Magnetic multi-effect multi-component composite amphiphilic particles, and preparation method and application thereof

Abstract

The present application relates to sewage treatment technical field, provide a kind of magnetic multi-effect multi-element composite amphiphilic particle and its preparation method and application.The particle includes the core-shell separation magnetic Fe3O4 Particle core and shell layer, the shell layer is the silica / titanium dioxide hybrid shell layer with micro-pore structure;The shell layer outer surface includes hydrophilic part and hydrophobic part, the hydrophilic part has amino group, the amino group is grafted with polydopamine, and gallic acid and catechin are compounded on the polydopamine;The shell layer inner surface and the surface of magnetic Fe3O4 Particle core graft with poly (dimethylamino ethyl methacrylate).The magnetic multi-effect multi-element composite amphiphilic particle provided by the present application has excellent emulsifying performance, can realize oil-water separation;It can selectively adsorb part of hydrolyzed polyacrylamide, and can efficiently treat oil-containing sewage containing part of hydrolyzed polyacrylamide in one step.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of sewage treatment, more particularly to a magnetic multi-effect multi-element composite amphiphilic particle and a preparation method and application thereof. BACKGROUND

[0002] Amphiphilic solid particle emulsifiers can realize emulsification by reducing the interfacial tension, have high interfacial desorption energy, and can be used to prepare oil / water dispersion systems that are very stable in kinetics and thermodynamics. The amphiphilic solid particles with magnetism can also make the emulsified droplets have magnetism, facilitating the manipulation of the dispersed phase droplets. By using the magnetic amphiphilic solid particles, stable dispersed phase oil droplets can be obtained by emulsifying the oil phase in water, and then the oil droplets can be migrated and enriched under the manipulation of an external magnetic field, so as to realize oil / water separation and achieve the effect of treating oily sewage.

[0003] Partially hydrolyzed polyacrylamide (HPAM) is a common polymer flooding component and is widely used in tertiary oil recovery of high water cut oilfields to effectively improve the recovery rate. The existing sewage treatment methods cannot achieve satisfactory results in treating partially hydrolyzed polyacrylamide in oily sewage, and multiple methods and multiple steps are often required to make the treatment results of the partially hydrolyzed polyacrylamide meet the standards. Although the existing magnetic amphiphilic solid particle emulsifiers can successfully realize oil / water separation when applied to treat partially hydrolyzed polyacrylamide in oily sewage, they cannot achieve one-step efficient removal of the partially hydrolyzed polyacrylamide in the oily sewage. SUMMARY

[0004] The present application aims to provide a magnetic multi-effect multi-element composite amphiphilic particle and a preparation method thereof, so as to solve the technical problem that the existing technology cannot achieve one-step treatment of oily sewage containing partially hydrolyzed polyacrylamide to meet the standards.

[0005] To achieve the above-mentioned purpose, the technical solution adopted by the present application is as follows:

[0006] In a first aspect, the present application provides a magnetic multi-effect multi-element composite amphiphilic particle, which comprises a core-shell separated magnetic Fe3O4 particle core and a shell layer, the shell layer is a silica / titania hybrid shell layer with a micro-porous structure; the outer surface of the shell layer comprises a hydrophilic part and a hydrophobic part, the hydrophilic part has an amino group, the amino group is grafted with polydopamine, and the polydopamine is complexed with gallic acid and catechin; the inner surface of the shell layer and the surface of the magnetic Fe3O4 particle core are grafted with poly (diethylaminoethyl methacrylate) (PDEAEMA).

[0007] It should be noted that the "micro-pore structure" in the present application includes intermolecular space existing in the silica / titania macromolecular framework and defects generated in the process of core-shell separation of the silica / titania hybrid shell layer from the magnetic Fe3O4 particle core, even micropores and capillary pores with a pore size of 0.5-50 nm.

[0008] The magnetic multi-effect multi-element composite amphiphilic particle provided by the present application is coated with a silica / titania hybrid shell layer outside the magnetic Fe3O4 particle core, which can protect the magnetic Fe3O4 particle core and resist corrosion of hydrochloric acid, sulfuric acid, nitric acid or various alkaline reagents on the magnetic Fe3O4 particle core within a certain time and within a certain PH range, thereby ensuring the industrial application of the magnetic particle.

[0009] The outer surface of the shell layer of the magnetic multi-effect multi-element composite amphiphilic particle provided by the present application simultaneously includes a hydrophilic part and a hydrophobic part, so that the magnetic multi-effect multi-element composite amphiphilic particle has amphiphilicity and more stable emulsification characteristics compared with traditional homogeneous particles, can more stably and more widely emulsify oil and water phases, and form a stable oil-in-water emulsion, thereby providing a stability basis for the manipulation of emulsion droplets.

[0010] The functional groups on the outer surface of the shell layer of the magnetic multi-effect multi-element composite amphiphilic particle provided by the present application have electrostatic interaction with partially hydrolyzed polyacrylamide, thereby promoting the adsorption of partially hydrolyzed polyacrylamide on the outer surface of the shell layer. In addition, the polydopamine grafted on the amino group of the hydrophilic part and the gallic acid and catechin complexed on the polydopamine through strong hydrogen bond interaction all contain polyhydroxy structures and have adhesion. The use of gallic acid and catechin in combination can effectively increase the adhesion and hydrogen bond interaction of the amphiphilic particle to partially hydrolyzed polyacrylamide, thereby facilitating the further improvement of the effect of the amphiphilic particle on the removal of partially hydrolyzed polyacrylamide in wastewater. After the adsorption and adhesion of partially hydrolyzed polyacrylamide are achieved, the wetting effect of the internal structure of the amphiphilic particle on the partially hydrolyzed polyacrylamide adsorbed on the outer surface of the shell layer will promote the adsorption process of the partially hydrolyzed polyacrylamide into the shell layer. The poly(N,N-dimethylaminoethyl methacrylate) (PDEAEMA) grafted on the inner surface of the shell layer and the surface of the magnetic Fe3O4 particle core forms a brush-like coating, thereby increasing the specific surface area and enhancing the hydrogen bond density. The micro-pore structure on the shell layer provides a channel for the migration and transmission of partially hydrolyzed polyacrylamide, and the weakly acidic characteristics of partially hydrolyzed polyacrylamide are more conducive to the transfer and adsorption of partially hydrolyzed polyacrylamide from the outer surface of the shell layer to the PDEAEMA in the shell layer, thereby realizing the adsorption and migration capture of PDEAEMA to partially hydrolyzed polyacrylamide. The magnetic multi-effect multi-element composite amphiphilic particle provided by the present application greatly improves the adsorption capacity and adsorption efficiency of partially hydrolyzed polyacrylamide through the combination of internal and external structures.

