Desulfurization extraction agent and method for removing thiophene by using same

Abstract

The invention belongs to the technical field of extraction separation, and relates to a desulfurization extraction agent and a method for removing thiophene by using the desulfurization extraction agent. The preparation method comprises the following steps: loading a deep eutectic solvent onto graphite phase carbon nitride coated graphene oxide nano-microspheres by an impregnation method to obtain a composite material for removing thiophene, and then mixing and stirring the composite material, a thiophene n-octane solution and hydrogen peroxide for desulfurization. Oxidation desulfurization, adsorption desulfurization and extraction desulfurization are comprehensively used, the desulfurization efficiency is high, the operation condition is mild, and the method is environment-friendly.

Description

Technical Field

[0001] The present invention relates to a method for preparing a composite material and for removing thiophene, belonging to the technical field of extraction and separation. Background Art

[0002] World economic growth is closely related to energy consumption. As an energy source, fuel is crucial for maintaining the chemical industry, transportation systems, electricity, and other human activities. However, sulfur elements in fuel produce sulfur oxides harmful to the environment and human health after combustion and are emitted into the atmospheric environment. These emissions cause acid rain, damage buildings, machines, rainforests, and acidify surface water and soil. Sulfur oxide emissions also harm human health, such as upper respiratory tract infections, asthma, bronchitis, lung cancer, and other serious diseases. Therefore, great attention has been paid to sulfur-containing compounds in fuel.

[0003] Catalytic hydrodesulfurization is a traditional method for removing organic sulfur compounds from fuel, which has good removal effects on small molecule organic sulfur compounds such as mercaptans and sulfides, but has poor removal effects on aromatic sulfur-containing organic compounds such as thiophene and its derivatives, and requires high-temperature and high-pressure reaction conditions. Other non-hydrodesulfurization methods such as biological desulfurization, adsorption desulfurization, extraction desulfurization, and oxidative desulfurization are alternative desulfurization methods with mild reaction conditions. Among them, oxidative desulfurization refers to oxidizing sulfur-containing organic compounds to corresponding sulfones / sulfoxides through oxidants, resulting in an increase in their polarity and molecular weight, thereby facilitating removal through methods such as extraction and adsorption. In patent CN 113025372 A, a method for oxidative desulfurization using a deep eutectic solvent loaded on graphene as a desulfurization extractant is disclosed, which obtains a high removal rate in removing dibenzothiophene. However, this method has a long desulfurization time, a high cost of the desulfurization extractant, and the preparation of reduced graphene oxide is complex and requires the use of strong acids and strong oxidants, posing potential risks. Summary of the Invention

[0004] In order to make up for the deficiencies of the prior art, the present invention removes thiophene through a deep eutectic solvent / nanomicrosphere composite material, conducts research on the removal of different organic sulfur compounds in fuel, and further increases the optional methods in the field of fuel desulfurization.

[0005] The present invention adopts the following technical solutions: The present invention provides a desulfurization extractant based on nanomicrospheres, and the desulfurization extractant loads a deep eutectic solvent on graphite carbon nitride@reduced graphene oxide nanomicrospheres; the mass ratio of the deep eutectic solvent to the nanomicrospheres is 10-60:1.

[0006] In the above technical solution, further, the preparation method of the graphite carbon nitride@reduced graphene oxide nanomicrospheres includes hydrothermal preparation using cetyltrimethylammonium bromide, melamine, glucose, glacial acetic acid, and water as raw materials.

[0007] In the above technical solution, further, the deep eutectic solvent includes a hydrogen bond acceptor and a hydrogen bond donor; the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1-2; the hydrogen bond acceptor is tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride or choline chloride;

[0008] The hydrogen bond donor is p-toluenesulfonic acid.

[0009] The present invention also provides a method for removing thiophene. The method uses the aforementioned desulfurization extractant, and mixes the desulfurization extractant, thiophene n-octane solution, and oxidant evenly, and then stands for layering.

[0010] In the above technical solution, further, the mass ratio of the desulfurization extractant, thiophene n-octane solution to the oxidant is 0.3-0.7:1:0.1; the concentration of the thiophene n-octane solution is 1400 ppm to 1800 ppm.

[0011] In the above technical solution, further, the mixing is carried out by stirring reaction at 25-60 °C and a rotation speed of 800-1200 rpm for 15-30 min.

[0012] In the above technical solution, further, the oxidant is 30% hydrogen peroxide solution or periodic acid.

