CN110813259B - Antibacterial multifunctional heavy metal ion adsorption membrane and preparation method of heavy metal ion imprinting composite membrane - Google Patents
Antibacterial multifunctional heavy metal ion adsorption membrane and preparation method of heavy metal ion imprinting composite membrane Download PDFInfo
- Publication number
- CN110813259B CN110813259B CN201911125850.3A CN201911125850A CN110813259B CN 110813259 B CN110813259 B CN 110813259B CN 201911125850 A CN201911125850 A CN 201911125850A CN 110813259 B CN110813259 B CN 110813259B
- Authority
- CN
- China
- Prior art keywords
- percent
- heavy metal
- polyvinyl alcohol
- adsorption
- metal ion
- 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
-
- 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
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention researches and develops a preparation method of an antibacterial multifunctional heavy metal ion adsorption membrane and a preparation method of a heavy metal ion imprinting composite membrane. The method comprises the following steps: the method comprises the following steps: mixing and dissolving the adsorbent, the fixing agent, the pore-increasing agent and the like according to a certain proportion at high temperature. Step two: naturally cooling the mixed solution to below 70 ℃, adding glutaraldehyde, and shaking for 10-24 hours; step three: pouring the vibrated mixed solution into a film-making die, and naturally drying in the air; step four: taking out the adsorption film, and adding CaCl with concentration 2 1 to 5 percent of boric acid and 2 to 5 percent of boric acid for 24 hours; step five: cleaning the formed adsorption film with deionized water, adding into 3-carboxymethyl rhodanine with the concentration of 5g/L-6g/L, shaking for 24 hours at 70 ℃, taking out, washing with water and drying. The adsorption film disclosed by the invention can quickly, comprehensively or specifically identify heavy metal ions, is antibacterial, has good corrosion resistance and swelling resistance, and does not cause secondary pollution to a water body.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to an antibacterial multifunctional heavy metal ion adsorption membrane and a preparation method of a heavy metal ion imprinting composite membrane.
Background
Industrial wastewater contains a large amount of heavy metal ions, and the heavy metal ions are difficult to degrade in natural environment and easy to enrich in organisms, so that the industrial wastewater becomes an environmental problem of global attention. Therefore, it is necessary to remove heavy metal ions from the sewage before discharging the sewage into the ecological environment. Nowadays, there are various methods for removing heavy metal ions, such as chemical deposition, electrolysis, solvent extraction, ion exchange, membrane separation, biological flocculation, and adsorption. Adsorption is considered to be a more efficient process due to its low cost and high efficiency. Common adsorbents include inorganic mineral adsorbents represented by activated carbon, zeolite and kaolin, natural polymeric adsorbents represented by cellulose, chitosan and cyclodextrin, and other novel adsorbents represented by ionic liquids and nano materials. The good adsorbent has the advantages of simple preparation process, large specific surface area, stable chemical property, strong reproducibility, good mechanical property and the like. Rhodanine and its derivatives have a variety of properties, such as antibacterial, anti-corrosive, etc. Meanwhile, 3 kinds of heteroatoms (N, O, S) which are regarded as adsorption centers in the molecular structure of the heavy metal ion adsorption material can share an electron pair with the heavy metal ion, so that the purpose of adsorbing the heavy metal is achieved. In the present invention, the toxic action of rhodanine on organisms is taken into account, and therefore, the derivative thereof is used for manufacturing the adsorption film. The existing heavy metal ion adsorption membrane mainly has three problems, one is that the toughness is not enough, and the secondary pollution of a water body can be caused by dissolution; secondly, the adsorption force is not enough, so that the heavy metal ions in the water body cannot be quickly adsorbed; and thirdly, the membrane blockage and damage caused by microorganism adhesion and corrosion cannot be prevented, so that the heavy metal adsorption efficiency is greatly reduced. At present, the three problems can be solved simultaneously by no film, so that the problem of excessive heavy metal in the water body by using an adsorption film technology is always solved, and the application is not ensured.
