Fuel oil catalytic oxidation desulfurization catalyst capable of being quickly and magnetically separated and recycled as well as preparation method and application of fuel oil catalytic oxidation desulfurization catalyst

Abstract

The invention relates to the technical field of oxidation desulfurization catalysts, in particular to a fuel oil catalytic oxidation desulfurization catalyst capable of being rapidly magnetically separated and recycled and a preparation method and application thereof.The fuel oil catalytic oxidation desulfurization catalyst is Fe3O4-ZrO2-PW12 / Ag, a core-shell structure magnetic composite material is obtained by taking magnetic Fe3O4-ZrO2 as a carrier and Fe3O4 as a core and wrapping Fe3O4 with ZrO2, and Fe3O4 magnetite particles are prepared; preparing to obtain a magnetic carrier Fe3O4 (at) ZrO2; the preparation method comprises the following steps: preparing Fe3O4 coated ZrO2-PW12; and preparing to obtain the Fe3O4 (at) ZrO2-PW12 / Ag. The separation process of catalyst recycling is greatly simplified through magnetic separation, and the obtained fuel oil catalytic oxidation desulfurization catalyst capable of being quickly and magnetically separated and recycled has the characteristics of small dosage, high activity, high desulfurization rate, mild operation conditions, easiness in recycling and high-efficiency reutilization.

Description

Technical Field

[0001] The present invention relates to the technical field of oxidative desulfurization catalysts, and is a fuel catalytic oxidative desulfurization catalyst that can be rapidly magnetically separated and recovered, and its preparation method and application. Background Art

[0002] Existing desulfurization methods are mainly divided into hydrodesulfurization and non-hydrodesulfurization. Hydrodesulfurization (HDS) is currently the main and mature desulfurization method in petroleum refining. However, this process encounters harsh operating conditions, requiring temperatures of 300°C to 400°C, pressures of 20 to 130 atmospheres, and a large consumption of hydrogen. In addition, completely eliminating aromatic sulfur compounds such as 4,6-DMDBT and DBT is still a major obstacle to the HDS method. To eliminate these sulfides, it is necessary to use elevated temperatures and pressures throughout the reaction process, resulting in higher H2 and energy consumption. Non-hydrodesulfurization can solve the limitations of the HDS process, including biological desulfurization (BDS), adsorption desulfurization (ADS), extraction desulfurization (EDS), and oxidative desulfurization (ODS) methods. These methods aim to eliminate aromatic sulfur compounds. Among them, ODS has become a promising desulfurization technology due to its advantages such as the ability to effectively eliminate refractory aromatic sulfur compounds, mild operating conditions, and easy recovery of oxidized sulfur compounds.

[0003] The ODS technology refers to the oxidation of organic sulfur compounds into more polar oxygen-containing sulfur compounds under the combined action of an oxidant and a catalyst, and then these substances are removed through operations such as extraction or adsorption. Among them, small-molecule sulfur-containing compounds in fuel are oxidized into sulfonic acid substances, while thiophene sulfur-containing compounds are easily oxidized into the corresponding sulfoxides or sulfones. For example, using ODS to convert dibenzothiophene (DBT) (which is a common sulfur pollutant in diesel fuel) into dibenzothiophene sulfone (DBTO2). DBTO2 is widely used in many fields.

[0004] Common oxidants used in the ODS technology include hydrogen peroxide, ozone, molecular oxygen, alkyl peroxides, etc. Ozone is a strong oxidant second only to fluorine in oxidizing ability. Because it is easily decomposed into oxygen by itself, it is regarded as an ideal green strong oxidant. However, its oxidizing ability is too strong and it is easy to cause over-oxidation, thus damaging the quality of oil products; molecular oxygen is a low-cost and pollution-free oxidant, but its oxidizing ability is weak. When using molecular oxygen, high-active catalysts or relatively high reaction conditions are often required; alkyl peroxide oxidants are oil-soluble oxidants, and oil emulsification will not occur during the oxidation process due to the introduction of the aqueous phase, but the content of active oxygen in them is low and the cost is high; hydrogen peroxide (H2O2) is a rational environmentally friendly oxidant, with only water as a by-product, having a relatively high content of active oxygen, and being inexpensive and easy to obtain. Therefore, H2O2 is widely used as an oxidant in the oxidative desulfurization process.

[0005] Catalysts also play a crucial role in ODS. Currently, common catalysts include organic acid catalysts, ionic liquid catalysts, metal-organic frameworks, transition metal oxides, transition metal carbides, Ti nanotubes, polyoxometalates, etc. Catalysts can not only promote the oxidative desulfurization of sulfur-containing compounds in fuels, but also optimize ODS to a large extent from a process perspective. Therefore, preparing high-performance oxidative desulfurization catalysts is the core to ensure the continuous and efficient operation of the oxidative desulfurization process.

