CN111151147B - Polyaniline modified aluminosilicate molecular sieve doped polyamide composite membrane - Google Patents
Polyaniline modified aluminosilicate molecular sieve doped polyamide composite membrane Download PDFInfo
- Publication number
- CN111151147B CN111151147B CN202010087978.1A CN202010087978A CN111151147B CN 111151147 B CN111151147 B CN 111151147B CN 202010087978 A CN202010087978 A CN 202010087978A CN 111151147 B CN111151147 B CN 111151147B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- polyaniline
- monomer solution
- composite membrane
- polyamide composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- 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
-
- 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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a polyamide composite membrane doped with a polyaniline modified aluminosilicate molecular sieve and a preparation method thereof, aiming at the problem that the molecular sieve is easy to agglomerate in the process of doping a polyamide membrane, wherein a polyamine aqueous phase monomer solution and a polyacyl chloride organic phase monomer solution mixed with the polyaniline modified molecular sieve are sequentially coated on a base material by utilizing an interfacial polymerization method, the polyaniline modified molecular sieve is formed in a mode that a nano molecular sieve occupied by a template agent in a pore channel is subjected to polyaniline modification, and then the template agent in the pore channel is removed at a low temperature under an ozone atmosphere, and the molecular sieve is an aluminosilicate molecular sieve. The method not only overcomes the problem of molecular sieve agglomeration, but also improves the water flux and chlorine resistance of the polyamide composite membrane through double modification of polyaniline and the molecular sieve.
Description
The invention relates to a polyamide composite film, in particular to an inorganic particle doped polyamide composite film.
The polyamide composite membrane is a polymer membrane commonly used in the membrane separation process, is prepared by the reaction of water-phase polyamine and oil-phase polybasic acyl chloride through an interfacial polymerization method, and forms a compact ultra-thin active layer with the rough peak-valley morphology and the thickness of hundreds of nanometers on the surface of a porous supporting layer. The existing polyamide composite membrane can be applied to multiple branches such as reverse osmosis, nanofiltration, forward osmosis and the like, and can be particularly and widely applied to multiple fields such as drinking water purification, boiler make-up water, medicine, food, brackish water desalination, industrial wastewater treatment and the like.
In order to meet the application requirements of the polyamide composite membrane, the polyamide membrane is modified by doping inorganic particles such as molecular sieves, silicon oxide, titanium dioxide, carbon nanotubes and the like in the prior art so as to improve the flux of the membrane. The molecular sieve is called as an ideal membrane-doped inorganic particle because the molecular sieve has a unique channel structure, can be used as a water transmission channel and has a good hydrophilic characteristic. Common molecular sieves used for doping include aluminosilicate molecular sieves and all-silica molecular sieves, and compared with all-silica molecular sieves, aluminosilicate molecular sieves have better hydrophilic performance. The document of the influx of zeolite crystal size on zeolite polyamide film bridges (Langmuir, 2009, 25 (17): 10139-10145) states that for a molecular sieve doped polyamide film, the smaller the particle size of the filled molecular sieve is, the more favorable the retention rate of the composite film is. However, the molecular sieve with the nano particle size has poor compatibility with an organic medium in the membrane doping process, and is easy to agglomerate, so that the molecular sieve is distributed in a polyamide separation layer unevenly, and the membrane performance is poor. Therefore, in order to avoid serious agglomeration, the mass content of the molecular sieve in the organic phase solution in the prior art is generally not more than 2wt%, which limits the upper limit of flux improvement of the molecular sieve modified polyamide composite membrane, and the low-content molecular sieve doping is difficult to avoid agglomeration.
Aiming at the defects of the prior art, the invention provides a polyamide composite membrane doped with a polyaniline modified molecular sieve and a preparation method thereof, and the problem of molecular sieve agglomeration is solved by performing polyaniline modification on the molecular sieve.
The polyamide composite membrane is formed by sequentially coating polyamine aqueous phase monomer solution and polyacyl chloride organic phase monomer solution mixed with polyaniline modified molecular sieve on a base material by utilizing an interfacial polymerization method, wherein the polyaniline modified molecular sieve is formed by performing polyaniline modification on a nano molecular sieve occupied by a template in a pore passage and then removing the template in the pore passage at a low temperature under an ozone atmosphere, and the molecular sieve is an aluminosilicate molecular sieve.