Disclosure of Invention
Aiming at the problems, the invention provides an antibacterial multifunctional heavy metal ion adsorption membrane and a preparation method of a heavy metal ion imprinting composite membrane on the basis of the prior art; the composite material not only ensures high-efficiency adsorption of heavy metal ions, has high strength and toughness and is not easy to swell or damage, but also has broad-spectrum antibacterial capability, prevents the problem of reduction of adsorption efficiency caused by membrane blockage and damage, and can also assist in improving water quality to a certain extent. The antibacterial multifunctional heavy metal adsorption film is very simple and convenient to manufacture and use, is convenient to use in various systems, and has good popularization.
In order to achieve the purpose, the invention develops a preparation method of an antibacterial multifunctional heavy metal ion adsorption film, which comprises the following steps:
the method comprises the following steps: adsorbing agent, fixing agent and pore-increasing agent: mixing and dissolving polyvinyl alcohol, polyvinyl alcohol-ethylene polymer, sodium alginate, active carbon and bentonite according to a certain proportion at a high temperature of 100-150 ℃; so that the final concentrations were: 6 to 10 percent of polyvinyl alcohol, 0.1 to 5 percent of polyvinyl alcohol-ethylene polymer, 3 to 10 percent of sodium alginate, 0.1 to 2 percent of active carbon and 1 to 10 percent of bentonite;
step two: naturally cooling the mixed solution in the step one to below 70 ℃, adding glutaraldehyde, and shaking for 10-24 hours;
step three: pouring the vibrated mixed solution into a film-making die, and naturally drying in the air;
step four: taking out the adsorption film in the third step, and adding CaCl with the concentration 2 1 to 5 percent of boric acid and 2 to 5 percent of boric acid for 24 hours;
step five: and (3) cleaning the adsorption film shaped in the fourth step with deionized water, then putting the adsorption film into 3-carboxymethyl rhodanine with the concentration of 5g/L-6g/L, shaking the adsorption film for 24 hours at 70 ℃, taking the adsorption film out, washing the adsorption film with water and drying the adsorption film.
Wherein, the bentonite is acidized by hydrochloric acid in advance, and the polyvinyl alcohol-ethylene polymer is treated by acetone;
in order to achieve the purpose, the preparation method of the heavy metal ion imprinting composite membrane comprises the following steps:
the method comprises the following steps: adsorbing agent, fixing agent and pore-increasing agent: mixing and dissolving polyvinyl alcohol, polyvinyl alcohol-ethylene polymer, sodium alginate, active carbon and bentonite according to a certain proportion at a high temperature of 100-150 ℃; so that the final concentrations were: 6 to 10 percent of polyvinyl alcohol, 0.1 to 5 percent of polyvinyl alcohol-ethylene polymer, 3 to 10 percent of sodium alginate, 0.1 to 2 percent of active carbon and 1 to 10 percent of bentonite, wherein the specific mixed concentration is determined according to the concentration of heavy metal ions contained in the sewage;
step two: naturally cooling the mixed solution in the step one to below 70 ℃, adding glutaraldehyde, and shaking for 10-24 hours;
step three: pouring the vibrated mixed solution into a film-making mould, and naturally drying in the air;
step four: taking out the adsorption film in the third step, and adding CaCl with the concentration 2 1 to 5 percent of boric acid and 2 to 5 percent of boric acid for 24 hours;
step five: adding required heavy metal ions to form imprints for modification;
step six: and (4) cleaning the adsorption film shaped in the fifth step with deionized water, then putting the adsorption film into 3-carboxymethyl rhodanine with the concentration of 5g/L-6g/L, shaking the adsorption film for 24 hours at 70 ℃, taking out the adsorption film, washing the adsorption film with water and drying the adsorption film.
Wherein, the bentonite is acidized by hydrochloric acid in advance, and the polyvinyl alcohol-ethylene polymer is treated by acetone;
in order to achieve the aim, the invention provides a multifunctional adsorbing material which comprises at least one layer of the heavy metal ion imprinting composite membrane prepared by the method. The heavy metal adsorption film has antibacterial capacity and high-efficiency capacity of adsorbing heavy metal ions in water, and the adsorption rate can reach 95% or more within 2 hours; meanwhile, the adsorption film can synchronously adsorb nutritive salt and partial organic matters in the water body.
