CN108837801A - A kind of double-core shell hydrophobic magnetic microballoon and preparation method thereof - Google Patents
A kind of double-core shell hydrophobic magnetic microballoon and preparation method thereof Download PDFInfo
- Publication number
- CN108837801A CN108837801A CN201810678839.9A CN201810678839A CN108837801A CN 108837801 A CN108837801 A CN 108837801A CN 201810678839 A CN201810678839 A CN 201810678839A CN 108837801 A CN108837801 A CN 108837801A
- Authority
- CN
- China
- Prior art keywords
- magnetic
- magnetic microsphere
- magnetic material
- microsphere
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention belongs to nano magnetic material technical fields, disclose a kind of double-core shell hydrophobic magnetic microballoon, and the kernel of the magnetic microsphere is magnetic material, and hypostracum is anti-corrosion layer, and outer shell is hydrophobicity carbon-coating, and the magnetic material is ferroso-ferric oxide, γ-Fe2O3Or cobaltosic oxide, the anti-corrosion layer are silica, titanium dioxide or aluminium oxide.The invention also discloses the preparation methods of the magnetic microsphere.Hydrophobic magnetic nanosphere of the invention have the advantages that resistance to highly acid, hydrophobicity, can magnetic recovery, the migration and collection of oil droplet or organic pollutant molecule are effectively driven in strongly acidic solution, complicated water system environment, and water-oil separating may be implemented；Magnetic microsphere high recycling rate, and hydrophobic performance is maintained after high-pressure extrusion.
Description
Technical field
The invention belongs to nano magnetic material technical field, specifically a kind of double-core shell hydrophobic magnetic microballoon and its preparation side
Method.
Background technique
Currently, process of industrialization considerably increases the degree of water pollution, water body contains a large amount of organic carcinogenic contaminants, cream
Changing phenomenon seriously causes such waste water control difficult, and treatment cost is high, and enterprise's sewage disposal technology is immature.
Magnetic material sewage treatment organic pollutant, emulsion breaking, noble-metal-supported, biology carry medicine, magnetic resonance at
As having important application.
However, magnetic material (such as Fe3O4With γ-Fe2O3) itself processing sewage benefit it is low, in acid condition can be molten
It solves and loses magnetism, thus the holding of its structural stability is one of main problem.In recent years, core-shell material is since its is special
Structure and performance and get more and more people's extensive concerning, kernel has magnetism, and shell can be effectively prevented kernel by acid corrosion, right
Practical application has self-evident importance.
Carbon shell is often used for the protection of magnetic material kernel by the prior art, has relevant report to claim in magnetic oxygenated iron surface packet
Polypyrrole is covered, the erosion of 48h can only be resistant under the conditions of 2M hydrochloric acid after high temperature cabonization.
101596435 A of Chinese patent CN discloses the preparation method and complex microsphere of acid resistance magnetic composite microsphere, directly
Atomization water-soluble carbon source solution is connect, directly coats carbon-coating in metal oxide surface after carbonization, it can be in 1M hydrochloric acid condition
Lower tolerance 10 days.101783217 A of Chinese patent CN, which is disclosed, to be realized by emulsion method in magnetic compound coated with uniform
Silicon dioxide layer can relatively accurately control partial size and magnetic content.
However, the acidity in industrial wastewater is even higher, current technology is caused all to be not enough to effectively remove industrial wastewater
In organic pollutant.
Summary of the invention
The object of the present invention is to provide a kind of double-core shell hydrophobic magnetic microballoons for being resistant to strong acid.
The object of the present invention is to provide the preparation methods of the magnetic microsphere.
One of in order to achieve the above objectives, the present invention uses following technical scheme：
The kernel of a kind of double-core shell hydrophobic magnetic microballoon, the magnetic microsphere is magnetic material, and hypostracum is anti-corrosion layer,
Outer shell is hydrophobicity carbon-coating.
Further, the magnetic material is ferroso-ferric oxide, γ-Fe2O3Or cobaltosic oxide.
Further, the anti-corrosion layer is silica, titanium dioxide or aluminium oxide.
Further, the magnetic microsphere is solid core-shell structure.
Double-core shell hydrophobic magnetic microballoon is successively from inside to outside：Kernel is the magnetic material of 100~350nm of diameter, inner casing
Layer is the anti-corrosion layer of fine and close 20~60nm of thickness, and outer shell is the hydrophobicity carbon-coating of 5~30nm of thickness, entire magnetic microsphere
Diameter be 150~530nm.
A kind of preparation method of magnetic microsphere, includes the following steps：
S1, magnetic material nano particle is prepared；
S2, anti-corrosion layer and hydrophobicity carbon-coating are successively coated in magnetic material nano particle surface.