[0011] The magnetic multi-effect multi-element composite amphiphilic particle provided by the application has reusability. The recovery of the amphiphilic particle can adopt a common recovery method, for example, washing and extracting the used magnetic multi-effect multi-element composite amphiphilic particle with a good solvent (for example, ethanol) of partially hydrolyzed polyacrylamide to remove the adsorbed partially hydrolyzed polyacrylamide, so that the magnetic multi-effect multi-element composite amphiphilic particle can be reused, and the material cost of sewage treatment is greatly reduced. In addition, the pH sensitivity of PDEAEMA can be used to realize the repeated recovery and use of the amphiphilic particle. Specifically, PDEAEMA shows hydrophilic properties at a low pH value and shows hydrophobic properties at a high pH value, and the repeated adsorption and desorption of PDEAEMA to partially hydrolyzed polyacrylamide can be realized by using this property, so that the magnetic multi-effect multi-element composite amphiphilic particle can be reused.

[0012] According to some embodiments of the application, the mass ratio of the silica and the titanium dioxide in the shell layer is 1:10-10:1.

[0013] According to some embodiments of the application, the amino-containing silane coupling agent comprises 3-aminopropyl triethoxysilane.

[0014] According to some embodiments of the application, the hydrophobic part is obtained by modifying the outer surface of the shell layer with an alkyl-containing silane coupling agent.

[0015] According to some embodiments of the application, the alkyl-containing silane coupling agent comprises n-octyl triethoxysilane.

[0016] According to some embodiments of the application, the area of the hydrophilic part accounts for 1 / 3-2 / 3 of the total area of the outer surface of the shell layer.

[0017] According to some embodiments of the application, the particle size of the magnetic multi-effect multi-element composite amphiphilic particle is 100nm

[0018] In a second aspect, the application provides a preparation method of a magnetic multi-effect multi-element composite amphiphilic particle, comprising:

[0019] S1. dispersing magnetic Fe3O4 particles, tetraethyl orthosilicate and tetra-n-butyl titanate into an alcohol solvent to obtain Fe3O4@SiO2 / TiO2 particles;

[0020] S2. dispersing the Fe3O4@SiO2 / TiO2 particles into water, adding paraffin, heating to completely melt the paraffin, stirring and mixing, and filtering after cooling to obtain paraffin balls formed by embedding the Fe3O4@SiO2 / TiO2 particles on the surface of paraffin;

[0021] S3. Dispersing the paraffin wax spheres into dimethyl sulfoxide, adding amino-containing silane coupling agent, stirring reaction, and redispersing the obtained solid particles into an alcohol solvent to obtain hydrophilic modified particles;

[0022] S4. Dispersing the hydrophilic modified particles into ethanol, adding alkyl-containing silane coupling agent, stirring reaction, and obtaining amphiphilic modified particles;

[0023] S5. Mixing the amphiphilic modified particles with acetic acid for 8-12 h to obtain core-shell separated amphiphilic modified particles;

[0024] S6. Dispersing the core-shell separated amphiphilic modified particles into an alcohol solvent, adding 4-(chloromethyl)phenyl trimethoxysilane to perform modification reaction, and then performing grafting reaction with methacrylic acid diethylaminoethyl ester to obtain grafted poly-methacrylic acid diethylaminoethyl ester particles;

[0025] S7. Dispersing the grafted poly-methacrylic acid diethylaminoethyl ester particles into a solvent, adding dopamine to perform first stirring reaction, then adding gallic acid to perform second stirring reaction, and then adding catechin to perform third stirring reaction, and obtaining the magnetic multi-effect multi-element composite amphiphilic particles after the reaction.

[0026] The preparation method of the magnetic multi-effect multi-element composite amphiphilic particle provided by the application is as follows: taking magnetic Fe3O4 particles as carriers, tetraethyl orthosilicate and tetra-n-butyl titanate are used to realize hydrolysis on the surface of the magnetic Fe3O4 particles, and through a sol-gel process, the magnetic Fe3O4 particles are coated to form a core-shell structure of effective silicon / titanium-embedded iron. Then, using paraffin with a phase transition temperature of 52 DEG C as an oil phase, and using Fe3O4@SiO2 / TiO2 particles as solid particle emulsifiers, the oil and water phases are emulsified when the temperature is higher than the phase transition temperature of paraffin, to form a stable water-in-paraffin emulsion. After the emulsion is cooled, the paraffin phase is solidified and separated from the water phase, to obtain paraffin balls in which Fe3O4@SiO2 / TiO2 particles are embedded on the surface of paraffin, and in which part of the Fe3O4@SiO2 / TiO2 particles are embedded in paraffin and part of the Fe3O4@SiO2 / TiO2 particles are exposed outside paraffin. Then, the outer surface of the Fe3O4@SiO2 / TiO2 particles exposed outside paraffin is modified to be hydrophilic, and then the paraffin is removed to expose the part of the Fe3O4@SiO2 / TiO2 particles which was protected by paraffin, and the outer surface of the part is modified to be hydrophobic, to obtain the amphiphilic particles with the surface including both hydrophilic and hydrophobic parts. Then, acid etching treatment is performed to reduce the size of the magnetic Fe3O4 particles, separate the magnetic Fe3O4 particles from the shell layer, and form a hollow structure between the core-shell structures. Further, 4-(chloromethyl)phenyl trimethoxysilane is used to modify benzyl chloride 【4-(chloromethyl)phenyl】 on the surface of the magnetic Fe3O4 particles and the inner surface of the shell layer. The benzyl chloride has high activity and can be grafted with poly (diethylaminoethyl methacrylate) (PDEAEMA) through ATRP (atom transfer radical polymerization). Finally, the particles are reacted with dopamine to graft polydopamine on the outer surface of the shell layer, and then gallic acid and catechin are compounded on the polydopamine through strong hydrogen bonding, to obtain the magnetic multi-effect multi-element composite amphiphilic particles.