The invention also provides a method for preparing the polyamide composite membrane, in particular to a method for preparing a polyamide composite membrane doped with a polyaniline modified aluminosilicate molecular sieve, which comprises the following steps:
(1) preparing a nano molecular sieve with channels occupied by a template agent by using a crystallization liquid hydrothermal method comprising a Si source, an Al source, water and an organic template agent;
(2) placing the nano molecular sieve in an aniline solution for ultrasonic treatment, and then placing the nano molecular sieve in an oxidant solution for polymerization to form a nano molecular sieve surrounded by polyaniline;
(3) removing the template agent in the molecular sieve pore channel of the nano molecular sieve surrounded by the polyaniline at low temperature under the ozone atmosphere to form a polyaniline modified molecular sieve;
(4) mixing the polyaniline-modified molecular sieve in a polyacyl chloride monomer solution to form an organic phase monomer solution, and sequentially coating a substrate with a polyamine aqueous phase monomer solution and the organic phase monomer solution to form a polyamide composite membrane through interfacial polymerization.
Specifically, the low-temperature removal temperature is 150-300 ℃.
Specifically, the concentration of ozone in the ozone atmosphere is 10-200 mg/L.
Specifically, the molecular sieve is a microporous molecular sieve, preferably a NaA molecular sieve or a ZSM-5 molecular sieve.
Specifically, the particle size of the molecular sieve is 50-200 nm.
Specifically, the oxidant is one of ammonium persulfate, ferric chloride or hydrogen peroxide.
Specifically, the polyacyl chloride monomer is one of trimesoyl chloride, isophthaloyl chloride, terephthaloyl chloride and phthaloyl chloride, and the polyamine monomer is one of piperazine, ethylenediamine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine and diaminotoluene.
Specifically, the content of the polyaniline-modified molecular sieve in the organic phase monomer solution is 0.5wt% -8 wt%.
The polyamide composite membrane doped with the polyaniline modified molecular sieve prepared by the invention can be applied to reverse osmosis, nanofiltration or forward osmosis, and can be particularly applied to the fields of drinking water purification, boiler make-up water, medicine, food, brackish water desalination, industrial wastewater treatment and the like.
Compared with the prior art, the invention carries out surface modification on the molecular sieve by polyaniline, thereby overcoming the problem of agglomeration of the molecular sieve in an organic phase solution and a polyamide separation layer. The invention also creatively takes the molecular sieve occupying the inside of the pore canal by the template as a molecular sieve source, thereby avoiding the problem that aniline occupies the molecular sieve channel by polymerization inside the molecular sieve, and the gas generated after the organic template is oxidized breaks through the coverage of the polyaniline layer by means of roasting at low temperature to remove the template, thereby avoiding the molecular sieve channel from being covered by the polyaniline layer, and the low roasting temperature avoids the melting of polyaniline. The polyamide composite membrane prepared by the method not only overcomes the problem of molecular sieve agglomeration, but also improves the water flux of the polyamide composite membrane through double modification of polyaniline and the molecular sieve, and improves the chlorine resistance of the composite membrane through the addition of the polyaniline.
Detailed Description
The invention is further illustrated below by way of example of a NaA molecular sieve, without restricting the scope of the invention thereto.
Example 1
(1) NaA nano molecular sieve
Stirring and ultrasonically treating a crystallization liquid containing sodium silicate, sodium metaaluminate, sodium hydroxide and a template agent TMAOH, then placing the crystallization liquid into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal crystallization for 12 hours at the temperature of 100 ℃. After the water heating is finished, cooling, centrifuging, cleaning and drying the crystallization liquid to obtain the NaA nano molecular sieve, wherein the average particle size of the NaA nano molecular sieve is 85nm through a particle size test.
(2) Polyaniline-surrounded molecular sieve
Placing the NaA nano molecular sieve prepared in the step (1) in a 1mol/L aniline solution for ultrasonic treatment for 30min, taking out the NaA nano molecular sieve, placing the NaA nano molecular sieve in a 1mol/L FeCl3 solution for continuously soaking for 30min, polymerizing an aniline monomer on the surface of the NaA molecular sieve, and drying after the reaction is finished to form the nano molecular sieve surrounded by polyaniline;
(3) polyaniline modified molecular sieve
And (3) putting the nano molecular sieve surrounded by the polyaniline prepared in the step (2) into a crucible, putting the crucible into a roasting furnace with the ozone concentration of 30mg/L, setting the roasting temperature to be 150 ℃, the roasting time to be 24h, and the temperature rising and reducing speed to be 1 ℃/min.
