阅读说明：本技术 一种脱除汽油中噻吩类硫分子印迹聚合物及制备方法 (Molecularly imprinted polymer for removing thiophene sulfur in gasoline and preparation method thereof ) 是由 胡廷平 李云雁 于 2021-02-07 设计创作，主要内容包括：本发明涉及一种脱除汽油中噻吩类硫分子印迹聚合物及制备方法。本分子印迹聚合物以SiO2为载体,含噻吩类硫化物为模板分子,在SiO2表面进行接枝、聚合反应和后处理,制得一种表面分子印迹聚合物。本发明解决现有汽油中含噻吩类硫化物脱除困难的问题,具有高效性、高选择性、节能廉价等特点。(The invention relates to a molecularly imprinted polymer for removing thiophene sulfur in gasoline and a preparation method thereof. The molecularly imprinted polymer takes SiO2 as a carrier and thiophene-containing sulfide as a template molecule, and grafting, polymerization reaction and post-treatment are carried out on the surface of SiO2 to prepare the surface molecularly imprinted polymer. The invention solves the problem that the existing gasoline containing thiophene sulfides is difficult to remove, and has the characteristics of high efficiency, high selectivity, energy conservation, low price and the like.)

1. A molecularly imprinted polymer for removing thiophene sulfur in gasoline is prepared through graft reaction on silica gel particles as carrier of imprinted polymer to introduce double bonds, adding template molecule (containing thiophene sulfide), functional monomer and cross-linking agent, polymerizing to obtain high-molecular thin layer, fixing the acting force between template molecule and functional monomer, and physically or chemically removing template molecule from high-molecular polymer material to form holes matched with template molecule in space structure and having multiple action sites.

2. The method according to claim 1, wherein the sulfur content in said gasoline is 5 to 800 μ g/g in terms of the weight of elemental sulfur.

3. The preparation method of the surface molecularly imprinted polymer of claim 1 comprises:

(1) activation of silica gel: adding silica gel particles into 0.01-10 mol/L HCl, stirring and refluxing at 20-80 ℃, performing suction filtration, washing with distilled water until the pH value is neutral, and drying for later use;

(2) preparing amino silicone rubber: adding the silica gel in the step (1) into an anhydrous toluene solution of aminosilane with the volume ratio of 1-20% according to the mass ratio of 0.5-30% of the silica gel to toluene, dripping a proper amount of pyridine, refluxing for 8-24 h at 90-130 ℃, performing suction filtration, washing with toluene, acetone, diethyl ether, methanol and the like, and drying for later use;

(3) acylation of amino silica gel: adding the silica gel in the step (2) into a dichloromethane solution of olefine acid or acyl chloride with the volume ratio of 2-20% according to the mass ratio of the silica gel to the dichloromethane of 0.5-30%, dripping pyridine for several drops, stirring for 5-20 min, stirring for 2-6 h at 85-95 ℃, filtering, washing with toluene, acetone, ether and methanol, and drying;

(4) synthesis of MIP: adding the silica gel in the step (3) into a pore-foaming agent according to the mass ratio of 0.5-30% of the silica gel to the pore-foaming agent, adding template molecules, functional monomers, an initiator and a crosslinking agent, and ultrasonically mixing uniformly, wherein the concentrations of the template molecules, the functional monomers and the crosslinking agent in toluene are 0.001-0.01 mmol/L, 0.005-0.020 mmol/L and 0.008-0.08 mmol/L respectively, magnetically stirring for 5-20 min, heating, reacting at 45-55 ℃ for 3-8 h, heating to 55-65 ℃, reacting for 8-20 h, and heating to 70-90 ℃ for reacting for 3-8 h;

(5) and (4) repeatedly washing the MIP obtained in the step (4) with toluene, drying, repeatedly washing with a mixed solution of methanol and acetic acid to remove template molecules, and performing suction filtration and drying to obtain the silica gel surface molecularly imprinted polymer.

4. The method for preparing a surface molecularly imprinted polymer according to claim 3, wherein the silica gel used in the step (1) has a particle size of 10 to 100 μm.

5. The method for preparing a surface molecularly imprinted polymer according to claim 3, the aminosilane used in the step (2) is one or a mixture of more of N-beta-aminoethyl-gamma-aminopropyltrimethoxysilane, N-beta-aminoethyl-gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, aniline methyltrimethoxysilane, aniline methyltriethoxysilane, diethylaminomethyltriethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-ethylenediamine propyldimethoxysilane and triaminopropylmethyldimethoxysilane.