The preparation method of magnetic material nano particle can be microwave method, hydro-thermal solvent-thermal method, coprecipitation etc., with magnetism
For iron oxide microballoon, source of iron is ferric chloride hexahydrate, trisodium citrate as surfactant, ethylene glycol as reducing agent,
Sodium acetate is as pH adjusting agent.
Anti-corrosion layer is coated by the precursor hydrolysis of silica, titanium dioxide or aluminium oxide and is formed, by taking silica as an example,
The corrosion resistant silicon dioxide layer being evenly coated on magnetic material surface is hydrolyzed by tetraethoxysilane (precursor) by alcoholysis method,
Condition is：The mechanical stirring at 20~40 DEG C, revolving speed are 300~550rpm, and the time is 15~25h；The precursor of titanium dioxide can
To be butyl titanate；The precursor of aluminium oxide can be aluminium isopropoxide.
Hydrophobicity carbon-coating does not have hydrophilic radical, shows as lipophilicity, play the role of it is erosion-resisting, presoma carbon source be rich in carboxylic
Base or hydroxyl can be citric acid, glucose, sucrose etc., and carburizing temperature is 600~800 DEG C, and carbonization time is 4~8h.
The invention has the advantages that：
The present invention provides the hydrophobic magnetic nanosphere of a kind of energy resisting high-concentration strong acid and stable double-nucleocapsid structure, has
Resistance to highly acid, hydrophobicity, can magnetic recovery the advantages of, can be under the conditions of 10M hydrochloric acid, temperature is at 10~35 DEG C, tolerance time
Up to 35 days, which can effectively drive in strongly acidic solution, complicated water system environment (high viscosity severe corrosive environment)
The migration and collection of dynamic oil droplet or organic pollutant molecule, improve water body environment；Magnetic microsphere has certain interfacial activity,
Water-oil separating may be implemented under magnetic response；After magnetic microsphere high recycling rate (is greater than 15 times), and high pressure (20Mpa) squeezes
Hydrophobic performance is maintained.
Preparation method of the present invention does not use toxic organic solvents, and method is simple, green, low energy consumption, uses cheap carbon source
As a raw material for production, volume production may be implemented.
Detailed description of the invention
Fig. 1 is the SEM figure and XRD diagram of the magnetic microsphere of embodiment 1；
Fig. 2 is the TEM figure and HRTEM figure of the magnetic microsphere of embodiment 1；
Fig. 3 is that sheet glass sprawls contact angle schematic diagram before and after magnetic microsphere；
Fig. 4 is the procedure chart of oil droplet in 2 magnetic microsphere adsorptive distillation water of embodiment；
Fig. 5 is the TEM figure impregnated after oil droplet in 3 magnetic microsphere of embodiment absorption hydrochloric acid 14 days；
Fig. 6 is the optical photograph and XRD diagram of 3 magnetic microsphere corrosion resistance of embodiment experiment；
Fig. 7 is the procedure chart that 4 magnetic microsphere of embodiment realizes water-oil separating；
Fig. 8 is the optical photograph after 4 magnetic microsphere of embodiment is demulsified 5 days；
Fig. 9 is 5 magnetic microsphere contact angle of embodiment variation schematic diagram.
Specific embodiment
The present invention is described further combined with specific embodiments below.
Embodiment 1
Double-core shell hydrophobic magnetic microballoon is prepared according to the following steps
1, hydro-thermal solvent-thermal method prepares magnetic ferroferric oxide nanometer particle：By 4.3g ferric chloride hexahydrate and 1g citric acid
Trisodium is dissolved in 10mL water, 70mL ethylene glycol is added in 60 DEG C of stirring in water bath 15min, 4g is added after solution clear
Anhydrous sodium acetate is transferred to 100mL polytetrafluoroethyllining lining, 200 DEG C of hydro-thermal reaction 10h, after cooling with steaming after stirring 10min
Distilled water and ethyl alcohol successively clean 3 times, 60 DEG C of vacuum drying 10h, and magnetic ferroferric oxide nanometer particle is made.
2, coated silica layer：Ferroferric oxide nano granules made from 250mg are taken to be dispersed to 45mL ethyl alcohol and 3mL water
Mixed solution in, ultrasonic 15min, under mechanical stirring be added 7.5mL mass fraction be 28% ammonia spirit, stirring
1.5mL tetraethoxysilane (TEOS) is added after 30min, 22h is stirred at room temperature, it is successively clear with distilled water and ethyl alcohol after completion of the reaction
Wash 3 times, then 60 DEG C of vacuum drying 10h.
3, carbon-coating is coated：Sample 500mg obtained above is taken to be dispersed in the ethyl alcohol of 100mL simultaneously ultrasound 10min again, it will
750mg glucose is dissolved in 5mL distilled water, 4h under mechanical stirring after mixing, then is placed in 60 DEG C of air dry oven dry 18h,
Dried sample is finally placed in tube furnace 600 DEG C of carbonization 4h under argon atmosphere protection, heating rate is 5 DEG C/min,
Argon flow rate is 80mL/min, and magnetic microsphere is made.
