CN114699930A - Polyazacyclic amide membrane for dye wastewater treatment and preparation method thereof - Google Patents
Polyazacyclic amide membrane for dye wastewater treatment and preparation method thereof Download PDFInfo
- Publication number
- CN114699930A CN114699930A CN202210193911.5A CN202210193911A CN114699930A CN 114699930 A CN114699930 A CN 114699930A CN 202210193911 A CN202210193911 A CN 202210193911A CN 114699930 A CN114699930 A CN 114699930A
- Authority
- CN
- China
- Prior art keywords
- membrane
- polyazacyclic
- amide
- wastewater treatment
- dye wastewater
- 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.)
- Granted
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
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
Abstract
The invention belongs to the field of dye wastewater treatment by membrane separation, and particularly relates to a polyazacyclic amide membrane for dye wastewater treatment and a preparation method thereof. The method takes a cyclic monomer azacycloalkane as an aqueous phase monomer, and adopts interfacial polymerization to prepare the polyazacyclic amide membrane. The invention adopts novel cyclic molecular azacycloalkane as a water phase monomer, loads the water phase monomer on the surface of a base membrane, and then reacts with trimesoyl chloride to carry out an interfacial polymerization process, thereby constructing the polyazacyclic amide membrane with stable structure and high selectivity. According to the polyazacyclic amide membrane prepared by the invention, the intra-ring pores of the nitrogen heterocycles are increased, and the characteristic of intercepting macromolecular dyes is kept, so that the dyes/salts are effectively separated.
Description
Technical Field
The invention belongs to the field of dye wastewater treatment by membrane separation, and particularly relates to a polyazacyclic amide membrane for dye wastewater treatment and a preparation method thereof.
Background
Due to the rapid growth of population, urbanization and industrialization, the discharge amount of textile dye wastewater is rapidly increasing. The dye pollutants can be damaged by polluting fresh water resourcesHuman health, but also harmful effects on aquatic life. Therefore, how to remove the dye pollutants efficiently is urgent. Heretofore, conventional techniques such as adsorption, distillation, flocculation, biodegradation, advanced oxidation, and the like have been widely used for the treatment of dye wastewater. While these methods are effective in removing dyes, one major challenge is the low selectivity of the dye/salt mixture, which impacts dye cleanup and recovery and inorganic salt recycling. Compared with the technology, the loose nanofiltration membrane has the advantages of high separation coefficient, high flux, environmental friendliness and the like due to the fact that the molecular size of the loose nanofiltration membrane is similar to that of most dyes, and is widely applied to a dye wastewater treatment separation system. More importantly, unlike conventional dense nanofiltration membranes, one of the main features of loose nanofiltration membranes is the high divalent salt (e.g., Na)2SO4) Permeability, which makes it possible to separate the dye/salt mixture.
At present, the loose nanofiltration membrane construction method mainly comprises blending-phase conversion, surface chemical modification, bionic material deposition, interfacial polymerization and the like. The interfacial polymerization is a method for industrially synthesizing a large-area film, and the method mainly utilizes piperazine as a water-phase monomer and trimesoyl chloride as an oil-phase monomer to prepare the polypiperazine amide nanofiltration membrane. However, such polyamide membranes have high retention rates for both dyes and multivalent inorganic salts, making it difficult to effectively separate dye/salt mixtures. Therefore, the crosslinking degree of the film is finely adjusted and the pore diameter and porosity are increased by adopting or introducing long-chain branched monomers, multiple primary amine monomers and hydroxyl cyclic monomers, so that the separation selectivity of the dye/salt is improved. However, amine monomers have high reactivity, and are easy to form compact polyamide, so that through-channels are difficult to obtain, and the increase of membrane flux is not obvious. Compared with the hydroxyl cyclic monomer, the hydroxyl cyclic monomer has the following advantages: the polyester film with lower crosslinking degree is formed, and meanwhile, the free volume and the pore canal connectivity of the film can be increased by the pores in the ring, so that the improvement of the dye/salt separation selectivity is facilitated. However, the weak acid and alkali resistance of the membrane limits the application of the membrane in dye wastewater treatment.
Disclosure of Invention
The invention aims to provide a polyazacyclic amide membrane for dye wastewater treatment and a preparation method thereof, which can better solve the problems of acid and alkali resistance of the membrane and effectively separate a dye/salt mixture.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a polyazacyclic amide membrane for dye wastewater treatment is obtained by the following preparation method: the polyazacyclic amide membrane is prepared by taking a cyclic monomer azacycloalkane as an aqueous phase monomer and adopting interfacial polymerization.