6. The method for preparing a surface molecularly imprinted polymer according to claim 3, wherein olefinic acid or acyl chloride reacts with amino silica gel in the step (3) to generate acylated silica gel, wherein a double bond is introduced to a side chain grafted on the surface of the silica gel, and the olefinic acid or the acyl chloride is any one of methacrylic acid, acrylic acid, crotonic acid, acryloyl chloride and crotonyl chloride.

7. The template molecule used in the step (4) according to claim 3 is a thiophene sulfur compound in gasoline, and thiophene, 3-methylthiophene, benzothiophene and dibenzothiophene are compounded in any ratio.

8. The porogenic agent used in the step (4) according to claim 3 is one or more of acetonitrile, toluene, chloroform and tetrahydrofuran;

the functional monomer is one of methacrylic acid, acrylic acid, methyl methacrylate, 4-vinylpyridine, 4-vinylbenzoic acid, acrylamide and 2-vinylpyridine;

the cross-linking agent is one of N, N '-methylene-bis-acrylamide, N' -1, 4-phenyl-bis-acrylamide, ethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, divinylbenzene, pentaerythritol tetraacrylate and trimethylolpropane triacrylate;

the initiator is one of azodiisobutyronitrile, azodiisobutyl amidine hydrochloride, dibenzoyl peroxide, potassium persulfate and hydrogen peroxide-ferrous salt.

Technical Field

The invention belongs to the technical field of oil product desulfurization, and particularly relates to a molecularly imprinted polymer for removing thiophene sulfur in gasoline and a preparation method thereof.

Background

Along with the continuous enhancement of environmental awareness of people, the automobile exhaust bringsContamination is becoming a focus of increasing attention. The presence of sulfur in fuel oils (especially motor gasoline and diesel oil) is one of the important causes of air pollution. According to statistics, there are about 2500 million tons of sulfur oxides SOx (SO) in China every year₂Or SO₃) And is discharged to the atmosphere, where a significant portion is derived from the combustion process of the vehicle fuel. The organic sulfur compounds in the oil products generate sulfur oxides SOx after combustion, which causes acid rain, pollutes the environment and harms human health. In addition, the existence of sulfide has obvious promotion effect on the emission of NO and CO, particularly NO and Particulate Matters (PM) in automobile exhaust, and can also poison noble metalants in an automobile exhaust converter, so that the pollution emission is increased, the engine is corroded, and the service life of the engine is shortened. Therefore, environmental regulations are made in various countries in the world, especially developed countries, to improve the quality standards of gasoline and diesel oil, and the sulfur content of automotive fuels (diesel oil and gasoline) is limited to 10 mu g.g^-1The following. In addition, the fuel cell technology in the sunward industry of the 21 st century is very demanding on the content of sulfur in fuel (sulfur content)<1 mug/g), so that the development of deep desulfurization technology is of great significance.

Sulfides in gasoline exist as thioethers, mercaptans, disulfides, as well as thiophenes, benzothiophenes, and the like. The sulfur contents of mercaptan and disulfide are low, the sulfur contents of mercaptan and disulfide are about 15% of the total sulfur content, the sulfur contents of thioether are about 25% of the total sulfur content, the most sulfur is thiophene sulfur, the relative content of the thiophene sulfur is more than 60%, and the sum of the sulfur contents of thioether and thiophene is more than 85% of the total sulfur content. At present, catalytic hydrogenation is generally adopted at home and abroad to carry out oil product desulfurization, mercaptan and thioether sulfides are basically removed after hydrodesulfurization, sulfides in the forms of thiophene, benzothiophene and the like have stable properties, and the removal rate in the hydrogenation process is relatively low. The deep desulfurization process needs high temperature and high pressure, the required equipment is expensive, the operation cost is high, the hydrogen consumption is large, the purity is high, olefin saturation is easy to cause, the octane number of the gasoline is reduced, and the application of the gasoline in deep and ultra-deep desulfurization is limited.

Compared with hydrodesulfurization, adsorption desulfurization is a new technology which is developed quickly and has a wide application prospect at present, can selectively remove sulfur-containing compounds in gasoline, has no influence on olefins in the gasoline, and does not cause the octane number reduction of the gasoline. In addition, the adsorption desulfurization technology has strong competitive advantages in investment cost, operation cost and desulfurization depth, and has attractive development space and application potential in industry, so the adsorption desulfurization method becomes a research hotspot in the gasoline desulfurization technology.

