Magnetic multi-functional organic-inorganic hybrid 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 organic-inorganic hybrid amphiphilic particle and its preparation method and application.The particle includes magnetic Fe3O4 particle core and the shell layer separated from the shell of the magnetic Fe3O4 particle core nucleus, the shell layer is the hybrid shell layer of fine pore structure existing silica / titania, the outer surface of the shell layer includes hydrophilic portion and hydrophobic portion, the hydrophilic portion has amino, and the amino is grafted polydopamine;The inner surface of the shell layer and the surface of magnetic Fe3O4 particle core nucleus are grafted with poly methacrylic acid diethylaminoethyl ester.The magnetic multi-effect organic-inorganic hybrid amphiphilic particle provided by the present application has excellent emulsifying performance, can realize oil-water separation;While selectively adsorbing part hydrolyzed polyacrylamide, it can efficiently treat oil-containing sewage containing part hydrolyzed polyacrylamide in one step.

Description

TECHNICAL FIELD

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

[0002] Partially hydrolyzed polyacrylamide is a water-soluble polymer, which has good flocculation, thickening and drag reduction properties, and has been widely used in oil recovery, especially in tertiary oil recovery, to improve oil recovery. However, the treatment of oily wastewater containing partially hydrolyzed polyacrylamide produced by using partially hydrolyzed polyacrylamide for oil recovery is more difficult than that of ordinary oily wastewater. The existing treatment methods generally require multiple steps to achieve the treatment of oily wastewater containing partially hydrolyzed polyacrylamide to meet the standards. How to efficiently remove partially hydrolyzed polyacrylamide while achieving oil-water separation in one step has been a difficult problem in the treatment of oily wastewater containing partially hydrolyzed polyacrylamide.

[0003] In addition, due to the differences in oil wells and oil displacement operations, the pH values of the oil well displacement fluids vary greatly, and a large amount of wastewater is acidic or alkaline, which significantly increases the difficulty of treatment.

[0004] Amphiphilic solid particle emulsifiers have excellent emulsifying ability, which can achieve emulsification by reducing the interfacial tension, and have high interfacial desorption energy, which can achieve efficient and stable emulsification of emulsions. If the amphiphilic solid particles have magnetism, the emulsified droplets will have magnetism, and then the dispersed phase droplets can be manipulated. Based on this, the magnetic amphiphilic solid particles can be used to treat oily wastewater, emulsify the oil phase in water, and achieve stable dispersion of the oil droplets. Under the control of an external magnetic field, the oil droplets can be migrated and enriched, and then oil-water separation can be achieved. However, the existing amphiphilic solid particle emulsifiers can successfully achieve oil-water separation when applied to treat oily wastewater containing partially hydrolyzed polyacrylamide, but they cannot efficiently remove partially hydrolyzed polyacrylamide at the same time in one step. SUMMARY

[0005] The present application aims to provide a magnetic multi-effect organic-inorganic hybrid amphiphilic particle and a preparation method thereof, to solve the technical problem that oily wastewater containing partially hydrolyzed polyacrylamide is difficult to be treated in one step to meet the standards in the prior art.

[0006] To achieve the above-mentioned purpose, the technical solution adopted by the present application is as follows:

[0007] In the first aspect, the present invention provides a magnetic multi-functional organic-inorganic hybrid amphiphilic particle, comprising a magnetic Fe3O4 particle core and a shell separated from the core of the magnetic Fe3O4 particle, wherein the shell is a silica / titanium dioxide hybrid shell with a microporous structure, and the outer surface of the shell comprises a hydrophilic part and a hydrophobic part, wherein the hydrophilic part has an amino group, and the amino group is grafted with polydopamine; the inner surface of the shell and the surface of the magnetic Fe3O4 particle core are grafted with polydiethylaminoethyl methacrylate (PDEAEMA).

[0008] It should be noted that the "micropore structure" mentioned in the present invention includes the intermolecular voids existing in the silica / titania macromolecular skeleton and the defects generated during the core-shell separation of the silica / titania hybrid shell from the core of the magnetic Fe3O4 particles, and even micropores and capillaries with a pore size of 0.5 to 50 nm.

[0009] The magnetic multi-functional organic-inorganic hybrid amphiphilic particles provided by the present invention are coated with a layer of silicon dioxide / titanium dioxide hybrid shell on the outer surface of the magnetic Fe3O4 particle core, which can protect the magnetic Fe3O4 particle core and resist corrosion of the magnetic Fe3O4 particle core by hydrochloric acid, sulfuric acid, nitric acid or various alkaline reagents within a certain time and a certain pH range, thereby ensuring the industrial application of the magnetic particles.

[0010] The outer surface of the silica / titania hybrid shell of the magnetic multi-functional organic-inorganic hybrid amphiphilic particles provided by the present invention includes both hydrophilic and hydrophobic parts, which makes the magnetic multi-functional organic-inorganic hybrid amphiphilic particles amphiphilic. Compared with traditional homogeneous particles, they have more stable emulsification properties and can emulsify oil and water phases more stably and more widely to form a stable oil-in-water emulsion, providing a stability basis for the manipulation of emulsion droplets.