The antibacterial multifunctional heavy metal ion adsorption membrane provided by the invention provides a multifunctional efficient heavy metal adsorption membrane form, and the adsorption membrane simultaneously solves the problem of purifying a heavy metal-rich water body by utilizing the membrane, realizes quick, comprehensive or specific identification of heavy metal ions, has good antibacterial, corrosion resistance and swelling resistance, does not cause secondary pollution of the water body, and is a heavy metal-rich water body treatment product with good market prospect.
Detailed Description
The invention is further described in the following with reference to the description.
Example 1
Mixing and dissolving polyvinyl alcohol, polyvinyl alcohol-ethylene polymer, sodium alginate, activated carbon and bentonite according to a certain proportion at a high temperature of 100-150 ℃; so that the final concentrations were: 6 to 10 percent of polyvinyl alcohol, 0.1 to 5 percent of polyvinyl alcohol-ethylene polymer, 3 to 10 percent of sodium alginate, 0.1 to 2 percent of active carbon and 1 to 10 percent of bentonite, and the specific mixed concentration is determined according to the concentration of heavy metal ions contained in the sewage. Wherein, the bentonite is required to be acidified by hydrochloric acid in advance, and the polyvinyl alcohol-ethylene polymer is required to be treated by acetone.
The well mixed solution is placed until T <70 ℃, glutaraldehyde is added, and shaking is carried out for 10-24 hours at 30 ℃ with the speed of > 50R.
Pouring the vibrated mixed solution into a film making mold, wherein the mold is a thin groove with the length and width of 1m, the specification of an adsorption film made by the mold is 1m multiplied by 1m, the thickness is about 1-5mm, and the mold can be changed according to the requirement and is naturally dried until the film is formed.
Uncovering the adsorption film from the film preparation tank, and adding CaCl with concentration 2 1% -5% of boric acid and 2% -5% of a setting solution for 24h, and the film is not allowed to adhere during the placing process, otherwise the film can be permanently adhered during the setting process.
Washing the formed adsorption film with deionized water, adding into 3-carboxymethyl rhodanine with concentration of 5-6 g/L, shaking at 70 deg.C for 24 hr, taking out, washing with water, and oven drying.
The prepared membrane is cut into a square with the length of 75 x 75cm, 10 membranes are placed into a reaction device containing 2.5 tons of industrial wastewater at equal intervals, the industrial wastewater contains nickel ions, copper ions and lead ions, the adsorption speed is about 60-90 mg/g.min in about initial 5-10min, the mass transfer rate is high, the removal rate of heavy metal ions in 2 hours reaches more than 95%, and no specificity is realized in the removal of the heavy metal ions.
And observing the swelling and corrosion of the immobilized adsorption membrane in the purification process. And finally, no increase of organic matters is detected in the water body, and the multifunctional heavy metal ion adsorption membrane is touched by hands without damage, so that organic matter molecules in the membrane are basically prevented from leaking, the fixing effect of the fixing agent is good, and the risk of secondary pollution is eliminated.
Example 2
Mixing and dissolving polyvinyl alcohol, polyvinyl alcohol-ethylene polymer, sodium alginate, activated carbon and bentonite according to a certain proportion at a high temperature of 100-150 ℃; so that the final concentrations were: 6 to 10 percent of polyvinyl alcohol, 0.1 to 5 percent of polyvinyl alcohol-ethylene polymer, 3 to 10 percent of sodium alginate, 0.1 to 2 percent of active carbon and 1 to 10 percent of bentonite, and the specific mixed concentration is determined according to the concentration of heavy metal ions contained in the sewage. Wherein, the bentonite is required to be acidified by hydrochloric acid in advance, and the polyvinyl alcohol-ethylene polymer is treated by acetone.
The well mixed solution is placed until T <70 ℃, glutaraldehyde is added, and shaking is carried out for 10-24 hours at 30 ℃ with the speed of > 50R.
Pouring the vibrated mixed solution into a film making mold, wherein the mold is a thin groove with the length and width of 1m, the specification of an adsorption film made by the mold is 1m multiplied by 1m, the thickness is about 1-5mm, and the mold can be changed according to the requirement and is naturally dried until the film is formed.
