HO ⁇ O 2 - ⁇ active oxygen. The generated active oxygen oxidizes the sulfides and converts them into highly polar sulfides, which remain in the extraction phase. As the oxidation reaction progresses, the sulfide in the oil phase is continuously transferred to the extraction phase and removed, thereby obtaining an oil phase with low sulfur content.
  • the tube furnace was heated from room temperature to 700°C at a rate of 5°C/min, and calcined at 700°C for 4 hours, and naturally cooled to room temperature to obtain phosphotungstic acid activated carbonized silk. Finally, rinse with distilled water and ethanol 3 times to remove the residual activator on the surface.
  • the sample is named LWS-700.
  • the catalyst product prepared in this example was characterized and analyzed.
  • the scanning electron micrograph of the carbonized silk material (LWS-700) activated by phosphotungstic acid is shown in Figure 3.
  • the tube furnace was heated from room temperature at 5°C/min to 500°C, and calcined at 500°C for 4 hours, and naturally cooled to room temperature to obtain carbonized silk co-activated by potassium chloride and oxalic acid. Finally, rinse with distilled water and ethanol 3 times to remove the residual activator on the surface.
  • the sample is named KCS-500.
  • the tube furnace was heated from room temperature to 500°C at a rate of 5°C/min, and calcined at 500°C for 4 hours, and naturally cooled to room temperature to obtain boric acid activated carbonized silk. Finally, rinse with distilled water and ethanol 3 times to remove the residual activator on the surface.
  • the sample is named PS-500.
  • the catalyst product prepared in this example was characterized and analyzed.
  • the scanning electron micrograph of the carbonized silk material (PS-500) activated by boric acid is shown in Figure 5.
  • the catalyst product prepared in this example was characterized and analyzed.
  • the scanning electron micrograph of the carbonized silk material (WH-500) without activator treatment is shown in Figure 6.
  • the fuel tested in the present invention is a simulated fuel composed of n-paraffins; further, the fuel is a simulated fuel composed of n-decane and tetradecane, and the sulfur content of the simulated fuel is 500 ppm to 1400 ppm.
  • the sulfur source of the fuel is selected from dibenzothiophene (DBT).
  • the application method is as follows:
  • Preparation of simulated fuel Add dibenzothiophene to n-decane and n-tetradecane to prepare a simulated fuel with a sulfur content of 500mg/L to 1400mg/L.
  • a simulated fuel with a sulfur content of 500 mg/L is prepared by adding 1.439 g of dibenzothiophene to 500 mL of n-decane and n-tetradecane.
  • the test method is: adding the photocatalyst to a jacketed quartz bottle equipped with magnetic stirring and cooling circulating water, and then adding simulated fuel and acetonitrile. Air is blown into the simulated oil through an air pump, or no air is blown into it. When air is not blown, the oxygen in the reaction system in the experiment comes from the dissolution of oxygen on the surface of the reaction liquid in contact with air.
  • the cooling circulating water is maintained at 22°C. First, stir under no light, and then react under the irradiation of a high-pressure mercury lamp with a dominant wavelength of 365nm. After standing, separate layers, extract the upper layer of oil, measure the sulfur content by gas chromatograph and calculate the desulfurization rate.
  • the calculation formula of the desulfurization rate is as follows:
  • Desulfurization rate (C 0 -C t )/C 0 ⁇ 100% (1)
  • C t the concentration of sulfide reaction time t in fuel, unit: mg/L.
  • KCS-500 prepared in Preparation Example 2 was added to 15 mL of DBT-containing simulated fuel oil, with a sulfur content of 500 mg/L, 2.5 mL of acetonitrile, and an air flow rate of 40 mL/min. First, stir under no light for 20 minutes, and then irradiate under UV light for 140 minutes to extract the upper oil, determine the sulfur content and calculate the desulfurization rate of 97.7%.
  • graphene oxide as a desulfurization catalyst to perform the same test, refer to "Deep desulfurization of liquid fuels with molecular oxygen through graphene photocatalytic oxidation" (Zeng X., Xiao X., Li Y., et al.. Applied Catalysis B: Environmental, 2017, 209(15): 98-109) disclosed content.