[0006] Chinese patent document with the publication number CN119236988A discloses a fuel oxidative desulfurization catalyst, its preparation method and use. In the present invention, a metal ion precursor, a solvent, a ligand and a multi-polymer are mixed and stirred to react to form a solution; then an aqueous solution of polyoxometalate is added dropwise, reacted at room temperature, centrifuged, washed with water and dried to obtain a ZIFs precursor modified by polyoxometalate-loaded multi-polymer; then the above precursor is pyrolyzed at high temperature to obtain a nitrogen-containing porous carbon-supported polyoxometalate catalyst, tungsten trioxide and molybdenum trioxide.

[0007] Chinese patent document with the authorization announcement number CN111068655B discloses a composite catalyst for liquid fuel oxidative desulfurization, its preparation method and application. The catalyst is tungsten trioxide supported on a tin oxide support, and its general formula is expressed as WO3@SnO2, and the content of tungsten trioxide accounts for 5-20% of the total mass of the catalyst.

[0008] In view of this, there is a need to provide a catalyst with effective recycling ability, higher cost-effectiveness and higher activity. Summary of the Invention

[0009] The present invention provides a fuel catalytic oxidative desulfurization catalyst that can be rapidly magnetically separated and recycled, its preparation method and application, overcoming the above-mentioned deficiencies of the prior art. The obtained fuel catalytic oxidative desulfurization catalyst that can be rapidly magnetically separated and recycled has the characteristics of high activity, high desulfurization rate, mild operating conditions, easy recovery and recyclability.

[0010] One of the technical solutions of the present invention is achieved by the following measures: a fuel catalytic oxidative desulfurization catalyst that can be rapidly magnetically separated and recycled, and the fuel catalytic oxidative desulfurization catalyst is Fe3O4@ZrO2-PW 12 / Ag, which is a novel core-shell structured magnetic composite material. The core-shell structured magnetic composite material uses magnetic Fe3O4@ZrO2 as the carrier and Fe3O4 as the core, and is obtained by wrapping Fe3O4 with ZrO2. Fe3O4@ZrO2-PW 12 / Ag is prepared according to the following method:

[0011] S01, Prepare Fe3O4 magnetite particles;

[0012] S02, Prepare magnetic carrier Fe3O4@ZrO2;

[0013] S03, Prepare Fe3O4@ZrO2-PW 12 ;

[0014] S04, Prepare Fe3O4@ZrO2-PW 12 / Ag.

[0015] The following is a further optimization or / and improvement of one of the above technical solutions of the invention:

[0016] The process of preparing the above-mentioned Fe3O4 magnetite particles includes:

[0017] S11, Add the required amount of FeCl3·6H2O to ethylene glycol, stir until uniform, and then add the required amount of polyethylene glycol and sodium acetate to obtain a first mixture;

[0018] S12, After calcining the first mixture, obtain a first product;

[0019] S13, Wash the first product with deionized water and ethanol and then vacuum dry to obtain Fe3O4 magnetite particles.

[0020] In the above step S11, 2.0 g of FeCl3·6H2O is added to every 60 mL of ethylene glycol, and 1.5 g of polyethylene glycol and 5.5 g of sodium acetate are added to every 2.0 g of FeCl3·6H2O.

[0021] In the above step S12, when calcining the first mixture, the calcination temperature is 180°C to 200°C, and the calcination time is 7.5 h to 8.5 h.

[0022] In the above step S13, the temperature of vacuum drying is 55°C to 65°C, and the time of vacuum drying is 5.5 h to 6.5 h.

[0023] The process of preparing the above-mentioned magnetic carrier Fe3O4@ZrO2 includes:

[0024] S21, Uniformly disperse the required amount of Fe3O4 magnetite particles prepared in step S01 in a mixed solution of deionized water and ethanol, and stir to obtain a first mixed solution;

[0025] S22, Add the required amount of ammonia water and ZrOCl2·6H2O to the first mixed solution and stir to obtain a second mixed solution;

[0026] S23. Under an externally applied magnetic field, wash the second mixed solution with a mixed solution of deionized water and ethanol to obtain the washed second mixed solution;

[0027] S24. Dissolve the required amount of cetyltrimethylammonium bromide in a mixed solution of deionized water and ethanol, and after ultrasonic treatment, obtain a third mixed solution;

[0028] S25. Disperse the third mixed solution in the washed second mixed solution, stir evenly, and add the required amounts of ammonia water and ZrOCl₂·6H₂O to react to obtain a second product;

[0029] S26. Wash the second product with ethanol and then dry it under vacuum to obtain the magnetic carrier Fe₃O₄@ZrO₂.

