CN108355621B - Magnetic porous bentonite chitosan composite microsphere and preparation method thereof - Google Patents

Magnetic porous bentonite chitosan composite microsphere and preparation method thereof Download PDF

Info

Publication number
CN108355621B
CN108355621B CN201810236507.5A CN201810236507A CN108355621B CN 108355621 B CN108355621 B CN 108355621B CN 201810236507 A CN201810236507 A CN 201810236507A CN 108355621 B CN108355621 B CN 108355621B
Authority
CN
China
Prior art keywords
bentonite
chitosan
microspheres
parts
magnetic
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
Application number
CN201810236507.5A
Other languages
Chinese (zh)
Other versions
CN108355621A (en
Inventor
蒲生彦
王可心
马慧
颜椿
王晓科
肖雨婷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chengdu Univeristy of Technology
Original Assignee
Chengdu Univeristy of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Chengdu Univeristy of Technology filed Critical Chengdu Univeristy of Technology
Priority to CN201810236507.5A priority Critical patent/CN108355621B/en
Publication of CN108355621A publication Critical patent/CN108355621A/en
Application granted granted Critical
Publication of CN108355621B publication Critical patent/CN108355621B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/12—Processing by absorption; by adsorption; by ion-exchange
    • 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
    • C02F2101/006—Radioactive compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Inorganic Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Dispersion Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a magnetic porous bentonite chitosan composite microsphere which is characterized by being prepared from the following raw materials in parts by weight: 1-10 parts of bentonite, 1-5 parts of acetic acid, 1-3 parts of chitosan, 1-6 parts of ferric chloride hexahydrate, 1-3 parts of ferrous chloride tetrahydrate, 10-15 parts of sodium hydroxide, 5-10 parts of sodium citrate and 250 parts of water 200. According to the invention, the high-porosity chitosan hydrogel microspheres are modified and introduced into a magnetic medium, and bentonite is loaded into the microspheres to successfully prepare the magnetic porous bentonite chitosan composite microspheres which have stronger cesium ion adsorption capacity and can be recovered by using a magnetic technology, and the magnetic porous bentonite chitosan composite microspheres have the characteristics of high adsorption rate, large adsorption capacity, insensitivity to pH (potential of hydrogen) and wide application range; the magnetic field can be gathered by the aid of an external magnetic field, solid-liquid separation is easy, and recovery is convenient; the whole preparation process is simple, short in operation time and easy to control.