(4) Preparation of polyamide composite film
Mixing the polyaniline-modified molecular sieve prepared in the step (4) in the n-hexane containing 0.5wt% of trimesoyl chloride according to the amount of 5wt% to obtain an organic phase monomer solution, and putting 2wt% of m-phenylenediamine in water to obtain an aqueous phase monomer solution. Soaking the polysulfone ultrafiltration membrane serving as a base material in an aqueous phase monomer solution for 5min, removing a surface solution by using filter paper, continuously placing the polysulfone ultrafiltration membrane in an organic phase monomer solution for reacting for 40s to form a polyamide separation layer, taking out the membrane material, and carrying out heat treatment at 60 ℃ for 1h to form the polyamide composite membrane.
Comparative example 1
(1) NaA nano molecular sieve
Stirring and ultrasonically treating a crystallization liquid containing sodium silicate, sodium metaaluminate, sodium hydroxide and a template agent TMAOH, then placing the crystallization liquid into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal crystallization for 12 hours at the temperature of 100 ℃. After the water heating is finished, cooling, centrifuging, cleaning and drying the crystallization liquid to obtain the NaA nano molecular sieve, wherein the average particle size of the NaA nano molecular sieve is 85nm through a particle size test.
(2) Molecular sieve template removing agent
And (3) putting the NaA molecular sieve prepared in the step (2) into a crucible, putting the crucible into a roasting furnace with the ozone concentration of 30mg/L, setting the roasting temperature to be 150 ℃, the roasting time to be 24h, and the temperature rising and reducing speeds to be 1 ℃/min.
(3) Preparation of polyamide composite film
Mixing the NaA molecular sieve calcined in the step (2) in the n-hexane containing 0.5wt% of trimesoyl chloride according to the amount of 5wt% to obtain an organic phase monomer solution, and putting 2wt% of m-phenylenediamine in water to obtain an aqueous phase monomer solution. Soaking the polysulfone ultrafiltration membrane serving as a base material in an aqueous phase monomer solution for 5min, removing a surface solution by using filter paper, continuously placing the polysulfone ultrafiltration membrane in an organic phase monomer solution for reacting for 40s to form a polyamide separation layer, taking out the membrane material, and carrying out heat treatment at 60 ℃ for 1h to form the polyamide composite membrane.
Comparative example 2
(1) NaA nano molecular sieve
Stirring and ultrasonically treating a crystallization liquid containing sodium silicate, sodium metaaluminate, sodium hydroxide and a template agent TMAOH, then placing the crystallization liquid into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal crystallization for 12 hours at the temperature of 100 ℃. After the water heating is finished, cooling, centrifuging, cleaning and drying the crystallization liquid to obtain the NaA nano molecular sieve, wherein the average particle size of the NaA nano molecular sieve is 85nm through a particle size test.
(2) Polyaniline-surrounded molecular sieve
Placing the NaA nano molecular sieve prepared in the step (1) in a 1mol/L aniline solution for ultrasonic treatment for 30min, taking out the NaA nano molecular sieve, placing the NaA nano molecular sieve in a 1mol/L FeCl3 solution for continuously soaking for 30min, polymerizing an aniline monomer on the surface of the NaA molecular sieve, and drying after the reaction is finished to form the nano molecular sieve surrounded by polyaniline;
(3) preparation of polyamide composite film
Mixing the molecular sieve surrounded by the polyaniline prepared in the step (2) in the n-hexane containing 0.5wt% of trimesoyl chloride according to the amount of 5wt% to obtain an organic phase monomer solution, and putting 2wt% of m-phenylenediamine in water to obtain an aqueous phase monomer solution. Soaking the polysulfone ultrafiltration membrane serving as a base material in an aqueous phase monomer solution for 5min, removing a surface solution by using filter paper, continuously placing the polysulfone ultrafiltration membrane in an organic phase monomer solution for reacting for 40s to form a polyamide separation layer, taking out the membrane material, and carrying out heat treatment at 60 ℃ for 1h to form the polyamide composite membrane.