  • Graphene oxide is prepared by a modified Hummers method. Strong acids and strong oxidants are required during the preparation process. There are potential explosion safety hazards during the preparation process, and a large amount of acid-containing wastewater will be generated during the cleaning process after the reaction, and an additional wastewater treatment unit is required .
  • Table 1 shows the desulfurization test results of application examples 1-8 and application comparative examples 1-2.
  • the catalyst of the present invention simulates the desulfurization of dibenzothiophene sulfides in fuel within 140 minutes under UV light radiation to reach 93.7% to 99.5%, and can effectively remove dibenzothiophene sulfides in fuel. .
  • the desulfurization process can be realized at room temperature, without high temperature and high pressure, mild reaction conditions, reducing operating costs and equipment maintenance costs; using air as the oxidant, without adding explosive peroxides (such as hydrogen peroxide, etc.), reducing potential Security risks.
  • the catalyst of the present invention has a simple preparation process, does not produce a large amount of industrial waste water during the preparation process, can use biomass operation raw materials, has low cost, and has good application value in fuel desulfurization.

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Abstract

一种碳化蚕丝光催化剂的制备方法，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。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。所述催化剂的制备工艺简单，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。所述催化剂在燃油脱硫方面具有良好的应用价值。

Description

一种碳化蚕丝光催化剂的制备方法及其应用 技术领域
本发明涉及一种燃油脱硫催化剂材料，特别涉及一种碳化蚕丝光催化剂的制备方法及其应用。
背景技术