Description

Magnetic porous bentonite chitosan composite microsphere and preparation method thereof
Technical Field
The invention relates to the technical field of radioactive waste treatment in nuclear waste and environmental protection, in particular to a magnetic porous bentonite chitosan composite microsphere and a preparation method thereof.
Background
The utilization of nuclear energy inevitably generates radioactive waste water, and the treatment of the radioactive waste water is always a hotspot and a difficult problem of research of various countries and is an important problem that the utilization of the nuclear energy must be properly solved. The radioactive element cesium is used as a radioactive source, and the radioactive half life of the radioactive element cesium is as long as 30.28 years. Cesium has high solubility and high fluidity, so that it can be easily present in terrestrial and aquatic organisms. In addition, cesium ions can enter and accumulate in the human body through water and food chains and are concentrated in human muscle tissue, which is difficult to eliminate.
To date, there are many techniques for removing cesium ions from water bodies to reduce their environmental impact, such as ion exchange methods, precipitation methods, solvent extraction methods, electrochemical methods, and membrane separation methods. Most of the extracting agents used in the extraction method are organic matters with high toxicity and complex structures, and have great influence on the environment. When cesium is removed by a chemical precipitation method, sodium tetraphenylborate is one of the best precipitants, but harmful gases are generated, and the safety has potential risks. Other treatment methods, such as ion exchange method, electrochemical method, membrane separation method, etc., can achieve certain treatment effect, but too high running cost also affects the practical application of the method. Therefore, the removal of cesium ions from radioactive wastewater has certain disadvantages in terms of economy, technology and practicality.
In recent years, the adsorption method is used for removing cesium ions in water, and is favored by people due to the characteristics of simple operation, low investment, good treatment effect and the like.
Chinese patent publication No. CN104307489a, published 2015, 01-month, 28-day, discloses a preparation method of a bentonite-loaded chitosan composite adsorbent, comprising the following steps: slowly dissolving chitosan with 5% acetic acid solution to prepare 1.0% chitosan solution, then mixing bentonite with the chitosan solution into paste according to a certain dosage proportion, fully soaking the paste, placing the paste into a heating furnace for heating and drying, grinding, and sieving with a 100-mesh sieve to obtain the bentonite-loaded chitosan composite adsorbent.
Chinese patent publication No. CN101475187, published as 2009, 07.08 discloses a method for preparing chitosan bentonite, which is characterized in that sodium bentonite and chitosan are used as raw materials for preparing chitosan bentonite, and a bentonite suspension is added into a chitosan solution, wherein the preparation method comprises the following steps: (1) adding sodium bentonite with the granularity of 100-400 meshes into water with the mass 10-30 times of that of the bentonite, stirring and dispersing for 0.5-3 hours to obtain bentonite suspension; (2) dissolving chitosan with the mass being 0.5-3 times of that of bentonite in an acetic acid solution with the mass concentration of 1% to prepare a chitosan solution with the mass concentration of 2-8% and the pH value of 3-6; (3) uniformly adding the bentonite suspension into the chitosan solution within 6-12 hours at 50-100 ℃ under stirring, and continuing to react for 20-50 hours after the bentonite suspension is added to obtain a reaction completion solution; (4) and filtering, washing and drying the reaction finished liquid to obtain the chitosan bentonite.
The prior art represented by the above patent documents has complicated preparation process, long operation time and difficult control, and the prepared bentonite chitosan has certain adsorbability, but is difficult to separate and inconvenient to recycle after the adsorption is finished.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a magnetic porous bentonite chitosan composite microsphere and a preparation method thereof, the invention modifies the high-porosity chitosan hydrogel microsphere into a magnetic medium, and loads bentonite into the microsphere to successfully prepare the magnetic porous bentonite chitosan composite microsphere which has stronger cesium ion adsorption capacity and can be recovered by using a magnetic technology, and the magnetic porous bentonite chitosan composite microsphere has the characteristics of high adsorption rate, large adsorption capacity, insensitivity to pH and wide application range; the magnetic field can be gathered by the aid of an external magnetic field, solid-liquid separation is easy, and recovery is convenient; the whole preparation process is simple, short in operation time and easy to control.
The invention is realized by the following technical scheme:
the magnetic porous bentonite chitosan composite microsphere is characterized by comprising the following raw materials in parts by weight: 1-10 parts of bentonite, 1-5 parts of acetic acid, 1-3 parts of chitosan, 1-6 parts of ferric chloride hexahydrate, 1-3 parts of ferrous chloride tetrahydrate, 10-15 parts of sodium hydroxide, 5-10 parts of sodium citrate and 250 parts of water 200.
A preparation method of magnetic porous bentonite chitosan composite microspheres is characterized by comprising the following steps:
a. dissolving bentonite in acetic acid solution, and mechanically stirring and fully mixing;
b. b, dissolving chitosan in the solution obtained in the step a, and mechanically stirring and fully mixing;
c. mixing Fe3+/Fe2+B, adding the mixed solution into the solution obtained in the step b, and mechanically stirring and fully mixing;
d. preparing a mixed solution of sodium citrate and sodium hydroxide;
e. c, dripping the mixed solution obtained in the step c into the solution obtained in the step d by using a peristaltic pump, and soaking and crosslinking to obtain microspheres;
f. after the crosslinking is finished, a magnetic field is added for separation, and the microspheres are washed by deionized water;
g. and f, freeze-drying the microspheres obtained in the step f to obtain the magnetic porous bentonite chitosan composite microspheres.
In the step a, the dosage of the bentonite is 0.75-10.5g, the volume concentration of the acetic acid solution is 1-5%, the rotation speed of the mechanical stirring is 800-1200r/min, and the stirring time is 30-60 min.
In the step b, the chitosan is 1.5g, the deacetylation degree is 80-95%, the rotation speed of mechanical stirring is 800-.
In said step c, Fe3+/Fe2+Fe in the mixed solution3+And Fe2+The molar ratio of (1 to 2), the rotation speed of mechanical stirring is 800-1200r/min, and the stirring time is 30-60 min.
In the step d, the concentration of the sodium hydroxide in the mixed solution is 0.75-1.5mol/L, and the concentration of the sodium citrate in the mixed solution is 0.05-0.2 mol/L.
In the step e, the rotating speed of the peristaltic pump is 0.1-1.5r/min, and the soaking and crosslinking time is 10-18 h.
In the step g, the freeze drying time of the microspheres is 25-32 h.
The principle of the invention is as follows:
