CN112316740A - Method for modifying polyamide film - Google Patents
Method for modifying polyamide film Download PDFInfo
- Publication number
- CN112316740A CN112316740A CN202011035935.5A CN202011035935A CN112316740A CN 112316740 A CN112316740 A CN 112316740A CN 202011035935 A CN202011035935 A CN 202011035935A CN 112316740 A CN112316740 A CN 112316740A
- Authority
- CN
- China
- Prior art keywords
- membrane
- solution
- film
- modifying
- polyamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
Abstract
The invention provides a method for modifying a polyamide composite film, relates to a method for improving the anti-pollution performance of a forward osmosis polyamide composite film by post-treatment modification, and solves the problems that the existing polyamide TFC film is easy to pollute by organisms, so that the water flux of the film is reduced, the cleaning frequency of the film is increased, the energy consumption is increased, the life cycle of the film is shortened, the treatment efficiency of the process is reduced, and the operation cost is increased. The modified TFC membrane obtained by the invention can effectively control the membrane biological pollution. For grafting the zwitterionic polymer, atom transfer radical polymerization is adopted, so that the controllability is high, the grafting length and the density of the organic polymer can be controlled by regulating and controlling parameters, and the performances of the membrane including pollution resistance and mass transfer are further optimized.
Description
Technical Field
The invention relates to a method for post-treating a modified polyamide composite film.
Background
With the rapid growth in the population of the world and the rapid consumption of fossil fuels, water shortages and energy crisis plague the world. Which are closely related. Making water resources available is a process of energy intensive concentration, and energy production often requires large amounts of water resources. The membrane filtration technology represented by microfiltration, ultrafiltration, nanofiltration, reverse osmosis and forward osmosis is one of the pillar technologies of the environmental engineering discipline, and has a series of advantages of energy conservation, high efficiency, economy, simplicity, convenience, no secondary pollution and the like, so that the membrane filtration technology is widely applied to brackish water desalination, seawater desalination, industrial water supply treatment, pure water and ultrapure water preparation, wastewater treatment, sewage recycling and the like in water treatment.
The polyamide composite film (TFC) has the characteristics of high water flux, good interception performance, capability of respectively modifying and optimizing an active layer and a supporting layer and the like, and is widely applied to the field of current membrane water treatment. However, polyamides are susceptible to biological contamination. Microorganisms are attached to the surface of the membrane and form a biological membrane through growth, so that the membrane cleaning frequency is increased, the energy consumption is increased, the life cycle of the membrane is shortened, and the like.
Disclosure of Invention
The invention aims to provide a method for modifying a polyamide film, which is characterized by comprising the following steps:
1) dissolving dopamine hydrochloride in dimethylformamide; then under the protection of inert gas, adding 2-bromine isobutyryl bromide and triethylamine, and reacting to obtain an initiator dopamine coupling solution;
2) adding a trihydroxymethyl aminomethane buffer solution into the initiator dopamine coupling solution prepared in the step 1) to obtain a mixed solution;
3) introduction of initiator at the membrane surface: reacting an active layer on the surface of the polyamide TFC membrane with the mixed solution prepared in the step 2), and grafting an initiator on the active layer;
4) grafting a zwitterionic polymer on the surface of the membrane: dissolving a zwitterionic monomer in an isopropanol aqueous solution, adding a copper chloride catalytic complex under the protection of inert gas, placing the membrane treated in the step 3), maintaining the atmosphere of the inert gas, adding an ascorbic acid solution, carrying out polymerization reaction for 0.5-3 hours, and then exposing the membrane to air to terminate the polymerization reaction to obtain a grafted zwitterionic polymer;
5) and after the surface of the membrane grafted with the zwitterion adsorbs the metal ion, carrying out reduction reaction on the metal ion on the surface of the membrane to obtain the modified polyamide composite membrane.
