CN110485158B - Chelating agent and preparation method and application thereof - Google Patents
Chelating agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN110485158B CN110485158B CN201910729153.2A CN201910729153A CN110485158B CN 110485158 B CN110485158 B CN 110485158B CN 201910729153 A CN201910729153 A CN 201910729153A CN 110485158 B CN110485158 B CN 110485158B
- Authority
- CN
- China
- Prior art keywords
- chelating agent
- ethylene glycol
- methacrylic acid
- butyl acrylate
- chelating
- 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
Images
Classifications
-
- 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
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/395—Isocyanates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention provides a chelating agent and a preparation method and application thereof, the method comprises the steps of mixing and dispersing methacrylic acid, vinyl siloxane, butyl acrylate, ethylene glycol methacrylate, an emulsifier, an initiator and a solvent to form an emulsion A, and then stirring and reacting for 2h-3h at 60-80 ℃ under the microwave condition to obtain a macromolecular chelating polymer; the chelating agent of the invention is obtained by crosslinking and curing macromolecule chelating polymer and-OH on the surface of the fabric through bonding action through-NCO group in the curing agent. The monomer reaction efficiency is greatly improved by the activation reaction under the microwave condition, the conversion rate of all monomer reactions reaches 99.99 percent, and the reaction can be completed within 3 hours after the reaction efficiency is greatly improved; the chelating agent can adsorb heavy metals and organic pollutants in wastewater treatment, has large specific surface area, and is easy to separate from water after being applied; is a multifunctional chelating agent for wastewater treatment and has important application value.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment chelating agents, and particularly relates to a chelating agent, and a preparation method and application thereof.
Background
With the development of industry, serious environmental pollution problems are caused, especially water environment pollution, including heavy metal water pollution and organic matter water pollution. Due to the characteristics of large diffusion area, difficult control, great harm and the like, according to related reports, millions of people die each year due to the pollution of heavy metal and organic dye molecules, and meanwhile, the property loss of billions of dollars is caused.
At present, research and reports are carried out on a preparation method for synthesizing the macromolecular chelating agent, but the preparation method still has the following defects of complexity, high raw material price and single function of the prepared chelating agent.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a chelating agent, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a method of preparing a chelating agent, the method comprising the steps of:
(1) mixing and dispersing methacrylic acid, vinyl siloxane, butyl acrylate, ethylene glycol methacrylate (PEGMA), an emulsifier, an initiator and a solvent to form emulsion A, wherein the solvent comprises ethanol and water;
(2) stirring the emulsion A obtained in the step (1) at the temperature of 60-80 ℃ for 2-3 h under the microwave condition to obtain a macromolecular chelating polymer;
(3) mixing the macromolecular chelating polymer obtained in the step (2), a curing agent containing-NCO groups and ethanol to form a solution B, soaking the cleaned non-woven fabric in the solution B for 20-30min, taking out the non-woven fabric soaked with the solution B, and drying at 60-80 ℃ to obtain the chelating agent.
The invention firstly prepares macromolecular chelate polymer with high-efficiency chelate adsorption function by free radical polymerization, and the activation reaction under the microwave condition greatly improves the reaction efficiency, the conversion rate of all monomer reactions reaches 99.99 percent, and the reaction rate is high, and the reaction can be completed within 3 hours; and the macromolecular chelating polymer and-OH on the surface of the fabric are crosslinked and cured through a bonding effect to form a three-dimensional network structure through-NCO groups in the curing agent, so that the specific surface area of the chelating agent can be increased, and the chelating agent is easy to separate from water after application.
Preferably, the initiator is a water-soluble persulfate.
More preferably, the initiator is ammonium persulfate or potassium persulfate.
Preferably, the initiator is used in an amount of 0.5% to 2% by weight based on the total weight of methacrylic acid, vinylsiloxane, butyl acrylate and ethylene glycol methacrylate.
Preferably, the curing agent containing an-NCO group is an isocyanate-based curing agent.
Preferably, the amount of the methacrylic acid, the vinyl siloxane, the butyl acrylate and the ethylene glycol methacrylate in the step (1) is as follows according to the percentage of the total mass of the methacrylic acid, the vinyl siloxane, the butyl acrylate and the ethylene glycol methacrylate: 30 to 50 percent of methacrylic acid, 0.1 to 10 percent of vinyl siloxane, 0.1 to 10 percent of butyl acrylate and 30 to 70 percent of ethylene glycol methacrylate.
Preferably, the emulsifier is OP-10 (polyoxyethylene octylphenol ether-10), and the amount of the emulsifier used in the step (1) is 0.1-0.5% of the total weight of the methacrylic acid, the vinyl siloxane, the butyl acrylate and the ethylene glycol methacrylate.