[0011] Furthermore, the functional groups on the outer surface of the silica / titania hybrid shell of the magnetic multi-effect organic-inorganic hybrid amphiphilic particles have electrostatic interactions with the partially hydrolyzed polyacrylamide, which promotes the adsorption of the partially hydrolyzed polyacrylamide on the outer surface of the silica / titania hybrid shell; and the polydopamine grafted on the amino groups of the hydrophilic part further increases the adhesion of the amphiphilic particles to the partially hydrolyzed polyacrylamide, which can improve the effect of the amphiphilic particles on removing the partially hydrolyzed polyacrylamide in wastewater. After the adsorption and adhesion of the partially hydrolyzed polyacrylamide are achieved, the partially hydrolyzed polyacrylamide adsorbed on the outer surface of the silica / titania hybrid shell is promoted to be absorbed into the silica / titania hybrid shell due to the wetting effect of the internal structure of the hybrid amphiphilic particles on the partially hydrolyzed polyacrylamide. The poly(N,N-dimethylaminoethyl methacrylate) (PDEAEMA) grafted on the inner surface of the silica / titania hybrid shell and the surface of the magnetic Fe3O4 core forms a brush-like coating, which increases the specific surface area and enhances the hydrogen bond density, and the micro-porous structure on the silica / titania hybrid shell provides a channel for the migration and transmission of the partially hydrolyzed polyacrylamide, thereby realizing the adsorption and migration capture of the PDEAEMA to the partially hydrolyzed polyacrylamide. The magnetic multi-effect organic-inorganic hybrid amphiphilic particles provided by the application greatly improve the adsorption capacity and adsorption efficiency of the partially hydrolyzed polyacrylamide by combining the internal and external structures.

[0012] Furthermore, the PDEAEMA has pH sensitivity, which shows hydrophilic properties at a low pH value and hydrophobic properties at a high pH value, and the pH sensitivity can be used to realize the repeated adsorption and desorption of the PDEAEMA to the partially hydrolyzed polyacrylamide, so that the magnetic multi-effect organic-inorganic hybrid amphiphilic particles can be reused, which greatly reduces the material cost of wastewater treatment. Moreover, the partially hydrolyzed polyacrylamide itself is weakly acidic, which is more conducive to the transfer adsorption of the partially hydrolyzed polyacrylamide from the outer surface of the silica / titania hybrid shell to the PDEAEMA in the silica / titania hybrid shell.

[0013] In addition, the used magnetic multi-effect organic-inorganic hybrid amphiphilic particles can be washed and extracted with a good solvent (for example, ethanol) of the partially hydrolyzed polyacrylamide, so that the adsorbed partially hydrolyzed polyacrylamide can be removed, and the magnetic multi-effect organic-inorganic hybrid amphiphilic particles can be reused.

[0014] According to some embodiments of the application, the mass ratio of the silica and the titania in the silica / titania hybrid shell is 1:10 to 10:1.

[0015] According to some embodiments of the application, the amino groups on the hydrophilic part are obtained by modifying the outer surface of the shell with an amino-containing silane coupling agent.

[0016] According to some embodiments of the present invention, the amino-containing silane coupling agent includes 3-aminopropyltriethoxysilane.

[0017] 3-Aminopropyltriethoxysilane modification is used to allow amino groups to exist on the hydrophilic portion of the outer surface of the silica / titanium dioxide hybrid shell, which can produce weak interactions with partially hydrolyzed polyacrylamide with carboxyl groups, thereby achieving adsorption of partially hydrolyzed polyacrylamide.

[0018] According to some embodiments of the present invention, the hydrophobic portion is obtained by modifying the outer surface of the silica / titania hybrid shell layer with an alkyl-containing silane coupling agent.

[0019] According to some embodiments of the present invention, the alkyl-containing silane coupling agent includes n-octyltriethoxysilane.

[0020] According to some embodiments of the present invention, the area of ​​the hydrophilic portion accounts for 1 / 3 to 2 / 3 of the total surface area of ​​the silica / titania hybrid shell layer.

[0021] According to some embodiments of the present invention, the particle size of the magnetic multi-functional organic-inorganic hybrid amphiphilic particles is 100 nm<r≤1000 nm.

[0022] In a second aspect, the present invention provides a method for preparing magnetic multi-functional organic-inorganic hybrid amphiphilic particles, comprising:

[0023] S1. Dispersing magnetic Fe3O4 particles, tetraethyl orthosilicate, and tetrabutyl titanate in an alcohol solvent to obtain Fe3O4@SiO2 / TiO2 particles;

[0024] S2. Fe3O4@SiO2 / TiO2 particles were dispersed in water, paraffin was added, heated until the paraffin was completely melted, stirred and mixed, cooled and filtered to obtain paraffin balls formed by Fe3O4@SiO2 / TiO2 particles embedded in the paraffin surface;

[0025] S3. The paraffin balls are dispersed in dimethyl sulfoxide, an amino-containing silane coupling agent is added, the reaction is stirred, and the obtained solid particles are dispersed in an alcohol solvent to obtain hydrophilic modified particles;

[0026] S4. The hydrophilic modified particles are dispersed in ethanol, an alkyl-containing silane coupling agent is added, and the reaction is stirred to obtain amphiphilic modified particles;

[0027] S5. The amphiphilic modified particles were mixed with acetic acid for 8-12 h to obtain core-shell separated amphiphilic modified particles;

[0028] S6. The amphiphilic modified core-shell particles separated were dispersed in an alcohol solvent, and 4-(chloromethyl)phenyltrimethoxysilane was added for modification reaction; and then grafted with diethylaminoethyl methacrylate to obtain grafted polydiethylaminoethyl methacrylate particles;

[0029] S7. dispersing the particles grafted with polydiethylaminoethyl methacrylate into a solvent, adding dopamine, and stirring to react. After the reaction is completed, the magnetic multi-functional organic-inorganic hybrid amphiphilic particles are obtained.