the bentonite is doped into the magnetic chitosan microspheres, although the bentonite can keep magnetism and is easy to recover, a substance which has no adsorption effect or poor effect on cesium ions is doped into the magnetic chitosan microspheres, and the adsorption effect of unit mass adsorption can be reduced3+/Fe2+The addition amount, the addition sequence and the reaction time of the solution enable the finally prepared material to form a net structure, increase the specific surface area, provide more available adsorption sites for cesium ions, ensure that the material has larger adsorption capacity for the cesium ions, can enable the cesium ions to have magnetism and is easy to recover.
The beneficial effects of the invention are mainly shown in the following aspects:
the invention relates to a magnetic porous bentonite-chitosan composite microsphere which is prepared from 1-10 parts of bentonite, 1-5 parts of acetic acid, 1-3 parts of chitosan, 1-6 parts of ferric chloride hexahydrate, 1-3 parts of ferrous chloride tetrahydrate, 10-15 parts of sodium hydroxide, 5-10 parts of sodium citrate and 250 parts of water 200, and is prepared from the specific components and a proportion, is an excellent load material, has a porous structure, high adsorption rate, large adsorption capacity, insensitivity to pH and wide application range; and the magnetic field can be gathered by the external magnetic field, so that the solid-liquid separation is easy and the recovery is convenient.
Secondly, in the invention, a, bentonite is dissolved in acetic acid solution and is fully mixed by mechanical stirring; b. b, dissolving chitosan in the solution obtained in the step a, and mechanically stirring and fully mixing; c. mixing Fe3+/Fe2+B, adding the mixed solution into the solution obtained in the step b, and mechanically stirring and fully mixing; d. preparing a mixed solution of sodium citrate and sodium hydroxide; e. c, dripping the mixed solution obtained in the step c into the solution obtained in the step d by using a peristaltic pump, and soaking and crosslinking to obtain microspheres; f. after the crosslinking is finished, a magnetic field is added for separation, and the microspheres are washed by deionized water; g. and f, freeze-drying the microspheres obtained in the step f to obtain the magnetic porous bentonite chitosan composite microspheres. In step c, Fe3+/Fe2+Dissolving the mixed solution in bentonite-chitosan solution, mechanically stirring and fully mixing,can ensure that the chitosan can fully adsorb Fe3+/Fe2+(ii) a In step e, Fe3+/Fe2+Magnetic ferroferric oxide is generated under the alkaline condition, and a magnetic medium is introduced, so that the subsequently prepared adsorbing material is convenient to recycle; the acid resistance of the adsorbing material prepared in the subsequent step can be enhanced by crosslinking in a sodium citrate solution, so that the applicability under any environment is facilitated; step g, freeze drying is adopted in the drying process, the moisture in the sample can be directly sublimated from ice under the condition of low temperature and high vacuum to achieve the drying purpose, the sample is not influenced by the action of surface tension in the drying process, the sample is not deformed, and the dried material can keep the original porous structure; the magnetic porous bentonite chitosan composite microspheres prepared by the steps a-g have uniform porous structures and magnetism, can increase the adsorption capacity, can load other substances on the structures, and have good expansibility and research prospect; the adsorption material has excellent adsorption performance on cesium ions in wastewater, high adsorption rate, large adsorption capacity, insensitivity to pH (potential of hydrogen), and wide application range; the magnetic field can be gathered by the aid of an external magnetic field, solid-liquid separation is easy, and recovery is convenient; compared with Chinese patent documents with the publication number of CN104307489A and the publication number of 2015, 01, 28, the preparation process does not need heating and sieving the complex processes, can be realized only by simple dosage dissolution, does not need to consume extra energy, and is easier to prepare; compared with the Chinese patent document with publication number CN101475187 and publication date 2009, 07/08, the preparation process is simpler, the operation is simple and the time is short.
In the step a, the using amount of bentonite is 0.75-10.5g, the volume concentration of an acetic acid solution is 1-5%, the rotation speed of mechanical stirring is 800-1200r/min, the stirring time is 30-60min, when the using amount of the bentonite is too small, the adsorption performance of an adsorption material on cesium ions is poor, when the using amount of the bentonite is too large, the magnetism of the adsorption material is not obvious, and when the using amount of the bentonite is controlled to be 0.75-10.5g, the adsorption material has both good adsorption capacity and obvious magnetism on the cesium ions; the chitosan is insoluble in water and soluble in acid, and when the concentration of acetic acid is too low, the solubility of chitosan is not high, and the volume concentration is 1-5%The acetic acid solution can not only control the production cost, but also ensure the solubility of the chitosan; when the mechanical stirring rotating speed is too low, the chitosan and the Fe3+/Fe2+Insufficient contact results in chitosan to Fe3+/Fe2+Coordination is reduced, and the performance of the adsorbing material is influenced; chitosan is a long-chain polymer, and once the rotating speed is too high, chitosan chains are broken possibly, so that the product quality is influenced, and the resource waste is caused; through numerous experiments, the magnetic stirring rotating speed is controlled to 800-1600r/min, so that the integrity of chitosan chains can be ensured, and the chitosan can sufficiently react with Fe3+/Fe2+Coordination, a good balance is achieved, and the performance of the final adsorbing material can be further ensured; stirring for 30-60min, and shortening chitosan to Fe3+/Fe2+The adsorption saturation can not be reached, and the excessive time can result in the deepening of the protonation degree of amino groups in chitosan molecules and influence on Fe3+/Fe2+The adsorption performance of the chitosan is specifically controlled to be 30-60min, the protonation degree of amino groups in chitosan molecules can be reduced, and the chitosan can react with Fe3+/Fe2+And (4) fully adsorbing.
Fourthly, in the invention, in the step b, the chitosan is 1.5g, the deacetylation degree is 80-95%, the rotation speed of mechanical stirring is 800-1200r/min, the stirring time is 30-60min, the higher the deacetylation degree is, the higher the amino content in chitosan molecules is, the more active sites are, the more Fe is favored3+/Fe2+The coordination is carried out by adopting 80-95% deacetylation degree, so that the production cost can be controlled, and the Fe can be ensured3+/Fe2+Effective coordination of (2).
Fifthly, in the invention, in step c, Fe3+/Fe2+Fe in the mixed solution3+And Fe2+The molar ratio of (1 to 2), the rotation speed of mechanical stirring is 800-1200r/min, the stirring time is 30-60min, and Fe3+And Fe2+When the molar ratio of the magnetic iron to the adsorbent is 2:1, magnetic ferroferric oxide can be generated, so that the subsequently prepared adsorbent has magnetism and is convenient to recover.