[0030] In the above step S21, every 50 mg of Fe₃O₄ magnetite particles are dispersed in a mixed solution composed of 30 mL of deionized water and 70 mL of ethanol.

[0031] In the above step S22, 2 mL of ammonia water and 0.1 mol / L ZrOCl₂·6H₂O are added to every 50 mg of Fe₃O₄ magnetite particles, the stirring temperature is room temperature, and the stirring time is 23 h to 25 h.

[0032] In the above step S24, every 1.4 g of cetyltrimethylammonium bromide is dissolved in a mixed solution composed of 30 mL of deionized water and 70 mL of ethanol, and the ultrasonic treatment time is 15 min to 25 min.

[0033] In the above step S25, the required amounts of 2 mL of ammonia water and 0.1 mol / L ZrOCl₂·6H₂O are added.

[0034] In the above step S26, the temperature for vacuum drying is 55 °C to 65 °C, and the time for vacuum drying is 5.5 h to 6.5 h.

[0035] Before the above step S26, after washing the second product with ethanol and before vacuum drying, it further includes: heating the second product obtained in step S25 to 75 °C to 85 °C in a fourth mixed solution and carrying out reflux for 5.5 h to 6.5 h, where the fourth mixed solution is composed of 0.6 g of NH₄Cl, 30 mL of deionized water, and 70 mL of ethanol.

[0036] The process for preparing the above Fe₃O₄@ZrO₂-PW 12 includes:

[0037] Disperse the magnetic carrier Fe₃O₄@ZrO₂ in deionized water, and then add the required amount of PW 12, after stirring evenly, evaporate the water, collect the product and then calcine it to obtain the third product, namely Fe3O4@ZrO2-PW 12 , wherein, every 0.1 g of magnetic carrier Fe3O4@ZrO2 is dispersed in 30 mL of deionized water, and the added PW 12 is 0.3917 g, the stirring time is 23 h to 25 h, the calcination temperature is 290 °C to 310 °C, and the calcination time is 1.5 h to 2.5 h.

[0038] The above-prepared Fe3O4@ZrO2-PW 12 / Ag process includes:

[0039] Disperse the Fe3O4@ZrO2-PW prepared in step S03 12 in a mixed solution composed of the required amount of isopropanol and deionized water. After illumination, add the required amount of AgNO3 while stirring to react, obtain the fourth product, wash the fourth product with deionized water and then vacuum dry it to obtain Fe3O4@ZrO2-PW 12 / Ag, wherein, every 0.1 g of magnetic carrier Fe3O4@ZrO2 obtains Fe3O4@ZrO2-PW 12 Disperse in a mixed solution composed of 5 mL of isopropanol and 45 mL of deionized water, the illumination time is 5.5 h to 6.5 h, the added AgNO3 is 0.0017 g, the stirring time is 0.5 h to 2.5 h, the temperature of vacuum drying is 55 °C to 65 °C, and the time of vacuum drying is 5.5 h to 6.5 h.

[0040] The second technical solution of the present invention is achieved by the following measures: A preparation method of a fuel catalytic oxidative desulfurization catalyst that can be rapidly magnetically separated and recovered is carried out according to the following method:

[0041] S01, prepare Fe3O4 magnetite particles;

[0042] S02, prepare magnetic carrier Fe3O4@ZrO2;

[0043] S03, prepare Fe3O4@ZrO2-PW 12 ;

[0044] S04, prepare Fe3O4@ZrO2-PW 12 / Ag.

[0045] The third technical solution of the present invention is achieved by the following measures: An application of a fuel catalytic oxidative desulfurization catalyst that can be rapidly magnetically separated and recovered in the deep oxidative desulfurization of fuel oil. In the deep oxidative desulfurization of fuel oil, the conditions for oxidative desulfurization are: the reaction temperature is 70 °C, the oxygen-sulfur ratio is 2:1, and the dosage of the fuel catalytic oxidative desulfurization catalyst that can be rapidly magnetically separated and recovered in every 500 ppm of model oil DBT is 30 mg.

[0046] The present invention greatly simplifies the separation process of catalyst reuse through magnetic separation. The fuel catalytic oxidative desulfurization catalyst that can be rapidly magnetically separated and recovered has the characteristics of small dosage, high activity, high desulfurization rate, mild operating conditions, easy recovery, and efficient reuse. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Attached Figure 1 is the desulfurization efficiency diagram of the model oil at different temperatures in the present invention.

[0048] Attached Figure 2 is the desulfurization efficiency diagram of the model oil at different oxygen-sulfur ratios in the present invention.