[0030] The preparation method of the magnetic multi-functional organic-inorganic hybrid amphiphilic particles provided by the present invention includes the processes of silica / titania hybrid shell coating, hydrophilic modification, hydrophobic modification, acid etching, 4-(chloromethyl)phenyltrimethoxysilane modification, grafting of polydiethylaminoethyl methacrylate (PDEAEMA) and grafting of polydopamine. Specifically, magnetic Fe3O4 particles are used as carriers, and ethyl orthosilicate and tetrabutyl titanate are used to jointly hydrolyze the surface of the magnetic Fe3O4 particles, and the magnetic Fe3O4 particles are coated by a sol-gel process to form an effective silicon / titanium-coated iron core-shell structure. Paraffin with a phase transition temperature of 52°C is then used as the oil phase, and Fe3O4@SiO2 / TiO2 particles are used as solid particle emulsifiers to emulsify the oil and water phases at a temperature higher than the paraffin phase transition temperature to form a stable water-in-paraffin emulsion. After the emulsion cools, the paraffin phase solidifies and separates from the aqueous phase, resulting in paraffin spheres formed by Fe3O4@SiO2 / TiO2 particles embedded in the paraffin wax. The Fe3O4@SiO2 / TiO2 particles are partially embedded in the paraffin wax and partially exposed. The exposed Fe3O4@SiO2 / TiO2 particles are then hydrophilically modified. The paraffin wax is then removed, exposing the previously paraffin-protected portion of the Fe3O4@SiO2 / TiO2 particles. This surface is then hydrophobically modified, resulting in amphiphilic particles with both hydrophilic and hydrophobic surfaces. Acid etching is then performed to reduce the size of the magnetic Fe3O4 particles, separating them from the silica / titanium dioxide hybrid shell and creating a hollow core-shell structure. 4-(Chloromethyl)phenyltrimethoxysilane was further used to modify the surface of the magnetic Fe3O4 particles and the inner surface of the silica / titanium dioxide hybrid shell with benzyl chloride [4-(chloromethyl)phenyl]. Benzyl chloride is highly reactive and can be grafted onto poly(diethylaminoethyl methacrylate) (PDEAEMA) via ATRP (atom transfer radical polymerization). Finally, the particles were reacted with dopamine to graft polydopamine, yielding magnetic multifunctional organic-inorganic hybrid amphiphilic particles.

[0031] In the present application, hydrolysis is realized on the surface of magnetic Fe3O4 particles by using tetraethyl orthosilicate and tetra-n-butyl titanate, a relatively dense silica / titanium dioxide hybrid shell structure is formed on the surface of the magnetic Fe3O4 particles through a sol-gel process, the magnetic Fe3O4 particles in the interior are protected, and the corrosion of hydrochloric acid, sulfuric acid, nitric acid or various alkaline reagents can be resisted within a certain time and a certain PH range, thereby ensuring the industrial application of the magnetic particles. Moreover, the silica / titanium dioxide hybrid shell in the present 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 is relatively dense, the macromolecular skeleton formed by the condensation reaction still has intermolecular gaps in the sol-gel process of hydrolysis of tetraethyl orthosilicate and tetra-n-butyl titanate, thereby ensuring the smooth progress of subsequent acid etching treatment, 4-(chloromethyl)phenyl trimethoxysilane modification and grafting PDEAEMA process.

[0032] In the present application, the magnetic Fe3O4 particles are reduced through acid etching treatment, and core-shell separation is generated. This process further causes defects, even micropores or capillary pores, in the silica / titanium dioxide hybrid shell. The micropore structure composed of the intermolecular gaps in the silica / titanium dioxide hybrid shell and the micropores or capillary pores provides a channel for the transmission and migration of partially hydrolyzed polyacrylamide to the interior of the silica / titanium dioxide hybrid shell.

[0033] In the present application, the acid etching reagent is acetic acid, which can make the etching process slow and controllable, and make the surface of the inner core 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, thereby making the particle magnetism too weak or even completely disappearing.

[0034] According to some embodiments of the present application, the alcohol solvent includes at least one of methanol, ethanol, propanol, butanol, isopropanol and cyclohexanol.

[0035] According to some embodiments of the present application, the stirring speed in the step S2 is 1000-5000 rpm.

[0036] In the present application, the stirring speed in the 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, 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 broken. Therefore, in order to ensure emulsification and interface stability, the stirring speed in the step S2 is preferably controlled to be 1000-5000 rpm.

[0037] According to some embodiments of the present application, the time for the stirring mixing in step S2 is 3-5 min.

[0038] According to some embodiments of the present application, the amino-containing silane coupling agent includes 3-aminopropyl triethoxysilane.

[0039] The local hydrophilic modification of the outer surface of Fe3O4@SiO2 / TiO2 particles with 3-aminopropyl triethoxysilane is carried out in dimethyl sulfoxide, which is realized by sol-gel complexing on the outer surface of Fe3O4@SiO2 / TiO2 particles exposed to paraffin, modification of amino on one side of the outer surface of Fe3O4@SiO2 / TiO2 particles, and adsorption of partially hydrolyzed polyacrylamide.

[0040] According to some embodiments of the present application, the alkyl-containing silane coupling agent includes n-octyl triethoxysilane.

[0041] The local hydrophilic modification of the outer surface of Fe3O4@SiO2 / TiO2 particles with 3-aminopropyl triethoxysilane is carried out in dimethyl sulfoxide, which is realized by sol-gel complexing on the outer surface of Fe3O4@SiO2 / TiO2 particles exposed to paraffin, modification of amino on one side of the outer surface of Fe3O4@SiO2 / TiO2 particles, and adsorption of partially hydrolyzed polyacrylamide.

[0042] 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).

[0043] According to some embodiments of the present application, the mass ratio of the magnetic Fe3O4 particles and the paraffin is 1:(10-200).

[0044] According to some embodiments of the present application, the mass ratio of the paraffin and water is 1:(2-10).

[0045] 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).

[0046] 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).