[0027] In the application, tetraethyl orthosilicate and tetra-n-butyl titanate are used to realize hydrolysis on the surface of the magnetic Fe3O4 particles, and through a sol-gel process, a relatively dense silica / titanium dioxide hybrid shell layer structure is formed on the surface of the magnetic Fe3O4 particles to protect the magnetic Fe3O4 particles inside, which can resist corrosion of hydrochloric acid, sulfuric acid, nitric acid or various alkaline reagents within a certain time and within a certain PH range, and thus guarantees the industrial application of the magnetic particles. Moreover, the silica / titanium dioxide hybrid shell layer in the application is a polymer formed by hydrolysis and condensation of tetraethyl orthosilicate and tetra-n-butyl titanate, although the formed silica / titanium dioxide hybrid shell layer is relatively dense, but in the sol-gel process of hydrolysis of tetraethyl orthosilicate and tetra-n-butyl titanate, the macromolecular skeleton formed by condensation reaction still has intermolecular gaps, which ensures the smooth progress of the subsequent acid etching treatment, 4-(chloromethyl)phenyl trimethoxysilane modification and PDEAEMA grafting process.

[0028] In the present application, the magnetic Fe3O4 particles are reduced in size by acid etching treatment, resulting in core-shell separation. This process further causes defects in the shell layer, even micro- or capillary pores, which together with the intermolecular space in the shell layer form a micro-pore structure to provide a channel for the transport of partially hydrolyzed polyacrylamide into the shell layer.

[0029] In the present application, the acid etching treatment reagent is acetic acid, which can slow down the etching process, ensure controllable etching process, and make the inner core surface of the magnetic Fe3O4 particles smoother. If hydrochloric acid, sulfuric acid, or the like is used, it is difficult to control the etching process, and it is easy to cause excessive etching, resulting in too weak magnetic particles or even complete disappearance.

[0030] According to some embodiments of the present application, the alcohol solvent includes at least one of methanol, ethanol, propanol, butanol, isopropanol, and cyclohexanol.

[0031] According to some embodiments of the present application, the stirring speed in step S2 is 1000-5000 rpm.

[0032] In the present application, the stirring speed in step S2 directly affects the emulsification process of the particle emulsifier (Fe3O4@SiO2 / TiO2 particles), and directly leads to the stability of the particle emulsifier to the emulsion interface. When the stirring speed is less than 1000 rpm, the stirring speed is too low, the particle emulsifier is difficult to deliver to the interface, and the interface cannot be stabilized, and the emulsion is easy to break; when the stirring speed is greater than 5000 rpm, the stirring speed is too high, the particle emulsifier is forced to be pulled at the interface, and the interface is easy to be unstable, and the emulsion is easy to break. Therefore, in order to ensure emulsification and interface stability, the stirring speed in step S2 is preferably controlled at 1000-5000 rpm.

[0033] According to some embodiments of the present application, the stirring time in step S2 is 3-5 min.

[0034] According to some embodiments of the present application, the amino-containing silane coupling agent includes 3-aminopropyl triethoxysilane.

[0035] The local hydrophilic modification of the outer surface of the Fe3O4@SiO2 / TiO2 particles by 3-aminopropyl triethoxysilane in dimethyl sulfoxide is realized by a sol-gel composite process on the outer surface of the Fe3O4@SiO2 / TiO2 particles exposed to paraffin, which modifies the amino group on one side of the outer surface of the Fe3O4@SiO2 / TiO2 particles, thereby realizing the adsorption of partially hydrolyzed polyacrylamide.

[0036] According to some embodiments of the present application, the alkyl-containing silane coupling agent includes n-octyl triethoxysilane.

[0037] The local hydrophobicity modification of the outer surface of the Fe3O4@SiO2 / TiO2 particles by using n-octyl triethoxysilane is to remove the paraffin wax by using an alcohol solvent, to expose the part of the Fe3O4@SiO2 / TiO2 particles embedded in the paraffin wax and protected, and to realize sol-gel composite on the surface of the Fe3O4@SiO2 / TiO2 particles by the hydrolysis process of n-octyl triethoxysilane from the exposed part of the Fe3O4@SiO2 / TiO2 particles embedded in the paraffin wax, and to modify n-octyl on the other side of the outer surface of the Fe3O4@SiO2 / TiO2 particles.

[0038] According to some embodiments of the present application, the mass ratio of the magnetic Fe3O4 particles, tetraethyl orthosilicate and titanium tetrabutoxide is 1:(0.1-1):(0.1-1).

[0039] According to some embodiments of the present application, the mass ratio of the magnetic Fe3O4 particles and paraffin wax is 1:(10-200).

[0040] According to some embodiments of the present application, the mass ratio of the paraffin wax and water is 1:(2-10).

[0041] According to some embodiments of the present application, the mass ratio of the magnetic Fe3O4 particles and the amino-containing silane coupling agent is 1:(0.001-0.01).

[0042] According to some embodiments of the present application, the mass ratio of the magnetic Fe3O4 particles and the alkyl-containing silane coupling agent is 1:(0.001-0.01).

[0043] According to some embodiments of the present application, the mass ratio of the magnetic Fe3O4 particles and 4-(chloromethyl)phenyl trimethoxysilane is 1:(0.001-0.01).

[0044] According to some embodiments of the present application, the mass ratio of the magnetic Fe3O4 particles and diethylaminoethyl methacrylate is 1:(0.02-0.1).

[0045] According to some embodiments of the present application, the mass ratio of the magnetic Fe3O4 particles and dopamine is 1:(0.001-0.01).

[0046] According to some embodiments of the present application, the mass ratio of the magnetic Fe3O4 particles and gallic acid is 1:(0.0005-0.01).

[0047] According to some embodiments of the present application, the mass ratio of the magnetic Fe3O4 particles and catechin is 1:(0.0005-0.01).

[0048] According to some embodiments of the present application, the magnetic Fe3O4 particles have a particle size of 100-500 nm.

[0049] According to some embodiments of the present application, the ratio of the particle size of the magnetic Fe3O4 particles to the particle size of the magnetic Fe3O4 particle core is 100:(10-99).

[0050] In the present application, if the ratio of the particle size of the magnetic Fe3O4 particles to the particle size of the magnetic Fe3O4 particle core is less than 100:99, the gap between the shell layer and the magnetic Fe3O4 particle core is too small, which will affect the adsorption capacity of the magnetic multi-effect and multi-component composite amphiphilic particles to partially hydrolyzed polyacrylamide; if the ratio of the particle size of the magnetic Fe3O4 particles to the particle size of the magnetic Fe3O4 particle core is greater than 100:10, the size of the magnetic Fe3O4 particle core is too small, which will cause serious magnetic decay and make it difficult to realize magnetic control of the external magnetic field.