The adsorption method mostly uses metal oxides, active carbon, natural montmorillonite, bentonite, molecular sieves and the like as adsorbents, has adsorption and removal effects on various components in gasoline, but also has the defects of low adsorption selectivity, small adsorption capacity, removal rate and the like. Therefore, the development of new high-selectivity adsorbents is urgent. Much work has been done in this regard and molecular imprinting techniques have unique advantages over a wide range of adsorption techniques.

Molecular Imprinting (MIT) is one of the major methods currently in development of highly selective materials. The molecular imprinting means that special template molecules are added into a polymer system, the template molecules and functional monomers form a compound through covalent or non-covalent interaction, and after cross-linking polymerization reaction is completed, the template molecules are removed, so that holes with the sizes, shapes and functional group arrangements complementary to the template molecules are left in the polymer. Molecularly Imprinted Polymers (MIPs) are becoming increasingly popular for their versatility and specific recognition.

So far, many reports on molecular imprinting techniques have been reported in literature and patents, but there are few studies on the application of molecular imprinting to oil desulfurization, particularly on thiophene, benzothiophene, and dibenzothiophene on the surface of silica gel particles. The method for preparing the adsorption material comprises the steps of preparing benzothiophene (one or more of benzothiophene, dibenzothiophene, dioxydibenzothiophene or dimethyl dibenzothiophene) adsorption resin by using methacrylic acid or acrylamide as a functional monomer, and washing and removing template molecules by using a mixed solution of acetic acid and methanol to prepare the adsorption material, wherein the preparation method has the defects of deep embedding of the template molecules, serious post-treatment waste, low adsorption efficiency and the like. Cinnariz, Renwei and the like (patent application No. 200810046661.2) provide a SiO2 particle surface molecularly imprinted adsorbent prepared in an aqueous phase system and a preparation method thereof, the preparation method comprises the steps of firstly activating SiO2 particles, then forming a compound precursor with a functional monomer and a target phenol pollutant (one of chlorophenols or nitrophenols), preparing the SiO2 particle surface molecularly imprinted adsorbent through polymerization reaction, and using the polymer for enrichment and separation of a target substance in water. Based on the problems, the surface molecularly imprinted polymer prepared by the invention is prepared in an organic solvent, can introduce adsorption sites to the surface of the polymer to the maximum extent, improves the adsorption rate and the adsorption capacity at the same time, and better removes sulfide containing thiophene groups from gasoline.

Disclosure of Invention

The invention provides a surface molecularly imprinted polymer of thiophene sulfides in gasoline and a preparation method thereof, aiming at the defects of low selectivity of removing thiophene sulfides in the existing gasoline, large oil product loss and the like.

According to the invention, silica gel particles are used as a carrier of a surface molecularly imprinted polymer, double bonds are introduced by grafting reaction on the surface of the silica gel particles, template molecules (containing thiophene groups), functional monomers and a cross-linking agent are added, a high polymer material thin layer is obtained by polymerization, the acting force between the template molecules and the functional monomers is fixed, the template molecules are removed from the high polymer material by using a physical or chemical method, holes which are matched with the spatial structure of the template molecules and have multiple acting sites are formed in the polymer, and the porous polymer material has specific selective adsorption capacity on the template molecules, so that the aim of removing thiophene sulfides from gasoline is fulfilled. A molecularly imprinted polymer for removing thiophene sulfur in gasoline and a preparation method thereof, wherein a mixture passes through an adsorbent bed layer, and is characterized in that the adsorbent is a surface molecularly imprinted polymer; the adsorption temperature is room temperature-100 ℃, and the pressure is normal pressure-1.0 MPa.

The preparation method of the surface molecularly imprinted polymer comprises the following steps:

(1) activation of silica gel: adding silica gel particles into 0.01-10 mol/L HCl, stirring and refluxing at 20-80 ℃, performing suction filtration, washing with distilled water until the pH value is neutral, and drying for later use;

(2) preparing amino silicone rubber: adding the silica gel in the step (1) into an anhydrous toluene solution of gamma-aminopropyl triethoxysilane with the volume ratio of 1-20% according to the mass ratio of the silica gel to the toluene of 0.5-30%, dripping a proper amount of pyridine, and refluxing for 8-24 h at 90-130 ℃. Filtering, washing with toluene, acetone, diethyl ether, methanol, etc., and drying;