[0049] Attached Figure 3 is the desulfurization efficiency diagram of the model oil at different catalyst dosages in the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0050] The present invention is not limited by the following embodiments, and the specific implementation manners can be determined according to the technical solutions of the present invention and the actual situation. All chemical reagents and chemical supplies mentioned in the present invention are well-known and commonly used chemical reagents and chemical supplies in the prior art unless otherwise specified; the percentages in the present invention are mass percentages unless otherwise specified; the solutions in the present invention are aqueous solutions with water as the solvent unless otherwise specified. For example, a hydrochloric acid solution is an aqueous solution of hydrochloric acid; normal temperature and room temperature in the present invention generally refer to a temperature range of 15 °C to 25 °C, and are generally defined as 25 °C.

[0051] The present invention will be further described below in conjunction with embodiments:

[0052] Example 1: The fuel catalytic oxidative desulfurization catalyst that can be rapidly magnetically separated and recovered, and the fuel catalytic oxidative desulfurization catalyst is Fe3O4@ZrO2-PW 12 / Ag, which is a novel core-shell structured magnetic composite material. The core-shell structured magnetic composite material uses magnetic Fe3O4@ZrO2 as the carrier and Fe3O4 as the core, and is obtained by wrapping Fe3O4 with ZrO2. Fe3O4@ZrO2-PW 12 / Ag is prepared according to the following method:

[0053] S01, Prepare Fe3O4 magnetite particles;

[0054] S02, prepare the magnetic carrier Fe3O4@ZrO2;

[0055] S03, prepare Fe3O4@ZrO2-PW 12 ;

[0056] S04, prepare Fe3O4@ZrO2-PW 12 / Ag.

[0057] Example 2: As an optimization of the above example, the process of preparing Fe3O4 magnetite particles includes:

[0058] S11, add the required amount of FeCl3·6H2O to ethylene glycol, stir until uniform, then add the required amount of polyethylene glycol and sodium acetate to obtain a first mixture;

[0059] S12, calcine the first mixture to obtain a first product;

[0060] S13, wash the first product with deionized water and ethanol and then vacuum dry to obtain Fe3O4 magnetite particles.

[0061] Example 3: As an optimization of the above example, in step S11, add 2.0 g of FeCl3·6H2O to every 60 mL of ethylene glycol, and add 1.5 g of polyethylene glycol and 5.5 g of sodium acetate to every 2.0 g of FeCl3·6H2O.

[0062] Example 4: As an optimization of the above example, in step S12, when calcining the first mixture, the calcination temperature is 180°C to 200°C, and the calcination time is 7.5 h to 8.5 h.

[0063] Example 5: As an optimization of the above example, in step S13, the temperature of vacuum drying is 55°C to 65°C, and the time of vacuum drying is 5.5 h to 6.5 h.

[0064] Example 6: As an optimization of the above example, the process of preparing the magnetic carrier Fe3O4@ZrO2 includes:

[0065] S21, uniformly disperse the required amount of Fe3O4 magnetite particles prepared in step S01 in a mixed solution of deionized water and ethanol, and stir to obtain a first mixed solution;

[0066] S22, add the required amount of ammonia water and ZrOCl2·6H2O to the first mixed solution and stir to obtain a second mixed solution;

[0067] S23, under the condition of an external magnetic field, wash the second mixed solution with a mixed solution of deionized water and ethanol to obtain a washed second mixed solution;

[0068] S24. Dissolve the required amount of cetyltrimethylammonium bromide in a mixed solution of deionized water and ethanol. After ultrasonic treatment, a third mixed solution is obtained.

[0069] S25. Disperse the third mixed solution in the washed second mixed solution. After stirring evenly, add the required amounts of ammonia water and ZrOCl₂·6H₂O to react, and a second product is obtained.

[0070] S26. Wash the second product with ethanol and then dry it under vacuum to obtain the magnetic carrier Fe₃O₄@ZrO₂.

[0071] Example 7: As an optimization of the above example, in step S21, every 50 mg of Fe₃O₄ magnetite particles are dispersed in a mixed solution composed of 30 mL of deionized water and 70 mL of ethanol.

[0072] Example 8: As an optimization of the above example, in step S22, 2 mL of ammonia water and 0.1 mol / L ZrOCl₂·6H₂O are added to every 50 mg of Fe₃O₄ magnetite particles. The stirring temperature is at room temperature, and the stirring time is 23 h to 25 h.

[0073] Example 9: As an optimization of the above example, in step S24, 1.4 g of cetyltrimethylammonium bromide is dissolved in a mixed solution composed of 30 mL of deionized water and 70 mL of ethanol, and the ultrasonic treatment time is 15 min to 25 min.

[0074] Example 10: As an optimization of the above example, in step S25, the required amounts of 2 mL of ammonia water and 0.1 mol / L ZrOCl₂·6H₂O are added.