Uncovering the adsorption film from the film preparation tank, and adding CaCl with concentration 2 1% -5% of boric acid and 2% -5% of a setting solution for 24h, and the film is not allowed to adhere during the placing process, otherwise the film can be permanently adhered during the setting process.
Washing the formed adsorption film with deionized water, adding into 3-carboxymethyl rhodanine with concentration of 5-6 g/L, shaking at 70 deg.C for 24 hr, taking out, washing with water, and oven drying.
In addition, in the embodiment, 1-vinylimidazole is used as a functional monomer, Ni (II) is used as a template ion, and a precipitation polymerization method is adopted to prepare the Ni (II) -IIP.
In the first step, 2mmol of Ni (NO) 3 ) 2 Dissolving in 100mL of methanol/DMF mixed solution, adding 8-10mmol of functional monomer vinyl imidazole under nitrogen atmosphere, introducing nitrogen for a while, sealing, and reacting the mixed solution at 60 ℃ for 2-8 h.
And secondly, after the prepolymerization reaction is finished, sequentially adding 20mmol of crosslinking agent EGDMA and 100mg of initiator AIBN into the solution, continuously introducing nitrogen for a period of time, sealing and heating to a temperature higher than 70 ℃, and carrying out polymerization reaction for 24 hours.
And thirdly, washing the light green precipitate by using methanol and deionized water in sequence, then eluting the precipitate by using 0.5mol/L nitric acid for multiple times to remove template ions Ni (II) in the polymer Ni (II) -IIP, then washing the precipitate to be neutral by using deionized water and soaking the precipitate by using ammonia water overnight.
Fourthly, the obtained white product is placed in a vacuum drying oven and dried to constant weight at the temperature of 60 ℃. The antibacterial adsorption film with the nickel ion molecular imprinting is prepared.
The method is cut into a square with 75 x 75cm, 10 prepared membranes are equidistantly placed into a reaction device containing 2.5 tons of industrial wastewater, the adsorption speed is about 60-80 mg/g.min in about initial 5-10min, the mass transfer rate is high, and the removal rate of nickel ions in 2 hours reaches more than 95%. And the adsorption efficiency of other heavy metal ions in the solution is very low. Wherein, the selectivity ratio of the engram molecules to nickel ions, copper ions, lead ions and cobalt ions is 87.82%, 5.15%, 2.91% and 4.12%.
And observing the swelling and corrosion of the immobilized adsorption film in the purification process. And finally, no increase of organic matters is detected in the water body, and the multifunctional heavy metal ion adsorption membrane is touched by hands without damage, so that organic matter molecules in the membrane are basically prevented from leaking, the fixing effect of the fixing agent is good, and the risk of secondary pollution is eliminated.
Example 3
Mixing and dissolving polyvinyl alcohol, polyvinyl alcohol-ethylene polymer, sodium alginate, activated carbon and bentonite according to a certain proportion at a high temperature of 100-150 ℃; so that the final concentrations were: 6 to 10 percent of polyvinyl alcohol, 0.1 to 5 percent of polyvinyl alcohol-ethylene polymer, 3 to 10 percent of sodium alginate, 0.1 to 2 percent of active carbon and 1 to 10 percent of bentonite, and the specific mixed concentration is determined according to the concentration of heavy metal ions contained in the sewage. Wherein, the bentonite is required to be acidified by hydrochloric acid in advance, and the polyvinyl alcohol-ethylene polymer is treated by acetone.
The well mixed solution is placed until T <70 ℃, glutaraldehyde is added, and shaking is carried out for 10-24 hours at 30 ℃ with the speed of > 50R.
Pouring the vibrated mixed solution into a film making mold, wherein the mold is a thin groove with the length and width of 1m, the specification of an adsorption film made by the mold is 1m multiplied by 1m, the thickness is about 1-5mm, and the mold can be changed according to the requirement and is naturally dried until the film is formed.
Uncovering the adsorption film from the film preparation tank, and adding CaCl with concentration 2 1% -5% of boric acid and 2% -5% of a setting solution for 24h, and the film is not allowed to adhere during the placing process, otherwise the film can be permanently adhered during the setting process.