Fig. 1 (a) is the SEM figure of magnetic microsphere, and wherein illustration is the SEM figure for intercepting single magnetic microsphere, and Fig. 1 (b) is magnetic
The XRD diagram of property microballoon.
Fig. 2 (a) is TEM (transmission electron microscope) figure of magnetic microsphere, and wherein illustration is partial enlarged view, and Fig. 2 (b) is magnetic micro-
HRTEM (high-resolution-ration transmission electric-lens) figure of ball, wherein illustration is the corresponding Fourier transformation figure of lattice fringe of magnetic iron oxide.
Fig. 3 (a) is the contact angle schematic diagram of sheet glass, and Fig. 3 (b) is after glass sheet surface has sprawled one layer of magnetic microsphere
Contact angle schematic diagram illustrates that magnetic microsphere has certain interfacial activity, can be used for water-oil separating experiment.
The diameter of magnetic microsphere is 230nm, interior nuclear diameter 150nm, silicon dioxide layer thickness 30nm, and carbon layers having thicknesses are
10nm。
Embodiment 2
Adsorb oil droplet experiment
It is poured into vial as shown in figure 4, measuring 10mL distilled water, red Ⅲ is added in methylene chloride, configuration
It is 0.284*10 at concentration-3The solution of M drips 100 μ L red Ⅲ solution in distilled water, forms small liquid pearl, be added a small amount of
The magnetic microsphere of embodiment 1, red Ⅲ oil droplet under the action of magnetism in adsorptive distillation water, until absorbing liquid level.
Measure hydrochloric acid that 10mL concentration is 10M respectively and sodium hydroxide solution pour into vial, red Ⅲ plus
Enter in methylene chloride, being configured to concentration is 0.284*10-3The solution of M drips 100 μ L red Ⅲ solution in hydrochloric acid and hydrogen-oxygen respectively
Change in sodium solution, form small liquid pearl, the magnetic microsphere of a small amount of embodiment 1 is added, hydrochloric acid and hydrogen are adsorbed under the action of magnetism
Red Ⅲ oil droplet in sodium hydroxide solution, until absorbing liquid level.
10mL concentration is measured respectively to pour into vial for the hydrochloric acid and sodium hydroxide solution of 5M, is added two Congo red
In chloromethanes, being configured to concentration is 0.284*10-3It is molten in hydrochloric acid and sodium hydroxide to drip the 100 Congo red solution of μ L respectively for the solution of M
In liquid, small liquid pearl is formed, the magnetic microsphere of a small amount of embodiment 1 is added, hydrochloric acid and sodium hydroxide are adsorbed under the action of magnetism
Congo red oil droplet in solution, until absorbing liquid level.
10mL concentration is measured respectively to pour into vial for the hydrochloric acid and sodium hydroxide solution of 1M, and dichloro is added in magenta
In methane, being configured to concentration is 0.284*10-3The solution of M drips 100 μ L fuchsin solutions in hydrochloric acid and sodium hydroxide solution respectively
In, small liquid pearl is formed, the magnetic microsphere of a small amount of embodiment 1 is added, hydrochloric acid is adsorbed under the action of magnetism and sodium hydroxide is molten
Pinkish red oil droplet in liquid, until absorbing liquid level.
10mL concentration is measured respectively pours into small glass for the hydrochloric acid and sodium hydroxide solution, 10wt% sodium chloride solution of 0.1M
In bottle, peacock green is added in methylene chloride, being configured to concentration is 0.284*10-3It is molten to drip 100 μ L peacock greens respectively for the solution of M
Liquid forms small liquid pearl in hydrochloric acid, sodium hydroxide solution, sodium chloride solution, and the magnetic microsphere of a small amount of embodiment 1 is added,
Peacock green oil pearl is adsorbed under the action of magnetism, until absorbing liquid level.
Respectively measure 10mL distilled water pour into vial, respectively Sudan red, Sudan II, SudanⅣ or
Triarylmethane dye is added in methylene chloride or chloroform, be configured to it is certain density have color solution, 100 μ L of drop are molten
Liquid forms small liquid pearl in distilled water, and the magnetic microsphere of a small amount of embodiment 1 is added, adsorptive distillation water under the action of magnetism
In tonyred oil droplet, until absorbing liquid level.
The above experiment show magnetic microsphere can various concentration, pH value solution system under realize organic matter oil droplet
Adsorbing separation, azo dyes, arylmethane dyes and quinoneimine dye etc. all have good adsorption effect, illustrate magnetic
Stability, the broad applicability of the absorption property of property microballoon.