The solvent of the azacyclane is an aqueous solution, and the mass concentration of the aqueous solution is 0.05-0.2 wt%.
The pH of the aqueous solution of the azacycloalkane is preferably 7 to 14, more preferably 12 to 14.
Taking a normal hexane solvent of trimesoyl chloride as an oil phase monomer, wherein the mass concentration is 0.05-0.2 wt%; the mass ratio of the aqueous solution of the azacycloalkane to the n-hexane solution of trimesoyl chloride is as follows: 1: 1-3.
Preferably, the azacycloalkane is 1,4, 7-triazacyclononane, 1,4,8, 11-tetraazacyclotetradecane or 1,4,7,10, 13-pentaazacyclopentadecane.
The molecular formula of the azacycloalkane is as follows:
firstly, soaking an aqueous solution of azacycloalkane on the surface of a base film for 3-10 min; then adding oil phase monomer solution to react for 0.5-2min, preferably 0.5-1min, and then heat treating at 50-80 deg.C for 1-5 min.
The basement membrane can be one of polysulfone, polyethersulfone, polyacrylonitrile or Kevlar basement membrane.
Specifically, the preparation method of the polyazacyclic amide membrane for treating the dye wastewater comprises the following steps:
(1) fixing a base membrane in a membrane component, soaking an azacyclo-alkane aqueous solution with the mass fraction of 0.05-0.2wt% on the surface of the base membrane for 3-10 minutes, and removing the excessive azacyclo-alkane aqueous solution until no obvious water stain exists on the membrane;
(2) pouring 0.05-0.2wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 0.5-2 min;
(3) after the reaction is finished, washing the surface of the membrane for 10-30s by using a normal hexane solvent, and then carrying out heat treatment at 50-80 ℃ for 1-5min to obtain the polyazacyclic amide membrane.
The invention uses novel cyclic monomer azacyclo-alkane as water phase monomer to construct the polyazacyclic amide membrane with stable structure and high selectivity. The azacycloalkane is a piperazine cyclic compound with secondary amine groups, and the existence of a plurality of secondary amine groups enables the compound to be subjected to interfacial polymerization reaction with trimesoyl chloride to form a polyamide membrane with a stable structure, and the formed amido bond is more stable than an ester bond. In addition, azacycloalkanes have unique advantages over piperazines in the design and development of high dye/salt selectivity films: with the increase of the number of carbon or nitrogen atoms on the azacycloalkane ring, the internal pore of the nitrogen heterocycle per se is increased, so that the free volume in the film and the connectivity in the pore channel can be increased in principle, the permeability of the composite film is improved, meanwhile, the increased steric hindrance and the reduced solubility of the composite film can weaken the reaction activity of the azacycloalkane, the degree of crosslinking of the film is reduced to a certain extent to obtain more and larger-sized through nanopores, a microchannel which is beneficial to the permeation of hydrated ions is formed, and in addition, the characteristic of intercepting macromolecular dye is retained, so that the effective separation of dye/salt is realized. In addition, by changing the interfacial polymerization conditions, for example, as the pH of the aza-cyclic monomer-water phase increases, the degree of cross-linking of the polyazacyclic amide membrane decreases, thereby increasing the flux of the composite membrane. In addition, the invention controls the monomer concentration and the interfacial polymerization reaction time, and optimizes the interfacial reaction condition, thereby increasing the porosity of the membrane and further optimizing the separation performance of the composite membrane.
In the method for preparing the polyazacyclic amide membrane, the azacycloalkane does not need to be pretreated, different kinds of polyazacyclic aqueous solutions are directly loaded on the surface of a base membrane such as a polysulfone membrane, and then an oil phase solution is added to carry out interfacial polymerization reaction, so that the polyazacyclic amide membrane for treating dye wastewater can be prepared.
Compared with the prior art, the invention has the following advantages:
the invention adopts novel cyclic molecular azacyclane as a water phase monomer, loads the water phase monomer on the surface of a base membrane, then reacts with trimesoyl chloride to carry out an interfacial polymerization process, and constructs the polyazacyclic amide membrane with stable structure and high selectivity. According to the polyazacyclic amide membrane prepared by the invention, the intra-ring pores of the nitrogen heterocycles are increased, and the characteristic of intercepting macromolecular dyes is kept, so that the dyes/salts are effectively separated.