In another aspect, the method comprises the steps of:
1) dissolving dopamine hydrochloride in dimethylformamide; then under the protection of inert gas, adding 2-bromine isobutyryl bromide and triethylamine, and reacting to obtain an initiator dopamine coupling solution;
2) adding a trihydroxymethyl aminomethane buffer solution into the initiator dopamine coupling solution prepared in the step 1) to obtain a mixed solution;
3) adsorbing metal ions on the surface of an active layer on the surface of the polyamide TFC membrane, then carrying out reduction reaction on the metal ions on the surface of the membrane, then reacting the active layer on the surface of the treated polyamide TFC membrane with the mixed solution prepared in the step 2), and grafting an initiator on the active layer;
4) grafting a zwitterionic polymer on the surface of the membrane: dissolving a zwitterionic monomer in an isopropanol aqueous solution, adding a copper chloride catalytic compound under the protection of inert gas, placing the film treated in the step 3), maintaining the atmosphere of the inert gas, adding an ascorbic acid solution, carrying out polymerization reaction for 0.5-3 hours, and then exposing the film to air to terminate the polymerization reaction, thereby obtaining the modified polyamide composite film.
Further, in the step 1), the ratio of the mass (mg) of the dopamine hydrochloride to the volume (mL) of the dimethylformamide is (20-40) to (1-2);
the volume ratio of the dimethylformamide to the 2-bromoisobutyryl bromide to the triethylamine is (2000-4000) to (13-26) to (15-30), wherein the concentration of the 2-bromoisobutyryl bromide is as follows: 4.04-8.08 mmol/mL and the concentration of triethylamine is 3.50-7.00 mmol/mL.
Further, in the step 2), the volume ratio of the trihydroxymethyl aminomethane buffer solution to the initiator dopamine coupling solution is (5-10): (1-2), the concentration of the tris buffer solution is 0.01-0.02 mmol/mL. (ii) a
Further, in the step 4), the ratio of the mass (g) of the zwitterionic monomer to the volume (mL) of the isopropanol aqueous solution is (39-79) to (500-1000), wherein the concentration of the isopropanol aqueous solution is 25-75%; the volume ratio of the isopropanol aqueous solution to the copper chloride catalytic complex to the ascorbic acid solution is (100-200) to (4-20) to (8-15).
Further, in the step 4), the zwitterionic monomer is a sulfobetaine methyl acrylate monomer or a carboxybetaine methyl acrylate monomer.
Further, in the step 4), the ascorbic acid solution is prepared by dissolving ascorbic acid in an isopropanol aqueous solution; the ratio of the mass (g) of ascorbic acid to the volume (mL) of the aqueous isopropanol solution is 1: 10-15, wherein the concentration of the aqueous isopropanol solution is 25-75%.
Further, in the step 4), the preparation method of the copper chloride catalytic complex is to dissolve the copper chloride and the tris (2-pyridylmethyl) amine in an isopropanol aqueous solution to obtain the copper chloride catalytic complex.
Wherein: the mass ratio of the copper chloride to the tri (2-pyridylmethyl) amine is as follows: (1-5) to (14-70);
the ratio of the mass (g) of copper chloride to the volume (mL) of the aqueous isopropanol solution is (1-5): (2000-10000), wherein the concentration of the aqueous isopropanol solution is 25-75%.
The mechanism of the invention is as follows: the zwitter-ion organic polymer is a super-hydrophilic organic matter with neutral electricity, and can react with water molecules to generate a relatively compact water molecular layer, so that the adhesion of various pollutants is effectively prevented, and the membrane pollution is reduced. In order to further control the biological pollution, metal with good sterilization performance is selected to be arranged on the modified functional layer, and close microorganisms can be effectively killed, so that the biological pollution problem commonly existing in the TFC film is effectively solved through the dual functions of the adsorption resistant functional layer and the sterilization resistant functional layer.