[0075] Example 11: As an optimization of the above example, in step S26, the temperature for vacuum drying is 55 °C to 65 °C, and the time for vacuum drying is 5.5 h to 6.5 h.

[0076] Example 12: As an optimization of the above example, in step S26, before washing the second product with ethanol and then drying it under vacuum, it further includes: heating the second product obtained in step S25 to 75 °C to 85 °C in a fourth mixed solution and carrying out reflux for 5.5 h to 6.5 h, where the fourth mixed solution is composed of 0.6 g of NH₄Cl, 30 mL of deionized water, and 70 mL of ethanol.

[0077] Example 13: As an optimization of the above example, the process for preparing Fe₃O₄@ZrO₂-PW 12 includes:

[0078] Disperse the magnetic carrier Fe₃O₄@ZrO₂ in deionized water, and then add the required amount of PW 12, After stirring evenly, evaporate the water, collect the product and calcine it to obtain the third product, which is Fe3O4@ZrO2-PW 12 , Among them, every 0.1 g of magnetic carrier Fe3O4@ZrO2 is dispersed in 30 mL of deionized water, and the added PW 12 is 0.3917 g, the stirring time is 23 h to 25 h, the calcination temperature is 290 °C to 310 °C, and the calcination time is 1.5 h to 2.5 h.

[0079] Example 14: As an optimization of the above example, Fe3O4@ZrO2-PW is prepared 12 / Ag. The process includes:

[0080] Disperse the Fe3O4@ZrO2-PW prepared in step S03 12 in a mixed solution composed of the required amount of isopropanol and deionized water. After illumination, add the required amount of AgNO3 while stirring to react, obtain the fourth product, wash the fourth product with deionized water and then vacuum dry it to obtain Fe3O4@ZrO2-PW 12 / Ag, among which, every 0.1 g of magnetic carrier Fe3O4@ZrO2 obtains Fe3O4@ZrO2-PW 12 dispersed in a mixed solution composed of 5 mL of isopropanol and 45 mL of deionized water, the illumination time is 5.5 h to 6.5 h, the added AgNO3 is 0.0017 g, the stirring time is 0.5 h to 2.5 h, the temperature of vacuum drying is 55 °C to 65 °C, and the time of vacuum drying is 5.5 h to 6.5 h.

[0081] Example 15: The preparation method of the fuel catalytic oxidative desulfurization catalyst that can be rapidly magnetically separated and recovered is carried out according to the following method:

[0082] S01, Prepare Fe3O4 magnetite particles;

[0083] S02, Prepare magnetic carrier Fe3O4@ZrO2;

[0084] S03, Prepare Fe3O4@ZrO2-PW 12 ;

[0085] S04, Prepare Fe3O4@ZrO2-PW 12 / Ag.

[0086] Example 16: The fuel catalytic oxidative desulfurization catalyst that can be rapidly magnetically separated and recovered is prepared according to the following method: (1) Prepare Fe3O4 magnetite particles

[0087] S11, Add 2.0 g of FeCl3·6H2O to 60 mL of ethylene glycol. After stirring until homogeneous, add 1.5 g of polyethylene glycol (PEG) and 5.5 g of sodium acetate (NaAc) to obtain a first mixture;

[0088] S12, Calcinate the first mixture in a reaction kettle at 190 °C for 8 h to obtain a first product (Fe3O4);

[0089] S13, Wash Fe3O4 with deionized water and ethanol, and vacuum dry at 60 °C for 6 h to obtain Fe3O4 magnetite particles.

[0090] (2) Prepare the magnetic carrier Fe3O4@ZrO2

[0091] S21, Mix 30 mL of deionized water and 70 mL of ethanol, and uniformly disperse 50 mg of Fe3O4 magnetite particles in the above solution, stir to obtain a first mixed solution;

[0092] S22, While stirring, drop 2 mL of ammonia water and 0.1 mol / L ZrOCl2·6H2O into the first mixed solution, and stir at room temperature for 24 h to obtain a second mixed solution;

[0093] S23, Under an external magnetic field, wash the second mixed solution with a mixed solution of ethanol and deionized water to obtain a washed second mixed solution;

[0094] S24, Dissolve 1.4 g of cetyltrimethylammonium bromide (CTAB) in a mixed solution of deionized water and ethanol, and ultrasonicate for 20 min to obtain a third mixed solution;

[0095] S25, Disperse the third mixed solution in the washed second mixed solution, stir evenly, add 2 mL of ammonia water, and then add 0.1 mol / L ZrOCl2·6H2O to react to obtain a second product. To further remove CTAB, heat the second product obtained in step S25 to 80 °C and reflux for 6 h in a mixed solution composed of 0.6 g of NH4Cl, ethanol, and deionized water;

[0096] S26, Wash the second product with ethanol and then vacuum dry to obtain the magnetic carrier Fe3O4@ZrO2.