Embodiment 3
Corrosion resistance experiment
The magnetic microsphere of embodiment 2 is soaked in the 10M hydrochloric acid solution of 10mL, and is kept for 14 days, is finally centrifugated
Magnetic microsphere is simultaneously respectively cleaned 3 times with water and ethyl alcohol, by whole be scattered in ethanol solution, take 2~3 drop dispersant liquid drops as copper
On the net, do TEM test after dried, result as shown in figure 5, kernel ferroso-ferric oxide there is no the erosion by hydrochloric acid, this
It may be the protective effect because of fine and close silicon dioxide layer and hydrophobic carbon-coating, illustrate that the magnetic microsphere has good anti-corruption
Corrosion energy.
Referring to the prior art and 1 preparation method of embodiment, magnetic material-is successively made by step 1 and 2, step 1 and 3
Silicon dioxide layer magnetic microsphere and the hydrophobic carbon-coating magnetic microsphere of magnetic material-, it is respectively that magnetic material-silicon dioxide layer magnetism is micro-
Ball, the hydrophobic carbon-coating magnetic microsphere of magnetic material-and the hydrophobic carbon-coating magnetic microsphere of magnetic material-silicon dioxide layer-are soaked in 12mL
10M hydrochloric acid solution in then keep 35 days, finally be centrifugated above-mentioned material do absorption oil droplet experiment and XRD test, such as Fig. 6
Shown, wherein Fig. 6 (a) and Fig. 6 (d) is optics of the magnetic material-silicon dioxide layer magnetic microsphere after 10M salt acid soak 35 days
Photo and corresponding XRD diagram, magnetic material are decomposed completely, and Fig. 6 (b) and Fig. 6 (e) are that the hydrophobic carbon-coating magnetism of magnetic material-is micro-
Optical photograph and corresponding XRD diagram of the ball after 10M salt acid soak 35 days, wherein black prismatic mark is graphitic carbon, Fig. 6 (c)
With Fig. 6 (f) be optical photograph of the hydrophobic carbon-coating magnetic microsphere of magnetic material-silicon dioxide layer-after 10M salt acid soak 35 days and
Corresponding XRD diagram, wherein black dot mark is the diffraction maximum of ferroso-ferric oxide, illustrates that there are also part ferroso-ferric oxides to exist.
Magnetic material-silicon dioxide layer magnetic microsphere becomes yellow after solution is added soon in experimentation, illustrates that magnetic core is dissolved,
100 μ L red Ⅲ oil droplets can not be absorbed to liquid level, and the hydrophobic carbon-coating magnetic microsphere of magnetic material-is added in solution and can produce
Raw a small amount of bubble, solution are green at the beginning, behind slowly become yellow, illustrating material, there are also be reduced generation when a small amount of calcining
Iron, but also cannot achieve the adsorbing separation of oil droplet, the hydrophobic carbon-coating magnetic microsphere structural integrity of magnetic material-silicon dioxide layer-,
Still oil droplet can be adsorbed.
This example demonstrates that the magnetic microsphere of single layer structure corrodes intolerant to 10M strong acid at all, and the magnetism of double-layer structure is micro-
Ball can be resistant to the corrosion of 10M strong acid for a long time.
Embodiment 4
Water-oil separating experiment
The toluene and 0.2wt% asphalitine for weighing 80g stir evenly, and are poured into 20g distilled water, are 600rpm magnetic in revolving speed
It is khaki water-in-oil emulsion that power, which stirs 1h to lower layer is formed, and the magnetic microsphere for weighing embodiment 1 is scattered in toluene (quality point
Number mixes water-in-oil emulsion and magnetic microsphere dispersion liquid 1%), to rock uniformly, with equal proportion, realizes grease under magnetic action
Separation.As shown in fig. 7, Fig. 7 (a) is the khaki water-in-oil emulsion of 2.5mL, Fig. 7 (b) is the magnetic that 2.5mL mass fraction is 1%
Property microballoon dispersion liquid, Fig. 7 (c) is that lotion realizes water-oil separating under the action of magnetic microsphere, and Fig. 7 (d) is khaki Water-In-Oil
Optical photograph under the metallographic microscope of lotion, Fig. 7 (e) are that the optics after water-oil separating under the metallographic microscope of lower liquid shines
Piece, Fig. 7 (f) are the optical photographs after water-oil separating under the metallographic microscope of supernatant liquid.
A kind of metastable lotion with the lotion that asphalitine prepares this ratio, but can also stablize at least one moon without
Spontaneously there is water-oil separating, i.e. the cohesion of droplet is sunk to the bottom.After such magnetic microsphere is added, the microballoon of this interfacial activity can be with
Be adsorbed on the interface of oil hydrosol, interact with asphalitine, can accelerate under magnetic action droplet in lotion or
The polymerization of oil droplet, to realize the water-oil separating of magnetic response type, the result under microscope is exactly that the upper and lower are not all bright
Aobvious oil droplet, droplet occur.