The invention has the advantages that: the invention grafts the super-hydrophilic anti-pollution amphoteric ion polymer on the TFC membrane surface to control the membrane biological pollution. For grafting the zwitterionic polymer, Atom Transfer Radical Polymerization (ATRP) is mainly adopted, so that the controllability is high, the grafting length and the grafting density of the organic polymer can be controlled by regulating and controlling parameters such as reaction time, reactant concentration and the like, and the performances of the membrane including pollution resistance, mass transfer and the like are further optimized. For grafting of metal, metal with high-efficiency sterilization performance can be adopted, so that the membrane has anti-adhesion and bacteriostatic effects, simple electrostatic adsorption and in-situ redox reaction are adopted, the dosage of the used medicament is small, the operation is simple and easy, and the relevant solution can be recycled. The biological pollution resistance of the modified membrane can be regulated and controlled by changing the grafting sequence of the modified functional layer. In addition, the invention belongs to a post-treatment modification method, and is suitable for the biological pollution resistance modification of all commercialized polyamide TFC membranes.
Drawings
FIG. 1 is a schematic view of the process of the present invention
FIG. 2 is a process flow diagram of the example
FIG. 3 shows the results of the experiment in example 2
Detailed Description
The present invention is further illustrated by the following examples, but it should not be construed that the scope of the above-described subject matter is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.
Example 1:
a method of modifying a polyamide film, comprising the steps of:
1) dissolving 800mg of dopamine hydrochloride in 40mL of dimethylformamide; then under the protection of dry nitrogen, adding 0.26mL of 2-bromoisobutyryl bromide and 0.30mL of triethylamine, and reacting to obtain an initiator dopamine coupling solution; wherein, the concentration of the 2-bromine isobutyryl bromide is as follows: 4.04mmol/mL and triethylamine concentration 3.5 mmol/mL.
2) Adding 200mL of tris buffer solution into the initiator dopamine coupling solution prepared in the step 1) to obtain a mixed solution; the concentration of tris buffer was 0.01 mmol/mL.
3) Introduction of initiator at the membrane surface: reacting an active layer on the surface of the polyamide TFC membrane with the mixed solution prepared in the step 2), and grafting an initiator on the active layer;
4) grafting a zwitterionic polymer on the surface of the membrane: dissolving 15.64g of zwitterionic monomer (sulfobetaine methyl acrylate monomer) in 200mL of isopropanol aqueous solution, blowing off for 10min by nitrogen, adding 20mL of copper chloride catalytic complex under the protection of nitrogen, placing the membrane treated in the step 3), continuously introducing nitrogen for 10min, adding ascorbic acid solution, carrying out polymerization reaction for 1 h, and exposing the membrane to air to terminate the polymerization reaction, thereby obtaining the modified membrane grafted with zwitterions.
The ascorbic acid solution was prepared by dissolving 1g of ascorbic acid in 10mL of an aqueous isopropanol solution having a concentration of 50%.
The copper chloride catalytic complex is prepared by dissolving 0.01g of copper chloride and 0.14g of tris (2-pyridylmethyl) amine in 20mL of an aqueous isopropanol solution at a concentration of 50%.
Example 2:
the main steps of the embodiment are the same as those of embodiment 1, and further, the modified membrane grafted with zwitterions obtained in the step 4) is placed in a silver nitrate solution with the concentration of 2mmol/L and is contacted for 10 minutes in the dark, so that a membrane adsorbed with silver ions is obtained; and adding a sodium borohydride solution with the concentration of 2mmol/L to the membrane adsorbed with the silver ions, and contacting for 5 minutes in the dark to reduce the silver ions to obtain the modified polyamide composite membrane. FIG. 2 shows the change in membrane flux before and after modification.
Example 3:
the main steps of this example are the same as example 1, and further, in step 3), after adsorbing metal ions on the surface of the active layer on the surface of the polyamide TFC membrane, placing the active layer on the surface of the polyamide TFC membrane in a silver nitrate solution with a concentration of 2mmol/L, and contacting for 10 minutes in the dark to obtain a membrane adsorbed with silver ions; adding a sodium borohydride solution with the concentration of 2mmol/L to the membrane adsorbed with silver ions, contacting for 5 minutes in the dark to reduce the silver ions, carrying out reduction reaction on metal ions on the surface of the membrane, and then reacting the active layer on the surface of the polyamide TFC membrane subjected to the treatment with the mixed solution prepared in the step 2).