[0097] (3) Prepare Fe3O4@ZrO2-PW 12

[0098] Fix phosphotungstic acid on Fe3O4@ZrO2 by the impregnation method, that is, weigh 0.1 g of the magnetic carrier Fe3O4@ZrO2, disperse it in 30 mL of an aqueous solution, and add 0.3917 g of PW 12, stir for 24 h, evaporate the water, collect the product, calcine at 300 °C for 2 h to obtain Fe3O4@ZrO2-PW 12 .

[0099] (4) Prepare Fe3O4@ZrO2-PW 12 / Ag

[0100] Mix 5 mL of isopropanol and 45 mL of deionized water evenly, and disperse Fe3O4@ZrO2-PW 12 in this solution. Irradiate with light for 6 h, add 0.0017 g of AgNO3 while stirring, stir for 1 h, then wash with deionized water, and then dry in vacuum for 6 h to obtain Fe3O4@ZrO2-PW 12 / Ag.

[0101] Use the Fe3O4@ZrO2-PW 12 / Ag obtained in Example 16 of the present invention for oxidative desulfurization. The process is as follows:

[0102] Dissolve DBT in 100 mL of n-octane to obtain a model oil of 500 ppm. During the oxidative desulfurization process, when the temperature reaches the specified temperature (70 °C), add the model oil (20 mL), acetonitrile (20 mL), the catalyst, i.e., Fe3O4@ZrO2-PW 12 / Ag (30 mg) and H2O2 into a two-necked flask, stir at a certain stirring speed, and start the oxidative desulfurization reaction. Sample at a certain time interval and test with an automatic sulfur and nitrogen analyzer (JF-TSN-3000). The results are shown in Table 1.

[0103] Calculate the DBT desulfurization rate (SR) using the following formula, where C t is the sulfur concentration after the reaction proceeds for a certain time, mg / L, and C0 is the initial sulfur concentration, mg / L.

[0104]

[0105] As can be seen from Table 1, the desulfurization rates of DBT are different under different catalysts.

[0106] First, as a blank experimental group, using Fe3O4 as the catalyst, the desulfurization rate of aromatic organic sulfides is only 58.51%. After coating with zirconia, the desulfurization rate increases to 65.66%. When the catalyst is Fe3O4@ZrO2-PW 12 , the desulfurization rate reaches 75.87%, which cannot achieve deep desulfurization. When the catalyst is Fe3O4@ZrO2-PW 12 / Ag, the desulfurization rate reaches 99.99%. It can be seen that compared with Fe3O4@ZrO2-PW 12 , the Fe3O4@ZrO2-PW of the present invention12 The oxidative desulfurization performance of Fe3O4@ZrO2-PW

[0107] Example 17: Application of the fuel oil catalytic oxidative desulfurization catalyst that can be rapidly magnetically separated and recovered in the deep oxidative desulfurization of fuel oil. In the deep oxidative desulfurization of fuel oil, the conditions for oxidative desulfurization are as follows: the reaction temperature is 70 °C, the oxygen-sulfur ratio is 2:1, and the dosage of the fuel oil catalytic oxidative desulfurization catalyst that can be rapidly magnetically separated and recovered in every 500 ppm of model oil DBT is 30 mg.

[0108] When investigating the application of the fuel oil catalytic oxidative desulfurization catalyst that can be rapidly magnetically separated and recovered in the deep oxidative desulfurization of fuel oil, three factors are considered: temperature, oxygen-sulfur ratio, and catalyst dosage.

[0109] 1. Desulfurization efficiency of model oil at different temperatures

[0110] The deep oxidative desulfurization rate of the fuel oil by the fuel oil catalytic oxidative desulfurization catalyst that can be rapidly magnetically separated and recovered according to the present invention at different temperatures is as Figure 1 shown. It can be Figure 1 seen that as the temperature increases, the catalytic activity of Fe3O4@ZrO2-PW 12 / Ag also increases. When the temperature rises to 70 °C, DBT is completely removed. Since the boiling point of acetonitrile is about 81 °C, further increasing the temperature may cause the evaporation of acetonitrile. Therefore, the reaction temperature of 70 °C is considered the most favorable. Therefore, 70 °C is selected as the optimal reaction temperature.

[0111] 2. Desulfurization efficiency of model oil at different oxygen-sulfur ratios (O / S)

[0112] The deep oxidative desulfurization rate of the fuel oil by the fuel oil catalytic oxidative desulfurization catalyst that can be rapidly magnetically separated and recovered according to the present invention at different temperatures is as Figure 2 shown. It can be Figure 2 seen that when other experimental conditions remain unchanged, the effect of the dosage of the oxidant on the oxidative desulfurization performance is investigated. The results show that as the O / S increases, the desulfurization performance improves significantly, and DBT is completely removed in 30 min. However, when the O / S increases from 3 to 5, the desulfurization performance of the catalyst decreases, which may be because the by-product water from the decomposition of H2O2 occupies the catalyst surface and inhibits the desulfurization process. Therefore, the optimal O / S is 2.