Comparative example 3
(1) NaA nano molecular sieve
Stirring and ultrasonically treating a crystallization liquid containing sodium silicate, sodium metaaluminate, sodium hydroxide and a template agent TMAOH, then placing the crystallization liquid into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal crystallization for 12 hours at the temperature of 100 ℃. After the water heating is finished, cooling, centrifuging, cleaning and drying the crystallization liquid to obtain the NaA nano molecular sieve, wherein the average particle size of the NaA nano molecular sieve is 85nm through a particle size test.
(2) Molecular sieve template removing agent
And (3) putting the NaA molecular sieve prepared in the step (2) into a crucible, putting the crucible into a roasting furnace with the ozone concentration of 30mg/L, setting the roasting temperature to be 150 ℃, the roasting time to be 24h, and the temperature rising and reducing speeds to be 1 ℃/min.
(3) Polyaniline-surrounded molecular sieve
Placing the NaA nano molecular sieve roasted in the step (2) in a 1mol/L aniline solution for ultrasonic treatment for 30min, taking out the NaA nano molecular sieve, placing the NaA nano molecular sieve in a 1mol/L FeCl3 solution for continuously soaking for 30min to ensure that an aniline monomer is polymerized on the surface of the NaA molecular sieve, and drying after the reaction is finished to form the nano molecular sieve surrounded by polyaniline;
(4) preparation of polyamide composite film
Mixing the molecular sieve surrounded by the polyaniline prepared in the step (3) in the n-hexane containing 0.5wt% of trimesoyl chloride according to the amount of 5wt% to obtain an organic phase monomer solution, and putting 2wt% of m-phenylenediamine in water to obtain an aqueous phase monomer solution. Soaking the polysulfone ultrafiltration membrane serving as a base material in an aqueous phase monomer solution for 5min, removing a surface solution by using filter paper, continuously placing the polysulfone ultrafiltration membrane in an organic phase monomer solution for reacting for 40s to form a polyamide separation layer, taking out the membrane material, and carrying out heat treatment at 60 ℃ for 1h to form the polyamide composite membrane.
Comparative example 4
(1) NaA nano molecular sieve
Stirring and ultrasonically treating a crystallization liquid containing sodium silicate, sodium metaaluminate, sodium hydroxide and a template agent TMAOH, then placing the crystallization liquid into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal crystallization for 12 hours at the temperature of 100 ℃. After the water heating is finished, cooling, centrifuging, cleaning and drying the crystallization liquid to obtain the NaA nano molecular sieve, wherein the average particle size of the NaA nano molecular sieve is 85nm through a particle size test.
(2) Polyaniline-surrounded molecular sieve
Placing the NaA nano molecular sieve prepared in the step (1) in a 1mol/L aniline solution for ultrasonic treatment for 30min, taking out the NaA nano molecular sieve, placing the NaA nano molecular sieve in a 1mol/L FeCl3 solution for continuously soaking for 30min, polymerizing an aniline monomer on the surface of the NaA molecular sieve, and drying after the reaction is finished to form the nano molecular sieve surrounded by polyaniline;
(3) polyaniline modified molecular sieve
And (3) putting the nano molecular sieve surrounded by the polyaniline prepared in the step (2) into a crucible, putting the crucible into a roasting furnace in an air atmosphere, setting the roasting temperature to be 450 ℃, the roasting time to be 6h, and the temperature rising and falling speeds to be 1 ℃/min.
(4) Preparation of polyamide composite film
Mixing the polyaniline-modified molecular sieve prepared in the step (4) in the n-hexane containing 0.5wt% of trimesoyl chloride according to the amount of 5wt% to obtain an organic phase monomer solution, and putting 2wt% of m-phenylenediamine in water to obtain an aqueous phase monomer solution. Soaking the polysulfone ultrafiltration membrane serving as a base material in an aqueous phase monomer solution for 5min, removing a surface solution by using filter paper, continuously placing the polysulfone ultrafiltration membrane in an organic phase monomer solution for reacting for 40s to form a polyamide separation layer, taking out the membrane material, and carrying out heat treatment at 60 ℃ for 1h to form the polyamide composite membrane.
Comparative example 5
The organic phase monomer solution was obtained by dissolving 0.5wt% of trimesoyl chloride in n-hexane, and the aqueous phase monomer solution was obtained by dissolving 2wt% of m-phenylenediamine in water. Soaking the polysulfone ultrafiltration membrane serving as a base material in an aqueous phase monomer solution for 5min, removing a surface solution by using filter paper, continuously placing the polysulfone ultrafiltration membrane in an organic phase monomer solution for reacting for 40s to form a polyamide separation layer, taking out the membrane material, and carrying out heat treatment at 60 ℃ for 1h to form the polyamide composite membrane.