Sixthly, in the invention, in the step d, the concentration of the sodium hydroxide in the mixed solution is 075-1.5mol/L, 0.05-0.2mol/L sodium citrate concentration, Fe3+/Fe2+Under the alkaline condition, ferroferric oxide can be generated, the concentration of a sodium hydroxide solution is too low, the amount of generated ferroferric oxide is small, the magnetism of an adsorption material is not obvious, and when the concentration of sodium hydroxide is 0.75-1.5mol/L, the production cost can be controlled, and the magnetism of the adsorption material can be ensured; when the concentration of the sodium citrate is too low, the crosslinking effect is poor, the stability of the adsorbing material is poor, and the concentration of the sodium citrate is 0.05-0.2mol/L, so that the production cost can be controlled, and the stability of the adsorbing material can be guaranteed.
Seventhly, in the step e, the rotating speed of a peristaltic pump is 0.1-1.5r/min, the soaking and crosslinking time is 10-18h, and when the rotating speed of the peristaltic pump is too high, the adsorbing material is difficult to be spherical; when the cross-linking soaking time is too short, the stability of the adsorbing material is poor, and when the cross-linking soaking time is too long, the subsequent steps are not easy to clean.
Eighthly, in the step g, the freeze drying time of the microspheres is 25-32h, the freeze drying time is too short, the moisture in the adsorption material cannot be completely removed, and the freeze drying time is 25-32h, so that the production cost can be controlled, and the moisture in the adsorption material can be completely removed.
Drawings
The invention will be further described in detail with reference to the drawings and the detailed description, wherein:
FIG. 1 is an external scanning electron microscope image of the magnetic porous bentonite chitosan composite microsphere of the invention;
FIG. 2 is a scanning electron microscope image of a vertical section of the magnetic porous bentonite chitosan composite microsphere of the present invention;
FIG. 3 is a scanning electron microscope image of a horizontal section of the magnetic porous bentonite chitosan composite microsphere of the present invention;
FIG. 4 is a schematic diagram of the magnetic porous bentonite chitosan composite microsphere of the present invention after magnetic separation;
FIG. 5 is a hysteresis loop diagram of the magnetic porous bentonite chitosan composite microsphere of the present invention;
FIG. 6 is a Fourier infrared spectrum of the magnetic porous bentonite chitosan composite microsphere of the present invention;
FIG. 7 is an X-ray photoelectron spectroscopy analysis chart of the magnetic porous bentonite-chitosan composite microsphere before and after adsorption of cesium ions;
FIG. 8 is a graph showing cesium ion removal rates at different times for the magnetic porous bentonite chitosan composite microspheres of the present invention;
FIG. 9 is a comparison of the adsorbability of the magnetic porous bentonite chitosan composite microspheres of the present invention with bentonite adsorption material and magnetic porous chitosan microspheres;
FIG. 10 is a bar graph of adsorption rates of magnetic porous bentonite chitosan composite microspheres to cesium ions under different pH conditions;
wherein: a is a chitosan adsorption material, b is a chitosan-bentonite adsorption material, c is a magnetic porous bentonite-chitosan composite microsphere, d is the magnetic porous bentonite-chitosan composite microsphere after adsorbing cesium ions, Bn-CS is the magnetic porous bentonite-chitosan composite microsphere, Bn is the bentonite adsorption material, and CS is the magnetic porous chitosan microsphere.
Detailed Description
Example 1
The magnetic porous bentonite chitosan composite microsphere is prepared from the following raw materials in parts by weight: 1 part of bentonite, 1 part of acetic acid, 1 part of chitosan, 1 part of ferric chloride hexahydrate, 1 part of ferrous chloride tetrahydrate, 10 parts of sodium hydroxide, 5 parts of sodium citrate and 200 parts of water.
Example 2
The magnetic porous bentonite chitosan composite microsphere is prepared from the following raw materials in parts by weight: 5 parts of bentonite, 3 parts of acetic acid, 3 parts of chitosan, 3 parts of ferric chloride hexahydrate, 2 parts of ferrous chloride tetrahydrate, 12 parts of sodium hydroxide, 8 parts of sodium citrate and 220 parts of water.
Example 3
The magnetic porous bentonite chitosan composite microsphere is prepared from the following raw materials in parts by weight: 10 parts of bentonite, 5 parts of acetic acid, 3 parts of chitosan, 6 parts of ferric chloride hexahydrate, 3 parts of ferrous chloride tetrahydrate, 15 parts of sodium hydroxide, 10 parts of sodium citrate and 250 parts of water.
Example 4
A preparation method of magnetic porous bentonite chitosan composite microspheres comprises the following steps:
a. dissolving bentonite in acetic acid solution, and mechanically stirring and fully mixing;
b. b, dissolving chitosan in the solution obtained in the step a, and mechanically stirring and fully mixing;
c. mixing Fe3+/Fe2+B, adding the mixed solution into the solution obtained in the step b, and mechanically stirring and fully mixing;
d. preparing a mixed solution of sodium citrate and sodium hydroxide;
e. c, dripping the mixed solution obtained in the step c into the solution obtained in the step d by using a peristaltic pump, and soaking and crosslinking to obtain microspheres;
f. after the crosslinking is finished, a magnetic field is added for separation, and the microspheres are washed by deionized water;
g. and f, freeze-drying the microspheres obtained in the step f to obtain the magnetic porous bentonite chitosan composite microspheres.
A, dissolving bentonite in an acetic acid solution, and fully mixing by mechanical stirring; b. b, dissolving chitosan in the solution obtained in the step a, and mechanically stirring and fully mixing; c. mixing Fe3+/Fe2+B, adding the mixed solution into the solution obtained in the step b, and mechanically stirring and fully mixing; d. preparing a mixed solution of sodium citrate and sodium hydroxide; e. c, dripping the mixed solution obtained in the step c into the solution obtained in the step d by using a peristaltic pump, and soaking and crosslinking to obtain microspheres; f. after the crosslinking is finished, a magnetic field is added for separation, and the microspheres are washed by deionized water; g. and f, freeze-drying the microspheres obtained in the step f to obtain the magnetic porous bentonite chitosan composite microspheres. In step c, Fe3+/Fe2+The mixed solution is dissolved in the bentonite-chitosan solution, and is fully mixed by mechanical stirring, so that the chitosan can be ensured to fully adsorb Fe3+/Fe2+(ii) a In step e, Fe3+/Fe2+Magnetic ferroferric oxide is generated under the alkaline condition, and a magnetic medium is introduced, so that the subsequently prepared adsorbing material is convenient to recycle; the acid resistance of the adsorbing material prepared in the subsequent step can be enhanced by crosslinking in a sodium citrate solution, so that the applicability under any environment is facilitated; in step g, driedIn the process, freeze drying is adopted, so that the moisture in the sample can be directly sublimated from ice under the condition of low temperature and high vacuum to achieve the purpose of drying, the sample is not deformed under the action of surface tension in the drying process, and the dried material can keep the original porous structure; the magnetic porous bentonite chitosan composite microspheres prepared by the steps a-g have uniform porous structures and magnetism, can increase the adsorption capacity, can load other substances on the structures, and have good expansibility and research prospect; the adsorption material has excellent adsorption performance on cesium ions in wastewater, high adsorption rate, large adsorption capacity, insensitivity to pH (potential of hydrogen), and wide application range; the magnetic field can be gathered by the aid of an external magnetic field, solid-liquid separation is easy, and recovery is convenient; compared with Chinese patent documents with the publication number of CN104307489A and the publication number of 2015, 01, 28, the preparation process does not need heating and sieving the complex processes, can be realized only by simple dosage dissolution, does not need to consume extra energy, and is easier to prepare; compared with the Chinese patent document with publication number CN101475187 and publication date 2009, 07/08, the preparation process is simpler, the operation is simple and the time is short.