(3) acylation of amino silica gel: adding the silica gel in the step (2) into a 2-20 vol% dichloromethane solution of methacrylic acid according to the mass ratio of the silica gel to the dichloromethane of 0.5-30%, dripping pyridine for several drops, stirring for 5-20 min, stirring for 2-6 h at 85-95 ℃, filtering, washing with toluene, acetone, ether and methanol, and drying;

(4) synthesis of MIP: adding the silica gel in the step (3) into a pore-foaming agent according to the mass ratio of 0.5-30% of the silica gel to the pore-foaming agent, adding template molecules, functional monomers, an initiator and a cross-linking agent, and ultrasonically mixing uniformly. The concentrations of the template molecule, the functional monomer and the cross-linking agent in toluene are 0.001-0.01 mmol/L, 0.005-0.020 mmol/L and 0.008-0.08 mmol/L respectively. Stirring for 5-20 min by magnetic force, heating, reacting for 3-8 h at 45-55 ℃, heating to 55-65 ℃, reacting for 8-20 h, and heating to 70-90 ℃ for reacting for 3-8 h. After the reaction is finished, repeatedly washing with toluene, drying, repeatedly washing with a mixed solution of methanol and acetic acid to remove template molecules, and performing suction filtration and drying to obtain a silica gel surface molecularly imprinted polymer;

the particle size of the silica gel used in the step (1) is 10-100 μm.

The pore-foaming agent used in the step (4) is one or more of acetonitrile, toluene, chloroform and tetrahydrofuran; the template molecules are thiophene, alkyl thiophene, benzothiophene and dibenzothiophene which are compounded in any proportion;

the functional monomer is one or more of methacrylic acid, acrylic acid, methyl methacrylate, 4-vinylpyridine, 4-vinylbenzoic acid, acrylamide and 2-vinylpyridine;

the cross-linking agent is one or more of N, N '-methylene-bis-acrylamide, N' -1, 4-phenyl-bis-acrylamide, ethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, divinylbenzene, pentaerythritol tetraacrylate and trimethylolpropane triacrylate;

the initiator is one of azodiisobutyronitrile, azodiisobutyl amidine hydrochloride, dibenzoyl peroxide, potassium persulfate and hydrogen peroxide-ferrous salt.

The existence of the imprinted polymer thin layer on the silica gel surface is confirmed by infrared, electron microscope and specific surface area measurement.

The silica gel surface molecular imprinting adsorbent prepared by the invention can directly use commercial silica particles as materials, has no harsh requirements on synthesis conditions, and has low cost. The prepared surface imprinting adsorbent can be used for removing thiophene organic sulfides such as thiophene, benzothiophene and dibenzothiophene in gasoline, and has the advantages of good adsorption performance, high identification, high adsorption and desorption balance speed, reusability and the like.

In addition to the objects, features and advantages described above, there are other objects, features and advantages of the present invention. The present invention will be described in further detail below with reference to the drawings.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:

FIG. 1 is an infrared spectrum of the aminated silica gel, acylated silica gel and MIP.

Curves (a), (b), (c) and (d) are the infrared spectra of the activated silica gel, the amino silica gel, the acylated silica gel and the imprinted silica gel, respectively.

Transmittance on the ordinate and wavenumber (cm) on the abscissa^-1)。

Detailed Description

The principles and features of this invention are described below in conjunction with specific embodiments, which are set forth merely to illustrate the invention and are not intended to limit the scope of the invention.

The invention is further illustrated by the following examples.

Example 1:

(1) activation of silica gel: adding 10 g of silicon rubber particles into 150 ml of 8 mol/L HCl, stirring and refluxing at 50 ℃, performing suction filtration, washing with distilled water until the pH value is neutral, and drying at 120 ℃ for later use;

(2) preparing amino silicone rubber: adding the activated silica gel into an anhydrous toluene solution containing 10 percent (volume ratio) of gamma-aminopropyl triethoxysilane, dripping a proper amount of pyridine, and refluxing for 12 hours at 115 ℃. Filtering, washing with toluene, acetone, diethyl ether, methanol, etc., and drying at 110 deg.C;

(3) acylation of amino silica gel: adding 10 g of amino silica gel into dichloromethane solution containing 20% (volume ratio) of methacrylic acid, dripping pyridine for several drops, stirring for 5 min, stirring at 90 deg.C for 4 h, filtering, washing with toluene, acetone, diethyl ether and methanol, and vacuum drying;

