CN108640262B - Magnetic nano-chitosan microspheres and preparation method thereof - Google Patents
Magnetic nano-chitosan microspheres and preparation method thereof Download PDFInfo
- Publication number
- CN108640262B CN108640262B CN201810733626.1A CN201810733626A CN108640262B CN 108640262 B CN108640262 B CN 108640262B CN 201810733626 A CN201810733626 A CN 201810733626A CN 108640262 B CN108640262 B CN 108640262B
- Authority
- CN
- China
- Prior art keywords
- magnetic nano
- precipitate
- magnetic
- primary
- chitosan microspheres
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
- C02F3/108—Immobilising gels, polymers or the like
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
- C02F3/107—Inorganic materials, e.g. sand, silicates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/109—Characterized by the shape
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microbiology (AREA)
- Organic Chemistry (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Cosmetics (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
本发明公开了一种磁性纳米壳聚糖微球及其制备方法，属于磁性纳米材料制备技术领域，包括如下步骤：①向氯化铁溶液中加入NaOH，调节至碱性，滤出初次沉淀，将初次沉淀与所述分散液相混合，去除乙醇得到初次沉淀的分散相；将所述初次沉淀的分散相置于高压釜中反应得到二次沉淀的分散相，所得二次沉淀即磁性纳米颗粒；②在壳聚糖溶液中加入所述磁性纳米颗粒，然后加入乳化剂和固定剂，分离得到三次沉淀，将所述三次沉淀干燥后即得磁性纳米壳聚糖微球。本发明拟提供一种磁性纳米载体，具有良好的生物性、带有多种活性基团、比表面积大、多孔、粒径分布窄等特点，其在外加磁场的作用下可进行快速运动和分离，使微球具有易回收、可再生等优点。The invention discloses a magnetic nano-chitosan microsphere and a preparation method thereof, belonging to the technical field of magnetic nano-material preparation, comprising the following steps: (1) adding NaOH to a ferric chloride solution, adjusting to alkaline, filtering out the primary precipitation, Mixing the primary precipitation with the disperse phase, removing ethanol to obtain the disperse phase of the primary precipitation; placing the disperse phase of the primary precipitation in an autoclave to react to obtain the disperse phase of the secondary precipitation, and the obtained secondary precipitation is the magnetic nanoparticles 2. Add the magnetic nano-particles to the chitosan solution, then add the emulsifier and the fixing agent, separate and obtain three precipitations, and dry the three precipitations to obtain magnetic nano-chitosan microspheres. The present invention intends to provide a magnetic nanocarrier, which has the characteristics of good biological properties, multiple active groups, large specific surface area, porosity, narrow particle size distribution, etc., which can perform rapid movement and separation under the action of an external magnetic field , so that the microspheres have the advantages of easy recovery and regeneration.
Description
Technical Field
The invention relates to the technical field of magnetic nano material preparation, in particular to a magnetic nano chitosan microsphere and a preparation method thereof.
Background
Cr (VI) is widely present in industrial wastewater of leather manufacturing, electroplating, printing, metallurgy and the like, has great harm to human bodies and the environment and is listed as a first toxic pollution element, so how to effectively treat chromium-containing wastewater is an important issue for environmental protection at present. At present, biological method, ion exchange method, electrolytic method, chemical precipitation method and adsorption method are mainly adopted for treating chromium-containing wastewater.
The commonly used biological adsorbents include bacteria, fungi, algae and the like, the microbial adsorbents which are researched more frequently include zoogloea, arthrobacter, filamentous fungi, yeasts and algae, and the research on the sphingobacterias as used as the microbial adsorbents is less, mainly because the separation and purification of the sphingobacterias are difficult. The sphingobacteria (Sheata Bacteria) are important filamentous Bacteria in activated sludge, can produce ferro-manganese oxidase, are in a filamentous structure, are not branched or have pseudo-branches, are surrounded by a sheath, and mainly comprise proteins, polysaccharides, lipids and other organic matters. The sphingobacteria has low requirement on nutrient conditions, can utilize various simple organic compounds such as alcohol, organic acid, saccharides and the like, and has stronger tolerance and transformation capability on industrial wastewater. Some researches in recent years show that the sphingomyelinase not only has strong degradation effect on organic matters and poisons in sewage, but also has the capability of adsorbing heavy metals, and has good adsorption effect on various metal ions such as lead, copper, zinc, chromium, iron and the like. In addition, the sphingobacteria can secrete and synthesize iron and manganese oxidases which play an important role in treating the sphingobacteria sewage. Therefore, the sphingomyelinase has wide application prospects in the aspects of heavy metal recovery, water quality purification, environmental monitoring and the like.