Drawings
FIG. 1 is a schematic representation of the polyazacyclic amide membranes obtained in example 3, example 4 and example 7, respectively.
Detailed Description
The technical solution of the present invention is described below by using specific examples, but the scope of the present invention is not limited thereto: example 1
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) fixing a polysulfone membrane in a membrane component, taking 0.18 wt% of 1,4, 7-triazacyclononane aqueous solution, adjusting the pH to 12, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing the excessive 1,4, 7-triazacyclononane aqueous solution until no obvious water stain exists on the membrane;
2) pouring 0.1 wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1 min;
3) after the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment for 3min at 80 ℃ to obtain the polyazacyclic amide membrane which is marked as a TFC-1 membrane.
Example 2
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) fixing a polysulfone membrane in a membrane component, taking 0.18 wt% of 1,4, 7-triazacyclononane aqueous solution, adjusting the pH to 13, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing the excessive 1,4, 7-triazacyclononane aqueous solution until no obvious water stain exists on the membrane;
2) pouring 0.1 wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1 min;
3) after the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment for 3min at 80 ℃ to obtain the polyazacyclic amide membrane which is marked as a TFC-2 membrane.
Example 3
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) fixing a polysulfone membrane in a membrane component, taking 0.18 wt% of 1,4, 7-triazacyclononane aqueous solution, adjusting the pH to 14, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing the excessive 1,4, 7-triazacyclononane aqueous solution until no obvious water stain exists on the membrane;
2) pouring 0.1 wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1 min;
3) after the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment for 3min at 80 ℃ to obtain the polyazacyclic amide membrane which is marked as a TFC-3 membrane.
Example 4
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) fixing a polysulfone membrane in a membrane component, taking 0.12 wt% of 1,4,8, 11-tetraazacyclotetradecane aqueous solution, adjusting the pH to 12, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing excessive aqueous phase solution until no obvious water stain exists on the membrane;
2) pouring 0.1 wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1 min;
3) after the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment for 3min at 80 ℃ to obtain the polyazacyclic amide membrane which is marked as a TFC-4 membrane.
Example 5
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) fixing a polysulfone membrane in a membrane component, taking 0.12 wt% of 1,4,8, 11-tetraazacyclotetradecane aqueous solution, adjusting the pH to 13, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing excessive aqueous phase solution until no obvious water stain exists on the membrane;
2) pouring 0.1 wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1 min;
3) after the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment for 3min at 80 ℃ to obtain the polyazacyclic amide membrane which is marked as a TFC-5 membrane.
Example 6
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) fixing a polysulfone membrane in a membrane component, taking 0.12 wt% of 1,4,8, 11-tetraazacyclotetradecane aqueous solution, adjusting the pH to 14, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing excessive aqueous phase solution until no obvious water stain exists on the membrane;
2) pouring 0.1 wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1 min;
3) after the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment for 3min at 80 ℃ to obtain the polyazacyclic amide membrane which is marked as a TFC-6 membrane.
Example 7
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) fixing a polysulfone membrane in a membrane component, taking 0.10 wt% of 1,4,7,10, 13-pentaazacyclopentadecane aqueous solution, adjusting the pH to 13, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing excessive aqueous phase solution until no obvious water stain exists on the membrane;
2) pouring 0.1 wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1 min;
3) after the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment for 3min at 80 ℃ to obtain the polyazacyclic amide membrane which is marked as a TFC-7 membrane.
Example 8
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) fixing a polysulfone membrane in a membrane component, taking 0.10 wt% of 1,4,7,10, 13-pentaazacyclopentadecane aqueous solution, adjusting the pH to 14, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing excessive aqueous phase solution until no obvious water stain exists on the membrane;
2) pouring 0.1 wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1 min;
3) after the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment for 3min at 80 ℃ to obtain the polyazacyclic amide membrane which is marked as a TFC-8 membrane.