随着汽车的普及，汽车尾气造成的环境污染问题已严重影响到人们的生产生活，因此，我国加紧修订和提出更高要求的清洁燃油标准。2017年开始在全国范围开始执行“国V”燃油标准，规定燃油中硫含量最高值不得超过10mg/kg。自2019年开始，并正在研讨实施更苛刻的“国VIA”标准，以持续推动空气质量改善。目前的燃油脱硫技术主要分为两大类：加氢脱硫技术和非加氢脱硫技术，当前工业上多采用加氢脱硫，但是该技术存在对噻吩类化合物脱除效果不佳，设备投资大，要求高，运行成本高等缺点。非加氢脱硫技术主要包括氧化脱硫、萃取脱硫、吸附脱硫和光催化脱硫等。其中光催化脱硫技术因具有绿色环保、碳中性和可持续生产的优点，是一种富有潜力的新型脱硫技术。
现在光催化脱硫技术主要基本于半导体光催化剂的光催化脱硫方法。如韩娜等报道了SBA-15分子筛负载的BiVO 4的光催化脱硫方法(韩娜，陈政利，苏炜等，BiVO 4/SBA-15催化剂的制备及其光催化氧化脱硫性能[J].燃料化学学报，2019，47(02)：191-198)；刘布雷等介绍了TiO 2/La 3+脱除模型汽油中硫化物的方法，在光辐射210min后，脱硫率可达91.5％(刘布雷，张改，高敏等，La 3+/TiO 2中空微球的制备及模型汽油光催化氧化脱硫性能[J].环境工程学报，2018，12(12)：3371-3378)。尽管半导体光催化剂表现出较好的脱硫性能，然后半导体材料的储量及其广泛应用限制其价格。
近年来，碳材料作为光催化剂不断涌现。如CN109650374A公开了一种类石墨烯碳材料的制备方法，主要是基于将细菌和培养基高温碳化的结果，获得碳材料具有丰富磷、氧、氮、硫元素。CN109626370A公开了于三球悬铃木种子的生物质基多孔碳材料，其所用活化剂主要为固体强碱。CN109626357A介绍了一种超细碳纳米管及其制备方法。这些碳材料的光催化剂主要基于石墨烯和氧化石墨烯、碳纳米管和多孔碳等碳材料，且没有尝试用于光催化脱硫研究。并且这些碳化材料因为成本较高，或反应时间较长，难以满足现代工业生产的需要。在庞大的碳材料家族里，还有一类生物质碳材料。生物质碳材料具有绿色可持续、杂元素多和价格低廉等优点。
蚕丝是一种天然高分子量的纤维蛋白，含有碳、氮、氧、氢等元素。通常来讲，直接对蚕丝进行高温度碳化，因为在高温过程中随着脱氧脱氢反应的发生，生成的碳化材料致密且活性官能团较少，光催化活性低。目前，并没有公开使用蚕丝应用于制成燃油脱硫光催化剂的报道。如何利用蚕丝制成一种性能良好的光催化剂，并将其应用于燃油脱硫处理中，从而扩展蚕丝这一传统材料的用途，为燃油光催化脱硫提供新型碳材料，成为本领域研究者需要解决的技术难题。
发明内容
为了克服现有技术存在的问题，本发明的目的在于提供一种碳化蚕丝光催化剂的制备方法及其在燃油光催化脱硫中的应用。
本发明采用来自天然蚕茧与活化剂浸泡后进行碳化，制备得到低价且具有高活性光催化剂。不仅拓展了蚕丝这一传统材料的用途，也为燃油光催化脱硫提供新型的碳材料。
为了实现上述的目的，本发明所采取的技术方案是：
本发明提供了一种碳化蚕丝光催化剂的制备方法。这种碳化蚕丝光催化剂的制备方法，包括以下步骤：
1)将天然蚕丝与活化剂浸泡于水中，取出浸泡后的蚕丝，干燥；
2)将干燥后的蚕丝在惰性气氛保护下焙烧，得到碳化蚕丝光催化剂；
步骤1)中，活化剂为草酸、磷钨酸、柠檬酸、月桂酸、硼酸、氯化钾中的一种或多种。
优选的，这种碳化蚕丝光催化剂的制备方法步骤1)中，天然蚕丝与活化剂的质量比为1∶(0.1～0.3)；进一步优选的，天然蚕丝与活化剂的质量比为1∶(0.15～0.25)；最优选的，天然蚕丝与活化剂的质量比为1∶0.2。
优选的，这种碳化蚕丝光催化剂的制备方法步骤1)中，天然蚕丝是通过以下处理方法制得：用水将天然蚕茧冲洗，然后将洗净的蚕茧剪成碎片，得到片状的蚕丝。用水冲洗的目的是洗掉蚕茧表面的杂质。碎片的面积优选为1cm 2(1cm×1cm)。将片状的蚕丝为原料，用于制备碳化蚕丝光催化剂。
优选的，这种碳化蚕丝光催化剂的制备方法步骤1)中，天然蚕丝与浸泡所用水的用量比为1g∶(50～200)mL；进一步优选的，天然蚕丝与浸泡所用水的用量比为1g∶(80～120)mL。