Although free live bacteria are used as a biological adsorbent, the method has the advantages of large contact area, good mass transfer performance, rapid reaction and the like, certain conditions such as temperature, nutrition, pH and the like need to be maintained in the adsorption process to ensure the self growth of microorganisms, and the physical and chemical properties of the live bacteria serving as the adsorbent have certain defects, such as difficult solid-liquid separation in the later period, poor stability, low adsorption strength and the like, so that the industrial application is difficult to realize. Therefore, an appropriate carrier is selected to load free cells so as to improve the mechanical strength and the biological stability of the cells, the solid-liquid separation at the later stage is easy to realize, and the method is one of the hotspots of the research of the prior biological adsorbent.
In recent years, with the rapid development of nanotechnology, more and more nano oxides (such as titanium oxide, iron oxide, etc.) are used as environmental repair materials due to their super-strong adsorption power to heavy metals, wherein magnetic nano materials are the most widely used and effective adsorbents. The special surface effect and magnetic response characteristic of the magnetic nano material enable the magnetic nano material to be efficiently recycled when being used as a heavy metal ion adsorbent, and the magnetic nano material is convenient to use and simple to elute, so that secondary pollution to a water body is avoided. Among them, iron oxide (ferric oxide, ferroferric oxide) is the most commonly used nano-adsorbent material. However, because the magnetic nanomaterial has a large specific surface area, under the driving of a surface effect, the unmodified magnetic nanomaterial is easily agglomerated, and therefore the surface of the magnetic nanomaterial needs to be modified, such as silicon dioxide, activated carbon, high molecular polymers and the like, which are commonly used modifying materials. The modified magnetic nano material is further grafted with some groups on the surface thereof, such as carboxyl, hydroxyl, sulfate radical, phosphate radical, amide, amino and other functional groups, so that the stability of the magnetic nano particles is improved, and the adsorption selectivity and the adsorption capacity of the magnetic nano material to metal ions are also improved.
Chitosan (Chitosan) is a deacetylated Chitin product, namely Chitin, which is an important component of shells of many higher animals, particularly arthropods (such as shrimps, crabs and the like), and is also present in cell walls of lower plants such as fungi, and is widely distributed. The natural polymer material has good biocompatibility and blood compatibility, is easy to modify, contains a large number of active groups such as amino (-NH 2) and hydroxyl (-OH) on the surface of the molecule, and can form a stable chelate with heavy metal ions.
The application of the sphingobacterium to sewage treatment requires a suitable carrier, and the preparation of the carrier becomes a priority for the present application.
Disclosure of Invention
Aiming at the technical problems, the magnetic nano chitosan microsphere and the preparation method thereof provided by the invention aim to provide a magnetic nano carrier suitable for loading the sphingobacteria S9, so that the magnetic nano carrier has good biocompatibility and biodegradability, has various active groups, has the characteristics of magnetic responsiveness, large specific surface area of nano particles, multiple pores, narrow particle size distribution and the like, can perform rapid movement and separation under the action of an external magnetic field, and has the advantages of easiness in recovery, reproducibility and the like.
In order to achieve the purpose, the preparation method of the magnetic nano chitosan microsphere comprises the following steps:
preparing magnetic nanoparticles: adding an alkaline substance into the ferric chloride solution, adjusting the pH value of the ferric chloride solution to 11-13, filtering out primary precipitates after the solution is layered, and dispersing the primary precipitates in absolute ethyl alcohol;
preparing a dispersion liquid, mixing the primary precipitate dispersed in absolute ethyl alcohol with the dispersion liquid, and drying after mixing to remove the absolute ethyl alcohol to obtain a dispersed phase of the primary precipitate;
placing the dispersed phase of the primary precipitate in an autoclave, and reacting for 10-14 hours at 210-250 ℃ to obtain a dispersed phase of a secondary precipitate;
centrifuging the dispersed phase of the secondary precipitate to collect the secondary precipitate, washing and drying to obtain magnetic nano particles;
preparing magnetic nano chitosan microspheres: and adding the magnetic nanoparticles into the chitosan solution, then adding the emulsifier, fully stirring, then adding the fixing agent, fully stirring again, carrying out centrifugal separation to obtain a third precipitate, and drying the third precipitate to obtain the magnetic nano chitosan microspheres.