[0047] According to some embodiments of the present invention, the mass ratio of the magnetic Fe3O4 particles to the 4-(chloromethyl)phenyltrimethoxysilane is 1:(0.001-0.01).

[0048] According to some embodiments of the present invention, the mass ratio of the magnetic Fe3O4 particles to the diethylaminoethyl methacrylate is 1:(0.02-0.1).

[0049] According to some embodiments of the present invention, the mass ratio of the magnetic Fe3O4 particles to the dopamine is 1:(0.001-0.01).

[0050] According to some embodiments of the present invention, the particle size of the magnetic Fe3O4 particles is 100 to 500 nm.

[0051] According to some embodiments of the present invention, the particle size ratio of the magnetic Fe3O4 particles to the magnetic Fe3O4 particle core is 100:(10-99).

[0052] In the present invention, if the particle size ratio of the magnetic Fe3O4 particles to the magnetic Fe3O4 particle core is less than 100:99, it means that the gap between the silica / titanium dioxide hybrid shell and the magnetic Fe3O4 particle core is too small, which will affect the adsorption capacity of the magnetic multi-performance organic-inorganic hybrid amphiphilic particles to partially hydrolyzed polyacrylamide; if the particle size ratio of the magnetic Fe3O4 particles to the magnetic Fe3O4 particle core is greater than 100:10, it means that the size of the magnetic Fe3O4 particle core is too small, which will lead to serious magnetic attenuation and difficulty in achieving magnetic manipulation of the external magnetic field.

[0053] According to some embodiments of the present invention, the grafting reaction includes: dissolving cuprous chloride and 2,2-bipyridine in a solvent, adding amphiphilic modified particles treated by the modification reaction and diethylaminoethyl methacrylate, and stirring the reaction under a nitrogen atmosphere at 60-100°C.

[0054] According to some embodiments of the present invention, the solvent used in the grafting reaction includes at least one of water, tetrahydrofuran (THF), and N,N-dimethylformamide (DMF).

[0055] According to some embodiments of the present invention, the solvent for dispersing the particles grafted with polydiethylaminoethyl methacrylate includes at least one of water, tetrahydrofuran (THF), and N,N-dimethylformamide (DMF).

[0056] According to some embodiments of the present invention, the stirring reaction time in step S3 is 5 to 6 hours.

[0057] According to some embodiments of the present invention, the stirring reaction time in step S4 is 5 to 6 hours.

[0058] According to some embodiments of the present invention, the magnetic Fe3O4 particles and tetrabutyl titanate are dispersed in an alcohol solvent by ultrasound and stirring for 12 to 24 hours. Preferably, the ultrasound frequency is 60 to 80 Hz and / or the stirring speed is 50 to 100 rpm.

[0059] According to some embodiments of the present invention, the Fe3O4@SiO2 / TiO2 particles are dispersed in water by ultrasound and stirring. Preferably, the ultrasound frequency is 60-80 Hz and / or the stirring speed is 50-100 rpm.

[0060] According to some embodiments of the present invention, the paraffin balls are dispersed in the dimethyl sulfoxide by stirring, preferably, the stirring speed is 50 to 100 rpm;

[0061] According to some embodiments of the present invention, the hydrophilic modified particles are dispersed in the alcohol solvent by ultrasound and stirring. Preferably, the ultrasound frequency is 60-80 Hz and / or the stirring speed is 200-300 rpm.

[0062] According to some embodiments of the present invention, mixing the amphiphilic modified particles with acetic acid for 8-12 hours comprises: dispersing the amphiphilic modified particles in water, adding acetic acid, and mixing by ultrasound and stirring for 8-12 hours. Preferably, the ultrasound frequency is 60-80 Hz and / or the stirring speed is 50-100 rpm.

[0063] In a third aspect, the present invention provides a magnetic multi-functional organic-inorganic hybrid amphiphilic particle prepared by the preparation method described in the second aspect.

[0064] In a fourth aspect, the present invention provides the use of the magnetic multi-functional organic-inorganic hybrid amphiphilic particles described in the first aspect or the magnetic multi-functional organic-inorganic hybrid amphiphilic particles described in the third aspect in the treatment of oily wastewater containing partially hydrolyzed polyacrylamide.

[0065] The beneficial effects of the present invention are at least:

[0066] (1) The magnetic multi-functional organic-inorganic hybrid amphiphilic particles provided by the present invention have uniform particle size and a wide size distribution window, which can achieve submicron / micron distribution.

[0067] (2) The magnetic multi-functional organic-inorganic hybrid amphiphilic particles provided by the present invention have excellent emulsification properties. The droplets stabilized by the emulsification of the magnetic multi-functional organic-inorganic hybrid amphiphilic particles can be manipulated by an external magnetic field to achieve the enrichment and migration of oil droplets, thereby achieving oil-water separation. At the same time, they also have selective adsorption characteristics and can efficiently treat oily wastewater containing partially hydrolyzed polyacrylamide in one step.

[0068] (3) The magnetic multi-functional organic-inorganic hybrid amphiphilic particles provided by the present invention can be reused multiple times, and the adsorption capacity for partially hydrolyzed polyacrylamide will not show a significant decrease, which can greatly reduce the material cost of sewage treatment.

[0069] (4) The structure of the magnetic multi-functional organic-inorganic hybrid amphiphilic particles provided by the present invention, in which the silica / titanium dioxide hybrid shell covers the magnetic Fe3O4 particle core, can protect the magnetic Fe3O4 particle core, and can improve the acid and alkali resistance of the hybrid amphiphilic particles, so that they can be used to treat sewage with more complex composition.