[0013] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0014] By loading the deep eutectic solvent onto the graphitic carbon nitride@reduced graphene oxide nanospheres, the present invention can achieve high-efficiency desulfurization in a short time of 15-30 min. The raw materials used for the preparation of the nanospheres have low cost, mild preparation conditions, and simple methods, and are more easily industrialized.

[0015] On the basis that the deep eutectic solvent has a high desulfurization efficiency, the present invention further improves the desulfurization efficiency of the material. The desulfurization operation is simple, the conditions are mild, the desulfurization efficiency is high, and it is environmentally friendly. Description of the Drawings

[0016] Figure 1 g-C 3 N 4 @GO SEM images; A. 1 μm, B 10 μm. Detailed Embodiments

[0017] The following non-limiting embodiments can enable those of ordinary skill in the art to understand the present invention more comprehensively, but do not limit the present invention in any way. Unless otherwise specified, the experimental methods used in the present invention are all conventional methods, and the experimental equipment, materials, reagents, etc. used can be purchased from chemical companies.

[0018] Preparation of graphitic carbon nitride@reduced graphene oxide nanospheres:

[0019] Take 0.14 g of cetyltrimethylammonium bromide, 1.0 g of melamine, 1.52 g of glucose, and 2.8 mL of glacial acetic acid into 50 mL of water, and continuously stir at 40 °C for 1 h to fully dissolve and mix, obtaining a clear and transparent solution. Transfer the solution to a 100 mL hydrothermal reactor, react at 180 °C for 6 h, then filter, wash, and dry the black-brown precipitate to obtain graphitic carbon nitride@graphene oxide nanospheres, which are used in the following examples and comparative examples. The prepared nanospheres were characterized by a scanning electron microscope JSM-7900F, Figure 1 which shows the morphology of the product. The product consists of g-C 3 N 4 @GO nanosheet-assembled microspheres. The nanospheres have a sunken center, and the structure is similar to a bird's nest. The main body diameter is 2-3 μm, and some diameters are >4 μm or <1 μm.

[0020] Example 1

[0021] Weigh and mix tetramethylammonium chloride and p-toluenesulfonic acid in a molar ratio of 1:2 to prepare 3 g of a deep eutectic solvent;

[0022] Load the above 3 g of deep eutectic solvent onto 0.1 g of graphitic carbon nitride@graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0023] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of a 1600 ppm thiophene solution, and 0.05 g of a 30% hydrogen peroxide solution. At a reaction temperature of 25 °C, stir and react at a speed of 800 rpm for 30 min. After standing and separating layers, use gas chromatography to detect the thiophene concentration in the n-octane layer, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 73.10%.

[0024] Example 2

[0025] Weigh and mix tetraethylammonium chloride and p-toluenesulfonic acid in a molar ratio of 1:2 to prepare 3 g of a deep eutectic solvent;

[0026] Load the above 3 g of deep eutectic solvent onto 0.1 g of graphitic carbon nitride@graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0027] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of a 1600 ppm thiophene solution, and 0.05 g of a 30% hydrogen peroxide solution. At a reaction temperature of 25 °C, stir and react at a speed of 800 rpm for 30 min. After standing and separating layers, use gas chromatography to detect the thiophene concentration in the n-octane layer, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 73.28%.

[0028] Example 3

[0029] Weigh the mixed tetrabutylammonium chloride and p-toluenesulfonic acid in a molar ratio of 1:2 to prepare 3 g of deep eutectic solvent;

[0030] Load the above 3 g of deep eutectic solvent onto 0.1 g of graphitic carbon nitride@reduced graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0031] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of 1600 ppm thiophene solution, and 0.05 g of 30% hydrogen peroxide solution. Stir and react at a reaction temperature of 25 °C and a rotation speed of 800 rpm for 30 min. After standing and separating layers, use gas chromatography to detect the thiophene concentration in the n-octane layer, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 82.93%.

[0032] Example 4

[0033] Weigh the mixed choline chloride and p-toluenesulfonic acid in a molar ratio of 1:1 to prepare 3 g of deep eutectic solvent;

[0034] Load the above 3 g of deep eutectic solvent onto 0.1 g of graphitic carbon nitride@reduced graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0035] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of 1600 ppm thiophene solution, and 0.05 g of 30% hydrogen peroxide solution. Stir and react at a reaction temperature of 25 °C and a rotation speed of 800 rpm for 30 min. After standing and separating layers, use gas chromatography to detect the thiophene concentration in the n-octane layer, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 92.94%.