[0051] According to some embodiments of the present application, the grafting reaction comprises: dissolving cuprous chloride and 2,2-bipyridine in a solvent, adding the amphiphilic modified particles after modification reaction treatment and diethylaminoethyl methacrylate, and stirring and reacting under the conditions of nitrogen atmosphere and 60-100°C.

[0052] According to some embodiments of the present application, the solvent used in the grafting reaction comprises at least one of water, tetrahydrofuran (THF), and N,N-dimethylformamide (DMF).

[0053] According to some embodiments of the present application, the solvent used for dispersing the particles of grafted poly(diethylaminoethyl methacrylate) comprises at least one of water, tetrahydrofuran (THF), and N,N-dimethylformamide (DMF).

[0054] According to some embodiments of the present application, the stirring reaction time in step S3 is 5-6 h.

[0055] According to some embodiments of the present application, the stirring reaction time in step S4 is 5-6 h.

[0056] According to some embodiments of the present application, the magnetic Fe3O4 particles and tetra-n-butyl titanate are dispersed in the alcohol solvent by ultrasonic and stirring for 12-24 h, preferably, the ultrasonic frequency is 60-80 Hz and / or the stirring speed is 50-100 rpm.

[0057] According to some embodiments of the present application, the Fe3O4@SiO2 / TiO2 particles are dispersed in water by ultrasonic and stirring, preferably, the ultrasonic frequency is 60-80 Hz and / or the stirring speed is 50-100 rpm.

[0058] According to some embodiments of the present application, the dispersing of the paraffin wax spheres into the dimethyl sulfoxide is performed by stirring, preferably at a speed of 50-100 rpm.

[0059] According to some embodiments of the present application, the dispersing of the hydrophilic modified particles into the alcohol solvent is performed by ultrasonic and stirring, preferably at an ultrasonic frequency of 60-80 Hz and / or a stirring speed of 200-300 rpm.

[0060] According to some embodiments of the present application, the mixing of the amphiphilic modified particles with acetic acid for 8-12 h comprises: dispersing the amphiphilic modified particles in water, adding acetic acid, and mixing by ultrasonic and stirring for 8-12 h, preferably at an ultrasonic frequency of 60-80 Hz and / or a stirring speed of 50-100 rpm.

[0061] In a third aspect, the present application provides a magnetic multi-effect multi-component composite amphiphilic particle, which is prepared by the method of the second aspect.

[0062] In a fourth aspect, the present application provides the use of the magnetic multi-effect multi-component composite amphiphilic particle of the first aspect or the magnetic multi-effect multi-component composite amphiphilic particle of the third aspect in the treatment of oil-containing wastewater containing partially hydrolyzed polyacrylamide.

[0063] The present application has at least the following beneficial effects:

[0064] (1) The magnetic multi-effect multi-component composite amphiphilic particle provided by the present application has excellent emulsifying performance. The liquid droplets emulsified by the magnetic multi-effect multi-component composite amphiphilic particle can be manipulated by an external magnetic field, realizing the enrichment and migration of oil droplets, and thus realizing oil-water separation. Furthermore, through the combination of the internal and external structures of the magnetic multi-effect multi-component composite amphiphilic particle, the oil-containing wastewater containing partially hydrolyzed polyacrylamide can be treated efficiently in one step.

[0065] (2) The magnetic multi-effect multi-component composite amphiphilic particle provided by the present application can be recycled multiple times, and the adsorption capacity for partially hydrolyzed polyacrylamide does not decrease significantly, which can greatly reduce the material cost of wastewater treatment.

[0066] (3) The magnetic multi-effect multi-component composite amphiphilic particle provided by the present application has a structure of a silica / titanium dioxide hybrid shell layer coating a magnetic Fe3O4 particle core, which can protect the magnetic Fe3O4 particle core and improve the acid and alkali resistance of the amphiphilic particle, making it applicable to the treatment of wastewater with more complex composition.

[0067] (4) The preparation method of the magnetic multi-effect multi-component composite amphiphilic particle provided by the present application is simple, the raw material cost is low and easy to obtain, and industrial ton-level batch production can be realized. DETAILED DESCRIPTION

[0068] In order to make the technical problems to be solved by the present application, technical solutions and beneficial effects more clearly understood, the present application will be further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to illustrate the present patent and do not limit the protection scope of the present application in any way.

[0069] Unless otherwise defined, the technical terms used in the following examples have the same meanings as commonly understood by those skilled in the art to which the present application belongs. The reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the raw materials, instruments and equipment used in the following examples can be purchased or obtained by existing methods; the reagent amount, unless otherwise specified, is the reagent amount in conventional experimental operation; the experimental method, unless otherwise specified, is a conventional method.

[0070] Example 1

[0071] S1. Disperse 2 g of magnetic Fe3O4 particles (particle size of 0.2 μm) into 200 mL of ethanol, while adding 1 g of tetraethyl orthosilicate and 1 g of tetra-n-butyl titanate, and additionally apply 60 Hz ultrasonic and 100 rpm overhead stirring to promote the dispersion of the magnetic Fe3O4 particles, and continue for 12 h, and then separate to obtain Fe3O4@SiO2 / TiO2 particles.

[0072] S2. Disperse the Fe3O4@SiO2 / TiO2 particles into 200 mL of water, while additionally applying 60 Hz ultrasonic and 100 rpm overhead stirring to promote the dispersion of the Fe3O4@SiO2 / TiO2 particles. Increase the water temperature to 80℃, and add 20 g of paraffin wax (phase transition temperature of 52℃), and continue stirring until the paraffin wax is completely melted. Turn off the ultrasonic and increase the stirring speed to 2000 rpm, and continue stirring for 3 min. Stop stirring and heating, and cool the sample to room temperature, and filter out the solidified paraffin wax balls, and separate them from the water. Disperse the paraffin wax balls on filter paper, and air dry to obtain paraffin wax ball powder with Fe3O4@SiO2 / TiO2 particles embedded in the surface of the paraffin wax.

[0073] S3. Disperse the paraffin wax ball powder into 100 mL of dimethyl sulfoxide, and slowly stir the dispersion using an overhead stirrer at a speed of 50 rpm. Add 20 mg of 3-aminopropyl triethoxysilane to the dispersion, and continue stirring for 6 h. Use an external magnetic field to separate the paraffin wax ball powder and the solvent, and air dry the paraffin wax ball powder. Disperse the paraffin wax ball powder in 100 mL of ethanol again, and dissolve the paraffin wax, and use an external magnetic field to separate the solid particles, to obtain Fe3O4@SiO2 / TiO2-NH2 particles with amino groups modified on one side of the surface.

