CN110052177B - Preparation method of hollow microsphere reinforced high-flux polyacrylonitrile filter membrane - Google Patents
Preparation method of hollow microsphere reinforced high-flux polyacrylonitrile filter membrane Download PDFInfo
- Publication number
- CN110052177B CN110052177B CN201910269986.5A CN201910269986A CN110052177B CN 110052177 B CN110052177 B CN 110052177B CN 201910269986 A CN201910269986 A CN 201910269986A CN 110052177 B CN110052177 B CN 110052177B
- Authority
- CN
- China
- Prior art keywords
- membrane
- aqueous solution
- flux
- polyacrylonitrile
- filter membrane
- 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
- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The surface of the traditional polymer filtering membrane is a compact layer, and the interior of the traditional polymer filtering membrane contains a large number of finger-shaped holes, so that bubbles are prevented from being introduced into the membrane casting solution to the utmost extent in the preparation process, and the bubbles in the compact layer on the surface of the membrane can cause membrane leakage. The polyacrylonitrile homogeneous film without finger-shaped pores can be prepared by using zinc chloride aqueous solution as solvent and water as coagulating bath. In order to further improve the flux of the membrane, the invention introduces double bonds into the surface of the hollow silica microsphere by silane modified hollow silica microsphere containing double bond functional groups, disperses the microsphere in zinc chloride aqueous solution, then adds acrylonitrile monomer, second comonomer and initiator, and initiates free radical polymerization reaction under stirring to obtain the casting membrane solution of polyacrylonitrile-second monomer copolymer grafted by the hollow silica microsphere. The hollow microsphere reinforced high-flux polyacrylonitrile filter membrane is prepared by taking water as a coagulating bath. The membrane has high retention on dye and low retention on inorganic salt, and has wide application prospect in the field of dye desalination and purification.
Description
Technical Field
The invention relates to a preparation method of a hollow microsphere reinforced high-flux polyacrylonitrile filter membrane, belonging to the field of functional materials and membrane separation.
The invention relates to the technical fields of polyacrylonitrile, a filtering membrane, polymerization reaction, hollow silicon dioxide microspheres and the like. In particular to a preparation method of a hollow microsphere reinforced high-flux polyacrylonitrile filter membrane and application thereof in dye wastewater treatment and dye desalination.
Background
Printing and dyeing wastewater is one of the main causes of water pollution due to its toxicity, high salinity and chroma [ water treatment technology, 2008, 34 (3): 48-48. The direct discharge of printing and dyeing wastewater can negatively impact the water ecosystem and waste large amounts of valuable dyes. Therefore, desalination is of great significance for treatment of printing and dyeing wastewater. Membrane separation techniques have great advantages in the field of water treatment due to low investment, low energy consumption, high recovery rate [ j.hazard.mater, 2016, 308: 75-83 deg. Traditional filtration membranes are mainly classified into nanofiltration membranes and ultrafiltration membranes. The nanofiltration membrane is usually prepared by an interfacial polymerization method, the aperture of the nanofiltration membrane is in a nanoscale range, the interception of macromolecular dye and micromolecular inorganic salt is high, and the flux is small; ultrafiltration membranes are typically prepared with added pore agents and have a greater flux but poor retention of dyes [ chemical equipment technology, 2002, 23 (8): 14-17. Therefore, there is a need for a high throughput, high large molecule cut-off and low small molecule cut-off filtration membrane for dye desalination.
Because of its good thermal stability, resistance to most organic solvents, resistance to bacteria and light radiation, polyacrylonitrile has been widely used in the fields of clothing, industrial fabrics, carbon fiber raw materials, hemodialysis, etc. The polyacrylonitrile membrane is prepared by dissolving and separating the phases by using an organic solvent, is easy to cause organic pollution, and has large curing rate parameter of the organic solvent, violent polymer solidification and obvious finger-shaped hole supporting layer in the formed membrane. While PAN wet spinning with inorganic solvent zinc chloride has been studied for many years and has achieved industrial production, polyacrylonitrile filtration membranes synthesized with zinc chloride as the solvent are less common. The group uses inorganic solvent ZnCl2 water solution as solvent, uses redox initiation system to initiate acrylonitrile polymerization to obtain casting solution, uses water as coagulating bath to prepare a series of homogeneous membranes with uniform and dense cross section and without finger-shaped holes [ patent ZL201610546688.2, ZL 201610415071.7, ZL201610414768.2, ZL 201610414879.3, ZL 2016104149372 ]. The polyacrylonitrile-based filter membranes have good retention effect on dyes with molecular weight more than 700, and have retention rate on inorganic salts below 10%.