Performance characterization
The samples prepared in the above examples and comparative examples were tested for initial performance of the membrane with 2000ppm aqueous sodium chloride solution at 25 ℃ under 1MPa pressure. Then, the sample is soaked in 100mg/L active chlorine solution for 24h, and the performance of the membrane is continuously measured.
The test results are shown in the following table:
| sample (I) | Initial rejection rate | Initial water flux (L/m)2h） | Retention after soaking | Water flux after soaking (L/m)2h） |
| Example 1 | 98.9% | 71.2 | 95.6% | 82.3 |
| Comparative example 1 | 93.4% | 40.3 | N/A | N/A |
| Comparative example 2 | 98.6% | 46.9 | N/A | N/A |
| Comparative example 3 | 98.2% | 58.3 | N/A | N/A |
| Comparative example 4 | 93.4% | 45.1 | N/A | N/A |
| Comparative example 5 | 94.3% | 32.2 | 85.7% | 50.4 |
The above is the embodiment of the present invention. It should be noted that, for a person skilled in the art, several modifications and adaptations can be made without departing from the basic inventive concept and are therefore considered to be within the scope of the present invention.
Claims (10)
1. A polyamide composite membrane doped with a polyaniline-modified aluminosilicate molecular sieve is characterized in that a substrate of the polyamide composite membrane is sequentially coated with a polyamine aqueous phase monomer solution and a polyacyl chloride organic phase monomer solution mixed with the polyaniline-modified molecular sieve by an interfacial polymerization method, the polyaniline-modified molecular sieve is formed by performing polyaniline modification on a nano molecular sieve occupied by a template in a pore channel and then removing the template in the pore channel at a low temperature under an ozone atmosphere, and the molecular sieve is an aluminosilicate molecular sieve; the temperature of the low-temperature removal is 150-300 ℃.
2. A preparation method of a polyamide composite membrane doped with a polyaniline-modified aluminosilicate molecular sieve comprises the following steps:
(1) preparing a nano molecular sieve with channels occupied by a template agent by using a crystallization liquid hydrothermal method comprising a Si source, an Al source, water and an organic template agent;
(2) placing the nano molecular sieve in an aniline solution for ultrasonic treatment, and then placing the nano molecular sieve in an oxidant solution for polymerization to form a nano molecular sieve surrounded by polyaniline;
(3) removing the template agent in the molecular sieve pore channel of the nano molecular sieve surrounded by the polyaniline at low temperature under the ozone atmosphere to form a polyaniline modified molecular sieve; the low-temperature removal temperature is 150-300 ℃;
(4) mixing the polyaniline-modified molecular sieve in a polyacyl chloride monomer solution to form an organic phase monomer solution, and sequentially coating a substrate with a polyamine aqueous phase monomer solution and the organic phase monomer solution to form a polyamide composite membrane through interfacial polymerization.
3. The method according to claim 2, wherein the ozone concentration in the ozone atmosphere is 10 to 200 mg/L.
4. The method of claim 2, wherein the molecular sieve is a microporous molecular sieve.
5. The process of claim 2, wherein the molecular sieve is a NaA molecular sieve or a ZSM-5 molecular sieve.
6. The method of claim 2, wherein the molecular sieve has a particle size of 50 to 200 nm.
7. The method of claim 2, wherein the oxidizing agent is one of ammonium persulfate, ferric chloride, or hydrogen peroxide.
8. The method according to claim 2, wherein the polyacyl chloride monomer is one of trimesoyl chloride, isophthaloyl chloride, terephthaloyl chloride and phthaloyl chloride, and the polyamine aqueous phase monomer solution is one of piperazine, ethylenediamine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine and diaminotoluene.
9. The method of claim 2, wherein the polyaniline-modified molecular sieve is present in the organic phase monomer solution in an amount of 0.5wt% to 8 wt%.