优选的，这种碳化蚕丝光催化剂的制备方法步骤1)中，浸泡的时间为12h～24h。
优选的，这种碳化蚕丝光催化剂的制备方法步骤1)中，浸泡所用的水为去离子水。
优选的，这种碳化蚕丝光催化剂的制备方法步骤1)中，干燥为在35℃～50℃下真空干燥20h～30h；进一步优选的，干燥为在38℃～42℃下真空干燥22h～26h。
优选的，这种碳化蚕丝光催化剂的制备方法步骤2)中，惰性气氛为氮气、氦气、氖气、氩气气氛中的一种或多种；进一步优选的，惰性气氛为氦气或氩气气氛。
优选的，这种碳化蚕丝光催化剂的制备方法步骤2)中，惰性气氛的气体流量为3mL/min～12mL/min；进一步优选的，惰性气氛的气体流量为5mL/min～10mL/min。
优选的，这种碳化蚕丝光催化剂的制备方法步骤2)中，焙烧的温度为450℃～900℃；进一步优选的，焙烧的温度为500℃～700℃。
优选的，这种碳化蚕丝光催化剂的制备方法步骤2)中，焙烧具体是从室温以4℃/min～6℃/min升温至上述的焙烧温度后，保温3h～5h；进一步优选的，焙烧具体是从室温以5℃/min升温至上述的焙烧温度后，保温3.5h～4.5h。
优选的，这种碳化蚕丝光催化剂的制备方法步骤2)中，焙烧后还包括对碳化蚕丝产物进行清洗的步骤，清洗具体是用水和醇进行冲洗，清洗的目的是除去碳化蚕丝产物表面残留的活化剂。
本发明提供了上述这种碳化蚕丝光催化剂的应用，具体是将其应用于燃油的光催化脱硫。
一种燃油脱硫的光催化剂，这种燃油脱硫的光催化剂是由上述碳化蚕丝光催化剂的制备方法制得。
本发明还提供了这种光催化剂具体的应用方法，即一种燃油的光催化脱硫方法。
一种燃油的光催化脱硫方法，包括如下步骤：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；其中，碳化蚕丝光催化剂由上述的制备方法制得。
优选的，这种燃油的光催化脱硫方法中，待脱硫的燃油与萃取剂的体积比为1∶(0.1～1)；进一步优选的，待脱硫的燃油与萃取剂的体积比为1∶(0.15～0.8)；再进一步优选的，待脱硫的燃油与萃取剂的体积比为1∶(0.16～0.5)。
优选的，这种燃油的光催化脱硫方法中，待脱硫的燃油与光催化剂的用量比为1L∶(0.3～1.5)g；进一步优选的，待脱硫的燃油与光催化剂的用量比为1L∶(0.33～1.33)g。
优选的，这种燃油的光催化脱硫方法中，通入空气参与光催化反应，空气的流量为0mL/min～50mL/min；进一步优选的，空气的流量为0mL/min～40mL/min。空气流量为0mL/min时，即反应体系未采用气管鼓入空气，反应体系的氧气来自反应液表面与空气接触的溶解氧；有空气流量时，反应体系采用气管将空气鼓入反应液底部，在搅拌的作用下气流被打散在反应液中逸出，这样使氧气充足，且接触也更充分，并可通过外接流量计控制鼓入空气的流速。
优选的，这种燃油的光催化脱硫方法中，待脱硫的燃油硫含量为400mg/L～1500mg/L；进 一步优选的，待脱硫的燃油硫含量为500mg/L～1400mg/L。
优选的，这种燃油的光催化脱硫方法中，萃取剂选自甲醇、乙醇、乙二醇、N-甲基吡咯烷酮、N，N-二甲基甲酰胺、乙腈、环丁砜、二甲基亚砜中的一种或多种；进一步优选的，萃取剂选自甲醇、N-甲基吡咯烷酮、乙腈中的一种或多种；最优选的，萃取剂为乙腈。
优选的，这种燃油的光催化脱硫方法中，光催化反应的辐射光源为紫外灯(UV光源)；进一步优选的，光催化反应的辐射光源为主波长是365nm的高压汞灯。
优选的，这种燃油的光催化脱硫方法中，光催化反应的温度为20℃～30℃；进一步优选的，光催化反应的温度为22℃～25℃。
优选的，这种燃油的光催化脱硫方法中，光催化反应的时间为120min～180min；进一步优选的，光催化反应的时间为130min～150min。
优选的，这种燃油的光催化脱硫方法中，分离上层油相的方法为静置；具体来说，光催化反应后，经静置分层，得到的上层油相即为脱硫后的燃油。
本发明的有益效果是：