Referring to the prior art and 1 preparation method of embodiment, magnetic material-is successively made by step 1 and 2, step 1 and 3
Silicon dioxide layer magnetic microsphere and the hydrophobic carbon-coating magnetic microsphere of magnetic material-, and tested for above-mentioned water-oil separating, finally send out
Existing, magnetic material-silicon dioxide layer magnetic microsphere is added in khaki lotion, still without oily phase color under magnetic action
Deepen, the bottom of vial also without liquid pearl occur, illustrate magnetic material-silicon dioxide layer magnetic microsphere do not have interfacial activity or
Person says that interfacial activity is very poor.
After the hydrophobic carbon-coating magnetic microsphere of magnetic material-is added to khaki lotion, it then will appear oily phase under magnetic action
It darkens, droplet appearance is arranged at the bottom of vial, illustrates that the hydrophobic carbon-coating magnetic microsphere of magnetic material-has certain interface living
Property.
After above-mentioned emulsion is placed 5 days at room temperature, as shown in figure 8, wherein Fig. 8 (a) is containing magnetic material-silica
Layer-hydrophobic carbon-coating magnetic microsphere lotion, is completely separated into water phase and oily phase, and Fig. 8 (b) is containing magnetic material-hydrophobic carbon
Also there is oily phase and aqueous phase separation in the lotion of layer magnetic microsphere, but still the lotion of some maintains as former state, and Fig. 8 (c) is
Containing magnetic material-silicon dioxide layer magnetic microsphere lotion, also there is oily phase and aqueous phase separation, but still quite a few
Lotion maintain as former state.
This example demonstrates that the interfacial activity of the hydrophobic carbon-coating magnetic microsphere of magnetic material-silicon dioxide layer-is than magnetic material-
Hydrophobic carbon-coating magnetic microsphere and magnetic material-silicon dioxide layer magnetic microsphere are stronger, are demulsified more efficient.
Embodiment 5
The 1M hydrochloric acid solution for preparing 10mL is placed in the vial of 20mL, instills 100 μ L red Ⅲ solution, is added few
The magnetic microsphere of the embodiment 1 of amount successively cleans magnetic microsphere 3 with water, ethyl alcohol after the completion of red Ⅲ oil droplet is adsorbed
It is secondary, it is dried in vacuo 2h, is repeated the above steps 15 times, red Ⅲ oil droplet can be adsorbed under magnetic action and is discharged by magnetic microsphere
Face achievees the purpose that oil droplet adsorbing separation.
Magnetic microsphere powder is pressed into thin slice at 20Mpa using the method for infrared tabletting by the magnetic microsphere for taking 0.1g, then
It smashs into thin slice to pieces powder, spreads on glass slide, as shown in figure 9, measuring contact angle is before wherein Fig. 9 (a) is extruding
135.5 °, Fig. 9 (b) is after 20Mpa is squeezed, and measuring contact angle is 136.5 °, and contact angle has almost no change.
This example demonstrates that magnetic microsphere high recycling rate (being greater than 15 times), and hydrophobicity after high pressure (20Mpa) extruding
It can be maintained.
Embodiment 6
Double-core shell hydrophobic magnetic microballoon is prepared according to the following steps
1, the synthesis of ferroso-ferric oxide：The green vitriol salt of 13.9g and 32.44g ferric chloride hexahydrate salt is molten
Solution is added in three-necked flask in the in the mixed solvent of 100mL water and 400mL ethylene glycol, the precipitating being added in nitrogen atmosphere
Agent ammonium hydroxide, is adjusted to pH>3h, the ferriferrous oxide nano-particle of black to be generated, centrifugation are at the uniform velocity stirred to react under 10,50 DEG C of water-baths
It collects, is successively cleaned and dried 3 times with water and ethyl alcohol, finally the vacuum oven at 60 DEG C is dried to obtain ferriferrous oxide nano grain
Son.
2, cladding titanium dioxide layer：Ferriferrous oxide nano-particle made from 500mg is taken to be dispersed to 90mL n-butanol and 2mL
In the mixed solution of water, the ammonia spirit that the mass fraction of 3mL is 28%, stirring is added in ultrasonic 15min under mechanical stirring
The butyl titanate of 1.5mL is added after 30min, 22h is stirred at room temperature, successively cleans 3 times with distilled water and ethyl alcohol after completion of the reaction, so
60 DEG C of vacuum drying 10h afterwards.
3, carbon-coating is coated：Sample 500mg obtained above is taken to be dispersed in the ethyl alcohol of 100mL simultaneously ultrasound 10min again, it will
750mg sucrose is dissolved in 5mL distilled water, 4h under mechanical stirring after mixing, then is placed in 60 DEG C of air dry oven dry 18h, most
Dried sample is placed in tube furnace 600 DEG C of carbonization 4h under argon atmosphere protection afterwards, heating rate is 5 DEG C/min, argon
Gas flow rate is 80mL/min, and magnetic microsphere is made.