Comparative example 1
Preparing a PIP-TMC polyamide nanofiltration membrane:
1) fixing a polysulfone membrane in a membrane component, soaking 0.10 wt% of piperazine aqueous solution on the surface of the polysulfone membrane, wherein the pH of the aqueous phase monomer solution is 11, and removing the excess piperazine aqueous solution after soaking for 5 minutes until no obvious water stain exists on the membrane;
2) pouring 0.1 wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1 min;
3) after the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment at 80 ℃ for 3min to obtain the polypiperazine amide membrane which is marked as a PIP/TMC-TFC membrane.
Comparative example 2
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) fixing a polysulfone membrane in a membrane component, taking 0.18 wt% of 1,4, 7-triazacyclononane aqueous solution, wherein the pH of the aqueous phase monomer solution is 9, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing the excessive 1,4, 7-triazacyclononane aqueous solution until no obvious water stain exists on the membrane;
2) pouring 0.1 wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1 min;
3) after the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment for 3min at 80 ℃ to obtain a polyazacyclic amide membrane which is marked as a TFC membrane of comparative example 2;
comparative example 3
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) fixing a polysulfone membrane in a membrane component, taking 0.12 wt% of 1,4,8, 11-tetraazacyclotetradecane aqueous solution, wherein the pH of the aqueous phase monomer solution is 10, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing excessive aqueous phase solution until no obvious water stain exists on the membrane;
2) pouring 0.1 wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1 min;
3) after the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment at 80 ℃ for 3min to obtain the polyazacyclic amide membrane which is marked as a comparative example 3TFC membrane.
Comparative example 4
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) fixing a polysulfone membrane in a membrane component, taking 0.10 wt% of 1,4,7,10, 13-pentaazacyclopentadecane aqueous solution, wherein the pH of the aqueous phase monomer solution is 12, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing excessive aqueous phase solution until no obvious water stain exists on the membrane;
2) pouring 0.1 wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1 min;
3) after the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment at 80 ℃ for 3min to obtain the polyazacyclic amide membrane, which is marked as a comparative example 4TFC membrane.
The water flux and the removal rate of dyes and inorganic salts from the dye wastewater of the polyazacyclic amide membranes prepared in examples 1 to 8 and the amide membranes prepared in comparative examples 1 to 4 were measured at room temperature, and the results are shown in tables 1 and 2. The test was carried out at normal temperature in a cross-flow apparatus at a pressure of 0.4 MPa.
Table 1 shows that the water flux of the polyazeamide membranes prepared in examples 1-8 and the water flux of the polypiperazine amide membranes prepared in comparative examples 1-4 and the retention rate of the nanofiltration membranes on the dye in the dye wastewater reported in the literature are within reasonable error ranges.
TABLE 1
It can be seen from the table that compared with the traditional polypiperazine polyamide membrane and the nanofiltration membrane reported in the literature, the polyazacyclic amide membrane has the water flux 5-10 times that of the traditional polypiperazine polyamide membrane on the premise of keeping higher retention rate of the dye, and shows excellent dye removal capability.
Table 2 shows that the water flux of the polyazacyclic amide membranes prepared in examples 1-8 and the water flux of the amide membranes prepared in comparative examples 1-4 and the retention rate of inorganic salts in dye wastewater by the nanofiltration membranes reported in the literature are within reasonable error ranges.
TABLE 2
As can be seen from the table, compared with the conventional polypiperazine amide membrane and the nanofiltration membrane reported in the literature, the polyazacyclic amide membrane has a higher retention rate of divalent salt without adjusting the pH of the aqueous phase monomer, and thus the separation of the divalent salt from the dye molecule cannot be realized. After the pH of the aqueous phase monomer solution is adjusted, the retention rate of the polyazacyclic amide membrane on inorganic salt is greatly reduced, and excellent dye/salt separation capability is shown.
Claims (8)
1. A preparation method of a polyazacyclic amide membrane for dye wastewater treatment is characterized in that a cyclic monomer azacycloalkane is used as an aqueous phase monomer, and interfacial polymerization is adopted to prepare the polyazacyclic amide membrane.
2. The method for preparing a polyazacyclic amide membrane for dye wastewater treatment according to claim 1, wherein the solvent of azacycloalkane is an aqueous solution having a mass concentration of 0.05 to 0.2 wt%.
3. The method for preparing a polyazacyclic amide membrane for dye wastewater treatment according to claim 2, wherein a n-hexane solvent of trimesoyl chloride is used as an oil phase monomer, and the mass concentration is 0.05-0.2 wt%; the mass ratio of the aqueous solution of the azacycloalkane to the n-hexane solution of trimesoyl chloride is as follows: 1:1-3.