Preferably, in the above step, the alkaline substance is a sodium hydroxide solution.
Preferably, the first precipitation and the second precipitation are separated and then are alternately washed by deionized water and absolute ethyl alcohol; and step two, washing by using deionized water after the third precipitation separation.
Preferably, in the above technical scheme, the dispersion liquid in the step (i) is a mixed liquid of octadecene and oleic acid, and the volume ratio of octadecene to oleic acid is 1.4-1.6: 1.
Preferably, in the step (i), the primary precipitate dispersed in the absolute ethyl alcohol is mixed with the dispersion liquid, and after mixing, the mixture is dried at 100 ℃ for 5 to 6 hours to remove the absolute ethyl alcohol.
Preferably, the centrifugal collection condition of the secondary precipitate in the step (r) is 5000r/min for 10 minutes.
Preferably, in the step (II), the mass ratio of the chitosan in the chitosan solution to the magnetic nanoparticles is 150-170: 1.
Preferably, in the step (II), the emulsifier is Span-80, and the addition amount of the Span-80 is 1ml per milligram of the magnetic nanoparticles.
Preferably, in the step (ii), the fixing agent is a glutaraldehyde aqueous solution with a volume fraction of 4%, and the addition amount of the fixing agent is 5ml of glutaraldehyde aqueous solution with a volume fraction of 4% per mg of the magnetic nanoparticles.
The magnetic nano chitosan microsphere is prepared by the preparation method of the magnetic nano chitosan microsphere.
Compared with the prior art, the embodiment of the invention has the following advantages and beneficial effects:
the embodiment of the invention provides a magnetic nano-carrier suitable for loading sphingobacteria S9, so that the magnetic nano-carrier has good biocompatibility and biodegradability, has various active groups, has the characteristics of magnetic responsiveness, large specific surface area of nano-particles, porosity, narrow particle size distribution and the like, can perform rapid movement and separation under the action of an external magnetic field, and has the advantages of easy recovery, reproducibility and the like;
the sphingobacterium S9 is a main filamentous bacterium group in activated sludge, the cell surface of the sphingobacterium S9 contains a large number of active groups such as acylamino, hydroxyl, amino, carboxyl, sulfydryl and the like, the sphingobacterium S9 has tolerance to various metal ions, and has good adsorption performance to hexavalent chromium ions, and because the stability of free cells is poor and the solid-liquid separation is difficult in the later period, the nano magnetic chitosan combined with the advantages of chitosan and Fe3O4 is adopted to load the sphingobacterium S9, so that the mechanical strength and the chemical stability of the sphingobacterium cells are increased, the advantages of chitosan and Fe3O4 are also provided to the sphingobacterium S9, the adsorption performance of the sphingobacterium S9 to Cr (VI) ions is greatly improved, and a novel biological adsorbent with high adsorption capacity and stability is provided for the treatment of industrial wastewater containing Cr (VI) ions.
Detailed Description
The present invention will be described in further detail with reference to specific examples below:
example 1: the preparation method of the magnetic nano chitosan microspheres comprises the following steps:
preparing magnetic nanoparticles: dropwise adding 3mol/L sodium hydroxide aqueous solution into 80ml 0.0375mol/L ferric chloride solution, adjusting the pH value to 12, filtering out primary precipitate after the solution is layered, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, and dispersing the primary precipitate in the absolute ethyl alcohol by adopting ultrasound;
mixing 20ml of octadecene and 13.5ml of oleic acid, performing ultrasonic dispersion to prepare a dispersion liquid, mixing primary precipitate dispersed in absolute ethyl alcohol with the dispersion liquid, performing ultrasonic treatment again for 30 minutes, and drying at 100 ℃ for 5.5 hours to remove the absolute ethyl alcohol to obtain a dispersion phase of the primary precipitate;
putting the dispersed phase of the primary precipitation into a high-pressure kettle, and reacting for 12 hours at 230 ℃ to obtain a dispersed phase of a secondary precipitation;
after cooling, centrifuging the dispersed phase of the secondary precipitate for 10 minutes under the condition of 5000r/min to collect the secondary precipitate, alternately washing with absolute ethyl alcohol and deionized water, and naturally drying to obtain magnetic nanoparticles;
preparing magnetic nano chitosan microspheres: adding 0.1mg of the magnetic nanoparticles into 4ml of chitosan solution with the concentration of 4g/L, then adding 0.1ml of span-80, magnetically stirring for 1 hour, then adding glutaraldehyde aqueous solution with the volume fraction of 4%, stirring for 2 hours under the condition of 350r/min, centrifugally separating to obtain three-time precipitate, washing with deionized water, drying the washed three-time precipitate to obtain magnetic nano chitosan microspheres, and storing the magnetic nano chitosan microspheres in a refrigerator.