[0070] (5) The preparation method of the magnetic multi-functional organic-inorganic hybrid amphiphilic particles provided by the present invention has a simple process, low cost and readily available raw materials, and can achieve industrial mass production at the ton level. DETAILED DESCRIPTION

[0071] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the present invention is 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 this patent in detail and do not limit the scope of protection of the present invention in any way.

[0072] 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 this invention 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, etc., are all commercially available or can be obtained by existing methods; the reagent amounts used, unless otherwise specified, are the amounts used in conventional experimental procedures; and the experimental methods described, unless otherwise specified, are all conventional methods.

[0073] Example 1

[0074] S1. Disperse 2 g of magnetic Fe3O4 particles (particle size of 0.2 μm) in 200 mL of ethanol, and add 1 g of ethyl orthosilicate and 1 g of tetrabutyl titanate. Add 60 Hz ultrasound and 100 rpm overhead stirring. Maintain ultrasound and stirring to promote the dispersion of magnetic Fe3O4 particles for 12 hours to separate and obtain Fe3O4@SiO2 / TiO2 particles.

[0075] S2. Disperse the Fe3O4@SiO2 / TiO2 particles into 200mL of water while applying 60Hz ultrasound and 100rpm overhead stirring. Maintaining ultrasound and stirring promotes the dispersion of Fe3O4@SiO2 / TiO2 particles. Raise the water temperature to 80°C, add 20g of paraffin wax (phase transition temperature is 52°C), and continue stirring until the paraffin wax is completely melted. Turn off the ultrasound and increase the stirring speed to 2000rpm, and continue stirring for 3min. Stop stirring and heating, cool the sample to room temperature, filter out the solidified paraffin wax balls, and separate them from the water. Spread the paraffin wax balls on filter paper and dry them naturally to obtain paraffin wax ball powder formed by Fe3O4@SiO2 / TiO2 particles embedded in the paraffin wax surface.

[0076] S3. Disperse the paraffin ball powder in 100 mL of dimethyl sulfoxide and slowly stir the dispersion at 50 rpm using an overhead stirrer. Add 20 mg of 3-aminopropyltriethoxysilane to the dispersion and continue stirring for 6 hours. Use an external magnetic field to separate the paraffin ball powder and the solvent, and dry the paraffin ball powder in a natural state. Then disperse the paraffin ball powder in 100 mL of ethanol, dissolve the paraffin, and separate the solid particles using an external magnetic field to obtain Fe3O4@SiO2 / TiO2-NH2 particles with amino groups modified on one side of the surface.

[0077] S4. Disperse Fe3O4@SiO2 / TiO2-NH2 particles in 100 mL of ethanol and stir the dispersion using an overhead stirrer at 300 rpm while applying 60 Hz ultrasound. Add 20 mg of n-octylpropyltriethoxysilane to the dispersion and continue stirring for 6 h. Separate the solid particles using an external magnetic field and dry them in the air to obtain

[0078] C8-Fe3O4@SiO2 / TiO2-NH2 particles.

[0079] S5. C8-Fe3O4@SiO2 / TiO2-NH2 particles were dispersed in 100 mL of water, 2 mL of acetic acid was added, and the dispersion was stirred for 10 h using an overhead stirrer at 100 rpm while ultrasonicating at 60 Hz to obtain core-shell separated C8-Fe3O4@SiO2 / TiO2-NH2 particles;

[0080] S6. The core-shell separated C8-Fe3O4@SiO2 / TiO2-NH2 particles were dispersed in 100 mL of ethanol, 10 mg of 4-(chloromethyl)phenyltrimethoxysilane was added, and the mixture was stirred 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 modified C8-Fe3O4@SiO2 / TiO2-NH2 particles were added, and 0.1 g of DEAEMA was added. At the same time, N2 was introduced for deoxygenation for 30 min, the temperature was raised to 80 ° C, and the mixture was stirred at 100 rpm for 3 h to obtain particles grafted with polydiethylaminoethyl methacrylate;

[0081] S7. The particles grafted with polydiethylaminoethyl methacrylate were dispersed in a solvent, 20 mg of dopamine was added, and the mixture was stirred for 6 h. After the reaction, magnetic multi-functional organic-inorganic hybrid amphiphilic particles were obtained.

[0082] Example 2

[0083] S1. Disperse 2 g of magnetic Fe3O4 particles (particle size of 0.2 μm) in 200 mL of ethanol, and add 0.3 g of ethyl orthosilicate and 0.3 g of tetrabutyl titanate. Add 60 Hz ultrasound and 100 rpm overhead stirring. Maintain ultrasound and stirring to promote the dispersion of magnetic Fe3O4 particles for 12 hours to separate and obtain Fe3O4@SiO2 / TiO2 particles.

[0084] S2. Disperse the Fe3O4@SiO2 / TiO2 particles into 200mL of water while applying 60Hz ultrasound and 100rpm overhead stirring. Maintaining ultrasound and stirring promotes the dispersion of Fe3O4@SiO2 / TiO2 particles. Raise the water temperature to 80°C, add 40g of paraffin wax (phase transition temperature is 52°C), and continue stirring until the paraffin wax is completely melted. Turn off the ultrasound and increase the stirring speed to 1000rpm, and continue stirring for 5min. Stop stirring and heating, cool the sample to room temperature, filter out the solidified paraffin wax balls, and separate them from the water. Spread the paraffin wax balls on filter paper and dry them naturally to obtain paraffin wax ball powder formed by Fe3O4@SiO2 / TiO2 particles embedded in the paraffin wax surface.

[0085] S3. Disperse the paraffin ball powder in 100 mL of dimethyl sulfoxide and slowly stir the dispersion at 50 rpm using an overhead stirrer. Add 3 mg of 3-aminopropyltriethoxysilane to the dispersion and continue stirring for 6 h. Use an external magnetic field to separate the paraffin ball powder and the solvent, and dry the paraffin ball powder in a natural state. Then disperse the paraffin ball powder in 100 mL of ethanol, dissolve the paraffin, and separate the solid particles using an external magnetic field to obtain Fe3O4@SiO2 / TiO2-NH2 particles with amino groups modified on one side of the surface.