The diameter of magnetic microsphere is 410nm, interior nuclear diameter 300nm, and titanium dioxide layer is with a thickness of 40nm, carbon layers having thicknesses
15nm。
Embodiment 7
Double-core shell hydrophobic magnetic microballoon is prepared according to the following steps
1, the synthesis of cobaltosic oxide：47.17g cobaltous sulfate is dissolved in 500mL water, it is molten in cobalt that 8g urea solid is added
In liquid, the presoma sediment of cobalt salt compound is generated, it is dry under 60 DEG C of vacuum conditions after being filtered, washed, in tube furnace
In calcine 4h under the conditions of 600 DEG C, obtain cobaltosic oxide product.
2, coated aluminum oxide layer：Cobaltosic oxide nanoparticles made from 500mg are taken to be dispersed to 90mL isopropanol and 2mL water
Mixed solution in, ultrasonic 15min, under mechanical stirring be added 3mL mass fraction be 28% ammonia spirit, stirring
The aluminium isopropoxide of 1.5mL is added after 30min, 22h is stirred at room temperature, successively cleans 3 times with distilled water and ethyl alcohol after completion of the reaction, so
60 DEG C of vacuum drying 10h afterwards.
3, carbon-coating is coated：Sample 500mg obtained above is taken to be dispersed in the ethyl alcohol of 100mL simultaneously ultrasound 10min again, it will
750mg citric acid solid is dissolved in 5mL distilled water, 4h under mechanical stirring after mixing, then is placed in 60 DEG C of dryings of air dry oven
18h is finally placed in dried sample in tube furnace under argon atmosphere protection and is carbonized, and heating rate is 5 DEG C/min, argon gas
Flow rate is 80mL/min, and magnetic microsphere is made.
The diameter of magnetic microsphere is 330nm, interior nuclear diameter 200nm, and alumina layer is with a thickness of 50nm, carbon layers having thicknesses
15nm。
Embodiment 8
Double-core shell hydrophobic magnetic microballoon is prepared according to the following steps
1、γ-Fe2O3Synthesis：The green vitriol salt of 13.9g and 32.44g ferric chloride hexahydrate salt are dissolved in
The in the mixed solvent of 100mL water and 400mL ethylene glycol, is added in three-necked flask, the precipitating reagent ammonia being added in nitrogen atmosphere
Water is adjusted to pH>3h, the ferriferrous oxide nano-particle of black to be generated are at the uniform velocity stirred to react under 10,50 DEG C of water-baths, centrifugation is received
Collection is successively cleaned and dried 3 times with water and ethyl alcohol, and finally the air dry oven at 100 DEG C is dried to obtain γ-Fe2O3Nanoparticle.
2, coated aluminum oxide layer：Take γ-Fe made from 500mg2O3Nanoparticle is dispersed to 90mL isopropanol and 2mL water
In mixed solution, the ammonia spirit that the mass fraction of 3mL is 28% is added under mechanical stirring, stirs 30min by ultrasonic 15min
The aluminium isopropoxide of 1.5mL is added afterwards, 22h is stirred at room temperature, successively cleans 3 times with distilled water and ethyl alcohol after completion of the reaction, then 60
DEG C vacuum drying 10h.
3, carbon-coating is coated：Sample 500mg obtained above is taken to be dispersed in the ethyl alcohol of 100mL simultaneously ultrasound 10min again, it will
750mg fructose is dissolved in 5mL distilled water, 4h under mechanical stirring after mixing, then is placed in 60 DEG C of air dry oven dry 18h, most
Dried sample is placed in tube furnace 600 DEG C of carbonization 4h under argon atmosphere protection afterwards, heating rate is 5 DEG C/min, argon
Gas flow rate is 80mL/min, and magnetic microsphere is made.
The diameter of magnetic microsphere is 410nm, and interior nuclear diameter 300nm, aluminium oxide is with a thickness of 40nm, carbon layers having thicknesses 15nm.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Belong to those skilled in the art in the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of, all answers
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be subject to the protection scope in claims.
Claims (9)
1. a kind of double-core shell hydrophobic magnetic microballoon, which is characterized in that the kernel of the magnetic microsphere is magnetic material, and hypostracum is
Anti-corrosion layer, outer shell are hydrophobicity carbon-coating.
2. magnetic microsphere according to claim 1, which is characterized in that the magnetic material is ferroso-ferric oxide, γ-Fe2O3
Or cobaltosic oxide.
3. magnetic microsphere according to claim 1, which is characterized in that the anti-corrosion layer is silica, titanium dioxide
Or aluminium oxide.