Example 5
A preparation method of magnetic porous bentonite chitosan composite microspheres comprises the following steps:
a. dissolving bentonite in acetic acid solution, and mechanically stirring and fully mixing;
b. b, dissolving chitosan in the solution obtained in the step a, and mechanically stirring and fully mixing;
c. mixing Fe3+/Fe2+B, adding the mixed solution into the solution obtained in the step b, and mechanically stirring and fully mixing;
d. preparing a mixed solution of sodium citrate and sodium hydroxide;
e. c, dripping the mixed solution obtained in the step c into the solution obtained in the step d by using a peristaltic pump, and soaking and crosslinking to obtain microspheres;
f. after the crosslinking is finished, a magnetic field is added for separation, and the microspheres are washed by deionized water;
g. and f, freeze-drying the microspheres obtained in the step f to obtain the magnetic porous bentonite chitosan composite microspheres.
In the step a, the using amount of the bentonite is 0.75g, the volume concentration of the acetic acid solution is 1%, the rotating speed of mechanical stirring is 800r/min, and the stirring time is 30 min.
In the step b, the chitosan is 1.5g, the deacetylation degree is 80%, the rotation speed of mechanical stirring is 800r/min, and the stirring time is 30 min.
In said step c, Fe3+/Fe2+Fe in the mixed solution3+And Fe2+The molar ratio of (A) to (B) is 2:1, the rotation speed of mechanical stirring is 800r/min, and the stirring time is 30 min.
In the step d, the concentration of the sodium hydroxide in the mixed solution is 0.75mol/L, and the concentration of the sodium citrate in the mixed solution is 0.05 mol/L.
In the step e, the rotating speed of the peristaltic pump is 0.1r/min, and the soaking and crosslinking time is 10 hours.
In the step g, the freeze drying time of the microspheres is 25 h.
Example 6
A preparation method of magnetic porous bentonite chitosan composite microspheres comprises the following steps:
a. dissolving bentonite in acetic acid solution, and mechanically stirring and fully mixing;
b. b, dissolving chitosan in the solution obtained in the step a, and mechanically stirring and fully mixing;
c. mixing Fe3+/Fe2+B, adding the mixed solution into the solution obtained in the step b, and mechanically stirring and fully mixing;
d. preparing a mixed solution of sodium citrate and sodium hydroxide;
e. c, dripping the mixed solution obtained in the step c into the solution obtained in the step d by using a peristaltic pump, and soaking and crosslinking to obtain microspheres;
f. after the crosslinking is finished, a magnetic field is added for separation, and the microspheres are washed by deionized water;
g. and f, freeze-drying the microspheres obtained in the step f to obtain the magnetic porous bentonite chitosan composite microspheres.
In the step a, the using amount of the bentonite is 2.5g, the volume concentration of the acetic acid solution is 2%, the rotating speed of mechanical stirring is 900r/min, and the stirring time is 40 min.
In the step b, the chitosan is 1.5g, the deacetylation degree is 90%, the rotation speed of mechanical stirring is 900r/min, and the stirring time is 40 min.
In said step c, Fe3+/Fe2+Fe in the mixed solution3+And Fe2+The molar ratio of (A) to (B) is 2:1, the rotation speed of mechanical stirring is 900r/min, and the stirring time is 40 min.
In the step d, the concentration of the sodium hydroxide in the mixed solution is 0.95mol/L, and the concentration of the sodium citrate in the mixed solution is 0.08 mol/L.
In the step e, the rotating speed of the peristaltic pump is 0.6r/min, and the soaking and crosslinking time is 12 hours.
In the step g, the freeze drying time of the microspheres is 28 h.
Example 7
A preparation method of magnetic porous bentonite chitosan composite microspheres comprises the following steps:
a. dissolving bentonite in acetic acid solution, and mechanically stirring and fully mixing;
b. b, dissolving chitosan in the solution obtained in the step a, and mechanically stirring and fully mixing;
c. mixing Fe3+/Fe2+B, adding the mixed solution into the solution obtained in the step b, and mechanically stirring and fully mixing;
d. preparing a mixed solution of sodium citrate and sodium hydroxide;
e. c, dripping the mixed solution obtained in the step c into the solution obtained in the step d by using a peristaltic pump, and soaking and crosslinking to obtain microspheres;
f. after the crosslinking is finished, a magnetic field is added for separation, and the microspheres are washed by deionized water;
g. and f, freeze-drying the microspheres obtained in the step f to obtain the magnetic porous bentonite chitosan composite microspheres.
In the step a, the using amount of the bentonite is 5g, the volume concentration of the acetic acid solution is 3%, the rotating speed of mechanical stirring is 1000r/min, and the stirring time is 50 min.
In the step b, the chitosan is 1.5g, the deacetylation degree is 92%, the rotation speed of mechanical stirring is 1000r/min, and the stirring time is 50 min.
In said step c, Fe3+/Fe2+Fe in the mixed solution3+And Fe2+The molar ratio of (A) to (B) is 2:1, the rotation speed of mechanical stirring is 1000r/min, and the stirring time is 50 min.
In the step d, the concentration of sodium hydroxide in the mixed solution is 1.2mol/L, and the concentration of sodium citrate in the mixed solution is 0.1 mol/L.
In the step e, the rotating speed of the peristaltic pump is 1r/min, and the soaking and crosslinking time is 15 hours.
In the step g, the freeze drying time of the microspheres is 30 h.
Example 8
A preparation method of magnetic porous bentonite chitosan composite microspheres comprises the following steps:
a. dissolving bentonite in acetic acid solution, and mechanically stirring and fully mixing;
b. b, dissolving chitosan in the solution obtained in the step a, and mechanically stirring and fully mixing;
c. mixing Fe3+/Fe2+B, adding the mixed solution into the solution obtained in the step b, and mechanically stirring and fully mixing;
d. preparing a mixed solution of sodium citrate and sodium hydroxide;
e. c, dripping the mixed solution obtained in the step c into the solution obtained in the step d by using a peristaltic pump, and soaking and crosslinking to obtain microspheres;
f. after the crosslinking is finished, a magnetic field is added for separation, and the microspheres are washed by deionized water;
g. and f, freeze-drying the microspheres obtained in the step f to obtain the magnetic porous bentonite chitosan composite microspheres.
In the step a, the using amount of the bentonite is 8.5g, the volume concentration of the acetic acid solution is 4%, the rotating speed of mechanical stirring is 1100r/min, and the stirring time is 55 min.