Example 2: the preparation method of the magnetic nano chitosan microspheres comprises the following steps:
preparing magnetic nanoparticles: dropwise adding 3mol/L sodium hydroxide aqueous solution into 80ml 0.0375mol/L ferric chloride solution, adjusting the pH value to 11, filtering out primary precipitate after the solution is layered, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, and dispersing the primary precipitate in the absolute ethyl alcohol by adopting ultrasound;
mixing 20ml of octadecene and 14.3ml of oleic acid, performing ultrasonic dispersion to prepare a dispersion liquid, mixing primary precipitate dispersed in absolute ethyl alcohol with the dispersion liquid, performing ultrasonic treatment again for 30 minutes, and drying at 100 ℃ for 5 hours to remove the absolute ethyl alcohol to obtain a dispersion phase of the primary precipitate;
putting the dispersed phase of the primary precipitation into an autoclave, and reacting for 14 hours at 210 ℃ to obtain a dispersed phase of a secondary precipitation;
after cooling, centrifuging the dispersed phase of the secondary precipitate for 10 minutes under the condition of 5000r/min to collect the secondary precipitate, alternately washing with absolute ethyl alcohol and deionized water, and naturally drying to obtain magnetic nanoparticles;
preparing magnetic nano chitosan microspheres: adding 0.1mg of the magnetic nanoparticles into 4ml of chitosan solution with the concentration of 3.75g/L, then adding 0.1ml of span-80, magnetically stirring for 1 hour, then adding glutaraldehyde aqueous solution with the volume fraction of 4%, stirring for 2 hours under the condition of 350r/min, centrifugally separating to obtain three-time precipitate, washing with deionized water, drying the washed three-time precipitate to obtain magnetic nano chitosan microspheres, and storing the magnetic nano chitosan microspheres in a refrigerator.
Example 3: the preparation method of the magnetic nano chitosan microspheres comprises the following steps:
preparing magnetic nanoparticles: dropwise adding 3mol/L sodium hydroxide aqueous solution into 80ml 0.0375mol/L ferric chloride solution, adjusting the pH value to 13, filtering out primary precipitate after the solution is layered, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, and dispersing the primary precipitate in the absolute ethyl alcohol by adopting ultrasound;
mixing 20ml of octadecene and 12.5ml of oleic acid, performing ultrasonic dispersion to prepare a dispersion liquid, mixing primary precipitate dispersed in absolute ethyl alcohol with the dispersion liquid, performing ultrasonic treatment again for 30 minutes, and drying at 100 ℃ for 6 hours to remove the absolute ethyl alcohol to obtain a dispersion phase of the primary precipitate;
putting the dispersed phase of the primary precipitation into a high-pressure kettle, and reacting for 10 hours at the temperature of 250 ℃ to obtain a dispersed phase of a secondary precipitation;
after cooling, centrifuging the dispersed phase of the secondary precipitate for 10 minutes under the condition of 5000r/min to collect the secondary precipitate, alternately washing with absolute ethyl alcohol and deionized water, and naturally drying to obtain magnetic nanoparticles;
preparing magnetic nano chitosan microspheres: adding 0.1mg of the magnetic nanoparticles into 4ml of chitosan solution with the concentration of 4.25g/L, then adding 0.1ml of span-80, magnetically stirring for 1 hour, then adding glutaraldehyde aqueous solution with the volume fraction of 4%, stirring for 2 hours under the condition of 350r/min, centrifugally separating to obtain three-time precipitate, washing with deionized water, drying the washed three-time precipitate to obtain magnetic nano chitosan microspheres, and storing the magnetic nano chitosan microspheres in a refrigerator.