Preferably, the power of the microwave in the step (3) is 500W-1000W.
Preferably, the drying manner in step (3) is vacuum drying.
Preferably, the nonwoven fabric in step (3) is cleaned by ultrasonic cleaning with absolute ethyl alcohol, acetone and ultrapure water in sequence.
More preferably, the non-woven fabric in the step (3) is cleaned by ultrasonic cleaning with absolute ethyl alcohol, acetone and ultrapure water for 30min in sequence and circularly cleaning for 3 times.
Preferably, the solute concentration of solution B is 10% to 30%.
Preferably, the solute concentration of solution B is 20% to 30%.
The invention also provides a chelating agent prepared by any one of the methods.
The chelating agent disclosed by the invention is simple in preparation method and low in raw material cost, can adsorb heavy metal ions in water and organic pollutants in water, is a multifunctional water pollutant chelating agent, has a large specific surface area, and is convenient to separate from water.
The invention also provides the application of the chelating agent in the treatment of the polluted wastewater, wherein the pollutants in the polluted wastewater comprise at least one of metal ions or organic pollutants.
The invention has the beneficial effects that: the invention provides a chelating agent and a preparation method and application thereof, the preparation method prepares macromolecular chelate with high-efficiency chelating adsorption function by free radical polymerization, the monomer reaction efficiency is greatly improved by activation reaction under the microwave condition, the conversion rate of all monomer reactions reaches 99.99 percent, and the reaction can be completed within 3 hours after the reaction efficiency is greatly improved; the macromolecular chelating polymer and-OH on the surface of the fabric are crosslinked and solidified through a bonding effect to form a three-dimensional network structure through-NCO groups in the curing agent, so that the specific surface area of the chelating agent can be increased, and the chelating agent is easy to separate from water after application; the method can accurately control the adsorption efficiency of the chelating agent on metal ions and organic dye molecules by regulating the grafting amount of the macromolecular chelate on the surface of the fabric. The chelating agent can adsorb heavy metals and organic pollutants in wastewater treatment, is a multifunctional wastewater treatment chelating agent, and has important application value.
Drawings
FIG. 1 is a diagram illustrating the effect of heavy metal ion adsorption of a chelating agent prepared according to an embodiment of the present invention;
FIG. 2 is a graph showing the effect of chelating agent prepared according to the embodiment of the present invention on adsorbing organic dye molecules;
FIG. 3 shows that the chelating agent prepared in the example of the present invention adsorbs Cu2+And a Methylene Blue (MB) durability effect graph.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
A method of preparing a chelating agent as an embodiment of the present invention, the method comprising the steps of:
(1) mixing and dispersing 50% by weight of methacrylic acid, 10% by weight of vinyl siloxane, 10% by weight of butyl acrylate, 30% by weight of ethylene glycol methacrylate, an emulsifier, an initiator and a solvent to form emulsion A, wherein the solvent comprises ethanol and water; the initiator is ammonium persulfate, the dosage of the initiator is 0.5-2% of the total weight of methacrylic acid, vinyl siloxane, butyl acrylate and ethylene glycol methacrylate, the dosage of the emulsifier is OP-10, and the dosage of the emulsifier is 0.1-0.5% of the total weight of methacrylic acid, vinyl siloxane, butyl acrylate and ethylene glycol methacrylate;
(2) magnetically stirring the emulsion A obtained in the step (1) at 60-80 ℃ under the microwave condition for reaction for 2-3 h to obtain a macromolecular chelating polymer;
(3) mixing the macromolecular chelating polymer obtained in the step (2), an isocyanate-based curing agent and ethanol to form a solution B, wherein the solute concentration of the solution B is 10%, cutting the non-woven fabric into 3cm multiplied by 3cm, sequentially carrying out ultrasonic cleaning for 30min by using absolute ethanol, acetone and ultrapure water, circularly cleaning for 3 times, soaking the cleaned non-woven fabric in the solution B for 30min, taking out the non-woven fabric soaked with the solution B, and drying in vacuum at the temperature of 60-80 ℃ for 1-2h to obtain the chelating agent.
Example 2
As a method for preparing a chelating agent according to an embodiment of the present invention, the only difference between this embodiment and embodiment 1 is: the solute concentration of solution B was 20%.
Example 3
As a method for preparing a chelating agent according to an embodiment of the present invention, the only difference between this embodiment and embodiment 1 is: the solute concentration of solution B was 30%.
Example 4
The application method of the chelating agent as the embodiment of the invention comprises the following steps:
(1) the chelating agent prepared in example was added to Cu at a concentration of 100mg/L2+，Ni2+，Zn2+Water in (2);
(2) the adsorption was shaken at a speed of 150 r/min.