[0074] S4. Disperse Fe3O4@SiO2 / TiO2-NH2 particles into 100 mL of ethanol, stir the dispersion with an overhead stirrer at 300 rpm, while adding 60 Hz ultrasound. Add 20 mg of n-octylpropyltriethoxysilane to the dispersion, continue stirring for 6 h. Isolate the solid particles using an external magnetic field, air dry at room temperature to obtain Fe3O4@SiO2 / TiO2-NH2 particles.

[0075] C8-Fe3O4@SiO2 / TiO2-NH2 particles.

[0076] S5. Disperse C8-Fe3O4@SiO2 / TiO2-NH2 particles in 100 mL of water, add 2 mL of acetic acid, stir the dispersion with an overhead stirrer at 100 rpm for 10 h, while adding 60 Hz ultrasound, to obtain core-shell separated C8-Fe3O4@SiO2 / TiO2-NH2 particles.

[0077] S6. Disperse core-shell separated C8-Fe3O4@SiO2 / TiO2-NH2 particles in 100 mL of ethanol, add 10 mg of 4-(chloromethyl)phenyltrimethoxysilane, stir at 100 rpm for 12 h, to obtain modified C8-Fe3O4@SiO2 / TiO2-NH2 particles; dissolve 0.02 g of cuprous chloride and 0.02 g of 2,2-bipyridine in 50 mL of DMF, add the above modified C8-Fe3O4@SiO2 / TiO2-NH2 particles, add 0.1 g of DEAEMA, while purging N2 to remove oxygen for 30 min, warm to 80 °C, stir at 100 rpm for 3 h, to obtain particles grafted with poly(diethylaminoethyl methacrylate);

[0078] S7. Disperse the particles grafted with poly(diethylaminoethyl methacrylate) into a solvent, add 20 mg of dopamine, stir the reaction for 6 h, add 10 mg of gallic acid, stir the reaction for 6 h, add 10 mg of catechin, stir the reaction for 6 h, to obtain magnetic multi-effect multi-element composite amphiphilic particles after the reaction is completed.

[0079] Example 2

[0080] S1. Disperse 2 g of magnetic Fe3O4 particles (particle size of 0.2 μm) into 200 mL of ethanol, while adding 0.3 g of tetraethyl orthosilicate and 0.3 g of titanium tetrabutoxide, add 60 Hz ultrasound and 100 rpm overhead stirring, maintain the ultrasound and stirring to promote the dispersion of the magnetic Fe3O4 particles, continue for 12 h, to obtain Fe3O4@SiO2 / TiO2 particles.

[0081] S2. Disperse Fe3O4@SiO2 / TiO2 particles into 200 mL water with 60 Hz ultrasound and 100 rpm overhead stirring. Keep the ultrasound and stirring to promote the dispersion of Fe3O4@SiO2 / TiO2 particles. Increase the water temperature to 80 °C and add 40 g paraffin (phase transition temperature is 52 °C). Continue stirring until the paraffin is completely melted. Turn off the ultrasound and increase the stirring speed to 1000 rpm for 5 min. Stop the stirring and heating, and cool the sample to room temperature. Filter out the solidified paraffin spheres and separate them from the water. Disperse the paraffin spheres on filter paper and dry naturally to obtain paraffin sphere powder with Fe3O4@SiO2 / TiO2 particles embedded in the paraffin surface.

[0082] S3. Disperse the paraffin sphere powder into 100 mL dimethyl sulfoxide and slowly stir the dispersion with an overhead stirrer at 50 rpm. Add 3 mg 3-aminopropyltriethoxysilane to the dispersion and continue stirring for 6 h. Separate the paraffin sphere powder from the solvent using an external magnetic field and dry the paraffin sphere powder naturally. Disperse the paraffin sphere powder in 100 mL ethanol to dissolve the paraffin, separate the solid particles using an external magnetic field, and obtain Fe3O4@SiO2 / TiO2-NH2 particles with amino groups modified on one side of the surface.

[0083] S4. Disperse Fe3O4@SiO2 / TiO2-NH2 particles into 100 mL ethanol and stir the dispersion with an overhead stirrer at 300 rpm with 60 Hz ultrasound. Add 3 mg n-octylpropyltriethoxysilane to the dispersion and continue stirring for 6 h. Separate the solid particles using an external magnetic field and dry them naturally to obtain

[0084] C8-Fe3O4@SiO2 / TiO2-NH2 particles.

[0085] S5. Disperse C8-Fe3O4@SiO2 / TiO2-NH2 particles in 100 mL water and add 2 mL acetic acid. Stir the dispersion with an overhead stirrer at 100 rpm for 10 h with 60 Hz ultrasound to obtain C8-Fe3O4@SiO2 / TiO2-NH2 particles with a core-shell separation;

[0086] S6. The core-shell separated C8-Fe3O4@SiO2 / TiO2-NH2 particles were dispersed in 100 mL of ethanol, 3 mg of 4-(chloromethyl)phenyl trimethoxysilane was added, and stirring was performed at 100 rpm for 12 h to obtain modified C8-Fe3O4@SiO2 / TiO2-NH2 particles; 0.02 g of cuprous chloride and 0.02 g of 2,2-bipyridine were dissolved in 50 mL of DMF, the above modified C8-Fe3O4@SiO2 / TiO2-NH2 particles were added, 0.04 g of DEAEMA was added, and N2 was introduced to remove oxygen for 30 min, and the temperature was increased to 80°C, and stirring was performed at 100 rpm for 3 h to obtain particles grafted with poly (diethylaminoethyl methacrylate) ;

[0087] S7. The particles grafted with poly (diethylaminoethyl methacrylate) were dispersed in a solvent, 3 mg of dopamine was added, and stirring was performed for 6 h, 1.5 mg of gallic acid was added, and stirring was performed for 6 h, 1.5 mg of catechin was added, and stirring was performed for 6 h, and after the reaction was completed, magnetic multi-effect multi-element composite amphiphilic particles were obtained.

[0088] Example 3

[0089] S1. 2 g of magnetic Fe3O4 particles (particle size of 0.2 μm) were dispersed in 200 mL of ethanol, 2 g of tetraethyl orthosilicate and 2 g of titanium tetrabutoxide were added, 60 Hz ultrasonic and 100 rpm overhead stirring were added, the ultrasonic and stirring were maintained to promote the dispersion of the magnetic Fe3O4 particles, and the dispersion was maintained for 12 h. Fe3O4@SiO2 / TiO2 particles were separated.