Claims (9)
1. A method of modifying a polyamide film, comprising the steps of:
1) dissolving the dopamine hydrochloride in dimethylformamide; then under the protection of inert gas, adding 2-bromine isobutyryl bromide and triethylamine, and reacting to obtain an initiator dopamine coupling solution;
2) adding a trihydroxymethyl aminomethane buffer solution into the initiator dopamine coupling solution prepared in the step 1) to obtain a mixed solution;
3) introduction of initiator at the membrane surface: reacting an active layer on the surface of the polyamide TFC membrane with the mixed solution prepared in the step 2), and grafting an initiator on the active layer;
4) grafting a zwitterionic polymer on the surface of the membrane: dissolving a zwitterion monomer in an isopropanol aqueous solution, adding a copper chloride catalytic complex under the protection of inert gas, putting the membrane treated in the step 3), maintaining the atmosphere of the inert gas, adding an ascorbic acid solution, carrying out polymerization reaction for 0.5-3 hours, and then exposing the membrane to the air to terminate the polymerization reaction, thereby obtaining the modified membrane grafted with zwitterions.
2. A method of modifying a polyamide film, comprising the steps of:
1) dissolving the dopamine hydrochloride in dimethylformamide; then under the protection of inert gas, adding 2-bromine isobutyryl bromide and triethylamine, and reacting to obtain an initiator dopamine coupling solution;
2) adding a trihydroxymethyl aminomethane buffer solution into the initiator dopamine coupling solution prepared in the step 1) to obtain a mixed solution;
3) adsorbing metal ions on the surface of an active layer on the surface of the polyamide TFC membrane, then carrying out reduction reaction on the metal ions on the surface of the membrane, and then reacting the active layer on the surface of the treated polyamide TFC membrane with the mixed solution prepared in the step 2);
4) grafting a zwitterionic polymer on the surface of the membrane: dissolving a zwitterionic monomer in an isopropanol aqueous solution, adding a copper chloride catalytic compound under the protection of inert gas, placing the film treated in the step 3), maintaining the atmosphere of the inert gas, adding an ascorbic acid solution, carrying out polymerization reaction for 0.5-3 hours, and then exposing the film to air to terminate the polymerization reaction, thereby obtaining the modified polyamide composite film.
3. A process for modifying a polyamide film as claimed in claim 1 or 2, characterized in that:
the volume ratio of the dimethylformamide to the 2-bromoisobutyryl bromide to the triethylamine is (2000-4000) to (13-26) to (15-30), wherein the concentration of the 2-bromoisobutyryl bromide is as follows: 4.04-8.08 mmol/mL and the concentration of triethylamine is 3.50-7.00 mmol/mL.
4. A process for modifying a polyamide film as claimed in claim 1 or 2, characterized in that: in the step 2), the volume ratio of the trihydroxymethyl aminomethane buffer solution to the initiator dopamine coupling solution is (5-10): (1-2), the concentration of the tris buffer solution is 0.01-0.02 mmol/mL.
5. A process for modifying a polyamide film as claimed in claim 1 or 3, characterized in that: in the step 4), the ratio of the mass (g) of the zwitterionic monomer to the volume (mL) of the isopropanol aqueous solution is (39-79) to (500-1000), wherein the concentration of the isopropanol aqueous solution is 25-75%;
the volume ratio of the isopropanol aqueous solution to the copper chloride catalytic complex to the ascorbic acid solution is (100-200) to (4-20) to (8-15).
6. A process for modifying a polyamide film as claimed in claim 1 or 2, characterized in that: in the step 4), the zwitterionic monomer is a sulfobetaine methyl acrylate monomer or a carboxyl betaine methyl acrylate monomer.