Example 4: the preparation method of the magnetic nano chitosan microspheres comprises the following steps:
preparing magnetic nanoparticles: dropwise adding 3mol/L sodium hydroxide aqueous solution into 80ml 0.0375mol/L ferric chloride solution, adjusting the pH value to 12, filtering out primary precipitate after the solution is layered, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, and dispersing the primary precipitate in the absolute ethyl alcohol by adopting ultrasound;
mixing 20ml of octadecene and 13.2ml of oleic acid, performing ultrasonic dispersion to prepare a dispersion liquid, mixing primary precipitate dispersed in absolute ethyl alcohol with the dispersion liquid, performing ultrasonic treatment again for 30 minutes, and drying at 100 ℃ for 6 hours to remove the absolute ethyl alcohol to obtain a dispersion phase of the primary precipitate;
putting the dispersed phase of the primary precipitation into a high-pressure kettle, and reacting for 11 hours at 240 ℃ to obtain a dispersed phase of a secondary precipitation;
after cooling, centrifuging the dispersed phase of the secondary precipitate for 10 minutes under the condition of 5000r/min to collect the secondary precipitate, alternately washing with absolute ethyl alcohol and deionized water, and naturally drying to obtain magnetic nanoparticles;
preparing magnetic nano chitosan microspheres: adding 0.1mg of the magnetic nanoparticles into 4ml of chitosan solution with the concentration of 4g/L, then adding 0.1ml of span-80, magnetically stirring for 1 hour, then adding glutaraldehyde aqueous solution with the volume fraction of 4%, stirring for 2 hours under the condition of 350r/min, centrifugally separating to obtain three-time precipitate, washing with deionized water, drying the washed three-time precipitate to obtain magnetic nano chitosan microspheres, and storing the magnetic nano chitosan microspheres in a refrigerator.
Example 5: the preparation method of the magnetic nano chitosan microspheres comprises the following steps:
preparing magnetic nanoparticles: dropwise adding 3mol/L sodium hydroxide aqueous solution into 80ml 0.0375mol/L ferric chloride solution, adjusting the pH value to 12, filtering out primary precipitate after the solution is layered, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, and dispersing the primary precipitate in the absolute ethyl alcohol by adopting ultrasound;
mixing 20ml of octadecene and 13.5ml of oleic acid, performing ultrasonic dispersion to prepare a dispersion liquid, mixing primary precipitate dispersed in absolute ethyl alcohol with the dispersion liquid, performing ultrasonic treatment again for 30 minutes, and drying at 100 ℃ for 6 hours to remove the absolute ethyl alcohol to obtain a dispersion phase of the primary precipitate;
putting the dispersed phase of the primary precipitation into a high-pressure kettle, and reacting for 12 hours at 210 ℃ to obtain a dispersed phase of a secondary precipitation;
after cooling, centrifuging the dispersed phase of the secondary precipitate for 10 minutes under the condition of 5000r/min to collect the secondary precipitate, alternately washing with absolute ethyl alcohol and deionized water, and naturally drying to obtain magnetic nanoparticles;
preparing magnetic nano chitosan microspheres: adding 0.1mg of the magnetic nanoparticles into 4ml of chitosan solution with the concentration of 4.1g/L, then adding 0.1ml of span-80, magnetically stirring for 1 hour, then adding glutaraldehyde aqueous solution with the volume fraction of 4%, stirring for 2 hours under the condition of 350r/min, centrifugally separating to obtain three-time precipitate, washing with deionized water, drying the washed three-time precipitate to obtain magnetic nano chitosan microspheres, and storing the magnetic nano chitosan microspheres in a refrigerator.
Examples 6 to 10: the magnetic nano chitosan microspheres prepared by the preparation methods of the magnetic nano chitosan microspheres described in the embodiments 1-5 respectively.