[0090] S2. The Fe3O4@SiO2 / TiO2 particles were dispersed in 200 mL of water, 60 Hz ultrasonic and 100 rpm overhead stirring were added, the ultrasonic and stirring were maintained to promote the dispersion of the Fe3O4@SiO2 / TiO2 particles. The water temperature was increased to 80°C, 20 g of paraffin (phase change temperature of 52°C) was added, and stirring was continued until the paraffin was completely melted. The ultrasonic was turned off and the stirring speed was increased to 5000 rpm, and the stirring was continued for 4 min. The stirring and heating were stopped, the sample was cooled to room temperature, and the solidified paraffin balls were filtered out and separated from the water. The paraffin balls were dispersed on filter paper and naturally air-dried to obtain paraffin ball powder formed by Fe3O4@SiO2 / TiO2 particles embedded in the surface of paraffin.

[0091] S3. The paraffin wax ball powder was dispersed in 100 mL of dimethyl sulfoxide, and the dispersion was stirred slowly by a overhead stirrer at a speed of 50 rpm. 10 mg of 3- aminopropyltriethoxysilane was added to the dispersion, and the stirring was continued for 6 h. The paraffin wax ball powder was separated from the solvent by an external magnetic field, and was dried naturally. The paraffin wax ball powder was dispersed in 100 mL of ethanol, and the paraffin wax was dissolved. The solid particles were separated by an external magnetic field, and Fe3O4@SiO2 / TiO2-NH2 particles with one side surface modified with amino groups were obtained.

[0092] S4. The Fe3O4@SiO2 / TiO2-NH2 particles were dispersed in 100 mL of ethanol, and the dispersion was stirred by a overhead stirrer at a speed of 300 rpm, while 60 Hz ultrasound was added. 10 mg of n-octylpropyltriethoxysilane was added to the dispersion, and the stirring was continued for 6 h. The solid particles were separated by an external magnetic field, and were dried naturally to obtain C8-Fe3O4@SiO2 / TiO2-NH2 particles.

[0093] C8-Fe3O4@SiO2 / TiO2-NH2 particles.

[0094] S5. The C8-Fe3O4@SiO2 / TiO2-NH2 particles were dispersed in 100 mL of water, and 2 mL of acetic acid was added. The dispersion was stirred by a overhead stirrer for 10 h at a speed of 100 rpm, while 60 Hz ultrasound was added. C8-Fe3O4@SiO2 / TiO2-NH2 particles with core-shell separation were obtained.

[0095] S6. The C8-Fe3O4@SiO2 / TiO2-NH2 particles with core-shell separation were dispersed in 100 mL of ethanol, and 15 mg of 4-(chloromethyl)phenyltrimethoxysilane was added. The stirring was continued for 12 h at a speed of 100 rpm. C8-Fe3O4@SiO2 / TiO2-NH2 particles with modification treatment were obtained. 0.02 g of cuprous chloride and 0.02 g of 2,2-bipyridine were dissolved in 50 mL of DMF, and the above C8-Fe3O4@SiO2 / TiO2-NH2 particles with modification treatment were added. 0.2 g of DEAEMA was added, and N2 was introduced to remove oxygen for 30 min. The temperature was increased to 80 °C, and the stirring was continued for 3 h at a speed of 100 rpm. Particles with grafted poly (diethylaminoethyl methacrylate) were obtained.

[0096] S7. The particles with grafted poly (diethylaminoethyl methacrylate) were dispersed in a solvent, and 10 mg of dopamine was added. The reaction was stirred for 6 h. 5 mg of gallic acid was added, and the reaction was stirred for 6 h. 5 mg of catechin was added, and the reaction was stirred for 6 h. After the reaction was completed, magnetic multi-effect multi-element composite amphiphilic particles were obtained.

[0097] Example 4

[0098] S1. 2 g of magnetic Fe3O4 particles (particle size of 0.2 μm) were dispersed in 200 mL of ethanol, while 1 g of tetraethyl orthosilicate and 1 g of tetra-n-butyl titanate were added, 60 Hz ultrasound and 100 rpm overhead stirring were added, the ultrasound and stirring were kept to promote the dispersion of the magnetic Fe3O4 particles, and the process was continued for 12 h, and Fe3O4@SiO2 / TiO2 particles were obtained by separation.

[0099] S2. The Fe3O4@SiO2 / TiO2 particles were dispersed in 200 mL of water, while 60 Hz ultrasound and 100 rpm overhead stirring were added, the ultrasound and stirring were kept to promote the dispersion of the Fe3O4@SiO2 / TiO2 particles. The water temperature was raised to 80 °C, 20 g of paraffin wax (phase transition temperature of 52 °C) was added, and the stirring was continued until the paraffin wax was completely melted. The ultrasound was turned off and the stirring speed was increased to 500 rpm.

[0100] Due to the low stirring speed, the particles could not be delivered to the oil-water interface by mechanical force, the silicon / titanium coated magnetic particles could not be stably arranged on the oil-water interface, the oil-water two phases could not be stably emulsified, and the water phase and the oil phase were still two phases, so the silicon / titanium coated magnetic particle embedded paraffin wax powder could not be prepared.

[0101] Example 5

[0102] S1. 2 g of magnetic Fe3O4 particles (particle size of 0.2 μm) were dispersed in 200 mL of ethanol, while 1 g of tetraethyl orthosilicate and 1 g of tetra-n-butyl titanate were added, 60 Hz ultrasound and 100 rpm overhead stirring were added, the ultrasound and stirring were kept to promote the dispersion of the magnetic Fe3O4 particles, and the process was continued for 12 h, and Fe3O4@SiO2 / TiO2 particles were obtained by separation.

[0103] S2. The Fe3O4@SiO2 / TiO2 particles were dispersed in 200 mL of water, while 60 Hz ultrasound and 100 rpm overhead stirring were added, the ultrasound and stirring were kept to promote the dispersion of the Fe3O4@SiO2 / TiO2 particles. The water temperature was raised to 80 °C, 20 g of paraffin wax (phase transition temperature of 52 °C) was added, and the stirring was continued until the paraffin wax was completely melted. The ultrasound was turned off and the stirring speed was increased to 6000 rpm.

[0104] Due to the high stirring speed, although the silicon / titanium coated magnetic particles were delivered to the oil-water interface by mechanical force to achieve emulsification, the fast mechanical stirring caused the particles to be stripped from the interface, the interface was destabilized, and demulsification occurred, so the silicon / titanium coated magnetic particle embedded paraffin wax powder could not be prepared.

