CN110379577B - Switch type emulsion based on magnetic particles and preparation method thereof - Google Patents
Switch type emulsion based on magnetic particles and preparation method thereof Download PDFInfo
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- 239000000839 emulsion Substances 0.000 title claims abstract description 70
- 239000006249 magnetic particle Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000002245 particle Substances 0.000 claims abstract description 24
- 238000004945 emulsification Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920002521 macromolecule Polymers 0.000 claims abstract description 12
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 11
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 49
- 239000002105 nanoparticle Substances 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000012071 phase Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 230000001804 emulsifying effect Effects 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229910018557 Si O Inorganic materials 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 239000000412 dendrimer Substances 0.000 claims description 2
- 229920000736 dendritic polymer Polymers 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 229940094933 n-dodecane Drugs 0.000 claims description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- SENLDUJVTGGYIH-UHFFFAOYSA-N n-(2-aminoethyl)-3-[[3-(2-aminoethylamino)-3-oxopropyl]-[2-[bis[3-(2-aminoethylamino)-3-oxopropyl]amino]ethyl]amino]propanamide Chemical compound NCCNC(=O)CCN(CCC(=O)NCCN)CCN(CCC(=O)NCCN)CCC(=O)NCCN SENLDUJVTGGYIH-UHFFFAOYSA-N 0.000 claims 1
- 230000005291 magnetic effect Effects 0.000 abstract description 19
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- 238000001000 micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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- C09K23/017—Mixtures of compounds
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- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
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- H01F1/0018—Diamagnetic or paramagnetic materials, i.e. materials with low susceptibility and no hysteresis
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- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
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Abstract
The invention discloses an emulsion based on magnetic particles and a preparation method thereof. The emulsion is prepared by using magnetic ferroferric oxide particles modified by dendritic macromolecules as an emulsifier to carry out oil-water emulsification; and by introducing an external magnetic field, the rapid emulsion breaking, the circulating emulsification and the emulsion breaking of the emulsion under the magnetic response are realized. The method has the advantages of simple operation, small magnetic particle consumption, low cost, reusability and environmental protection.
Description
Technical Field
The invention belongs to the field of surfactants, and particularly relates to a magnetic particle-based switch type emulsion and a preparation method thereof.
Background
A plurality of environment sensitive groups are introduced into the molecules of the surfactant, when environmental factors change, the internal molecular structure of the surfactant changes under the stimulation of external environment (temperature, inorganic salt, magnetic field, pH value, carbon dioxide and the like), and the surface/interface characteristics of the surfactant change remarkably by influencing the characteristics of polarity, electrostatic acting force and the like, so that the activity of an oil-water interface is controllable.
The magnetic response type surfactant is a novel surfactant, and the surfactant is a nano-scale particle with superparamagnetism. Superparamagnetism refers to a ferromagnetic substance with a single-domain structure when the particle size is smaller than a critical size, and the ferromagnetic substance has the paramagnetic characteristic when the temperature is lower than the Curie temperature and higher than the transition temperature, but the paramagnetic susceptibility of the ferromagnetic substance is far higher than that of a common paramagnetic material under the action of an external magnetic field. The magnetization curve of the superparamagnetic body is different from that of a ferromagnetic body, and has no hysteresis phenomenon. When the external magnetic field is removed, the remanence disappears quickly. At present, research on magnetic particles is limited to the preparation of Pickering emulsion (magnetic emulsion) by using the magnetic particles as an emulsion stabilizer or the demulsification of the emulsion through magnetic response under the action of an external magnetic field, but the research on the simultaneous realization of the two functions is still deficient.
Disclosure of Invention
One purpose of the invention is to provide a dendritic macromolecule modified superparamagnetic ferroferric oxide nanoparticle (Fe)3O4@ PAMAM magnetic particles).
The dendritic macromolecule modified superparamagnetic ferroferric oxide nanoparticle provided by the invention is of a core-shell structure, the core of the dendritic macromolecule modified superparamagnetic ferroferric oxide nanoparticle is a superparamagnetic ferroferric oxide nanoparticle, and the shell of the dendritic macromolecule modified superparamagnetic ferroferric oxide nanoparticle is a Polyamidoamine (PAMAM) dendritic molecule; the core and the shell are connected through a Si-O bond.
Wherein, the branching generation number of the Polyamidoamine (PAMAM) dendrimer can be 1-3 (the generation number is an integer).
The particle size of the ferroferric oxide nano particles with superparamagnetism is 10-20 nm.
The invention also aims to provide a preparation method of the dendrimer modified superparamagnetic ferroferric oxide nanoparticle.