And after the adsorption is finished, centrifugally collecting the complex, and calculating the content of the complex to obtain the adsorption quantity of the chelating agent to the metal ions.
The chelating agents were the chelating agents obtained in example 1, example 2, and example 3, respectively.
The results of the experiments are shown in FIG. 1, and it is shown that the chelating agents obtained in examples 1, 2 and 3 are effective for Cu in water2+，Ni2+，Zn2+All had good adsorption effect, and the adsorption effect of example 3 was the best.
Example 5
The application method of the chelating agent as the embodiment of the invention comprises the following steps:
(1) the chelating agent prepared in example was added to water having a concentration of 10mg/L of Methylene Blue (MB);
(2) the adsorption was shaken at a speed of 150 r/min.
The adsorption amount of methylene blue was tested by ultraviolet absorption spectroscopy.
The chelating agents were the chelating agents obtained in example 1, example 2, and example 3, respectively.
The experimental results are shown in fig. 2, and the results show that the chelating agents obtained in examples 1, 2 and 3 have good adsorption effect on methylene blue in water, and the adsorption effect of example 3 is the best.
Example 6
The application method of the chelating agent as the embodiment of the invention comprises the following steps:
(1) the chelating agent prepared in example 3 was added to Methylene Blue (MB) at a concentration of 10mg/L and Cu at a concentration of 100mg/L2+Water in (2);
(2) oscillating and adsorbing at the speed of 150 r/min;
(3) separating the adsorbed chelating agent, and chelating with 1mol/L hydrochloric acid to obtain a recovered chelating agent;
(4) and (4) repeating the steps (1), (2) and (3) by using the recovered chelating agent obtained in the step (3).
The adsorption removal efficiency of the chelating agent at each time is detected and calculated, and the result is shown in fig. 3, which shows that the chelating agent has good adsorption stability for metal ions and organic pollutants, can be recycled after being adsorbed, and has good repeatability.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. A method of preparing a chelating agent, the method comprising the steps of:
(1) mixing and dispersing methacrylic acid, vinyl siloxane, butyl acrylate, ethylene glycol methacrylate, an emulsifier, an initiator and a solvent to form emulsion A, wherein the solvent comprises ethanol and water;
(2) stirring the emulsion A obtained in the step (1) at the temperature of 60-80 ℃ for 2-3 h under the microwave condition to obtain a macromolecular chelating polymer;
(3) mixing the macromolecular chelating polymer obtained in the step (2) and a curing agent containing-NCO groups with ethanol to form a solution B, soaking the cleaned non-woven fabric in the solution B for 20-30min, taking out the non-woven fabric soaked with the solution B, and drying at 60-80 ℃ to obtain the chelating agent;
the dosage of the methacrylic acid, the vinyl siloxane, the butyl acrylate and the ethylene glycol methacrylate in the step (1) is as follows according to the percentage of the total mass of the methacrylic acid, the vinyl siloxane, the butyl acrylate and the ethylene glycol methacrylate: 30 to 50 percent of methacrylic acid, 0.1 to 10 percent of vinyl siloxane, 0.1 to 10 percent of butyl acrylate and 30 to 70 percent of ethylene glycol methacrylate;
the curing agent containing-NCO groups is an isocyanate group curing agent;
the surface of the nonwoven fabric contains-OH.
2. The method of claim 1, wherein the initiator is ammonium persulfate or potassium persulfate.
3. The method according to claim 1, wherein the emulsifier is OP-10, and the amount of the emulsifier used in step (1) is 0.1 to 0.5% by weight based on the total weight of methacrylic acid, vinylsiloxane, butyl acrylate and ethylene glycol methacrylate.
4. The method of claim 1, wherein the initiator is used in an amount of 0.5% to 2% by weight based on the total weight of methacrylic acid, vinyl siloxane, butyl acrylate, and ethylene glycol methacrylate.
5. The method according to claim 1, wherein the power of the microwaves in the step (3) is 500W-1000W; the method for cleaning the non-woven fabric in the step (3) comprises the following steps: and (4) ultrasonically cleaning the substrate by using absolute ethyl alcohol, acetone and ultrapure water in sequence, wherein the drying mode in the step (3) is vacuum drying.