10. The polyaniline-modified molecular sieve-doped polyamide composite membrane of claim 1 for use in reverse osmosis, nanofiltration, or forward osmosis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010087978.1A CN111151147B (en) | 2020-02-12 | 2020-02-12 | Polyaniline modified aluminosilicate molecular sieve doped polyamide composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010087978.1A CN111151147B (en) | 2020-02-12 | 2020-02-12 | Polyaniline modified aluminosilicate molecular sieve doped polyamide composite membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111151147A CN111151147A (en) | 2020-05-15 |
| CN111151147B true CN111151147B (en) | 2021-09-03 |
Family
ID=70565608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010087978.1A Active CN111151147B (en) | 2020-02-12 | 2020-02-12 | Polyaniline modified aluminosilicate molecular sieve doped polyamide composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111151147B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113856492B (en) * | 2021-10-26 | 2023-12-26 | 宁波灏钻科技有限公司 | Polyamide reverse osmosis membrane with molecular sieve doped porous supporting layer |
| CN116159446B (en) * | 2023-03-24 | 2023-11-28 | 泰州九润环保科技有限公司 | Molecular sieve/polyamide mixed matrix membrane |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2451864A (en) * | 2007-08-15 | 2009-02-18 | Exxonmobil Chem Patents Inc | Composite core-shell catalysts and absorbents having outer inorganic layers |
| CN105217649B (en) * | 2015-10-26 | 2017-10-27 | 中国科学院广州能源研究所 | A kind of method of two steps in low temperature removing organic formwork agent and the device for realizing this method |
| CN109225325B (en) * | 2018-09-11 | 2020-07-28 | 西安交通大学 | Fe-PANI/zeolite catalyst and preparation method thereof |
| CN109876679B (en) * | 2019-04-01 | 2021-03-30 | 泰州禾益新材料科技有限公司 | Reverse osmosis membrane for polyamide wastewater and preparation method thereof |
-
2020
- 2020-02-12 CN CN202010087978.1A patent/CN111151147B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111151147A (en) | 2020-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111151146B (en) | Polyaniline-modified all-silicon molecular sieve-doped polyamide composite membrane | |
| Emadzadeh et al. | Synthesis, modification and optimization of titanate nanotubes-polyamide thin film nanocomposite (TFN) membrane for forward osmosis (FO) application | |
| US10589216B2 (en) | Membranes for fluid separation | |
| JP5696361B2 (en) | Composite semipermeable membrane and method for producing the same | |
| CN111151147B (en) | Polyaniline modified aluminosilicate molecular sieve doped polyamide composite membrane | |
| CN114471200B (en) | Method for improving preparation of Zr-based MOF membrane by using intermediate modification layer and forward osmosis application of Zr-based MOF membrane | |
| WO2018201924A1 (en) | Composite reverse osmosis membrane, and manufacturing method thereof | |
| US4681605A (en) | Anisotropic membranes for gas separation | |
| JP2010158665A (en) | Method for producing ddr type zeolite membrane-containing body | |
| CN113856492B (en) | Polyamide reverse osmosis membrane with molecular sieve doped porous supporting layer | |
| CN112870989B (en) | Anti-pollution composite reverse osmosis membrane and preparation method thereof | |
| Junaidi et al. | Fouling mitigation in humic acid ultrafiltration using polysulfone/SAPO-34 mixed matrix membrane | |
| CN110559889A (en) | Hollow nano-particle composite nanofiltration membrane and preparation method and application thereof | |
| CN106492657A (en) | A kind of allophane nano-tube hydridization forward osmosis membrane | |
| KR20140073354A (en) | Polyamide composite membrane having high quality and manufacturing method thereof | |
| CN112191112B (en) | Polyamide reverse osmosis membrane with acid resistance and preparation method thereof | |
| CN111151139B (en) | Organic ultrafiltration membrane modified by molecular sieve | |
| JP5287353B2 (en) | Composite semipermeable membrane | |
| KR102169137B1 (en) | A polyamide composite membrane having improved salt and boron rejection and method for preparation thereof | |
| CN114984774B (en) | Preparation method of reverse osmosis composite membrane and obtained reverse osmosis composite membrane | |
| CN115888441A (en) | Composite nanofiltration membrane and preparation method thereof | |
| JP5120006B2 (en) | Manufacturing method of composite semipermeable membrane | |
| JP3242185B2 (en) | Method for producing polyamide-based composite hollow fiber type reverse osmosis membrane | |
| JP2000117076A (en) | Composite semipermeable membrane and its production | |
| da Silva | Polyimide and polyetherimide organic solvent nanofiltration membranes |
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 |