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。
附图说明
图1是蚕丝碳化机理示意图；
图2是蚕丝碳化材料光催化脱硫机理示意图；
图3是本发明磷钨酸活化处理的蚕丝碳化材料的扫描电镜图；
图4是本发明氯化钾和草酸共活化处理的蚕丝碳化材料的扫描电镜图；
图5是本发明硼酸活化处理的蚕丝碳化材料的扫描电镜图；
图6是本发明无活化剂处理的蚕丝碳化材料的扫描电镜图。
具体实施方式
附图1是蚕丝碳化机理示意图。结合图1，说明本发明碳化蚕丝光催化剂的制备机理如下：天然蚕丝在活化剂溶液中浸泡一定时间后，吸附一定量的活化剂。在惰性气氛的保护下，于高温条件下发生脱氧脱氮反应。由于活化剂的存在，可提供一定的氢原子，从而有利于碳化过程中脱水反应，碳化后蚕丝形成高度石墨化的材料。
附图2是蚕丝碳化材料光催化脱硫机理示意图。结合图2，说明本发明燃油光催化脱硫 的机理如下：硫化物存在于油相，而碳化蚕丝存在于萃取相中。油相中硫化物通过萃取转移至萃取相，碳化蚕丝在光辐射下，生成HO·和O 2 -·等活性氧。生成的活性氧将硫化物氧化，转化为高极性的硫化物，高极性的硫化物留在萃取相。随着氧化反应的进行，油相中硫化物持续转移至萃取相而被脱除掉，从而获得低硫含量的油相。
以下通过具体的实施例对本发明的内容作进一步详细的说明。实施例中所用的原料如无特殊说明，均可从常规商业途径得到。
制备实施例1
用去离子水将天然蚕茧冲洗3次，洗掉蚕茧表面的杂质。然后将洗净的蚕茧剪成面积约为1cm 2(1cm×1cm)的碎片。将1g片状的蚕丝与0.1g磷钨酸浸泡在100mL去离子水中，浸泡24h后，取出浸泡后蚕丝置于40℃真空干燥箱干燥24h。继续将干燥后蚕丝置于管式炉中，管式炉中通入氩气，氩气流量为5mL/min。管式炉从室温以5℃/min升温至700℃，且在700℃下焙烧4h，自然冷却到室温得到磷钨酸活化的碳化蚕丝。最后用蒸馏水和乙醇冲洗3次，除去表面残留的活化剂，样品命名为LWS-700。
对本例制成的催化剂产物进行表征分析，磷钨酸活化处理的蚕丝碳化材料(LWS-700)扫描电镜图见附图3。
制备实施例2
用去离子水将天然蚕茧冲洗3次，洗掉蚕茧表面的杂质。然后将洗净的蚕茧剪成面积约为1cm 2(1cm×1cm)的碎片。将1g片状的蚕丝与0.1g氯化钾和0.2g草酸浸泡在100mL去离子水中，浸泡18h后，取出浸泡后蚕丝置于40℃真空干燥箱干燥24h。继续将干燥后蚕丝置于管式炉中，管式炉中通入氩气，氩气流量为10mL/min。管式炉从室温以5℃/min升温至500℃，且在500℃下焙烧4h，自然冷却到室温得到氯化钾和草酸共活化的碳化蚕丝。最后用蒸馏水和乙醇冲洗3次，除去表面残留的活化剂，样品命名为KCS-500。
对本例制成的催化剂产物进行表征分析，氯化钾和草酸共活化处理的蚕丝碳化材料(KCS-500)扫描电镜图见附图4。
制备实施例3
用去离子水将天然蚕茧冲洗3次，洗掉蚕茧表面的杂质。然后将洗净的蚕茧剪成面积约为1cm 2(1cm×1cm)的碎片。将1g片状的蚕丝与0.2g硼酸浸泡在100mL去离子水中，浸泡24h后，取出浸泡后蚕丝置于40℃真空干燥箱干燥24h。继续将干燥后蚕丝置于管式炉中，管式炉中通入氩气，氩气流量为5mL/min。管式炉从室温以5℃/min升温至500℃，且在500℃下焙烧4h，自然冷却到室温得到硼酸活化的碳化蚕丝。最后用蒸馏水和乙醇冲洗3次，除去 表面残留的活化剂，样品命名为PS-500。
对本例制成的催化剂产物进行表征分析，硼酸活化处理的蚕丝碳化材料(PS-500)扫描电镜图见附图5。
制备对比例
用去离子水将天然蚕茧冲洗3次，洗掉蚕茧表面的杂质。然后将洗净的蚕茧剪成面积约为1cm 2(1cm×1cm)的碎片。将1g片状的蚕丝浸泡在100mL去离子水中，浸泡12h后，取出浸泡后蚕丝置于40℃真空干燥箱干燥24h。继续将干燥后蚕丝置于管式炉中，管式炉中通入氩气，氩气流量为5mL/min。管式炉从室温以5℃/min升温至500℃，且在500℃下焙烧4h，自然冷却到室温得到未活化的碳化蚕丝，命名WH-500。