[0105] Comparative Example 1

[0106] S1. 2 g of magnetic Fe3O4 particles (particle size of 0.2 μm) were dispersed in 200 mL of ethanol, while 1 g of tetraethyl orthosilicate and 1 g of tetra-n-butyl titanate were added, with the addition of 60 Hz ultrasonication and 100 rpm overhead stirring, maintaining the ultrasonication and stirring to promote the dispersion of the magnetic Fe3O4 particles for 12 h, and Fe3O4@SiO2 / TiO2 particles were obtained by separation.

[0107] S2. The Fe3O4@SiO2 / TiO2 particles were dispersed in 200 mL of water, while 60 Hz ultrasonication and 100 rpm overhead stirring were added, maintaining the ultrasonication and stirring to promote the dispersion of the Fe3O4@SiO2 / TiO2 particles. The water temperature was raised to 80 °C, 20 g of paraffin wax (phase transition temperature of 52 °C) was added, and stirring was continued until the paraffin wax was completely melted. The ultrasonication was turned off and the stirring speed was increased to 2000 rpm for 3 min. The stirring and heating were stopped, and the sample was cooled to room temperature, and the solidified paraffin wax spheres were filtered off and separated from the water. The paraffin wax spheres were dispersed on filter paper and air-dried to obtain paraffin wax sphere powder with Fe3O4@SiO2 / TiO2 particles embedded in the surface of the paraffin wax.

[0108] S3. The paraffin wax sphere powder was dispersed in 100 mL of dimethyl sulfoxide, and the dispersion was slowly stirred using an overhead stirrer at a speed of 50 rpm. 20 mg of 3- aminopropyltriethoxysilane was added to the dispersion, and stirring was continued for 6 h. The paraffin wax sphere powder and the solvent were separated using an external magnetic field, and the paraffin wax sphere powder was air-dried in a natural state. The paraffin wax sphere powder was again dispersed in 100 mL of ethanol, and the paraffin wax was dissolved. The solid particles were separated using an external magnetic field to obtain Fe3O4@SiO2 / TiO2-NH2 particles with amino groups modified on one side of the surface.

[0109] S4. The Fe3O4@SiO2 / TiO2-NH2 particles were dispersed in 100 mL of ethanol, and the dispersion was stirred using an overhead stirrer at a speed of 300 rpm, while 60 Hz ultrasonication was added. 20 mg of n-octylpropyltriethoxysilane was added to the dispersion, and stirring was continued for 6 h. The solid particles were separated using an external magnetic field to obtain C8-Fe3O4@SiO2-NH2 particles.

[0110] S5. The C8-Fe3O4@SiO2-NH2 particles were dispersed in a solvent, 20 mg of dopamine was added, and stirring was continued for 6 h. 10 mg of gallic acid was added, and stirring was continued for 6 h. 10 mg of catechin was added, and stirring was continued for 6 h to obtain the particles.

[0111] Comparative Example 2

[0112] S1. 2 g of magnetic Fe3O4 particles (particle size of 0.2 μm) were dispersed in 200 mL of ethanol, while 1 g of tetraethyl orthosilicate and 1 g of tetra-n-butyl titanate were added, 60 Hz ultrasound and 100 rpm overhead stirring were added to promote the dispersion of the magnetic Fe3O4 particles, and the ultrasound and stirring were maintained for 12 h. Fe3O4@SiO2 / TiO2 particles were obtained by separation.

[0113] S2. The Fe3O4@SiO2 / TiO2 particles were dispersed in 100 mL of water, 2 mL of acetic acid was added, and the dispersion was stirred for 10 h at a speed of 100 rpm using an overhead stirrer, while 60 Hz ultrasound was added to obtain core-shell separated Fe3O4@SiO2 / TiO2 particles.

[0114] S3. The core-shell separated Fe3O4@SiO2 / TiO2 particles were dispersed in 100 mL of ethanol, 10 mg of 4-(chloromethyl)phenyltrimethoxysilane was added, and stirring was performed at 100 rpm for 12 h to obtain modified Fe3O4@SiO2 / TiO2 particles. 0.02 g of cuprous chloride and 0.02 g of 2,2-bipyridine were dissolved in 50 mL of DMF, the above modified Fe3O4@SiO2 / TiO2 particles were added, 0.1 g of DEAEMA was added, and N2 was introduced to remove oxygen for 30 min. The temperature was raised to 80°C, and stirring was performed at 100 rpm for 3 h. The particles were obtained after the reaction was completed.

[0115] Comparative Example 3

[0116] The particles were prepared according to the preparation method of Example 1, except that acetic acid was replaced with an equal volume of dilute hydrochloric acid (PH 6).

[0117] Comparative Example 4

[0118] The particles were prepared according to the preparation method of Example 1, except that acetic acid was replaced with an equal volume of sulfuric acid.

[0119] Performance Evaluation

[0120] (1) The particle size of the particles of each example and comparative example was measured by scanning electron microscopy, and the results are shown in the following table:

[0121] Group Particle diameter (nm) Example 1 320 Example 2 223 Example 3 320 Comparative Example 1 320 Comparative Example 2 240 Comparative Example 3 320 Comparative Example 4 320

[0122] (2) Wastewater treatment effect

[0123] 1 kg of each of the particles prepared in the examples and the comparative examples was added to 10 t of oil-containing wastewater containing partially hydrolyzed polyacrylamide (COD value: 2020, oil content: 52.3 mg / L, partially hydrolyzed polyacrylamide content: 103.05 mg / L), and the oil-containing wastewater was emulsified by using a shearing machine to stir at 1000 rpm for 1 min; then the migration and enrichment of the oil droplets emulsified by the magnetic particles were achieved by external magnetic field control. The treated wastewater was detected, and the detection methods are shown in the following table:

[0124]

[0125]

[0126] The detection results are shown in the following table:

[0127]

[0128] (III) Recycling performance

[0129] The magnetic multi-effect multi-component amphiphilic particles were washed and regenerated by using a solvent method, so as to realize the recycling of the magnetic multi-effect multi-component amphiphilic particles. The specific treatment method includes: collecting the magnetic multi-effect multi-component amphiphilic particles prepared in Example 1 after wastewater treatment, washing with ethanol, and the mass ratio of ethanol to the amphiphilic particles is 10:1; after washing, the particles are treated by freeze-drying to obtain regenerated particles.