[0086] S4. Disperse Fe3O4@SiO2 / TiO2-NH2 particles in 100 mL of ethanol and stir the dispersion using an overhead stirrer at 300 rpm while applying 60 Hz ultrasound. Add 3 mg of n-octylpropyltriethoxysilane to the dispersion and continue stirring for 6 h. Separate the solid particles using an external magnetic field and dry them in the air to obtain

[0087] C8-Fe3O4@SiO2 / TiO2-NH2 particles.

[0088] S5. C8-Fe3O4@SiO2 / TiO2-NH2 particles were dispersed in 100 mL of water, 2 mL of acetic acid was added, and the dispersion was stirred for 10 h using an overhead stirrer at 100 rpm while ultrasonicating at 60 Hz to obtain core-shell separated C8-Fe3O4@SiO2 / TiO2-NH2 particles;

[0089] S6. The core-shell separated C8-Fe3O4@SiO2 / TiO2-NH2 particles were dispersed in 100 mL of ethanol, 3 mg of 4-(chloromethyl)phenyltrimethoxysilane was added, and the mixture was stirred 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 modified C8-Fe3O4@SiO2 / TiO2-NH2 particles were added, and 0.04 g of DEAEMA was added. At the same time, N2 was introduced for deoxygenation for 30 min, the temperature was raised to 80 ° C, and the mixture was stirred at 100 rpm for 3 h to obtain particles grafted with polydiethylaminoethyl methacrylate;

[0090] S7. The particles grafted with polydiethylaminoethyl methacrylate were dispersed in a solvent, 3 mg of dopamine was added, and the mixture was stirred for 6 h. After the reaction, magnetic multi-functional organic-inorganic hybrid amphiphilic particles were obtained.

[0091] Example 3

[0092] S1. Disperse 2 g of magnetic Fe3O4 particles (particle size of 0.2 μm) in 200 mL of ethanol, and add 2 g of ethyl orthosilicate and 2 g of tetrabutyl titanate. Add 60 Hz ultrasound and 100 rpm overhead stirring. Maintain ultrasound and stirring to promote the dispersion of magnetic Fe3O4 particles for 12 hours to separate and obtain Fe3O4@SiO2 / TiO2 particles.

[0093] S2. Disperse the Fe3O4@SiO2 / TiO2 particles into 200mL of water while applying 60Hz ultrasound and 100rpm overhead stirring. Maintaining ultrasound and stirring promotes the dispersion of Fe3O4@SiO2 / TiO2 particles. Raise the water temperature to 80°C, add 20g of paraffin wax (phase transition temperature is 52°C), and continue stirring until the paraffin wax is completely melted. Turn off the ultrasound and increase the stirring speed to 5000rpm, and continue stirring for 4 minutes. Stop stirring and heating, cool the sample to room temperature, filter out the solidified paraffin wax balls, and separate them from the water. Spread the paraffin wax balls on filter paper and dry them naturally to obtain paraffin wax ball powder formed by Fe3O4@SiO2 / TiO2 particles embedded in the paraffin wax surface.

[0094] S3. Disperse the paraffin ball powder in 100 mL of dimethyl sulfoxide and slowly stir the dispersion at 50 rpm using an overhead stirrer. Add 10 mg of 3-aminopropyltriethoxysilane to the dispersion and continue stirring for 6 h. Use an external magnetic field to separate the paraffin ball powder and the solvent, and dry the paraffin ball powder in a natural state. Then disperse the paraffin ball powder in 100 mL of ethanol, dissolve the paraffin, and separate the solid particles using an external magnetic field to obtain Fe3O4@SiO2 / TiO2-NH2 particles with amino groups modified on one side of the surface.

[0095] S4. Disperse Fe3O4@SiO2 / TiO2-NH2 particles in 100 mL of ethanol and stir the dispersion using an overhead stirrer at 300 rpm while applying 60 Hz ultrasound. Add 10 mg of n-octylpropyltriethoxysilane to the dispersion and continue stirring for 6 h. Separate the solid particles using an external magnetic field and dry them in the air to obtain

[0096] C8-Fe3O4@SiO2 / TiO2-NH2 particles.

[0097] S5. C8-Fe3O4@SiO2 / TiO2-NH2 particles were dispersed in 100 mL of water, 2 mL of acetic acid was added, and the dispersion was stirred for 10 h using an overhead stirrer at 100 rpm while ultrasonicating at 60 Hz to obtain core-shell separated C8-Fe3O4@SiO2 / TiO2-NH2 particles;

[0098] S6. The core-shell separated C8-Fe3O4@SiO2 / TiO2-NH2 particles were dispersed in 100 mL of ethanol, 15 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, 0.2 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) ;

[0099] S7. The particles grafted with poly (diethylaminoethyl methacrylate) were dispersed in a solvent, 10 mg of dopamine was added, and stirring was performed for 6 h, and after the reaction was completed, magnetic multi-functional organic-inorganic hybrid amphiphilic particles were obtained.

[0100] Example 4

[0101] S1. 2 g of magnetic Fe3O4 particles (particle size of 0.2 μm) were dispersed in 200 mL of ethanol, 1 g of tetraethyl orthosilicate and 1 g of tetra-n-butyl titanate 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 process was continued for 12 h, and Fe3O4@SiO2 / TiO2 particles were separated.

[0102] 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 the stirring was continued until the paraffin was completely melted. The ultrasonic was turned off and the stirring speed was increased to 500 rpm.