Claims (8)
1. The preparation method of the magnetic nano chitosan microspheres is characterized by comprising the following steps:
preparing magnetic nanoparticles: adding an alkaline substance into the ferric chloride solution, adjusting the pH value of the ferric chloride solution to 11-13, filtering out primary precipitates after the solution is layered, and dispersing the primary precipitates in absolute ethyl alcohol;
preparing a dispersion liquid, wherein the dispersion liquid is a mixed liquid of octadecene and oleic acid, the volume ratio of octadecene to oleic acid is 1.4-1.6: 1, mixing primary precipitates dispersed in absolute ethyl alcohol with the dispersion liquid, drying for 5-6 hours at 100 ℃ after mixing to remove absolute ethyl alcohol, and obtaining a dispersed phase of the primary precipitates;
placing the dispersed phase of the primary precipitate in an autoclave, and reacting for 10-14 hours at 210-250 ℃ to obtain a dispersed phase of a secondary precipitate;
centrifuging the dispersed phase of the secondary precipitate to collect the secondary precipitate, washing and drying to obtain magnetic nano particles;
preparing magnetic nano chitosan microspheres: and adding the magnetic nanoparticles into the chitosan solution, then adding the emulsifier, fully stirring, then adding the fixing agent, fully stirring again, carrying out centrifugal separation to obtain a third precipitate, and drying the third precipitate to obtain the magnetic nano chitosan microspheres.
2. The method for preparing magnetic nano chitosan microspheres according to claim 1, wherein: the alkaline substance is sodium hydroxide solution.
3. The method for preparing magnetic nano chitosan microspheres according to claim 1, wherein: after separating the primary precipitate and the secondary precipitate, alternately washing the primary precipitate and the secondary precipitate by deionized water and absolute ethyl alcohol; and step two, washing by using deionized water after the third precipitation separation.
4. The method for preparing magnetic nano chitosan microspheres according to claim 1, wherein: and (4) centrifuging the secondary precipitate in the step (i) for 10 minutes at the centrifugal collection condition of 5000 r/min.
5. The method for preparing magnetic nano chitosan microspheres according to claim 1, wherein: in the second step, the mass ratio of the chitosan in the chitosan solution to the magnetic nanoparticles is 150-170: 1.
6. The method for preparing magnetic nano chitosan microspheres according to claim 1, wherein: in the step II, the emulsifier is Span-80, and the addition amount is 1ml of Span-80 added to each mg of magnetic nanoparticles.
7. The method for preparing magnetic nano chitosan microspheres according to claim 1, wherein: in the step two, the fixing agent is glutaraldehyde aqueous solution with the volume fraction of 4%, and the adding amount is 5ml of glutaraldehyde aqueous solution with the volume fraction of 4% added into each mg of magnetic nano-particles.
8. The magnetic nano chitosan microsphere is characterized in that: the magnetic nano chitosan microsphere prepared by the method of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810733626.1A CN108640262B (en) | 2018-07-06 | 2018-07-06 | Magnetic nano-chitosan microspheres and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810733626.1A CN108640262B (en) | 2018-07-06 | 2018-07-06 | Magnetic nano-chitosan microspheres and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108640262A CN108640262A (en) | 2018-10-12 |
| CN108640262B true CN108640262B (en) | 2021-01-15 |
Family
ID=63750409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810733626.1A Active CN108640262B (en) | 2018-07-06 | 2018-07-06 | Magnetic nano-chitosan microspheres and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108640262B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603765B (en) * | 2018-12-14 | 2021-07-16 | 陕西师范大学 | A kind of oligomeric chitosan magnetic beads, preparation method and application thereof |
| CN109699687A (en) * | 2019-02-27 | 2019-05-03 | 陕西省微生物研究所 | A kind of preparation method of environment-friendly type pyrethrin control-release microsphere |
| CN110627509B (en) * | 2019-10-11 | 2022-03-15 | 航天特种材料及工艺技术研究所 | Preparation method of aluminum nitride powder |
| CN118122268A (en) * | 2024-03-01 | 2024-06-04 | 重庆理工大学 | Biochar-based magnetic material, preparation method and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101458985B (en) * | 2007-12-13 | 2012-08-22 | 比亚迪股份有限公司 | Preparation method for magnetic fluid and chitosan magnetic micro-sphere |