对本例制成的催化剂产物进行表征分析，无活化剂处理的蚕丝碳化材料(WH-500)扫描电镜图见附图6。
下面对制备实施例1～3和制备对比例制成的催化剂进行应用测试。为示例说明，本发明测试的燃油为正构烷烃组成的模拟燃油；进一步的，燃油为正癸烷和十四烷组成的模拟燃油，模拟燃油的硫含量为500ppm～1400ppm。燃油的硫源选自二苯并噻吩(DBT)。
应用方法具体如下：
模拟燃油的配制：在正癸烷和正十四烷中加入二苯并噻吩，配制成硫含量为500mg/L～1400mg/L的模拟燃油。举例，硫含量为500mg/L的模拟燃油是在500mL正癸烷和正十四烷中加入1.439g的二苯并噻吩配制成。
测试方法为：将光催化剂加入到配有磁力搅拌和冷却循环水的夹套石英瓶中，然后加入模拟燃油和乙腈。通过气泵鼓入空气至模拟油中，或不鼓入空气。不鼓入空气时，实验时反应体系中氧气来源于反应液表面与空气接触的氧气溶解。冷却循环水维持在22℃。首先在无光照下搅拌，然后在主波长为365nm的高压汞灯辐射下发生反应，静置后分层，抽取上层油品，通过气相色谱仪测定硫含量并计算脱硫率。脱硫率的计算公式如下：
脱硫率＝(C 0-C t)/C 0×100％   (1)
式(1)中：
C 0——燃油中硫化物的初始浓度，单位：mg/L；
C t——燃油中硫化物反应时间t的浓度，单位：mg/L。
下面分别对制备实施例1～3和制备对比例制成的催化剂应用测试作进一步说明。
应用实施例1
将0.01g制备实施例1制成的LWS-700加入到15mL含DBT的模拟燃油中，硫含量为 500mg/L，加入7.5mL乙腈，空气流量为20mL/min。首先在无光照下搅拌20min，然后在UV光下辐射140min抽取上层油品，测定硫含量并计算脱硫率为99.5％。
应用实施例2
将0.005g制备实施例1制成的LWS-700加入到15mL含DBT的模拟燃油中，硫含量为500mg/L，加入5mL乙腈，空气流量为10mL/min。首先在无光照下搅拌20min，然后在UV光下辐射140min抽取上层油品，测定硫含量并计算脱硫率为96.7％。
应用实施例3
将0.008g制备实施例2制成的KCS-500加入到15mL含DBT的模拟燃油中，硫含量为500mg/L，加入2.5mL乙腈，空气流量为40mL/min。首先在无光照下搅拌20min，然后在UV光下辐射140min抽取上层油品，测定硫含量并计算脱硫率为97.7％。
应用实施例4
将0.02g制备实施例3制成的PS-500加入到15mL含DBT的模拟燃油中，硫含量为500mg/L，加入7.5mL乙腈，无空气鼓入。首先在无光照下搅拌20min，然后在UV光下辐射140min抽取上层油品，测定硫含量并计算脱硫率为93.7％。
应用实施例5
将0.005g制备实施例1制成的LWS-700加入到15mL含DBT的模拟燃油中，硫含量为500mg/L，加入7.5mL乙腈，空气流量为5mL/min。首先在无光照下搅拌20min，然后在UV光下辐射140min抽取上层油品，测定硫含量并计算脱硫率为96.5％。
应用实施例6
将0.005g制备实施例1制成的LWS-700加入到15mL含DBT的模拟燃油中，硫含量为800mg/L，加入7.5mL乙腈，空气流量为20mL/min。首先在无光照下搅拌20min，然后在UV光下辐射140min抽取上层油品，测定硫含量并计算脱硫率为98.5％。
应用实施例7
将0.005g制备实施例1制成的LWS-700加入到15mL含DBT的模拟燃油中，硫含量为1400mg/L，加入7.5mL乙腈，空气流量为20mL/min。首先在无光照下搅拌20min，然后在UV光下辐射140min抽取上层油品，测定硫含量并计算脱硫率为96.9％。
应用实施例8
将0.005g制备实施例1制成的LWS-700加入到15mL含DBT的模拟燃油中，硫含量为500mg/L，加入7.5mL乙腈，空气流量为20mL/min。首先在无光照下搅拌20min，然后在UV光下辐射140min抽取上层油品，测定硫含量并计算脱硫率为98.9％。
应用对比例1