Washing the formed adsorption film with deionized water, adding into 3-carboxymethyl rhodanine with concentration of 5-6 g/L, shaking at 70 deg.C for 24 hr, taking out, washing with water, and oven drying.
In addition, for the adsorption of lead ions, 2-nicotinic acid with multiple coordination effects on lead ions is added as a functional monomer in this example, and a precipitation polymerization method is also used to prepare a lead ion imprinted polymer with a single particle size, and the preparation steps are similar to those in example 2.
The polymer can selectively adsorb lead ions in water, the adsorption speed is high, the removal rate of the lead ions in industrial wastewater in 2 hours reaches more than 96%, and the adsorbed water reaches the national emission standard, so that the antibacterial heavy metal adsorption film has a good effect on removing the lead ions in the industrial wastewater.
And observing the swelling and corrosion of the immobilized adsorption membrane in the purification process. Finally, no increase of organic matters is detected in the water body, the multifunctional heavy metal ion adsorption membrane is touched by hands, damage is avoided, organic matter molecules in the membrane are basically prevented from leaking, the fixing effect of the fixing agent is good, and the risk of secondary pollution is eliminated.
Example 4
Mixing and dissolving polyvinyl alcohol, polyvinyl alcohol-ethylene polymer, sodium alginate, activated carbon and bentonite according to a certain proportion at a high temperature of 100-150 ℃; so that the final concentrations were: 6 to 10 percent of polyvinyl alcohol, 0.1 to 5 percent of polyvinyl alcohol-ethylene polymer, 3 to 10 percent of sodium alginate, 0.1 to 2 percent of active carbon and 1 to 10 percent of bentonite, and the specific mixed concentration is determined according to the concentration of heavy metal ions contained in the sewage. Wherein, the bentonite is required to be acidified by hydrochloric acid in advance, and the polyvinyl alcohol-ethylene polymer is required to be treated by acetone.
The well mixed solution is placed until T <70 ℃, glutaraldehyde is added, and shaking is carried out for 10-24 hours at 30 ℃ with the speed being more than 50R. And pouring the vibrated mixed solution into a film-making mold, wherein the mold is a thin groove with the length and the width of 1m, the specification of an adsorption film made of the mold is 1m multiplied by 1m, the thickness of the adsorption film is about 1-5mm, and the mold can be changed as required and is naturally dried to form the film.
Uncovering the adsorption film from the film preparation tank, and adding CaCl with concentration 2 1% -5% of boric acid and 2% -5% of a setting solution for 24h, and the film is not allowed to adhere during the placing process, otherwise the film can be permanently adhered during the setting process. Washing the formed adsorption film with deionized water, adding into 3-carboxymethyl rhodanine with concentration of 5-6 g/L, shaking at 70 deg.C for 24 hr, taking out, washing with water, and oven drying.
In addition, Fe 3 O 4 The method combines magnetic property with surface imprinting technology, simultaneously takes allylthiourea as a functional monomer, prepares a novel magnetic mercury ion imprinting polymer thermally, and the specific preparation steps are similar to those in the embodiment 2.
The polymer can remove Hg in water environment with high selectivity 2+ . The adsorption rate ratio of the polymerized monomer to various heavy metal ions is respectively as follows: hg: cu: co: ni 478: 1.31: 0.69: 4.24. finally, the removal rate of lead ions in the industrial wastewater reaches more than 99% in 2 hours, and the water body after adsorption reaches the national discharge standard, so that the antibacterial heavy metal adsorption film has a good effect on removing the lead ions in the industrial wastewater, and the prepared polymer containing the molecular imprinting also has good specific adsorption.