| CN101885512B (en) * | 2010-01-05 | 2012-02-15 | 河北医科大学 | Hydrothermal synthesis process of magnetic ferroferric oxide nanometer ultrafine particles in non-N2 atomosphere |
| CN103212377B (en) * | 2013-04-19 | 2014-09-24 | 哈尔滨益材新材料有限公司 | A kind of preparation method and application of agarose immunomagnetic microspheres |
-
2018
- 2018-07-06 CN CN201810733626.1A patent/CN108640262B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108640262A (en) | 2018-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108640262B (en) | Magnetic nano-chitosan microspheres and preparation method thereof | |
| Katırcıoğlu et al. | Removal of cadmium (II) ion from aqueous system by dry biomass, immobilized live and heat-inactivated Oscillatoria sp. H1 isolated from freshwater (Mogan Lake) | |
| Ayub et al. | RETRACTED ARTICLE: Arsenic in drinking water: overview of removal strategies and role of chitosan biosorbent for its remediation | |
| CN111068632A (en) | Lead ion composite adsorbent and preparation method thereof | |
| CN112791714A (en) | Magnetic core-shell nano-microsphere for adsorbing phenolic pollutants, preparation method and application | |
| CN101314123A (en) | A kind of magnetic biosorbent and preparation method thereof | |
| CN109939649A (en) | A kind of preparation method of magnetic chitosan-sodium alginate gel ball | |
| CN112958043B (en) | Preparation method of goethite/carboxylated cellulose nanocrystalline composite for removing heavy metal ions | |
| JP4478022B2 (en) | Heavy metal adsorbent composition | |
| CN113289502B (en) | Preparation method of amyloid fiber ferric oxide composite membrane and method for removing phosphate in tail water of municipal sewage treatment plant | |
| CN114713181B (en) | Biosynthesis method of exogenous seed crystal-added mediated Schwerner mineral, product and application thereof | |
| Wang et al. | Pb (II) biosorption by compound bioflocculant: performance and mechanism | |
| CN104785227A (en) | Chitosan-grafting amino acid magnetic composite microsphere as well as preparation method and application | |
| CN101979633A (en) | Method for preparing Fe3O4 magnetotactic bacterial cellulose spheres | |
| Qu et al. | Adsorption of Ni2+ and Pb2+ from water using diethylenetriamine-grafted Spirodela polyrhiza: behavior and mechanism studies | |
| Tural et al. | Removal of lead (II) and toluidine blue from wastewater with new magnetic Bacillus niacini nano-biosorbent: Lead and toluidine blue removal by magnetic Bacillus niacini nano-biosorbent | |
| CN110665466A (en) | Magnetic composite material for adsorbing Cd in water and preparation method thereof | |
| CN105771912A (en) | Multifunctional biological adsorbent and preparation method thereof | |
| CN113842900A (en) | A kind of preparation method of magnetic hectorite composite polymer heavy metal ion adsorbent | |
| CN100540162C (en) | Method for removing heavy metals from incineration ash | |
| CN107056965A (en) | It is a kind of go water removal in divalent cadmium ion low-cost bio adsorbent preparation method | |
| CN108772044A (en) | Chitosan loaded sheath bacteria composite biological adsorption of magnetic Nano and preparation method thereof | |
| CN113171759B (en) | A kind of imprinted chitosan composite film, its preparation method and application | |
| CN113509915B (en) | Modified graphene oxide composite material and preparation method and application thereof | |
| CN114950352B (en) | Lanthanum carbonate modified Fe 3 O 4 Dephosphorization adsorbent at@C and preparation method and application 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 | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Deng Jiacong Inventor after: Zheng Hong Inventor after: Du Ke Inventor after: Han Yanli Inventor after: Zhang Yuting Inventor before: Zheng Hong Inventor before: Du Ke Inventor before: Han Yanli Inventor before: Zhang Yuting |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 350300 Fuqing, Fujian, Longjiang, Fuzhou Street Village, No. 1 Patentee after: Fujian Normal University of Technology Country or region after: China Address before: 350300 Fuqing, Fujian, Longjiang, Fuzhou Street Village, No. 1 Patentee before: FUQING BRANCH OF FUJIAN NORMAL University Country or region before: China |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20251212 Address after: 350101 Fujian Province Fuzhou City Minhou County Jingxi Town Jingxi Community Xujia Village No. 352 Patentee after: Fun Food Development Co.,Ltd. Fujian Country or region after: China Address before: 350300 Fuqing, Fujian, Longjiang, Fuzhou Street Village, No. 1 Patentee before: Fujian Normal University of Technology Country or region before: China |