[0103] Due to the low stirring speed, the particles cannot be delivered to the oil-water interface by mechanical force, the silicon / titanium coated iron magnetic particles cannot be stably arranged on the oil-water interface, and the oil-water two phases cannot be stably emulsified, so the water phase and the oil phase are still two phases, and the silicon / titanium coated iron magnetic particle embedded paraffin powder cannot be prepared.

[0104] Example 5

[0105] S1. 2 g of magnetic Fe3O4 particles (particle size of 0.2 pm) 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. Fe3O4@SiO2 / TiO2 particles were obtained by separation.

[0106] 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 (phase transition temperature of 52°C) was added, and stirring was continued until the paraffin completely melted. The ultrasound was turned off and the stirring speed was increased to 6000 rpm.

[0107] Due to the high stirring speed, the silicon / titanium coated magnetic particles were mechanically delivered to the oil-water interface to achieve emulsification, but the high-speed mechanical stirring caused the particles to peel off at the interface, resulting in interface instability and demulsification, and the silicon / titanium coated magnetic particle embedded paraffin ball powder could not be prepared.

[0108] Comparative Example 1

[0109] S1. 2 g of magnetic Fe3O4 particles (particle size of 0.2 pm) 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. Fe3O4@SiO2 / TiO2 particles were obtained by separation.

[0110] 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 (phase transition temperature of 52°C) was added, and stirring was continued until the paraffin completely melted. The ultrasound 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. 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 with Fe3O4@SiO2 / TiO2 particles embedded on the surface of the paraffin balls.

[0111] S3. Disperse the paraffin ball powder in 100 mL of dimethyl sulfoxide and slowly stir the dispersion at 50 rpm using an overhead stirrer. Add 20 mg of 3-aminopropyltriethoxysilane to the dispersion and continue stirring for 6 hours. Use an external magnetic field to separate the paraffin ball powder and the solvent, and dry the paraffin ball powder in a natural state. Then disperse the paraffin ball powder in 100 mL of ethanol, dissolve the paraffin, and separate the solid particles using an external magnetic field to obtain Fe3O4@SiO2 / TiO2-NH2 particles with amino groups modified on one side of the surface.

[0112] S4. Disperse the Fe3O4@SiO2 / TiO2-NH2 particles in 100 mL of ethanol. Stir the dispersion at 300 rpm using an overhead stirrer with 60 Hz ultrasound. Add 20 mg of n-octylpropyltriethoxysilane to the dispersion and continue stirring for 6 h. Separate the solid particles using an external magnetic field to obtain C8-Fe3O4@SiO2-NH2 particles.

[0113] S5. Disperse the C8-Fe3O4@SiO2-NH2 particles in a solvent, add 20 mg of dopamine, and stir the reaction for 6 h to obtain particles.

[0114] Comparative Example 2

[0115] S1. Disperse 2 g of magnetic Fe3O4 particles (particle size of 0.2 μm) in 200 mL of ethanol, and add 1 g of ethyl orthosilicate and 1 g of tetrabutyl titanate. Add 60 Hz ultrasound and 100 rpm overhead stirring. Maintain ultrasound and stirring to promote the dispersion of magnetic Fe3O4 particles for 12 hours to separate and obtain Fe3O4@SiO2 / TiO2 particles.

[0116] S2. 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 using an overhead stirrer at 100 rpm while ultrasonicating at 60 Hz to obtain core-shell separated Fe3O4@SiO2 / TiO2 particles.

[0117] 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 the mixture was stirred 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-mentioned modified Fe3O4@SiO2 / TiO2 particles were added, and 0.1 g of DEAEMA was added at the same time. N2 was introduced for deoxygenation for 30 min, the temperature was raised to 80°C, and the mixture was stirred at 100 rpm for 3 h. After the reaction, particles were obtained.

[0118] Comparative Example 3

[0119] The particles were prepared according to the preparation method of Example 1, except that the acetic acid was replaced by an equal volume of dilute hydrochloric acid (pH 6).

[0120] Comparative Example 4

[0121] Particles were prepared by referring to the preparation method of Example 1, except that acetic acid was replaced by an equal volume of sulfuric acid.

[0122] Performance evaluation

[0123] (1) The particle size of the particles of each embodiment and comparative example was measured using a scanning electron microscope. The results are shown in the following table:

[0124]

[0125]

[0126] (2) Wastewater treatment effect

[0127] 1 kg of particles prepared in each example and comparative example were added to 10 tonnes of partially hydrolyzed polyacrylamide-containing oily wastewater (COD value 2020, petroleum pollutant content 52.3 mg / L, partially hydrolyzed polyacrylamide content 103.05 mg / L). The oily wastewater was stirred at 1000 rpm for 1 minute using a shearing machine to emulsify the wastewater. An external magnetic field was then used to control the migration and enrichment of the emulsified oil droplets. The treated wastewater was tested, and the testing methods are shown in the following table:

[0128]

[0129] The test results are shown in the following table:

[0130]

[0131]

[0132] (3) Cyclic performance

[0133] The magnetic multi-functional organic-inorganic hybrid amphiphilic particles are washed and regenerated using a solvent method, thereby achieving the recycling of the magnetic multi-functional organic-inorganic hybrid amphiphilic particles. The specific treatment method includes collecting the magnetic multi-functional organic-inorganic hybrid amphiphilic particles prepared in Example 1 after wastewater treatment, washing them with ethanol at a mass ratio of ethanol to amphiphilic particles of 10:1, and then freeze-drying them to obtain regenerated particles.