The preparation method of the dendritic macromolecule modified superparamagnetic ferroferric oxide nanoparticle provided by the invention comprises the following steps:
1) dispersing ferroferric oxide nano particles with superparamagnetism in ethanol, taking methylbenzene as a solvent, and adding a 3-aminopropyltrimethoxysilane reagent for reaction to obtain black particles;
2) adding methyl acrylate into the black particles by taking absolute methanol as a solvent for reaction to obtain magnetic particles modified by 0.5GPAMAM dendritic molecules;
3) adding ethylenediamine into the magnetic particles modified by the 0.5G PAMAM dendritic molecules by using anhydrous methanol as a solvent for reaction to obtain 1G Fe3O4@ PAMAM magnetic particles.
The reactions of the above steps 1) to 3) are all carried out in a nitrogen atmosphere.
In the step 1), the molar ratio of the ferroferric oxide nanoparticles with superparamagnetism to the 3-aminopropyltrimethoxysilane reagent is 1 (1-3).
In the step 1) of the method, the dispersion concentration of the ferroferric oxide nanoparticles with superparamagnetism in ethanol is 1-4% by mass.
In the step 1) of the method, the reaction temperature is 90-130 ℃, and the reaction time is 6-10 hours.
In the step 2) of the method, the amount of the methyl acrylate is 1 to 5 mol.
In the step 2) of the method, the reaction temperature is 30-40 ℃, and the reaction time is 38-45 hours.
In the step 3), the amount of the ethylenediamine is 3 to 10 mol.
In the step 3), the reaction temperature is 40-50 ℃ and the reaction time is 48-55 hours.
It is a further object of the present invention to provide an emulsion based on the above magnetic particles.
The emulsion is prepared according to a method comprising the following steps:
dispersing the prepared dendritic macromolecule modified superparamagnetic ferroferric oxide nano particles into a proper amount of oil phase, and then adding the oil phase and the water phase according to the proportion of the volume ratio of the oil to the water (2-0.5):1Emulsifying to obtain stable Fe3O4@ PAMAM is an emulsion of an emulsifier.
Wherein the oil phase can be n-dodecane, n-decane or n-heptane; the aqueous phase is water (e.g., secondary water).
The dispersion mode is ultrasonic dispersion.
The emulsification mode is as follows: emulsifying at 2000-3000r/s speed for 20-90s on a vortex emulsifying machine.
The Fe3O4Fe in emulsion with @ PAMAM as emulsifier3O4The concentration of @ PAMAM is 0.1 wt% to 1 wt%.
The invention realizes the on-off of the emulsion by synthesizing the superparamagnetic ferroferric oxide particles modified by the dendritic macromolecules and emulsifying and demulsifying the emulsion by using the magnetic particles.
Demulsification of magnetic particle-based emulsions:
an additional magnet is introduced to the bottom of the emulsion and the emulsion breaking is carried out under low-speed stirring, so that the emulsion can be broken in a short time.
Circulating emulsification and demulsification based on the magnetic particle emulsion:
selection of Fe3O4@ PAMAM one concentration (0.4 wt%), the above emulsification and demulsification method was repeated five times.
In some embodiments, the Fe in the switch-on emulsion3O4The concentrations of the @ PAMAM magnetic particles are 0.1 wt%, 0.2 wt% and 0.4 wt%, respectively, the emulsification time is 30s, the oil phase is analytically pure dodecane, and the water phase is secondary water.
In some embodiments, a large magnet with a 0.4T magnetic field is applied to the demulsification, and the low-speed stirring speed is 30 r/min.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention successfully realizes the rapid emulsification and emulsion breaking of the emulsion under the magnetic response;
2) the emulsion formed by the invention has the advantages of small using amount of magnetic particles, cyclic utilization, short emulsifying time and good emulsion stability.
3) When an external magnetic field is introduced to the bottom of the emulsion, the magnetic particles are subjected to the action of magnetic field force to destroy the original stress balance state, and the magnetic particles move to the bottom of the container, so that the emulsion is rapidly broken.
Drawings
FIG. 1 is Fe3O4A schematic diagram of the preparation process of the @ PAMAM magnetic particles;
FIG. 2 is Fe3O4And Fe3O4A @ PAMAM magnetic particle topography;
FIG. 3 is Fe3O4And Fe3O4@ PAMAM magnetic particle magnetic property diagram;
FIG. 4 shows different concentrations of Fe3O4The @ PAMAM magnetic particle emulsion effect graph and the emulsion micrograph; wherein (A) immediately after preparation, (B) is left for 25 days, (C) is left for 52 days, and (D) - (F) different concentrations of Fe immediately after emulsification3O4@ PAMAM magnetic particle emulsion micrographs.