4. magnetic microsphere according to claim 1, which is characterized in that the magnetic microsphere is solid core-shell structure.
5. magnetic microsphere according to claim 1,2,3 or 4, which is characterized in that the diameter of the kernel be 100~
350nm。
6. magnetic microsphere according to claim 1,2,3 or 4, which is characterized in that the hypostracum with a thickness of 20~
60nm。
7. magnetic microsphere according to claim 1,2,3 or 4, which is characterized in that the outer shell with a thickness of 5~
30nm。
8. a kind of preparation method of the described in any item magnetic microspheres of claim 1~7, which is characterized in that include the following steps：
S1, magnetic material nano particle is prepared；
S2, anti-corrosion layer and hydrophobicity carbon-coating are successively coated in magnetic material nano particle surface.
9. preparation method according to claim 8, which is characterized in that the anti-corrosion layer is coated by precursor hydrolysis to be formed,
The hydrophobicity carbon-coating is carbonized by citric acid, glucose or sucrose to be formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810678839.9A CN108837801A (en) | 2018-06-27 | 2018-06-27 | A kind of double-core shell hydrophobic magnetic microballoon and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810678839.9A CN108837801A (en) | 2018-06-27 | 2018-06-27 | A kind of double-core shell hydrophobic magnetic microballoon and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108837801A true CN108837801A (en) | 2018-11-20 |
Family
ID=64202772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810678839.9A Pending CN108837801A (en) | 2018-06-27 | 2018-06-27 | A kind of double-core shell hydrophobic magnetic microballoon and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108837801A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109396459A (en) * | 2018-12-20 | 2019-03-01 | 淮海工学院 | A kind of preparation method and applications of magnetic Nano stick |
| CN110270332A (en) * | 2019-07-22 | 2019-09-24 | 福州大学 | A kind of magnetism TiO2(R) composite photo-catalyst and preparation method thereof |
| CN110496600A (en) * | 2019-08-26 | 2019-11-26 | 中国石油化工股份有限公司 | A kind of preparation method and application of the core-shell structure magnetic material of porous carbon package cobalt |
| CN111575267A (en) * | 2020-05-06 | 2020-08-25 | 吕梁学院 | Artificial micro-nano robot and preparation method thereof |
| CN111804248A (en) * | 2020-06-02 | 2020-10-23 | 浙江海洋大学 | Oil storage tank soil leakage monitoring technology adopting magnetic tracer |
| CN112915592A (en) * | 2021-02-09 | 2021-06-08 | 天津大学 | Magnetic nano material and preparation method and application thereof |
| US11414555B2 (en) * | 2019-08-05 | 2022-08-16 | The Boeing Company | Systems, compositions, and methods for enhanced electromagnetic shielding and corrosion resistance |
| CN115745015A (en) * | 2023-01-07 | 2023-03-07 | 山东泰和科技股份有限公司 | Magnetic nanoscale Co 3 O 4 Material, preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762587A (en) * | 2005-09-16 | 2006-04-26 | 山西大学 | CO low temperature oxidation catalyst and its preparation process |
| CN102247803A (en) * | 2011-05-04 | 2011-11-23 | 中国科学院化学研究所 | Core-shell type magnetic mesoporous nano-microsphere as well as preparation method and application thereof |
| CN104415741A (en) * | 2013-09-10 | 2015-03-18 | 中国科学院大连化学物理研究所 | Composite nanometer material with core-shell structure, preparation method and application of composite nanometer material |
| CN105565265A (en) * | 2016-03-17 | 2016-05-11 | 齐鲁工业大学 | Preparation method of composite microsphere lithium ion battery cathode material in yolk structure |
-
2018
- 2018-06-27 CN CN201810678839.9A patent/CN108837801A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762587A (en) * | 2005-09-16 | 2006-04-26 | 山西大学 | CO low temperature oxidation catalyst and its preparation process |
| CN102247803A (en) * | 2011-05-04 | 2011-11-23 | 中国科学院化学研究所 | Core-shell type magnetic mesoporous nano-microsphere as well as preparation method and application thereof |
| CN104415741A (en) * | 2013-09-10 | 2015-03-18 | 中国科学院大连化学物理研究所 | Composite nanometer material with core-shell structure, preparation method and application of composite nanometer material |
| CN105565265A (en) * | 2016-03-17 | 2016-05-11 | 齐鲁工业大学 | Preparation method of composite microsphere lithium ion battery cathode material in yolk structure |
Non-Patent Citations (2)
| Title |
|---|
| 石微微: "若干新型微/纳米复合材料的制备及应用研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 蒋开喜: "《加压湿法冶金》", 31 January 2016, 冶金工业出版社 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109396459A (en) * | 2018-12-20 | 2019-03-01 | 淮海工学院 | A kind of preparation method and applications of magnetic Nano stick |