将0.005g制备对比例制成的WH-500加入到15mL含DBT的模拟燃油中，硫含量为500mg/L，加入7.5mL乙腈，空气流量为20mL/min。首先在无光照下搅拌20min，然后在UV光下辐射140min抽取上层油品，测定硫含量并计算脱硫率为63.7％。
应用对比例2
使用氧化石墨烯作为脱硫催化剂进行同样的试验，参照《Deep desulfurization of liquid fuels with molecular oxygen through graphene photocatalytic oxidation》(Zeng X.，Xiao X.，Li Y.，et al..Applied Catalysis B：Environmental，2017，209(15)：98-109)公开的内容。氧化石墨烯为改性的Hummers方法制备，制备过程中需要使用强酸和强氧化剂，制备过程中存在易爆安全隐患，且反应结束后清洗过程会产生大量的含酸废水，需要额外的废水处理单元。脱硫过程中额外的加入了甲酸，少量溶入油品中的酸会导致油品质量下降。氧化石墨烯虽然脱硫效果较好，但其制备复杂，生产成本昂贵，且脱硫后与油品分离较难，不适用于实际推广应用。
应用实施例1～8和应用对比例1～2的脱硫测试试验结果如表1所示。
表1应用测试的试验结果
Figure PCTCN2020102830-appb-000001
通过以上的试验结果可知，本发明的催化剂在UV光辐射下在140min内模拟燃油中二苯并噻吩类硫化物脱硫达93.7％～99.5％，可有效脱除燃油中二苯并噻吩类硫化物。脱硫过程均在室温下即可实现，无需高温高压，反应条件温和，降低操作成本与设备维护费用；采用空气为氧化剂，无需加入易爆性过氧化物(如过氧化氢等)，降低了潜在安全隐患。与现有的催 化剂相比，本发明的催化剂制备工艺简单，制备过程中不产生大量工业废水，可利用生物质作业原料，成本低廉，在燃油脱硫方面具有良好的应用价值。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种碳化蚕丝光催化剂的制备方法，其特征在于：包括以下步骤：
    1)将天然蚕丝与活化剂浸泡于水中，取出浸泡后的蚕丝，干燥；
    2)将干燥后的蚕丝在惰性气氛保护下焙烧，得到碳化蚕丝光催化剂；
    所述步骤1)中，活化剂为草酸、磷钨酸、柠檬酸、月桂酸、硼酸、氯化钾中的一种或多种。
  2. 根据权利要求1所述的一种碳化蚕丝光催化剂的制备方法，其特征在于：所述步骤1)中，天然蚕丝与活化剂的质量比为1∶(0.1～0.3)。
  3. 根据权利要求1所述的一种碳化蚕丝光催化剂的制备方法，其特征在于：所述步骤2)中，焙烧的温度为450℃～900℃。
  4. 一种燃油脱硫的光催化剂，其特征在于：是由权利要求1～3任一项所述的制备方法制得。
  5. 一种燃油的光催化脱硫方法，其特征在于：包括如下步骤：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；所述碳化蚕丝光催化剂由权利要求1～3任一项所述的制备方法制得。
  6. 根据权利要求5所述的光催化脱硫方法，其特征在于：所述待脱硫的燃油与萃取剂的体积比为1∶(0.1～1)；待脱硫的燃油与光催化剂的用量比为1L∶(0.3～1.5)g。
  7. 根据权利要求6所述的光催化脱硫方法，其特征在于：所述待脱硫的燃油硫含量为400mg/L～1500mg/L。
  8. 根据权利要求6所述的光催化脱硫方法，其特征在于：所述萃取剂选自甲醇、乙醇、乙二醇、N-甲基吡咯烷酮、N，N-二甲基甲酰胺、乙腈、环丁砜、二甲基亚砜中的一种或多种。
  9. 根据权利要求5所述的光催化脱硫方法，其特征在于：所述光催化反应的辐射光源为紫外灯。
  10. 根据权利要求5所述的光催化脱硫方法，其特征在于：所述光催化反应的温度为20℃～30℃；光催化反应的时间为120min～180min。
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