In the step b, the chitosan is 1.5g, the deacetylation degree is 93%, the rotation speed of mechanical stirring is 1100r/min, and the stirring time is 55 min.
In said step c, Fe3+/Fe2+Fe in the mixed solution3+And Fe2+The molar ratio of (A) to (B) is 2:1, the rotation speed of mechanical stirring is 1100r/min, and the stirring time is 55 min.
In the step d, the concentration of sodium hydroxide in the mixed solution is 1.3mol/L, and the concentration of sodium citrate in the mixed solution is 0.15 mol/L.
In the step e, the rotating speed of a peristaltic pump is 1.2r/min, and the soaking and crosslinking time is 16 h.
In the step g, the freeze drying time of the microspheres is 31 h.
Example 9
A preparation method of magnetic porous bentonite chitosan composite microspheres comprises the following steps:
a. dissolving bentonite in acetic acid solution, and mechanically stirring and fully mixing;
b. b, dissolving chitosan in the solution obtained in the step a, and mechanically stirring and fully mixing;
c. mixing Fe3+/Fe2+B, adding the mixed solution into the solution obtained in the step b, and mechanically stirring and fully mixing;
d. preparing a mixed solution of sodium citrate and sodium hydroxide;
e. c, dripping the mixed solution obtained in the step c into the solution obtained in the step d by using a peristaltic pump, and soaking and crosslinking to obtain microspheres;
f. after the crosslinking is finished, a magnetic field is added for separation, and the microspheres are washed by deionized water;
g. and f, freeze-drying the microspheres obtained in the step f to obtain the magnetic porous bentonite chitosan composite microspheres.
In the step a, the using amount of the bentonite is 10.5g, the volume concentration of the acetic acid solution is 5%, the rotating speed of mechanical stirring is 1200r/min, and the stirring time is 60 min.
In the step b, the chitosan is 1.5g, the deacetylation degree is 95%, the rotation speed of mechanical stirring is 1200r/min, and the stirring time is 60 min.
In said step c, Fe3+/Fe2+Fe in the mixed solution3+And Fe2+The molar ratio of (A) to (B) is 2:1, the rotation speed of mechanical stirring is 1200r/min, and the stirring time is 60 min.
In the step d, the concentration of sodium hydroxide in the mixed solution is 1.5mol/L, and the concentration of sodium citrate in the mixed solution is 0.2 mol/L.
In the step e, the rotating speed of the peristaltic pump is 1.5r/min, and the soaking and crosslinking time is 18 hours.
In the step g, the freeze drying time of the microspheres is 32 h.
The following description of the comparison of the adsorption of the bentonite adsorption material and the magnetic porous chitosan microspheres with the magnetic porous bentonite chitosan composite microspheres prepared by the invention through specific experiments:
0.1g of magnetic porous bentonite chitosan composite microspheres, bentonite adsorbing materials and magnetic porous chitosan microspheres are respectively added into 20mL of cesium ion solutions with initial concentrations of 50mg/L, 100mg/L, 200mg/L, 300mg/L,/400 mg/L and 500mg/L, the cesium ion solutions are vibrated at room temperature for 12 hours at 120r/min, the magnetic porous bentonite chitosan composite microspheres, the bentonite adsorbing materials and the magnetic porous chitosan microspheres are centrifugally separated, and the cesium ion concentrations in the solutions are measured by a flame atomic absorption spectrophotometry, which is shown in figure 9.
From fig. 9, it can be seen that when the cesium ion concentration is between 50mg/L and 500mg/L, the cesium ion removal rate of the magnetic porous bentonite chitosan composite microspheres is higher than that of the bentonite adsorption material and the magnetic porous chitosan microspheres, which indicates that the magnetic porous bentonite chitosan composite microspheres prepared by the present invention have good adsorption performance.
The experiment on the pH adaptability of the magnetic porous bentonite chitosan composite microsphere is as follows:
0.1g of magnetic porous bentonite chitosan composite microspheres are added into 20mL of cesium ion solution with the initial concentration of 200mg/L and the pH values of 3.5, 4.4, 5.3, 7, 8.5 and 9.8 respectively, the cesium ion solution is vibrated at room temperature for 12h at 120r/min, magnetic separation is carried out, and the cesium ion concentration in the solution is measured by a flame atomic absorption spectrophotometry, which is shown in figure 10.
As can be seen from fig. 10, the removal rate of cesium ions by using the magnetic porous bentonite chitosan composite microspheres can reach over 90% under acidic and alkaline conditions, and the magnetic porous bentonite chitosan composite microspheres have good pH adaptability.
Experiments on the adsorption capacity of the magnetic porous bentonite chitosan composite microspheres, the bentonite adsorption material and the magnetic porous chitosan microspheres to cesium ions are as follows:
0.1g of magnetic porous bentonite chitosan composite microspheres, bentonite adsorption materials and magnetic porous chitosan microspheres are respectively taken and added into 20mL of cesium ion solutions with initial concentrations of 50, 100, 200, 300, 400 and 500mg/L, the cesium ion solutions are vibrated at room temperature of 120r/min until adsorption balance is achieved, magnetic separation is carried out, the cesium ion concentrations in the solutions are measured by a flame atomic absorption spectrophotometry, and isothermal lines of Langmuir and Freund adsorption are fitted to obtain fitting parameters, which are shown in Table 1.
Figure BDA0001604122150000101
Figure BDA0001604122150000111
TABLE 1
As can be seen from table 1, the adsorption capacity of the magnetic porous bentonite chitosan composite microsphere to cesium ions is higher than that of a bentonite adsorption material, much higher than that of the magnetic porous chitosan microsphere, and higher than the superposed adsorption capacity of the magnetic porous bentonite chitosan composite microsphere and the magnetic porous bentonite chitosan microsphere, which indicates that the adsorption capacity of the magnetic porous bentonite chitosan composite microsphere prepared by the invention to cesium ions is greatly improved.
The present invention is compared with the prior art represented by the Chinese patent documents listed in the background art as follows:
table 2 is a comparison table of adsorption equilibrium time for different materials.
Table 3 is a comparative table of different material preparation steps.
Table 4 is a comparative table of different material separation methods.
Figure BDA0001604122150000112
TABLE 2
As can be seen from Table 2, the magnetic porous bentonite chitosan composite microsphere of the invention reaches adsorption equilibrium in about 8 hours; CN04307489A reached adsorption equilibrium for about 14 hours; CN101475187 reached adsorption equilibrium in about 16 hours, indicating that the adsorption rate of the material of the invention is faster.
Figure BDA0001604122150000113
TABLE 3
As can be seen from Table 3, the preparation method of the invention does not need grinding and heating steps, and the dissolution time is within 1h, compared with CN104307489A and CN101475187, the preparation method of the invention has the characteristics of simple preparation conditions, low energy consumption and high speed.
Figure BDA0001604122150000114
Figure BDA0001604122150000121
TABLE 4
As can be seen from Table 4, the present invention can separate the material from the sewage by magnetic technology, and has the characteristics of easy recovery and reuse and environmental protection.