(4) synthesis of MIP: adding 10 g of acylated silica gel into 200 g of anhydrous toluene, adding 0.5 g of thiophene, 2 ml of methacrylic acid, 100 mg of azodiisobutyronitrile and 20 ml of ethylene glycol dimethacrylate, and carrying out ultrasonic mixing uniformly. Magnetically stirring for 5 min under the protection of nitrogen, heating, reacting at 50 deg.C for 6 h, heating to 65 deg.C, reacting for 12 h, and heating to 90 deg.C for 6 h. And after the reaction is finished, repeatedly washing with toluene, drying, repeatedly washing with a mixed solution of methanol and acetic acid (volume ratio of 1: 9) to remove template molecules, and performing suction filtration and drying to obtain the surface molecularly imprinted polymer. The surface molecularly imprinted polymer is packed into a column, and can be used for separating and enriching thiophene in gasoline at room temperature and normal pressure.

Example 2:

(1) activation of silica gel: adding 10 g of silicon rubber particles into 150 ml of 8 mol/L HCl, stirring and refluxing at 50 ℃, performing suction filtration, washing with distilled water until the pH value is neutral, and drying at 120 ℃ for later use;

(2) preparing amino silicone rubber: adding the activated silica gel into an anhydrous toluene solution containing 10 percent (volume ratio) of gamma-aminopropyl triethoxysilane, dripping a proper amount of pyridine, and refluxing for 12 hours at 115 ℃. Filtering, washing with toluene, acetone, diethyl ether, methanol, etc., and drying at 110 deg.C;

(3) acylation of amino silica gel: adding 10 g of amino silica gel into dichloromethane solution containing 20% (volume ratio) of methacrylic acid, dripping pyridine for several drops, stirring for 5 min, stirring at 90 deg.C for 4 h, filtering, washing with toluene, acetone, diethyl ether and methanol, and vacuum drying;

(4) synthesis of MIP: adding 10 g of acylated silica gel into 200 g of anhydrous toluene, adding 0.5 g of 3-methylthiophene, 2 ml of methacrylic acid, 100 mg of azodiisobutyronitrile and 20 ml of ethylene glycol dimethacrylate, and carrying out ultrasonic mixing uniformly. Magnetically stirring for 5 min under the protection of nitrogen, heating, reacting at 50 deg.C for 6 h, heating to 65 deg.C, reacting for 12 h, and heating to 90 deg.C for 6 h. And after the reaction is finished, repeatedly washing with toluene, drying, repeatedly washing with a mixed solution of methanol and acetic acid (volume ratio of 1: 9) to remove template molecules, and performing suction filtration and drying to obtain the surface molecularly imprinted polymer. The surface molecularly imprinted polymer is packed into a column, and can be used for separating and enriching 3-methylthiophene in gasoline at room temperature and normal pressure.

Example 3:

(1) activation of silica gel: adding silicon 12 g of rubber particles into 150 ml of 7 mol/L HCl, stirring and refluxing at 50 ℃, performing suction filtration, washing with distilled water until the pH value is neutral, and drying at 120 ℃ for later use;

(2) preparing amino silicone rubber: adding the activated silica gel into an anhydrous toluene solution containing 20 percent (volume ratio) of gamma-aminopropyl triethoxysilane, dripping a proper amount of pyridine, and refluxing at 115 ℃ for 12 hours. Filtering, washing with toluene, acetone, diethyl ether, methanol, etc., and drying at 120 deg.C;

(3) acylation of amino silica gel: adding 12 g of the amino silica gel into a dichloromethane solution containing 20% (volume ratio) of methacrylic acid, dripping pyridine for several drops, stirring for 10 min, stirring for 4 h at 95 ℃, filtering, washing with toluene, acetone, diethyl ether and methanol, and vacuum drying;

(4) synthesis of MIP: 12 g of acylated silica gel is added into 200 ml of anhydrous chloroform, 0.8 g of benzothiophene, 3 ml of methacrylic acid, 100 mg of azobisisobutyronitrile and 20 ml of ethylene glycol dimethacrylate are added, and the mixture is ultrasonically mixed uniformly. Magnetically stirring for 5 min under the protection of nitrogen, heating, reacting at 50 deg.C for 7 h, heating to 65 deg.C, reacting for 15 h, and heating to 90 deg.C again, and reacting for 5 h. After the reaction is finished, repeatedly washing and drying by using chloroform, repeatedly washing by using a mixed solution of methanol and acetic acid (the volume ratio is 1: 9) to remove template molecules, and performing suction filtration and drying to obtain the surface molecularly imprinted polymer. The surface molecularly imprinted polymer is packed into a column, can be used for removing benzothiophene in gasoline, and has the temperature of room temperature and the pressure of normal pressure.