[0113] 3. Desulfurization efficiency of model oil at different catalyst dosages

[0114] The deep oxidative desulfurization rate of the fuel oil by the fuel oil catalytic oxidative desulfurization catalyst that can be rapidly magnetically separated and recovered according to the present invention at different catalyst dosages is as Figure 3 shown. It can be Figure 3It can be seen that when the catalyst dosage increases from 10 mg to 30 mg, the desulfurization performance gradually improves due to the presence of more effective active sites. When the catalyst dosage is further increased to 40 mg, the desulfurization performance does not further improve. Obviously, during the oxidative desulfurization process, the increase in catalyst dosage will cause aggregation, resulting in a decrease in desulfurization performance. Therefore, the optimal dosage of the catalyst is 30 mg.

[0115] In summary, the present invention greatly simplifies the separation process of catalyst reuse through magnetic separation. The fuel catalytic oxidative desulfurization catalyst that can be rapidly magnetically separated and recovered has the characteristics of small dosage, high activity, high desulfurization rate, mild operating conditions, easy recovery, and efficient reuse.

[0116] The above technical features constitute the embodiments of the present invention, which have strong adaptability and implementation effects. Non-essential technical features can be increased or decreased according to actual needs to meet the requirements of different situations.

[0117] Table 1

[0118] Catalyst Temperature Oxygen-sulfur ratio Catalyst dosage Desulfurization rate <![CDATA[Fe3O4]]> 70℃ 2 30mg 58.51％ <![CDATA[Fe3O4@ZrO2]]> 70℃ 2 30mg 65.66％ <![CDATA[Fe3O4@ZrO2-PW 12 > 70℃ 2 30mg 75.87％ <![CDATA[Fe3O4@ZrO2-PW 12 / Ag]]> 70℃ 2 30mg 99.99％

Claims

1. A fuel catalytic oxidation desulfurization catalyst capable of rapid magnetic separation and recovery, characterized in that The fuel catalytic oxidation desulfurization catalyst is Fe3O4@ZrO2-PW 12 / Ag, is a new type of coated core-shell structure magnetic composite material, the core-shell structure magnetic composite material uses magnetic Fe3O4@ZrO2 as a carrier, Fe3O4 as a core, and is obtained by ZrO2 wrapping Fe3O4, Fe3O4@ZrO2-PW 12 / Ag was prepared according to the following method: S01, preparing Fe3O4 magnetite particles; S02, the magnetic carrier Fe3O4@ZrO2 is prepared; S03, Fe3O4@ZrO2-PW was prepared 12 ; S04, Fe3O4@ZrO2-PW was prepared 12 / Ag.

2. The fuel catalytic oxidation desulfurization catalyst capable of rapid magnetic separation and recovery according to claim 1, characterized in that The process of preparing Fe3O4 magnetite particles includes: S11, adding a required amount of FeCl3·6H2O to ethylene glycol, stirring until uniform, and then adding a required amount of polyethylene glycol and sodium acetate to obtain a first mixture; S12, calcining the first mixture to obtain a first product; S13, washing the first product with deionized water and ethanol and then vacuum drying to obtain Fe3O4 magnetite particles.

3. The fuel catalytic oxidation desulfurization catalyst capable of rapid magnetic separation and recovery according to claim 1 or 2 is characterized in that In step S11, 2.0 g of FeCl3·6H2O is added to every 60 mL of ethylene glycol, and 1.5 g of polyethylene glycol and 5.5 g of sodium acetate are added to every 2.0 g of FeCl3·6H2O; or / and, in step S12, when the first mixture is calcined, the calcination temperature is 180°C to 200°C, and the calcination time is 7.5 h to 8.5 h; or / and, in step S13, the vacuum drying temperature is 55°C to 65°C, and the vacuum drying time is 5.5 h to 6.5 h.

4. The fuel catalytic oxidation desulfurization catalyst capable of rapid magnetic separation and recovery according to claim 3, characterized in that The process of preparing the magnetic carrier Fe3O4@ZrO2 includes: S21, uniformly dispersing a required amount of Fe3O4 magnetite particles obtained in step S01 in a mixed solution of deionized water and ethanol, stirring, to obtain a first mixed solution; S22, adding a required amount of ammonia water and ZrOCl2·6H2O to the first mixed solution and stirring to obtain a second mixed solution; S23, washing the second mixed solution with a mixed solution of deionized water and ethanol under an external magnetic field to obtain a washed second mixed solution; S24, dissolving a required amount of hexadecyltrimethylammonium bromide in a mixed solution of deionized water and ethanol, and performing ultrasonic treatment to obtain a third mixed solution; S25, dispersing the third mixed solution in the washed second mixed solution, stirring evenly, and adding a required amount of ammonia water and ZrOCl2·6H2O to react to obtain a second product; S26, washing the second product with ethanol and then drying it in vacuum to obtain the magnetic carrier Fe3O4@ZrO2.