| CN110270332A (en) * | 2019-07-22 | 2019-09-24 | 福州大学 | A kind of magnetism TiO2(R) composite photo-catalyst and preparation method thereof |
| CN110270332B (en) * | 2019-07-22 | 2021-06-01 | 福州大学 | Magnetic TiO2(R) composite photocatalyst and preparation method thereof |
| US11414555B2 (en) * | 2019-08-05 | 2022-08-16 | The Boeing Company | Systems, compositions, and methods for enhanced electromagnetic shielding and corrosion resistance |
| US11965116B2 (en) | 2019-08-05 | 2024-04-23 | The Boeing Company | Systems, compositions, and methods for enhanced electromagnetic shielding and corrosion resistance |
| CN110496600A (en) * | 2019-08-26 | 2019-11-26 | 中国石油化工股份有限公司 | A kind of preparation method and application of the core-shell structure magnetic material of porous carbon package cobalt |
| CN110496600B (en) * | 2019-08-26 | 2022-02-22 | 中国石油化工股份有限公司 | Preparation method and application of core-shell structure magnetic material with porous carbon coated with cobalt |
| CN111575267A (en) * | 2020-05-06 | 2020-08-25 | 吕梁学院 | Artificial micro-nano robot and preparation method thereof |
| CN111804248A (en) * | 2020-06-02 | 2020-10-23 | 浙江海洋大学 | Oil storage tank soil leakage monitoring technology adopting magnetic tracer |
| CN111804248B (en) * | 2020-06-02 | 2022-03-25 | 浙江海洋大学 | Oil storage tank soil leakage monitoring technology adopting magnetic tracer |
| CN112915592A (en) * | 2021-02-09 | 2021-06-08 | 天津大学 | Magnetic nano material and preparation method and application thereof |
| CN115745015A (en) * | 2023-01-07 | 2023-03-07 | 山东泰和科技股份有限公司 | Magnetic nanoscale Co 3 O 4 Material, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108837801A (en) | A kind of double-core shell hydrophobic magnetic microballoon and preparation method thereof | |
| Sun et al. | Chemically stable superhydrophobic polyurethane sponge coated with ZnO/epoxy resin coating for effective oil/water separation | |
| CN102989398A (en) | Magnetic inorganic nano particle/large-aperture ordered mesopore oxide nuclear shell microspheres and preparation method thereof | |
| CN109796019B (en) | Hollow silicon dioxide nanosphere and preparation method and application thereof | |
| CN103143721B (en) | Preparation method of Ag@SiO2 core-shell structure nano composite | |
| CN111437792B (en) | Synthetic method of magnetic mesoporous silica for removing copper ions in water | |
| CN104759260A (en) | Amino-functionalization magnetic silicon dioxide-ferroferric oxide composite nanomaterial and preparation method thereof | |
| CN106637929B (en) | Hydrophobic oleophylic cotton fiber and preparation method and application thereof | |
| Sun et al. | Efficient adsorption of Cu (II), Pb (II) and Ni (II) from waste water by PANI@ APTS-magnetic attapulgite composites | |
| CN105289433A (en) | Method for large-scale preparation of transition metal oxide porous microsphere | |
| CN111632581B (en) | Raspberry-like super-hydrophobic oleophylic cotton fiber oil-water adsorption/separation membrane and preparation method and application thereof | |
| CN102807254B (en) | Amino functionalized superparamagnetism carbon nanosphere and preparation method thereof | |
| CN107176646A (en) | A kind of optical drive is used for the preparation method of the microrobot of environment remediation | |
| CN106179197A (en) | The preparation method of nano-material modified zeolite and the application in environment remediation thereof | |
| CN103143705B (en) | A kind of alumina-coated type nano-iron particle and preparation method thereof and application | |
| CN109678137A (en) | A kind of preparation method of hollow Nano carbon balls | |
| CN102936028A (en) | Method for preparing platy lanthanum hydroxide nanocrystalline through microwave-ultrasonic method | |
| Kong et al. | Structural study on PVA assisted self-assembled 3D hierarchical iron (hydr) oxides | |
| Wang et al. | Fabrication of robust superhydrophobic magnetic multifunctional coatings and liquid marbles | |
| CN101342486B (en) | Metallic oxide nano-material | |
| CN106430324B (en) | A kind of flower-shaped porous micro-nano balls of α FeOOH and preparation method thereof | |
| CN105854821B (en) | A kind of porous magnetic spheroidal material and preparation method thereof with sewage purification function | |
| CN106111030B (en) | A kind of gold/carbon complex microsphere and preparation method thereof | |
| CN108975414B (en) | Hollow tubular nano material and preparation method and application thereof | |
| CN101391211A (en) | Alumina substrate shaped titanium dioxide-nucleus/shell structure composite microsphere photocatalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181120 |
|
| RJ01 | Rejection of invention patent application after publication |