6. The method according to claim 1, wherein the solute concentration of solution B is 10% -30%.
7. A chelating agent prepared by the method of any one of claims 1 to 6.
8. Use of the chelating agent as defined in claim 7 for treating contaminated wastewater, the contaminants in the contaminated wastewater comprising at least one of metal ions or organic contaminants.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910729153.2A CN110485158B (en) | 2019-08-06 | 2019-08-06 | Chelating agent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910729153.2A CN110485158B (en) | 2019-08-06 | 2019-08-06 | Chelating agent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110485158A CN110485158A (en) | 2019-11-22 |
| CN110485158B true CN110485158B (en) | 2022-02-22 |
Family
ID=68549965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910729153.2A Active CN110485158B (en) | 2019-08-06 | 2019-08-06 | Chelating agent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110485158B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111138108A (en) * | 2019-12-30 | 2020-05-12 | 四川欧迅能源工程科技有限公司 | Method for preparing chelating agent in construction industry |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750380A (en) * | 2016-11-28 | 2017-05-31 | 吉林大学珠海学院 | A kind of polymer-modified environmentally friendly composite aquogel and its application in heavy metal containing sewage is processed |
| CN107446096A (en) * | 2017-09-01 | 2017-12-08 | 中车唐山机车车辆有限公司 | Heavy metal ion porous adsorbent and its preparation method and application |
-
2019
- 2019-08-06 CN CN201910729153.2A patent/CN110485158B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750380A (en) * | 2016-11-28 | 2017-05-31 | 吉林大学珠海学院 | A kind of polymer-modified environmentally friendly composite aquogel and its application in heavy metal containing sewage is processed |
| CN107446096A (en) * | 2017-09-01 | 2017-12-08 | 中车唐山机车车辆有限公司 | Heavy metal ion porous adsorbent and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| "聚丙烯非织造布的亲金属离子功能化改性";孔祥曌 等;《纺织学报》;20160430;第37卷(第4期);第33-37页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110485158A (en) | 2019-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bessbousse et al. | Removal of heavy metal ions from aqueous solutions by filtration with a novel complexing membrane containing poly (ethyleneimine) in a poly (vinyl alcohol) matrix | |
| Benamer et al. | Radiation synthesis of chitosan beads grafted with acrylic acid for metal ions sorption | |
| CN105289316A (en) | Preparation method of composite separating film filled by interpenetrating polymer network hydrogel | |
| JP6697205B2 (en) | Chelate microfiltration membrane manufacturing method, recycling method and application | |
| CN105771701B (en) | The preparation method of one metal ion species trace composite membrane | |
| CN102886250B (en) | Preparation method of polyaniline/montmorillonite composite adsorbent with sheet structure | |
| CN106279698B (en) | 2, 4-dinitrophenol surface molecularly imprinted polymer and preparation method and application thereof | |
| CN107262061A (en) | A kind of heavy metal ion adsorbing material based on graphene and preparation method thereof | |
| CN110485158B (en) | Chelating agent and preparation method and application thereof | |
| Chu et al. | Desorption of copper from polyvinyl alcohol‐immobilized seaweed biomass | |
| CN104772051A (en) | Copolymer hydrophilically modified ultrafilter membrane, and production method and application thereof | |
| CN112516968A (en) | Preparation method of metal organic framework material loaded modified diatomite adsorbent | |
| Su et al. | One-pot synthesis of brewer's spent grain-supported superabsorbent polymer for highly efficient uranium adsorption from wastewater | |
| CN101053823A (en) | Poly (m-phenylene diamine) used as mercury ion adsorbent | |
| CN110801741A (en) | Surface modification method of polyvinylidene fluoride membrane | |
| CN110117038A (en) | A kind of selective absorption and the method for recycling heavy metal in sewage | |
| CN111203197A (en) | Adsorbing material based on epoxy and amino crosslinking and preparation method thereof | |
| JP2003531724A5 (en) | ||
| CN107446096A (en) | Heavy metal ion porous adsorbent and its preparation method and application | |
| CN111589429B (en) | Phenanthroline polymer and preparation method and application thereof | |
| CN113145083B (en) | Janus bifunctional blotting membrane and preparation method and application thereof | |
| CN108159902B (en) | Preparation method of chelate polyacrylonitrile hollow fiber membrane | |
| CN107629178B (en) | hydroximic acid type montmorillonite ion imprinted material and preparation method and application thereof | |
| CN104826507B (en) | A kind of albumen using cellulose fibre as base material is hydrophobic to isolate and purify film | |
| JP2004292479A (en) | Boron-adsorbing gel, and treating method for boron-containing waste water |
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 | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee after: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Patentee after: Guangzhou University Address before: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee before: Institute of resources comprehensive utilization, Guangdong Academy of Sciences Patentee before: Guangzhou University |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee after: Institute of resources comprehensive utilization, Guangdong Academy of Sciences Patentee after: Guangzhou University Address before: 510000 courtyard, no.363, Changxing Road, Tianhe District, Guangzhou City, Guangdong Province Patentee before: GUANGDONG INSTITUTE OF RESOURCES COMPREHENSIVE UTILIZATION Patentee before: Guangzhou University |