5. The fuel catalytic oxidation desulfurization catalyst capable of rapid magnetic separation and recovery according to any one of claims 1 to 4, characterized in that In step S21, every 50 mg of Fe3O4 magnetite particles are dispersed in a mixture of 30 mL of deionized water and 70 mL of ethanol; or / and, in step S22, 2 mL of ammonia water and 0.1 mol / L ZrOCl2·6H2O are added to every 50 mg of Fe3O4 magnetite particles, the stirring temperature is room temperature, and the stirring time is 23 h to 25 h; or / and, in step S24, every 1.4 g of hexadecyltrimethylammonium bromide is dissolved in a mixture of 30 mL of deionized water and 70 mL of ethanol, and the ultrasonic treatment time is 15 min to 25 min; or / and, in step S25, 2 mL of ammonia water and 0.1 mol / L ZrOCl2·6H2O are added in the required amount; or / and, in step S26, the vacuum drying temperature is 55°C to 65°C, and the vacuum drying time is 5.5 h to 6.5 h.

6. The fuel catalytic oxidation desulfurization catalyst capable of rapid magnetic separation and recovery according to claim 5, characterized in that Step S26, before vacuum drying after washing the second product with ethanol, also includes: heating the second product obtained in step S25 to 75°C to 85°C in a fourth mixed solution, and reflux for 5.5h to 6.5h, wherein the fourth mixed solution is composed of 0.6g NH4Cl, 30mL deionized water and 70mL ethanol.

7. The fuel catalytic oxidation desulfurization catalyst capable of rapid magnetic separation and recovery according to any one of claims 1 to 6, characterized in that Fe3O4@ZrO2-PW was prepared 12 The process includes: The magnetic carrier Fe3O4@ZrO2 is dispersed in deionized water, and then the required amount of PW is added. 12 After stirring evenly, evaporate the water, collect the product and calcine it to obtain the third product, which is Fe3O4@ZrO2-PW 12 , where 0.1g of magnetic carrier Fe3O4@ZrO2 is dispersed in 30mL of deionized water, and PW is added 12 The amount of calcined carbon is 0.3917 g, the stirring time is 23 to 25 h, the calcination temperature is 290 to 310 ° C, and the calcination time is 1.5 to 2.5 h.

8. The fuel catalytic oxidation desulfurization catalyst capable of rapid magnetic separation and recovery according to any one of claims 1 to 7, characterized in that Fe3O4@ZrO2-PW was prepared 12 The / Ag process includes: The Fe3O4@ZrO2-PW prepared in step S03 12 Dispersed in a mixture of isopropanol and deionized water, after irradiation, add the required amount of AgNO3 while stirring to react to obtain the fourth product, wash the fourth product with deionized water and vacuum dry to obtain Fe3O4@ZrO2-PW 12 / Ag, wherein the Fe3O4@ZrO2-PW obtained by 0.1g of magnetic carrier Fe3O4@ZrO2 12 Dispersed in a mixture of 5 mL of isopropanol and 45 mL of deionized water, the illumination time is 5.5 h to 6.5 h, 0.0017 g of AgNO3 is added, the stirring time is 0.5 h to 2.5 h, the vacuum drying temperature is 55°C to 65°C, and the vacuum drying time is 5.5 h to 6.5 h.

9. A method for preparing a fuel catalytic oxidation desulfurization catalyst capable of rapid magnetic separation and recovery according to any one of claims 2 to 8, characterized in that Proceed as follows: S01, preparing Fe3O4 magnetite particles; S02, the magnetic carrier Fe3O4@ZrO2 is prepared; S03, Fe3O4@ZrO2-PW was prepared 12 ; S04, Fe3O4@ZrO2-PW was prepared 12 / Ag.

10. Use of the fuel oil catalytic oxidation desulfurization catalyst capable of rapid magnetic separation and recovery according to any one of claims 1 to 8 in deep oxidation desulfurization of fuel oil, characterized in that In the deep oxidative desulfurization of fuel oil, the conditions for oxidative desulfurization are: reaction temperature of 70°C, oxygen-sulfur ratio of 2:1, and the amount of fuel catalytic oxidative desulfurization catalyst that can be quickly magnetically separated and recovered in every 500ppm model oil DBT is 30mg.

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