[0134] The regenerated particles were used to repeat the treatment process for partially hydrolyzed polyacrylamide-containing oily wastewater in step (2). The treated wastewater achieved similar performance to the initial treatment using the magnetic multi-functional organic-inorganic hybrid amphiphilic particles in Example 1. The magnetic multi-functional organic-inorganic hybrid amphiphilic particles can be recycled over 100 times without significantly diminishing their effectiveness in removing COD, petroleum, and partially hydrolyzed polyacrylamide.

[0135] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation of the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein. On the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A magnetic multi-functional organic-inorganic hybrid amphiphilic particle, characterized in that: The magnetic multi-functional organic-inorganic hybrid amphiphilic particles include a magnetic Fe3O4 particle core and a shell separated from the magnetic Fe3O4 particle core. The shell is a silica / titanium dioxide hybrid shell with a microporous structure. The outer surface of the shell includes a hydrophilic part and a hydrophobic part. The hydrophilic part has an amino group, and the amino group is grafted with polydopamine. The inner surface of the shell and the surface of the magnetic Fe3O4 particle core are grafted with polydiethylaminoethyl methacrylate.

2. The magnetic multi-functional organic-inorganic hybrid amphiphilic particles according to claim 1, characterized in that: The amino groups on the hydrophilic part are obtained by modifying the outer surface of the shell with an amino-containing silane coupling agent; And / or, the hydrophobic portion is obtained by modifying the outer surface of the silica / titania hybrid shell layer with an alkyl-containing silane coupling agent.

3. The magnetic multi-functional organic-inorganic hybrid amphiphilic particles according to claim 2, characterized in that: The amino-containing silane coupling agent includes 3-aminopropyltriethoxysilane; And / or, the alkyl-containing silane coupling agent includes n-octyltriethoxysilane.

4. The magnetic multi-functional organic-inorganic hybrid amphiphilic particles according to any one of claims 1 to 3, characterized in that: The particle size of the magnetic multi-functional organic-inorganic hybrid amphiphilic particles is 100 nm < r ≤ 1000 nm.

5. A method for preparing magnetic multi-functional organic-inorganic hybrid amphiphilic particles, characterized in that: include: S1. Dispersing magnetic Fe3O4 particles, tetraethyl orthosilicate, and tetrabutyl titanate in an alcohol solvent to obtain Fe3O4@SiO2 / TiO2 particles; S2. Disperse Fe3O4@SiO2 / TiO2 particles in water, add paraffin wax, heat until the wax is completely melted, stir and mix, cool, and filter to obtain paraffin spheres formed by Fe3O4@SiO2 / TiO2 particles embedded in the paraffin wax. S3. Dispersing the paraffin wax spheres in dimethyl sulfoxide, adding an amino-containing silane coupling agent, stirring to react, and then dispersing the resulting solid particles in an alcohol solvent to obtain hydrophilically modified particles. S4. Dispersing the hydrophilic modified particles in ethanol, adding an alkyl-containing silane coupling agent, and stirring to react to obtain amphiphilic modified particles; S5. Mixing the amphiphilic modified particles with acetic acid for 8-12 hours to obtain core-shell separated amphiphilic modified particles; S6. Dispersing the core-shell separated amphiphilic modified particles in an alcohol solvent, adding 4-(chloromethyl)phenyltrimethoxysilane to cause a modification reaction; then grafting with diethylaminoethyl methacrylate to obtain particles grafted with polydiethylaminoethyl methacrylate; S7. Dispersing the grafted polydiethylaminoethyl methacrylate particles in a solvent, adding dopamine, and stirring to react, and obtaining the magnetic multi-functional organic-inorganic hybrid amphiphilic particles after the reaction is completed.

6. The preparation method according to claim 5, characterized in that The stirring and mixing speed in step S2 is 1000-5000 rpm; And / or, the amino-containing silane coupling agent includes 3-aminopropyltriethoxysilane; And / or, the alkyl-containing silane coupling agent includes n-octyltriethoxysilane.

7. The preparation method according to claim 6, characterized in that The stirring and mixing time in step S2 is 3 to 5 minutes.

8. The preparation method according to any one of claims 5 to 7, characterized in that The mass ratio of the magnetic Fe3O4 particles, ethyl orthosilicate and tetrabutyl titanate is 1: (0.1-1): (0.1-1); and / or, the mass ratio of the magnetic Fe3O4 particles to the paraffin wax is 1:(10-200); and / or, the mass ratio of the magnetic Fe3O4 particles to the amino-containing silane coupling agent is 1:(0.001-0.01); and / or, the mass ratio of the magnetic Fe3O4 particles to the alkyl-containing silane coupling agent is 1:(0.001-0.01); and / or, the mass ratio of the magnetic Fe3O4 particles to the 4-(chloromethyl)phenyltrimethoxysilane is 1:(0.001-0.01); and / or, the mass ratio of the magnetic Fe3O4 particles to the diethylaminoethyl methacrylate is 1:(0.02-0.1); And / or, the mass ratio of the magnetic Fe3O4 particles to the dopamine is 1:(0.001-0.01).

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

10. The preparation method according to any one of claims 5 to 7, characterized in that: The grafting reaction comprises: dissolving cuprous chloride and 2,2-bipyridine in a solvent, adding amphiphilic modified particles treated by the modification reaction and diethylaminoethyl methacrylate, and stirring the reaction under a nitrogen atmosphere at 60-100° C.

11. A magnetic multi-functional organic-inorganic hybrid amphiphilic particle prepared by the preparation method according to any one of claims 5 to 10.

12. Use of the magnetic multifunctional organic-inorganic hybrid amphiphilic particles according to any one of claims 1 to 4 or the magnetic multifunctional organic-inorganic hybrid amphiphilic particles according to claim 11 in the treatment of oily wastewater containing partially hydrolyzed polyacrylamide.

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