[0130] The above regenerated particles were used to repeat the treatment process of the oil-containing wastewater containing partially hydrolyzed polyacrylamide in (II), and the indicators of the treated wastewater were similar to the treatment effect of the magnetic multi-effect multi-component amphiphilic particles of Example 1 in the first wastewater treatment. The recycling number of the magnetic multi-effect multi-component amphiphilic particles can reach more than 100 times, and the removal effect of COD, oil and partially hydrolyzed polyacrylamide will not be significantly deteriorated.

[0131] It should be noted that the above examples are only used to explain the present application and do not constitute any limitation on the present application. The present application is described by referring to typical examples, but it should be understood that the words used therein are descriptive and explanatory words, rather than limiting words. The present application can be modified as specified within the scope of the claims of the present application, and the present application can be revised within the scope and spirit of the present application. Although the present application described therein relates to specific methods, materials and examples, it does not mean that the present application is limited to the specific examples disclosed therein, on the contrary, the present application can be extended to all other methods and applications with the same function.

Claims

1. A magnetic multi-effect multi-component amphiphilic particle, characterized in that, The magnetic multi-effect multi-element composite amphiphilic particle comprises a core-shell separated magnetic Fe3O4 particle core and a shell layer, and the shell layer is a silica / titanium dioxide hybrid shell layer with a micro-pore structure; the outer surface of the shell layer comprises a hydrophilic part and a hydrophobic part, the hydrophilic part has an amino group, the amino group is grafted with polydopamine, and the polydopamine is compounded with gallic acid and catechin; the inner surface of the shell layer and the surface of the magnetic Fe3O4 particle core are grafted with polydimethylaminoethyl methacrylate.

2. The magnetic multi-effect multi-component amphiphilic particulate according to claim 1, wherein The amino group on the hydrophilic part is obtained by modifying the outer surface of the shell layer with an amino-containing silane coupling agent; And / or, the hydrophobic part is obtained by modifying the outer surface of the shell layer with an alkyl-containing silane coupling agent.

3. The magnetic multi-effect multi-functional amphiphilic particle according to claim 2, wherein The amino-containing silane coupling agent comprises 3-aminopropyl triethoxysilane; And / or, the alkyl-containing silane coupling agent comprises n-octyl triethoxysilane.

4. The magnetic multi-effect multi-component amphiphilic particle according to any one of claims 1-3, wherein, The particle size of the magnetic multi-effect multi-element composite amphiphilic particle is 100nm 5. A method for preparing magnetic multi-effect multi-component amphiphilic particles, characterized by, Comprise: S1. Disperse the magnetic Fe3O4 particles, tetraethyl orthosilicate and tetra-n-butyl titanate into an alcohol solvent to obtain Fe3O4@SiO2 / TiO2 particles; S2. Disperse the Fe3O4@SiO2 / TiO2 particles into water, add paraffin, heat to completely melt the paraffin, stir and mix, cool, and then filter to obtain paraffin balls formed by embedding the surface of the Fe3O4@SiO2 / TiO2 particles in paraffin; S3. Disperse the paraffin balls into dimethyl sulfoxide, add an amino-containing silane coupling agent, stir and react, disperse the obtained solid particles into an alcohol solvent to obtain hydrophilic modified particles; S4. Disperse the hydrophilic modified particles into ethanol, add an alkyl-containing silane coupling agent, stir and react to obtain amphiphilic modified particles; S5. Mix the amphiphilic modified particles with acetic acid for 8-12 hours to obtain core-shell separated amphiphilic modified particles; S6. Disperse the core-shell separated amphiphilic modified particles into an alcohol solvent, add 4-(chloromethyl)phenyl trimethoxysilane to modify; then graft with diethylaminoethyl methacrylate to obtain particles grafted with polydiethylaminoethyl methacrylate; S7. Disperse the particles grafted with polydiethylaminoethyl methacrylate into a solvent, add dopamine to perform a first stirring reaction; then add gallic acid to perform a second stirring reaction; and then add catechin to perform a third stirring reaction; and obtain the magnetic multi-effect multi-element composite amphiphilic particle after the reaction is completed.

6. The production method according to claim 5, wherein The stirring and mixing speed in step S2 is 1000-5000 rpm; And / or, the amino-containing silane coupling agent comprises 3-aminopropyl triethoxysilane; And / or, the alkyl-containing silane coupling agent comprises n-octyl triethoxysilane.

7. The production method according to claim 6, wherein The stirring and mixing time in step S2 is 3-5 min.

8. The production method according to any one of claims 5 to 7, characterized by, The mass ratio of the magnetic Fe3O4 particles, tetraethyl orthosilicate and tetra-n-butyl titanate is 1:(0.1-1):(0.1-1); And / or, the mass ratio of the magnetic Fe3O4 particles and paraffin is 1:(10-200). And / or, the mass ratio of the magnetic Fe3O4 particles and the amino-containing silane coupling agent is 1: (0.001-0.01); And / or, the mass ratio of the magnetic Fe3O4 particles and the alkyl-containing silane coupling agent is 1: (0.001-0.01); And / or, the mass ratio of the magnetic Fe3O4 particles and 4- (chloromethyl) phenyl trimethoxysilane is 1: (0.001-0.01); And / or, the mass ratio of the magnetic Fe3O4 particles and methacrylate diethylaminoethyl is 1: (0.02~0.1); And / or, the mass ratio of the magnetic Fe3O4 particles and dopamine is 1: (0.001-0.01); And / or, the mass ratio of the magnetic Fe3O4 particles and gallic acid is 1: (0.0005-0.01); And / or, the mass ratio of the magnetic Fe3O4 particles and catechin is 1: (0.0005-0.01).

9. The production method according to any one of claims 5 to 7, characterized by, The particle size of the magnetic Fe3O4 particles is 100~500nm; And / or, the particle size ratio of the magnetic Fe3O4 particles and the magnetic Fe3O4 particle core is 100: (10~99).

10. The production method according to any one of claims 5 to 7, characterized by, The grafting reaction comprises: dissolving cuprous chloride and 2,2-bipyridine in a solvent, adding the amphiphilic modified particles after modification reaction treatment and diethylaminoethyl methacrylate, stirring and reacting under the conditions of nitrogen atmosphere and 60~100℃.

11. A magnetic multi-effect multi-element composite amphiphilic particle prepared by the preparation method of any one of claims 5-10.

12. The application of the magnetic multi-effect multi-element composite amphiphilic particle of any one of claims 1-4 or the magnetic multi-effect multi-element composite amphiphilic particle of claim 11 in the treatment of oil-containing wastewater containing partially hydrolyzed polyacrylamide.

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