[0036] Example 5

[0037] Weigh the mixed choline chloride and p-toluenesulfonic acid in a molar ratio of 1:2 to prepare 3 g of deep eutectic solvent;

[0038] Load the above 3 g of deep eutectic solvent onto 0.1 g of graphitic carbon nitride@reduced graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0039] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of 1600 ppm thiophene solution, and 0.05 g of 30% hydrogen peroxide solution. Stir and react at a reaction temperature of 25 °C and a rotation speed of 800 rpm for 30 min. After standing and separating layers, use gas chromatography to detect the thiophene concentration in the n-octane layer, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 98.16%.

[0040] Example 6

[0041] Mix choline chloride and p-toluenesulfonic acid in a molar ratio of 1:2 to prepare 3 g of deep eutectic solvent;

[0042] Load the above 3 g of deep eutectic solvent onto 0.1 g of graphite phase carbon nitride@reduced graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0043] Weigh 0.30 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of a 1600 ppm thiophene solution, and 0.05 g of a 30% hydrogen peroxide solution. Stir and react at a reaction temperature of 25 °C and a rotation speed of 800 rpm for 25 min. After standing and separating layers, detect the thiophene concentration in the n-octane layer by gas chromatography, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 98.12%.

[0044] Example 7

[0045] Mix choline chloride and p-toluenesulfonic acid in a molar ratio of 1:2 to prepare 3 g of deep eutectic solvent;

[0046] Load the above 3 g of deep eutectic solvent onto 0.1 g of graphite phase carbon nitride@reduced graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0047] Weigh 0.35 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of a 1600 ppm thiophene solution, and 0.05 g of a 30% hydrogen peroxide solution. Stir and react at a reaction temperature of 25 °C and a rotation speed of 800 rpm for 20 min. After standing and separating layers, detect the thiophene concentration in the n-octane layer by gas chromatography, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 98.10%.

[0048] Example 8

[0049] Mix choline chloride and p-toluenesulfonic acid in a molar ratio of 1:2 to prepare 3 g of deep eutectic solvent;

[0050] Load the above 3 g of deep eutectic solvent onto 0.1 g of graphite phase carbon nitride@reduced graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0051] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of a 1600 ppm thiophene solution, and 0.05 g of a 30% hydrogen peroxide solution. Stir and react at a reaction temperature of 25 °C and a rotation speed of 1200 rpm for 20 min. After standing and separating layers, detect the thiophene concentration in the n-octane layer by gas chromatography, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 97.96%.

[0052] Example 9

[0053] Mix choline chloride and p-toluenesulfonic acid in a molar ratio of 1:2 to prepare 3 g of deep eutectic solvent;

[0054] Load the above 3 g of deep eutectic solvent onto 0.1 g of graphite phase carbon nitride@reduced graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0055] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of 1600 ppm thiophene solution, and 0.05 g of 30% hydrogen peroxide solution. Stir and react at a reaction temperature of 40 °C and a rotation speed of 800 rpm for 25 min. After standing and separating layers, use gas chromatography to detect the thiophene concentration in the n-octane layer, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 97.93%.

[0056] Example 10

[0057] Mix choline chloride and p-toluenesulfonic acid in a molar ratio of 1:2 to prepare 3 g of deep eutectic solvent;

[0058] Load the above 3 g of deep eutectic solvent onto 0.1 g of graphite phase carbon nitride@reduced graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0059] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of 1600 ppm thiophene solution, and 0.05 g of 30% hydrogen peroxide solution. Stir and react at a reaction temperature of 60 °C and a rotation speed of 800 rpm for 15 min. After standing and separating layers, use gas chromatography to detect the thiophene concentration in the n-octane layer, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 98.70%.

[0060] Example 11

[0061] Mix choline chloride and p-toluenesulfonic acid in a molar ratio of 1:2 to prepare 3 g of deep eutectic solvent;

[0062] Load the above 3 g of deep eutectic solvent onto 0.1 g of graphite phase carbon nitride@reduced graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0063] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of 1600 ppm thiophene solution, and 0.05 g of periodic acid. Stir and react at a reaction temperature of 25 °C and a rotation speed of 800 rpm for 30 min. After standing and separating layers, use gas chromatography to detect the thiophene concentration in the n-octane layer, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 95.83%.