FIG. 5 shows different concentrations of Fe3O4A @ PAMAM magnetic particle emulsion breaking effect diagram;
FIG. 6 is Fe3O4The @ PAMAM magnetic particle emulsion has the effect of circulating emulsification and emulsion breaking.
Detailed Description
The present invention is described below with reference to specific embodiments, but the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
In the quantitative tests in the following examples, three replicates were set up and the results averaged.
Superparamagnetic Fe used in the following examples3O4Nanoparticles were purchased from alatin reagent, inc.
Practice ofExample 1 dendrimer-modified superparamagnetic ferroferric oxide particles Fe3O4Preparation of @ PAMAM
Fe3O4The synthetic route of the @ PAMAM magnetic particles is shown in FIG. 1.
The specific method comprises the following steps: under nitrogen atmosphere, 0.01mol of Fe3O4Dispersing nano particles in 100ml of ethanol, taking 200ml of toluene as a solvent, adding 0.0232mol of 3-aminopropyltrimethoxysilane reagent to react for 8h at 110 ℃ to obtain black particles, then taking anhydrous methanol as a solvent, slowly adding 0.05mol of methyl acrylate to react for 40h at 35 ℃ to obtain 0.5GPAMAM dendritic molecule modified magnetic particles, finally taking 200ml of anhydrous methanol as a solvent, slowly adding 0.1mol of ethylenediamine to react for 50h at 45 ℃ to obtain 1G Fe3O4@ PAMAM magnetic particles.
Prepared superparamagnetic ferroferric oxide particle Fe modified by dendritic macromolecules3O4@ PAMAM. As shown in FIG. 2, Fe before modification3O4The magnetic particles are seriously agglomerated, and after the dendritic macromolecule is modified, the magnetic particles have better dispersibility, the size of the particles is about 10-20nm, and the particles are made of Fe3O4The core-shell structure (indicated by blue arrows) can be seen in TEM images at higher magnification of @ PAMAM.
Prepared superparamagnetic ferroferric oxide particle Fe modified by dendritic macromolecules3O4The magnetic properties of @ PAMAM were characterized. As shown in FIG. 3, the hysteresis loops of the particles were free of remanence and remanence, indicating that Fe was contained in the above3O4Particles and Fe3O4The @ PAMAM magnetic particles all have superparamagnetism. From the hysteresis loop, it can also be seen that superparamagnetic Fe3O4Particles and Fe3O4The saturation magnetizations of @ PAMAM are 70emu/g and 56emu/g, respectively, due to Fe3O4The presence of a non-magnetic organic layer on the surface of the particles reduces the saturation magnetization of the particles.
Example 2 preparation of an emulsion based on magnetic particles
Dispersed with different concentrations of Fe prepared in example 13O4@ PAMAM magnetic particle dodecane (oil phase): adding water into a container at a volume ratio of 2:1, and emulsifying for 30s on a vortex emulsifying machine at a speed of 2500r/s to obtain stable Fe3O4@ PAMAM is an emulsion of an emulsifier.
As shown in FIG. 4, with emulsifier Fe3O4Increased content of @ PAMAM, volume V of stable emulsion formedeIncreased and this state can be maintained for a long time and with the emulsifier Fe3O4The content of @ PAMAM is increased, and the volume of the stable emulsion accounts for the volume V of the total systemtotalRatio (V) ofe/Vtotal) Respectively 80%, 90% and 100%, the emulsion has little change after standing for a period of time, until standing for 25 days, little emulsion breaking occurs in the emulsion, and Fe is taken as emulsifier3O4The content of @ PAMAM is increased, and the volume of the stable emulsion accounts for the volume V of the total systemtotalRatio (V) ofe/Vtotal) To 75%, 85% and 90% and then substantially stabilized, with little change to 52 days. From the micrograph, Fe3O4The reason why the particle size of the emulsion droplet becomes smaller when the content of the @ PAMAM magnetic particles is increased is that when the content of the emulsifier is lower, the surface of the formed emulsion droplet is not provided with enough emulsifier particles to stabilize the emulsion droplet, so that the droplet is agglomerated and coalesced until the emulsion droplet is stabilized, and the particle size of the droplet is larger, whereas the particle size of the droplet is smaller.
Example 3 demulsification of emulsions based on magnetic particles
The different concentrations of Fe as prepared in example 23O4The @ PAMAM magnetic particle emulsion is placed on a large magnet (0.4T) and stirred at a low speed (the stirring speed is 30r/min) to carry out magnetic response emulsion breaking, and the emulsion breaking effect is shown in figure 5. It can be seen that different concentrations of Fe3O4The @ PAMAM magnetic particle emulsion has good demulsification effect, achieves complete oil-water separation, can observe an obvious oil-water interface in liquid, and can be accompanied with Fe3O4The longer the time for the emulsion to completely break the emulsion is, the harder the emulsion is broken, and the breaking time is respectively 1min20s, 8min and 17min20 s.