And observing the swelling and corrosion of the immobilized adsorption membrane in the purification process. Finally, no increase of organic matters is detected in the water body, the multifunctional heavy metal ion adsorption membrane is touched by hands, damage is avoided, organic matter molecules in the membrane are basically prevented from leaking, the fixing effect of the fixing agent is good, and the risk of secondary pollution is eliminated.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
Claims (5)
1. The preparation method of the antibacterial multifunctional heavy metal ion adsorption membrane is characterized by comprising the following steps:
the method comprises the following steps: adsorbing agent, fixing agent and pore-increasing agent: mixing and dissolving polyvinyl alcohol, polyvinyl alcohol-ethylene polymer, sodium alginate, active carbon and bentonite according to a certain proportion at a high temperature of 100-150 ℃; so that the final concentrations were: 6 to 10 percent of polyvinyl alcohol, 0.1 to 5 percent of polyvinyl alcohol-ethylene polymer, 3 to 10 percent of sodium alginate, 0.1 to 2 percent of active carbon and 1 to 10 percent of bentonite;
step two: naturally cooling the mixed solution in the step one to below 70 ℃, adding glutaraldehyde, and shaking for 10-24 hours;
step three: pouring the vibrated mixed solution into a film-making mold, and naturally drying;
step four: taking out the adsorption film in the third step, and adding CaCl with concentration 2 1 to 5 percent of boric acid and 2 to 5 percent of boric acid for 24 hours;
step five: cleaning the adsorption film shaped in the fourth step by using deionized water, then putting the adsorption film into 3-carboxymethyl rhodanine with the concentration of 5g/L-6g/L, shaking for 24 hours at 70 ℃, taking out, washing and drying.
2. The method for preparing an antibacterial multifunctional heavy metal ion adsorption membrane according to claim 1, wherein the bentonite is acidified by hydrochloric acid in advance, and the polyvinyl alcohol-ethylene polymer is treated by acetone.
3. A preparation method of a heavy metal ion imprinting composite membrane is characterized by comprising the following steps:
the method comprises the following steps: adsorbing agent, fixing agent and pore-increasing agent: mixing and dissolving polyvinyl alcohol, polyvinyl alcohol-ethylene polymer, sodium alginate, active carbon and bentonite according to a certain proportion at a high temperature of 100-150 ℃; so that the final concentrations were: 6 to 10 percent of polyvinyl alcohol, 0.1 to 5 percent of polyvinyl alcohol-ethylene polymer, 3 to 10 percent of sodium alginate, 0.1 to 2 percent of active carbon and 1 to 10 percent of bentonite, wherein the specific mixed concentration is determined according to the concentration of heavy metal ions contained in the sewage;
step two: naturally cooling the mixed solution in the step one to below 70 ℃, adding glutaraldehyde, and shaking for 10-24 hours;
step three: pouring the vibrated mixed solution into a film-making mold, and naturally drying;
step four: taking out the adsorption film in the third step, and adding CaCl with concentration 2 1 to 5 percent of boric acid and 2 to 5 percent of boric acid for 24 hours;
step five: adding required heavy metal ions to form a print for modification;
step six: and (4) cleaning the adsorption film shaped in the fifth step with deionized water, then putting the adsorption film into 3-carboxymethyl rhodanine with the concentration of 5g/L-6g/L, shaking the adsorption film for 24 hours at 70 ℃, taking out the adsorption film, washing the adsorption film with water and drying the adsorption film.
4. The method for preparing the heavy metal ion imprinted composite membrane according to claim 3, wherein the bentonite is acidified by hydrochloric acid in advance, and the polyvinyl alcohol-ethylene polymer is treated by acetone.