4. The method for preparing polyazacyclic amide membrane for dye wastewater treatment according to claim 2, wherein the pH of the aqueous solution of azacycloalkane is 7 to 14.
5. The method for preparing polyazacyclic amide membrane for dye wastewater treatment according to claim 4, wherein the pH of the aqueous solution of azacycloalkane is 12 to 14.
6. The method for preparing a polyazacyclic amide membrane for dye wastewater treatment according to any one of claims 1 to 5, wherein the azacycloalkane is 1,4, 7-triazacyclononane, 1,4,8, 11-tetraazacyclotetradecane, or 1,4,7,10, 13-pentaazacyclopentadecane.
7. The method of claim 6, wherein the aqueous solution of azacycloalkane is first soaked on the surface of the base membrane for 3-10 min; then adding oil phase monomer solution to react for 0.5-2min, and then carrying out heat treatment at 50-80 ℃ for 1-5 min.
8. Polyazacyclic amide membranes obtainable by the process of any of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210193911.5A CN114699930B (en) | 2022-03-01 | 2022-03-01 | Polyazacyclic amide membrane for dye wastewater treatment and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210193911.5A CN114699930B (en) | 2022-03-01 | 2022-03-01 | Polyazacyclic amide membrane for dye wastewater treatment and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114699930A true CN114699930A (en) | 2022-07-05 |
| CN114699930B CN114699930B (en) | 2023-04-14 |
Family
ID=82167138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210193911.5A Active CN114699930B (en) | 2022-03-01 | 2022-03-01 | Polyazacyclic amide membrane for dye wastewater treatment and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114699930B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115301085A (en) * | 2022-08-24 | 2022-11-08 | 郑州大学 | Low-pressure nanofiltration membrane for treating mono/divalent salt and/or antibiotic wastewater and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4337154A (en) * | 1979-04-04 | 1982-06-29 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Crosslinked composite semipermeable membrane |
| GB9918113D0 (en) * | 1999-08-03 | 1999-10-06 | Saehan Ind Inc | Polyamide reverse osmosis membrane and method of producing the same |
| CN102814126A (en) * | 2011-06-09 | 2012-12-12 | 中国科学院城市环境研究所 | Preparation method of high-flux antioxidant nanofiltration membrane |
| CN104387336A (en) * | 2014-10-24 | 2015-03-04 | 上海应用技术学院 | Preparation methods of 1,4,7,10-tetraazacyclododecane and nanofiltration membrane |
| CN104667759A (en) * | 2013-11-29 | 2015-06-03 | 贵阳时代沃顿科技有限公司 | Preparation method of high-throughput anti-pollution composite nanofiltration membrane |
| KR20170029971A (en) * | 2015-09-08 | 2017-03-16 | 주식회사 엘지화학 | Method for manufacturing water-treatment membrane, water-treatment membrane manufactured by thereof, and water treatment module comprising membrane |
| CN106574008A (en) * | 2014-08-15 | 2017-04-19 | 普罗米鲁斯有限责任公司 | Polycyclo-olefinic block polymers and pervaporation membranes made therefrom |
| CN111921378A (en) * | 2020-08-11 | 2020-11-13 | 郑州大学 | Polyamide membrane for separating dye and salt and preparation method thereof |
| CN112316755A (en) * | 2020-08-14 | 2021-02-05 | 同济大学 | Composite nanofiltration membrane and preparation method thereof |
-
2022
- 2022-03-01 CN CN202210193911.5A patent/CN114699930B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4337154A (en) * | 1979-04-04 | 1982-06-29 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Crosslinked composite semipermeable membrane |
| GB9918113D0 (en) * | 1999-08-03 | 1999-10-06 | Saehan Ind Inc | Polyamide reverse osmosis membrane and method of producing the same |
| CN102814126A (en) * | 2011-06-09 | 2012-12-12 | 中国科学院城市环境研究所 | Preparation method of high-flux antioxidant nanofiltration membrane |
| CN104667759A (en) * | 2013-11-29 | 2015-06-03 | 贵阳时代沃顿科技有限公司 | Preparation method of high-throughput anti-pollution composite nanofiltration membrane |
| CN106574008A (en) * | 2014-08-15 | 2017-04-19 | 普罗米鲁斯有限责任公司 | Polycyclo-olefinic block polymers and pervaporation membranes made therefrom |
| CN104387336A (en) * | 2014-10-24 | 2015-03-04 | 上海应用技术学院 | Preparation methods of 1,4,7,10-tetraazacyclododecane and nanofiltration membrane |