Example 4, Fe3O4@ PAMAM magnetic particle emulsion circulating emulsification and emulsion breaking
Selecting one Fe of example 23O4@ PAMAM magnetic particle concentration 0.4%, the emulsification and emulsion breaking were carried out in cycles of five times by the emulsification and emulsion breaking methods in examples 2 and 3, and the effect is shown in fig. 6. As can be seen from FIG. 6, Fe3O4The original property of the PAMAM magnetic particles can be kept for emulsification and emulsion breaking again after emulsification and emulsion breaking, the emulsification and emulsion breaking effects are still good, an obvious oil-water interface appears after emulsion breaking, complete oil-water separation is achieved, and Fe3O4The @ PAMAM magnetic particles can achieve demulsification under the physical action of an external magnetic field, do not need to add other agents, and can be recycled.
Claims (8)
1. A preparation method of an emulsion of superparamagnetic ferroferric oxide nanoparticles based on dendrimer modification comprises the following steps:
mixing Fe3O4The @ PAMAM magnetic particles are dispersed in a proper amount of oil phase, and then the oil phase and the water phase are added according to the proportion of the oil-water volume ratio (2-0.5):1 for emulsification to obtain Fe3O4@ PAMAM is an emulsion of an emulsifier;
said Fe3O4The @ PAMAM magnetic particles are superparamagnetic ferroferric oxide nanoparticles modified by dendritic macromolecules; the superparamagnetic ferroferric oxide nano particles modified by the dendritic macromolecules are of a core-shell structure, the core of the core is superparamagnetic ferroferric oxide nano particles, and the shell is polyamidoamine dendritic molecules; the core and the shell are connected through a Si-O bond.
2. The method of claim 1, wherein: the oil phase is n-dodecane, n-decane or n-heptane; the aqueous phase is water;
the dispersion mode is ultrasonic dispersion;
the emulsification mode is as follows: emulsifying for 20-90s on a vortex emulsifying machine at the speed of 2000-3000 r/s;
the Fe3O4Fe in emulsion with @ PAMAM as emulsifier3O4The concentration of @ PAMAM is 0.1 wt% to 1 wt%.
3. The production method according to claim 1 or 2, characterized in that: the branching generation number of the polyamidoamine dendritic molecule is 1, 2 or 3;
the particle size of the ferroferric oxide nano particles with superparamagnetism is 10-20 nm.
4. The method of claim 1, wherein: the preparation method of the dendritic macromolecule modified superparamagnetic ferroferric oxide nanoparticle comprises the following steps:
1) dispersing ferroferric oxide nano particles with superparamagnetism in ethanol, taking methylbenzene as a solvent, and adding a 3-aminopropyltrimethoxysilane reagent for reaction to obtain black particles;
2) adding methyl acrylate into the black particles by taking absolute methanol as a solvent for reaction to obtain 0.5G PAMAM dendrimer modified magnetic particles;
3) adding ethylenediamine into the magnetic particles modified by the 0.5G PAMAM dendritic molecules by using anhydrous methanol as a solvent for reaction to obtain 1G Fe3O4@ PAMAM magnetic particles.
5. The method of claim 4, wherein: the reactions in the steps 1) -3) are carried out in a nitrogen atmosphere;
in the step 1), the molar ratio of the ferroferric oxide nano particles with superparamagnetism to the 3-aminopropyltrimethoxysilane reagent is 1 (1-3);
in the step 1), the dispersion concentration of the ferroferric oxide nanoparticles with superparamagnetism in ethanol is 1-4% by mass;
in the step 1), the reaction temperature is 90-130 ℃, and the reaction time is 6-10 hours;
in the step 2), the using amount of the methyl acrylate is 1-5 mol;
in the step 2), the reaction temperature is 30-40 ℃, and the reaction time is 38-45 hours;
in the step 3), the dosage of the ethylenediamine is 3-10 mol;
in the step 3), the reaction temperature is 40-50 ℃, and the reaction time is 48-55 hours.
6. An emulsion prepared by the method of any one of claims 1 to 5.
7. A method of demulsifying the emulsion of claim 6 comprising the steps of: an external magnet is introduced at the bottom of the emulsion of claim 6 and magnetically responsive with agitation.
8. The method of claim 7, wherein: the additional magnet is 0.3-0.6T magnet; the stirring is low-speed stirring, and the stirring speed is 20-100 r/min.
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| CN116119796B (en) * | 2023-03-03 | 2023-07-14 | 斯坦德技术工程(青岛)有限公司 | Ferroferric oxide nano-composite adsorption flocculant and preparation method thereof |
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