5. A multifunctional adsorbent material, characterized in that it comprises at least one layer of a heavy metal ion imprinted composite membrane prepared according to the method of claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911125850.3A CN110813259B (en) | 2019-11-15 | 2019-11-15 | Antibacterial multifunctional heavy metal ion adsorption membrane and preparation method of heavy metal ion imprinting composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911125850.3A CN110813259B (en) | 2019-11-15 | 2019-11-15 | Antibacterial multifunctional heavy metal ion adsorption membrane and preparation method of heavy metal ion imprinting composite membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110813259A CN110813259A (en) | 2020-02-21 |
| CN110813259B true CN110813259B (en) | 2022-08-30 |
Family
ID=69556253
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911125850.3A Active CN110813259B (en) | 2019-11-15 | 2019-11-15 | Antibacterial multifunctional heavy metal ion adsorption membrane and preparation method of heavy metal ion imprinting composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110813259B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112551631A (en) * | 2020-12-01 | 2021-03-26 | 长春工业大学 | Method for rapidly reducing concentration of heavy metal chromium ions in water |
| CN115193416B (en) * | 2022-05-16 | 2024-01-05 | 江苏大学 | Preparation method and application of rapid high-selectivity gold extraction adsorbent of bionic magnetotactic bacteria |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6989102B1 (en) * | 1997-07-01 | 2006-01-24 | Samsung General Chemicals Co., Ltd. | Alginate gel based adsorbents for heavy metal removal |
| CN101254457A (en) * | 2007-12-06 | 2008-09-03 | 中国科学院长春应用化学研究所 | Heavy metal ion adsorbed film and preparation |
| CN102430398A (en) * | 2011-10-25 | 2012-05-02 | 中国科学院新疆理化技术研究所 | Composite type mercury ion adsorbent and preparation method thereof |
| CN103446897A (en) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | Chemical and ionic cross-linked alginate hydrogel flat membrane for filtration and preparation method thereof |
| CN103769062A (en) * | 2014-02-27 | 2014-05-07 | 江南大学 | Functionalized polyvinyl alcohol hydrogel and preparation method thereof |
| CN103789295A (en) * | 2014-01-16 | 2014-05-14 | 烟台大学 | Preparation method and application of biological membrane for toxicity determination biosensor |
| CN103804828A (en) * | 2014-02-14 | 2014-05-21 | 江南大学 | Compound hydrogel capable of adsorbing heavy metal ions and preparation method of compound hydrogel |
| CN104226281A (en) * | 2014-10-13 | 2014-12-24 | 江南大学 | Composite hydrogel for adsorption of heavy metal ions and preparation method thereof |
| CN106862262A (en) * | 2017-03-24 | 2017-06-20 | 四川大学 | A kind of soil biochemistry complex repairation agent and preparation method and application |
| CN108176383A (en) * | 2018-01-05 | 2018-06-19 | 天津工业大学 | A kind of preparation method of antibacterial absorption sponge material |
| CN108816201A (en) * | 2018-06-25 | 2018-11-16 | 南昌航空大学 | A kind of silver ion adsorbent material and the preparation method and application thereof |
| CN109603750A (en) * | 2018-12-27 | 2019-04-12 | 曲阜师范大学 | One kind includes Fe3O4The preparation method of the plural gel adsorbed film of-GQDs |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160136572A (en) * | 2015-05-20 | 2016-11-30 | 한국화학연구원 | Double crosslinked sodium alginate/polyvinyl alcohol composite nanofiltration membrane and preparation method thereof |
-
2019
- 2019-11-15 CN CN201911125850.3A patent/CN110813259B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6989102B1 (en) * | 1997-07-01 | 2006-01-24 | Samsung General Chemicals Co., Ltd. | Alginate gel based adsorbents for heavy metal removal |
| CN101254457A (en) * | 2007-12-06 | 2008-09-03 | 中国科学院长春应用化学研究所 | Heavy metal ion adsorbed film and preparation |
| CN102430398A (en) * | 2011-10-25 | 2012-05-02 | 中国科学院新疆理化技术研究所 | Composite type mercury ion adsorbent and preparation method thereof |
| CN103446897A (en) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | Chemical and ionic cross-linked alginate hydrogel flat membrane for filtration and preparation method thereof |
| CN103789295A (en) * | 2014-01-16 | 2014-05-14 | 烟台大学 | Preparation method and application of biological membrane for toxicity determination biosensor |
| CN103804828A (en) * | 2014-02-14 | 2014-05-21 | 江南大学 | Compound hydrogel capable of adsorbing heavy metal ions and preparation method of compound hydrogel |
| CN103769062A (en) * | 2014-02-27 | 2014-05-07 | 江南大学 | Functionalized polyvinyl alcohol hydrogel and preparation method thereof |