7. A process for modifying a polyamide film as claimed in claim 1 or 3, characterized in that: in the step 4), the ascorbic acid solution is prepared by dissolving ascorbic acid in an aqueous isopropanol solution.
8. A process for modifying a polyamide film as claimed in claim 1 or 2, characterized in that: in the step 4), the preparation method of the copper chloride catalytic complex is to dissolve copper chloride and tri (2-pyridylmethyl) amine in an isopropanol aqueous solution to obtain the copper chloride catalytic complex.
Wherein: the mass ratio of the copper chloride to the tri (2-pyridylmethyl) amine is as follows: (1-5) and (14-70).
9. A process for modifying a polyamide film as claimed in claim 1, wherein: and 4) adsorbing metal ions on the surface of the membrane grafted with the zwitterion, and then carrying out reduction reaction on the metal ions on the surface of the membrane to obtain the modified composite membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011035935.5A CN112316740A (en) | 2020-09-27 | 2020-09-27 | Method for modifying polyamide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011035935.5A CN112316740A (en) | 2020-09-27 | 2020-09-27 | Method for modifying polyamide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112316740A true CN112316740A (en) | 2021-02-05 |
Family
ID=74303309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011035935.5A Pending CN112316740A (en) | 2020-09-27 | 2020-09-27 | Method for modifying polyamide film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112316740A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113083019A (en) * | 2021-03-29 | 2021-07-09 | 哈尔滨工业大学 | Amphoteric substance-based polyamide nanofiltration membrane surface modification method |
| CN114307682A (en) * | 2021-11-16 | 2022-04-12 | 中国科学院生态环境研究中心 | Method for repairing water treatment performance of polyamide composite membrane |
| CN114307678A (en) * | 2022-02-17 | 2022-04-12 | 天津工业大学 | Preparation method of composite nanofiltration membrane based on zwitterion regulation and control |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140339166A1 (en) * | 2013-05-14 | 2014-11-20 | Pall Corporation | High throughput membrane with channels |
| CN106823805A (en) * | 2017-03-08 | 2017-06-13 | 哈尔滨工业大学 | A kind of method that post processing prepares the positive impregnating polyamide composite membrane of antipollution |
| CN106916330A (en) * | 2017-03-08 | 2017-07-04 | 哈尔滨工业大学 | The method of modified polyamide laminated film |
| US20180369756A1 (en) * | 2017-06-22 | 2018-12-27 | Teledyne Scientific & Imaging, Llc | High flux, chlorine resistant coating for sulfate removal membranes |
| CN109550406A (en) * | 2019-01-11 | 2019-04-02 | 浙江工业大学 | Both sexes particles in-situ constructs the preparation method of metal organic frame seperation film |
| CN109603584A (en) * | 2018-12-29 | 2019-04-12 | 安徽智泓净化科技股份有限公司 | A kind of preparation method of hydrophilic polyamide reverse osmosis membrane |
-
2020
- 2020-09-27 CN CN202011035935.5A patent/CN112316740A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140339166A1 (en) * | 2013-05-14 | 2014-11-20 | Pall Corporation | High throughput membrane with channels |
| CN106823805A (en) * | 2017-03-08 | 2017-06-13 | 哈尔滨工业大学 | A kind of method that post processing prepares the positive impregnating polyamide composite membrane of antipollution |
| CN106916330A (en) * | 2017-03-08 | 2017-07-04 | 哈尔滨工业大学 | The method of modified polyamide laminated film |
| US20180369756A1 (en) * | 2017-06-22 | 2018-12-27 | Teledyne Scientific & Imaging, Llc | High flux, chlorine resistant coating for sulfate removal membranes |
| CN109603584A (en) * | 2018-12-29 | 2019-04-12 | 安徽智泓净化科技股份有限公司 | A kind of preparation method of hydrophilic polyamide reverse osmosis membrane |
| CN109550406A (en) * | 2019-01-11 | 2019-04-02 | 浙江工业大学 | Both sexes particles in-situ constructs the preparation method of metal organic frame seperation film |
Non-Patent Citations (3)
| Title |
|---|