[0064] Example 12

[0065] Weigh the mixed choline chloride and p-toluenesulfonic acid in a molar ratio of 1:2 to prepare 1 g of deep eutectic solvent;

[0066] Load the above 1 g of deep eutectic solvent onto 0.1 g of graphitic carbon nitride@reduced graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0067] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of 1600 ppm thiophene solution, and 0.05 g of 30% hydrogen peroxide solution. Stir and react at a reaction temperature of 25 °C and a rotation speed of 800 rpm for 15 min. After standing and separating layers, use gas chromatography to detect the thiophene concentration in the n-octane layer, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 45.90%.

[0068] Example 13

[0069] Weigh the mixed choline chloride and p-toluenesulfonic acid in a molar ratio of 1:2 to prepare 2 g of deep eutectic solvent;

[0070] Load the above 2 g of deep eutectic solvent onto 0.1 g of graphitic carbon nitride@reduced graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0071] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of 1600 ppm thiophene solution, and 0.05 g of 30% hydrogen peroxide solution. Stir and react at a reaction temperature of 25 °C and a rotation speed of 800 rpm for 15 min. After standing and separating layers, use gas chromatography to detect the thiophene concentration in the n-octane layer, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 73.58%.

[0072] Example 14

[0073] Weigh the mixed choline chloride and p-toluenesulfonic acid in a molar ratio of 1:2 to prepare 3 g of deep eutectic solvent;

[0074] Load the above 3 g of deep eutectic solvent onto 0.1 g of graphitic carbon nitride@reduced graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0075] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of 1600 ppm thiophene solution, and 0.05 g of 30% hydrogen peroxide solution. Stir and react at a reaction temperature of 25 °C and a rotation speed of 800 rpm for 15 min. After standing and separating layers, use gas chromatography to detect the thiophene concentration in the n-octane layer, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 88.58%.

[0076] Example 15

[0077] Weigh the mixed choline chloride and p-toluenesulfonic acid in a molar ratio of 1:2 to prepare 4 g of deep eutectic solvent;

[0078] Load the above 4 g of deep eutectic solvent onto 0.1 g of graphitic carbon nitride@reduced graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0079] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of 1600 ppm thiophene solution, and 0.05 g of 30% hydrogen peroxide solution. At a reaction temperature of 25 °C, stir and react at a speed of 800 rpm for 30 min. After standing and separating the layers, detect the thiophene concentration in the n-octane layer by gas chromatography, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 79.40%.

[0080] Example 16

[0081] Weigh the mixed choline chloride and p-toluenesulfonic acid in a molar ratio of 1:2 to prepare 5 g of deep eutectic solvent;

[0082] Load the above 5 g of deep eutectic solvent onto 0.1 g of graphitic carbon nitride@reduced graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0083] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of 1600 ppm thiophene solution, and 0.05 g of 30% hydrogen peroxide solution. At a reaction temperature of 25 °C, stir and react at a speed of 800 rpm for 15 min. After standing and separating the layers, detect the thiophene concentration in the n-octane layer by gas chromatography, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 74.06%.

[0084] Example 17

[0085] Weigh the mixed choline chloride and p-toluenesulfonic acid in a molar ratio of 1:2 to prepare 6 g of deep eutectic solvent;

[0086] Load the above 6 g of deep eutectic solvent onto 0.1 g of graphitic carbon nitride@reduced graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0087] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of 1600 ppm thiophene solution, and 0.05 g of 30% hydrogen peroxide solution. At a reaction temperature of 25 °C, stir and react at a speed of 800 rpm for 15 min. After standing and separating the layers, detect the thiophene concentration in the n-octane layer by gas chromatography, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 70.16%.

[0088] Comparative Example 1

[0089] Weigh the mixed choline chloride and p-toluenesulfonic acid in a molar ratio of 1:2 to prepare 3 g of deep eutectic solvent;

[0090] Load the above 3 g of deep eutectic solvent onto 0.1 g of graphite phase carbon nitride@graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0091] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of 1600 ppm thiophene solution, and 0.05 g of tert-butyl hydroperoxide. Stir and react at a reaction temperature of 25 °C and a rotation speed of 800 rpm for 30 min. After standing and separating layers, detect the thiophene concentration in the n-octane layer by gas chromatography, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 52.66%.