Example 4:

(1) activation of silica gel: adding 8 g of silicon rubber particles into 200 ml of 4 mol/L HCl, stirring and refluxing at 40 ℃, performing suction filtration, washing with distilled water until the pH value is neutral, and drying at 120 ℃ for later use;

(2) preparing amino silicone rubber: the activated silica gel was added to 200 ml of an anhydrous toluene solution containing 15% (by volume) of gamma-aminopropyltriethoxysilane, and an appropriate amount of pyridine was added dropwise thereto, followed by reflux at 115 ℃ for 12 hours. Filtering, washing with toluene, acetone, diethyl ether, methanol, etc., and drying at 120 deg.C;

(3) acylation of amino silica gel: adding 15 g of the above-mentioned amino silica gel into 100 ml of dichloromethane solution containing 20% (volume ratio) of methacrylic acid, dripping several drops of pyridine, stirring for 20 min, stirring at 95 deg.C for 4 h, filtering, washing with toluene, acetone, diethyl ether and methanol, and vacuum drying;

(4) synthesis of MIP: adding 8 g of acylated silica gel into 200 ml of anhydrous chloroform, adding 0.5 g of dibenzothiophene, 3 ml of methyl methacrylate, 40 mg of azobisisobutyronitrile and 18 ml of ethylene glycol dimethacrylate, and carrying out ultrasonic mixing uniformly. Magnetically stirring for 5 min under the protection of nitrogen, heating, reacting at 50 deg.C for 6 hr, heating to 65 deg.C, reacting for 15 hr, and heating to 85 deg.C, and reacting for 7 hr. And after the reaction is finished, repeatedly washing with chloroform, drying, repeatedly washing with a mixed solution of methanol and acetic acid (volume ratio of 1: 9) to remove template molecules, and performing suction filtration and drying to obtain the surface molecularly imprinted polymer. The surface molecularly imprinted polymer is packed into a column, can be used for removing dibenzothiophene in gasoline at room temperature and normal pressure.

Example 5:

(1) activation of silica gel: adding 15 g of silica gel particles into 200 ml of 5 mol/L HCl, stirring and refluxing at 50 ℃, performing suction filtration, washing with distilled water until the pH value is neutral, and drying at 120 ℃ for later use;

(2) preparing amino silicone rubber: adding the activated silica gel into an anhydrous toluene solution containing 20 percent (volume ratio) of gamma-aminopropyl triethoxysilane, dripping a proper amount of pyridine, and refluxing at 115 ℃ for 12 hours. Filtering, washing with toluene, acetone, diethyl ether, methanol, etc., and drying at 120 deg.C;

(3) acylation of amino silica gel: adding 15 g of the amino silica gel into a dichloromethane solution containing 20% (volume ratio) of methacrylic acid, dripping pyridine for several drops, stirring for 20 min, stirring for 4 h at 85 ℃, filtering, washing with toluene, acetone, diethyl ether and methanol, and vacuum drying;

(4) synthesis of MIP: adding 15 g of acylated silica gel into 200 ml of anhydrous toluene, adding 150 g of each of thiophene, 3-methylthiophene, benzothiophene and dibenzothiophene, 3 ml of 4-vinylpyridine, 100 mg of azodiisobutyronitrile and 22 ml of ethylene glycol dimethacrylate, and carrying out ultrasonic mixing uniformly. Magnetically stirring for 5 min under the protection of nitrogen, heating, reacting at 50 deg.C for 6 h, heating to 65 deg.C, reacting for 12 h, and heating to 90 deg.C for 6 h. And after the reaction is finished, repeatedly washing and drying the mixture by using methylbenzene, repeatedly washing the mixture by using a mixed solution of methanol and acetic acid (the volume ratio is 1: 9) to remove template molecules, and performing suction filtration and drying to obtain the surface molecularly imprinted polymer. The surface molecularly imprinted polymer is packed into a column and can be used for removing thiophene sulfur compounds such as thiophene, 3-methylthiophene, benzothiophene, dibenzothiophene and the like in gasoline at room temperature and normal pressure.

In the above examples, the sulfur content in gasoline can be removed to 10 mu g.g^-1The national fuel oil sulfur content standard is met.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.