| CAIHONG LIU等: "Antifouling Thin-Film Composite Membranes by Controlled Architecture of Zwitterionic Polymer Brush Layer", 《ENVIRON. SCI. TECHNOL》 * |
| CAIHONG LIU等: "Mitigation of Biofilm Development on Thin-Film Composite Membranes Functionalized with Zwitterionic Polymers and Silver Nanoparticles", 《ENVIRON. SCI. TECHNOL》 * |
| 刘彩虹: "聚酰胺复合膜功能层抗污染调控机制研究", 《中国优秀硕博士学位论文全文数据库(博士) 工程科技II辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113083019A (en) * | 2021-03-29 | 2021-07-09 | 哈尔滨工业大学 | Amphoteric substance-based polyamide nanofiltration membrane surface modification method |
| CN114307682A (en) * | 2021-11-16 | 2022-04-12 | 中国科学院生态环境研究中心 | Method for repairing water treatment performance of polyamide composite membrane |
| CN114307678A (en) * | 2022-02-17 | 2022-04-12 | 天津工业大学 | Preparation method of composite nanofiltration membrane based on zwitterion regulation and control |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112316740A (en) | Method for modifying polyamide film | |
| Zhang et al. | Selective ion separation by capacitive deionization (CDI) based technologies: a state-of-the-art review | |
| Chen et al. | Bioelectrochemical systems-driven directional ion transport enables low-energy water desalination, pollutant removal, and resource recovery | |
| CN102634054B (en) | Preparation method of modified polymer film material for effectively removing trace heavy metal ions in water body | |
| CN102452753B (en) | Saliferous organic wastewater treatment method | |
| CN110170309B (en) | Two-dimensional metal organic framework composite membrane material, preparation method and application | |
| CN106916330A (en) | The method of modified polyamide laminated film | |
| Xing et al. | MOFs self-assembled molecularly imprinted membranes with photoinduced regeneration ability for long-lasting selective separation | |
| CN110697958A (en) | High-efficiency salt separating membrane concentration process | |
| CN110124735B (en) | Hydrophilic conductive hydrogel cathode catalytic membrane and preparation method and application thereof | |
| Li et al. | Metal-organic frameworks (MOFs) as efficient catalysts for electro-Fenton (EF) reactions: Current progress and prospects | |
| CN109293100B (en) | Heavy metal sewage treatment method | |
| Zhu et al. | Critical review of catalysis-assisted nanofiltration for micropollutants removal: Catalytic coupled nanofiltration system vs catalytic nanofiltration membrane | |
| CN109354304B (en) | Sewage treatment and energy recovery method based on three-stage membrane separation technology | |
| CN108211825B (en) | Metal organic framework composite membrane material and preparation and application thereof | |
| Sun et al. | Overview of electrochemical method in the treatment of municipal sewage | |
| Lu et al. | Bio-synthesis of molecularly imprinted membrane with photo-regeneration availability for selective separation applications | |
| CN104961298A (en) | Acrylon wastewater deep treatment method based on dry method | |
| CN114011251A (en) | Conductive film for efficiently removing nitrate in water and preparation method thereof | |
| CN112316738A (en) | Method for preparing anti-pollution forward osmosis polyamide composite membrane through post-treatment | |
| CN111925051A (en) | MBR and ozone combined sewage advanced treatment process | |
| CN112794416A (en) | Flocculation-adsorption reagent and method for synchronously removing turbidity, ammonia nitrogen and TP in black and odorous water body | |
| Wang et al. | Rational design of recyclable metal-organic frameworks-based materials for water purification: An opportunity for practical application | |
| CN111729662A (en) | Preparation method and application of MXene membrane material for in-situ growth of Bi-MOF | |
| CN108283941B (en) | Nonlinear photocatalytic film for total nitrogen treatment in tail water of sewage treatment plant 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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210205 |
|
| WD01 | Invention patent application deemed withdrawn after publication |