[0092] Comparative Example 2

[0093] Weigh the mixed choline chloride and p-toluenesulfonic acid in a molar ratio of 1:2 to prepare 3 g of deep eutectic solvent;

[0094] Load the above 3 g of deep eutectic solvent onto 0.1 g of graphite phase carbon nitride@graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0095] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of 1600 ppm thiophene solution, and 0.05 g of cyclohexanone peroxide. Stir and react at a reaction temperature of 25 °C and a rotation speed of 800 rpm for 30 min. After standing and separating layers, detect the thiophene concentration in the n-octane layer by gas chromatography, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 39.96%.

[0096] Comparative Example 3

[0097] Weigh the mixed choline chloride and 5-sulfosalicylic acid in a molar ratio of 1:2 to prepare 3 g of deep eutectic solvent;

[0098] Load the above 3 g of deep eutectic solvent onto 0.1 g of graphite phase carbon nitride@graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite material;

[0099] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite material, 0.5 g of 1600 ppm thiophene solution, and 0.05 g of 30% hydrogen peroxide solution. Stir and react at a reaction temperature of 25 °C and a rotation speed of 800 rpm for 30 min. After standing and separating layers, detect the thiophene concentration in the n-octane layer by gas chromatography, and calculate that the desulfurization efficiency of the composite material for the thiophene solution is 23.62%.

[0100] Comparative Example 4

[0101] Weigh the mixed tetraethylammonium chloride and 5-sulfosalicylic acid in a molar ratio of 1:2 to prepare 3 g of deep eutectic solvent;

[0102] Load the above 3 g of deep eutectic solvent onto 0.1 g of graphitic carbon nitride@reduced graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite;

[0103] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite, 0.5 g of 1600 ppm thiophene solution, and 0.05 g of 30% hydrogen peroxide solution. At a reaction temperature of 25 °C, stir and react at a speed of 800 rpm for 30 min. After standing and separating layers, use gas chromatography to detect the thiophene concentration in the n-octane layer, and calculate that the desulfurization efficiency of the composite for the thiophene solution is 19.07%.

[0104] Comparative Example 5

[0105] Weigh the mixed choline chloride and p-aminosalicylic acid in a molar ratio of 1:2 to prepare 3 g of deep eutectic solvent;

[0106] Load the above 3 g of deep eutectic solvent onto 0.1 g of graphitic carbon nitride@reduced graphene oxide nanospheres by the impregnation method to obtain a deep eutectic solvent / nanosphere composite;

[0107] Weigh 0.25 g of the deep eutectic solvent / nanosphere composite, 0.5 g of 1600 ppm thiophene solution, and 0.05 g of 30% hydrogen peroxide solution. At a reaction temperature of 25 °C, stir and react at a speed of 800 rpm for 30 min. After standing and separating layers, use gas chromatography to detect the thiophene concentration in the n-octane layer, and calculate that the desulfurization efficiency of the composite for the thiophene solution is 21.86%.

Claims

1. A desulfurization extractant based on nanospheres, characterized in that: The desulfurization extractant loads the deep eutectic solvent on the graphite phase carbon nitride@graphene oxide nanospheres; the mass ratio of the deep eutectic solvent to the nanospheres is 10-60:

1.

2. The desulfurization extractant according to claim 1, characterized in that The preparation method of the graphite phase carbon nitride@graphene oxide nanospheres comprises the following steps: using hexadecyltrimethylammonium bromide, melamine, glucose, glacial acetic acid and water as raw materials to prepare the nanospheres through a hydrothermal method.

3. The desulfurization extractant according to claim 1, characterized in that: The deep eutectic solvent comprises a hydrogen bond acceptor and a hydrogen bond donor; the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1-2; the hydrogen bond acceptor is tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride or choline chloride; The hydrogen bond donor is p-toluenesulfonic acid.

4. A method for removing thiophene, characterized in that: The method uses the desulfurization extractant according to any one of claims 1 to 3, and mixes the desulfurization extractant, thiophene n-octane solution and an oxidant, and allows the mixture to stand for stratification.

5. The method according to claim 4, characterized in that The mass ratio of the desulfurization extractant, the thiophene n-octane solution and the oxidant is 0.3-0.7:1:0.1; the concentration of the thiophene n-octane solution is 1400ppm-1800pm.

6. The method according to claim 4, characterized in that The mixing is carried out at 25-60° C. and 800-1200 rpm for 15-30 min.

7. The method according to claim 4, characterized in that The oxidant is 30% hydrogen peroxide solution with periodic acid.

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