| KR20170029971A (en) * | 2015-09-08 | 2017-03-16 | 주식회사 엘지화학 | Method for manufacturing water-treatment membrane, water-treatment membrane manufactured by thereof, and water treatment module comprising membrane |
| CN111921378A (en) * | 2020-08-11 | 2020-11-13 | 郑州大学 | Polyamide membrane for separating dye and salt and preparation method thereof |
| CN112316755A (en) * | 2020-08-14 | 2021-02-05 | 同济大学 | Composite nanofiltration membrane and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| LIZONDO-SABATER, J; SEGULI, MJ等: "New membrane perchlorate-selective electrodes containing polyazacycloalkanes as carriers" * |
| XIAOQUAN FENG等: "Recent advances of loose nanofiltration membranes for dye/salt separation" * |
| 王兴华;王薇;: "界面聚合法制备复合膜中的改性研究" * |
| 谢锐,褚良银,曲剑波: "pH响应型微囊膜的研究与应用进展" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115301085A (en) * | 2022-08-24 | 2022-11-08 | 郑州大学 | Low-pressure nanofiltration membrane for treating mono/divalent salt and/or antibiotic wastewater and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114699930B (en) | 2023-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111992049B (en) | Polyamide reverse osmosis membrane and preparation method thereof | |
| CN109603573B (en) | Preparation method of zeolite imidazole ester framework polyamine nanoparticle composite membrane | |
| CN106731841A (en) | A kind of supermolecule composite nanometer filtering film and its preparation method and application | |
| CN110066415B (en) | Preparation method of porous membrane with functionalized surface | |
| CN110201544B (en) | High-flux high-selectivity nanofiltration membrane and preparation method thereof | |
| CN114699930B (en) | Polyazacyclic amide membrane for dye wastewater treatment and preparation method thereof | |
| CN115178109B (en) | Composite nanofiltration membrane based on covalent organic framework compound NCOF and preparation method thereof | |
| CN105566383A (en) | Acyl chloride monomer and preparation method thereof and reverse osmosis composite membrane and preparation method thereof | |
| CN112808022A (en) | Polyvinyl amine membrane with hydrophilic and hydrophobic functional groups and preparation method and application thereof | |
| CN115608161A (en) | Method for preparing loose nanofiltration membrane by promoting rapid deposition of polydopamine through carbon quantum dots | |
| CN111841343A (en) | Asymmetric polyamide nano-film and preparation method thereof | |
| CN113457466B (en) | Oxidized hyperbranched polyethyleneimine nanofiltration membrane, preparation method and application | |
| CN110152503A (en) | A kind of preparation method for the solvent resistant nanofiltration membrane that graphene oxide is compound with tool microporous polymer certainly | |
| CN113398783A (en) | Polyacrylonitrile film containing aqueous polymer coating and preparation method thereof | |
| CN111097294B (en) | Preparation method of nanofiltration membrane for reclaimed water treatment | |
| CN110385046B (en) | Method for preparing high-flux reverse osmosis membrane by replacing cyclic macromolecules with polyacyl chloride | |
| CN115554849A (en) | Preparation method of polyethyleneimine-based positively-charged nanofiltration membrane | |
| CN114713042A (en) | Nanofiltration membrane with high resolution and water flux and preparation method thereof | |
| CN111282453B (en) | Preparation method of high-performance seawater desalination membrane and prepared seawater desalination membrane | |
| CN113522065B (en) | Chlorine-resistant pollution-resistant polyamide reverse osmosis composite membrane and preparation method thereof | |
| CN113713635A (en) | Metal organic framework ZIF-8 composite membrane containing amino ligand, preparation and application thereof | |
| CN114345149A (en) | High-boron-removal polyamide reverse osmosis membrane and preparation method thereof | |
| CN113304618A (en) | MOFs (metal-organic frameworks) -based in-situ growth forward osmosis membrane and preparation method thereof | |
| KR20010081730A (en) | Fabrication of high permeable reverse osmosis membranes | |
| CN115041026B (en) | Preparation method of organic solvent nanofiltration membrane with introduced macrocyclic molecules |
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 |