Claims (2)

1. A preparation method of magnetic porous bentonite chitosan composite microspheres is characterized by comprising the following steps:
a. dissolving bentonite in acetic acid solution, and mechanically stirring and fully mixing;
b. b, dissolving chitosan in the solution obtained in the step a, and mechanically stirring and fully mixing;
c. mixing Fe3+/Fe2+B, adding the mixed solution into the solution obtained in the step b, and mechanically stirring and fully mixing;
d. preparing a mixed solution of sodium citrate and sodium hydroxide;
e. c, dripping the mixed solution obtained in the step c into the solution obtained in the step d by using a peristaltic pump, and soaking and crosslinking to obtain microspheres;
f. after the crosslinking is finished, a magnetic field is added for separation, and the microspheres are washed by deionized water;
g. f, freeze-drying the microspheres obtained in the step f to obtain magnetic porous bentonite chitosan composite microspheres;
in the step a, the using amount of the bentonite is 0.75-10.5g, the volume concentration of the acetic acid solution is 1-5%, the rotating speed of mechanical stirring is 800-;
in the step b, the chitosan is 1.5g, the deacetylation degree is 80-95%, the rotation speed of mechanical stirring is 800-;
in said step c, Fe3+/Fe2+Fe in the mixed solution3+And Fe2+The molar ratio of (1 to 2), the rotation speed of mechanical stirring is 800-;
in the step d, the concentration of sodium hydroxide in the mixed solution is 0.75-1.5mol/L, and the concentration of sodium citrate is 0.05-0.2 mol/L;
in the step e, the rotating speed of the peristaltic pump is 0.1-1.5r/min, and the soaking and crosslinking time is 10-18 h.
2. The preparation method of the magnetic porous bentonite chitosan composite microsphere as claimed in claim 1, which is characterized in that: in the step g, the freeze drying time of the microspheres is 25-32 h.
CN201810236507.5A 2018-03-21 2018-03-21 Magnetic porous bentonite chitosan composite microsphere and preparation method thereof Active CN108355621B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810236507.5A CN108355621B (en) 2018-03-21 2018-03-21 Magnetic porous bentonite chitosan composite microsphere and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810236507.5A CN108355621B (en) 2018-03-21 2018-03-21 Magnetic porous bentonite chitosan composite microsphere and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108355621A CN108355621A (en) 2018-08-03
CN108355621B true CN108355621B (en) 2022-04-01