| CN104226281A (en) * | 2014-10-13 | 2014-12-24 | 江南大学 | Composite hydrogel for adsorption of heavy metal ions and preparation method thereof |
| CN106862262A (en) * | 2017-03-24 | 2017-06-20 | 四川大学 | A kind of soil biochemistry complex repairation agent and preparation method and application |
| CN108176383A (en) * | 2018-01-05 | 2018-06-19 | 天津工业大学 | A kind of preparation method of antibacterial absorption sponge material |
| CN108816201A (en) * | 2018-06-25 | 2018-11-16 | 南昌航空大学 | A kind of silver ion adsorbent material and the preparation method and application thereof |
| CN109603750A (en) * | 2018-12-27 | 2019-04-12 | 曲阜师范大学 | One kind includes Fe3O4The preparation method of the plural gel adsorbed film of-GQDs |
Non-Patent Citations (1)
| Title |
|---|
| 改性聚乙烯醇-乙烯共聚物纳米纤维膜对重金属离子的吸附性能;王遥等;《纺织学报》;20170615;第第38卷卷(第06期);第12页摘要和第1.2.2节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110813259A (en) | 2020-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huang et al. | Preparation of polyethylene polyamine@ tannic acid encapsulated MgAl-layered double hydroxide for the efficient removal of copper (II) ions from aqueous solution | |
| Wang et al. | Enhanced selective removal of Cu (II) from aqueous solution by novel polyethylenimine-functionalized ion imprinted hydrogel: Behaviors and mechanisms | |
| Uğuzdoğan et al. | The use of polyethyleneglycolmethacrylate-co-vinylimidazole (PEGMA-co-VI) microspheres for the removal of nickel (II) and chromium (VI) ions | |
| Hui et al. | Preparation of PVA hydrogel beads and adsorption mechanism for advanced phosphate removal | |
| Jana et al. | Chitosan based ceramic ultrafiltration membrane: Preparation, characterization and application to remove Hg (II) and As (III) using polymer enhanced ultrafiltration | |
| He et al. | Carboxymethyl chitosan-kaolinite composite hydrogel for efficient copper ions trapping | |
| CN110813259B (en) | Antibacterial multifunctional heavy metal ion adsorption membrane and preparation method of heavy metal ion imprinting composite membrane | |
| Tokuyama et al. | Removal of heavy metal ions and humic acid from aqueous solutions by co-adsorption onto thermosensitive polymers | |
| Sahiner et al. | The use of superporous p (3-acrylamidopropyl) trimethyl ammonium chloride cryogels for removal of toxic arsenate anions | |
| CN103084075B (en) | Nano-loading zero-valent-iron-based PVDF (Polyvinylidene Fluoride) compound material as well as preparation method and application thereof | |
| Sutirman et al. | Chitosan-based adsorbents for the removal of metal ions from aqueous solutions | |
| Ilgin et al. | The efficient removal of anionic and cationic dyes from aqueous media using hydroxyethyl starch-based hydrogels | |
| CN112679731A (en) | Covalent organic framework material containing sulfonic acid group and preparation and application thereof | |
| CN108636387B (en) | Iron ion adsorption sponge and preparation method and application thereof | |
| Zheng et al. | Kapok fiber structure-oriented polyallylthiourea: Efficient adsorptive reduction for Au (III) for catalytic application | |
| Ozay et al. | Dual use of colorimetric sensor and selective copper removal from aqueous media with novel p (HEMA-co-TACYC) hydrogels: Cyclen derivative as both monomer and crosslinker | |
| CN112452302A (en) | Three-dimensional gallium imprinted Chinese gall tannin silicon-based composite material and application thereof in gallium recovery | |
| CN113171759B (en) | Print chitosan composite membrane, preparation method and application thereof | |
| Vo | Progresses and expansions of chitosan-graphene oxide hybrid networks utilizing as adsorbents and their organic dye removal performances: A short review | |
| CN105457505A (en) | Heavy-metal-ion adsorption type anti-pollution hybrid flat-sheet separation membrane and preparation method thereof | |
| Tan et al. | Harnessing the power of polyethyleneimine in modifying chitosan surfaces for efficient anion dyes and hexavalent chromium removal | |
| CN110256637A (en) | A kind of two dimension aromatic polyamide type quaternary ammonium salt and preparation method thereof | |
| CN112915980B (en) | Phenol adsorption film based on double-drive self-assembly method and application thereof in wastewater purification | |
| Xu et al. | Synthesis and adsorption performance of temperature-sensitive imprinted composite poly (vinylidene fluoride) resin membranes with chitosan modification for selective separation of ReO4− | |
| CN114471478A (en) | Chitosan-humic acid composite broad-spectrum amphoteric adsorbent 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 |