Family

ID=63001267

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810236507.5A Active CN108355621B (en) 2018-03-21 2018-03-21 Magnetic porous bentonite chitosan composite microsphere and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108355621B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109894097A (en) * 2019-04-09 2019-06-18 合肥工业大学 A kind of method of tetracycline antibiotics in removal water body
CN114130367A (en) * 2021-11-29 2022-03-04 北京师范大学 Magnetic adsorption material for cleaning and decontaminating radioactive contaminated soil
CN115254044B (en) * 2022-04-29 2024-02-06 湖州师范学院 Preparation method of magnetic bentonite gelatin composite microsphere for removing Cu ions in water bottom mud
CN115231789A (en) * 2022-08-17 2022-10-25 东南大学 Preparation method of printing and dyeing biochemical sludge composite dehydrating agent

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040041473A (en) * 2002-11-11 2004-05-17 서희동 Manufacturing method of magnetic minerals
CN102580690A (en) * 2012-03-06 2012-07-18 杭州师范大学 Nano-aperture granular adsorbent and preparation and application thereof
CN103920472A (en) * 2014-04-11 2014-07-16 江苏大学 Preparation method of magnetic chitosan composite microsphere adsorbent
CN104307489A (en) * 2014-10-17 2015-01-28 陕西华陆化工环保有限公司 Preparation method of bentonite loaded chitosan composite adsorbent
CN106582561A (en) * 2017-03-03 2017-04-26 成都理工大学 Preparation method and application of magnetic chitosan adsorption material
CN107282013A (en) * 2016-04-01 2017-10-24 成都理工大学 The porous magnetic chitosan gel rubber microballoon and preparation method of a kind of size tunable

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040041473A (en) * 2002-11-11 2004-05-17 서희동 Manufacturing method of magnetic minerals
CN102580690A (en) * 2012-03-06 2012-07-18 杭州师范大学 Nano-aperture granular adsorbent and preparation and application thereof
CN103920472A (en) * 2014-04-11 2014-07-16 江苏大学 Preparation method of magnetic chitosan composite microsphere adsorbent
CN104307489A (en) * 2014-10-17 2015-01-28 陕西华陆化工环保有限公司 Preparation method of bentonite loaded chitosan composite adsorbent
CN107282013A (en) * 2016-04-01 2017-10-24 成都理工大学 The porous magnetic chitosan gel rubber microballoon and preparation method of a kind of size tunable
CN106582561A (en) * 2017-03-03 2017-04-26 成都理工大学 Preparation method and application of magnetic chitosan adsorption material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Facile solvothermal synthesis of Fe3O4/bentonite for efficient removal of heavy metals from aqueous solution";Liangguo Yan等;《Powder Technology》;20160702;第301卷;第632-640页 *
"The highly effective removal of Cs+ by low turbidity chitosan-grafted magnetic bentonite";Shubin Yang等;《Journal of Hazardous Materials》;20150822;第201卷;第8-16页 *
"磁性壳聚糖硅胶复合微球的制备及其吸附Cu2+的性能研究";吕浩永等;《分析科学学报》;20160630;第32卷(第3期);第309-314页 *

Also Published As

Publication number Publication date
CN108355621A (en) 2018-08-03

Similar Documents

Publication Publication Date Title
CN108355621B (en) Magnetic porous bentonite chitosan composite microsphere and preparation method thereof
Zhou et al. Cellulose/chitin beads for adsorption of heavy metals in aqueous solution
Cadogan et al. Facile synthesis of chitosan derivatives and Arthrobacter sp. biomass for the removal of europium (III) ions from aqueous solution through biosorption
CN109621910A (en) Nano zero valence iron-metal organic frame core-shell material preparation method and applications
CN108514870B (en) Hydrotalcite-poly (m-phenylenediamine) composite material and preparation method and application thereof
CN106582561A (en) Preparation method and application of magnetic chitosan adsorption material
KR101531231B1 (en) Microalgae bead, and preparing method of the same
CN111686703A (en) Remove aquatic Cs+Composite microcapsule adsorbent and preparation method thereof
Ma et al. Efficient removal of U (VI) in acidic environment with spent coffee grounds derived hydrogel
CN113058554A (en) Activated carbon prepared from natural rubber seed shells and preparation method and application thereof
JP2016040032A (en) Adsorbent comprising cellulose derivative and/or cross-linked chitosan derivative and adsorption method and recovery method for metal ion
CN113600133A (en) Phosphorus removal adsorbent and preparation method and application thereof
CN105664864A (en) Preparation method and application of vascular plant based porous oxidative polymerization chelating adsorption material
CN113209942A (en) Cellulose-based heavy metal composite adsorption material and preparation method thereof
CN115779847B (en) In-situ adsorption material and preparation method and application thereof
CN108428486B (en) Cesium ion removal method based on bentonite chitosan composite microspheres
CN113351187B (en) Heavy metal ion imprinted hydrogel ball and preparation method and application thereof
CN113952940B (en) Preparation method of surface imprinting microsphere adsorption material for selectively removing Sb ions
Jain et al. Sesame (Sesamum indicum) oil cake—Industrial waste biomass for sequestration of Basic Blue 26 from aqueous media
CN104069838A (en) Magnetic polybenzimidazole molecular imprinted adsorbing agent, preparation and use thereof
CN109735713B (en) Method for adsorbing and separating indium by using metal organic framework material UiO-66
CN113559829A (en) Preparation method and application of uranium/lithium synchronous adsorption material
CN113371708A (en) Method for preparing semicoke-based activated carbon by ball milling assisted organic fermentation technology
CN115228448A (en) Preparation and application of chitosan-based high-molecular polymer adsorbent
CN115634670B (en) PEI modified sodium alginate loaded clay mineral gel microsphere 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
GR01 Patent grant
GR01 Patent grant