The membrane flux is an important process operation parameter in the membrane separation process, and under the condition of keeping the retention rate unchanged, the higher the membrane flux is, the higher the separation efficiency of the membrane is. At present, the mainstream method for improving the membrane flux is to carry out post-treatment on the prepared membrane by an organic solvent. However, the use of organic solvents tends to degrade the mechanical properties of the membrane, which is detrimental to the long-term operation of the membrane.
In the past decades, monodisperse hollow microspheres have attracted considerable interest to researchers due to their good morphology, uniform size, large specific surface area, and broad potential application value. For example: the internal cavity of the hollow microsphere can be used for loading and controlling the release of drugs, genes, biological macromolecules and the like. SiO is the main of inorganic hollow microspheres2、TiO2、Fe3O4And the like. Wherein, the hollow SiO2The microspheres are nontoxic and harmless, have good chemical stability, and are widely applied to the fields of ultrasonic imaging, drug sustained release, catalysis, heavy metal ion adsorption and the like. Hollow SiO2The wall of the microsphere is thin, water molecules and inorganic salts can penetrate through the microsphere, and macromolecules, particularly macromolecules with high viscosity, cannot penetrate through the microsphere. Hollow SiO2The microspheres added into the filter membrane can improve the pollution resistance of the membrane on one hand and can improve the flux of the membrane on the other hand.
In order to further improve the flux of the membrane, the invention introduces double bonds into the surface of the hollow silica microsphere by silane modified hollow silica microsphere containing double bond functional groups, disperses the microsphere in zinc chloride aqueous solution, then adds acrylonitrile monomer, second comonomer and initiator, and initiates free radical polymerization reaction under stirring to obtain the casting membrane solution of polyacrylonitrile-second monomer copolymer grafted by the hollow silica microsphere. The hollow microsphere reinforced high-flux polyacrylonitrile filter membrane is prepared by taking water as a coagulating bath. The membrane has high retention on dye and low retention on inorganic salt, and has wide application prospect in the field of dye desalination and purification.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the technical problems of environmental pollution, poor hydrophilicity of a polyacrylonitrile filter membrane, lower membrane flux and the like caused by using an organic solvent in the traditional membrane preparation process.
The invention provides a preparation method of a hollow microsphere reinforced high-flux polyacrylonitrile filter membrane, which solves the problems of environmental pollution, poor hydrophilicity of a polyacrylonitrile filter membrane, lower membrane flux and the like caused by using an organic solvent in the traditional membrane preparation process.
The invention provides a preparation method of a hollow microsphere reinforced high-flux polyacrylonitrile filter membrane, which is characterized by comprising the following steps of:
a) preparing a silane aqueous solution containing double bond functional groups with the mass percentage concentration of 0.01-5%, and soaking the activated silicon dioxide hollow microspheres in the silane aqueous solution for 0.5-24h to obtain the silicon dioxide hollow microspheres containing double bond functional groups on the surfaces;
b) preparing a zinc chloride aqueous solution with the mass percentage concentration of 60%, weighing the silica hollow microspheres with the surface containing double bond functional groups obtained in the step a) and accounting for 0.01-10% of the mass percentage of the aqueous solution, dispersing the silica hollow microspheres in the zinc chloride aqueous solution, introducing nitrogen for oxygen discharge, and adding acrylonitrile accounting for 2-50% of the mass percentage of the aqueous solution and a second comonomer accounting for 1-20% of the mass percentage of the aqueous solution under stirring;
c) dropwise adding an initiator accounting for 0.1-10% of the total mass of the acrylonitrile and the second comonomer under stirring to initiate the graft polymerization of the acrylonitrile and the second comonomer on the silicon dioxide hollow microspheres with double-bond functional groups on the surfaces, wherein the reaction time is 10-240min, and obtaining a casting solution;
d) preparing aqueous solution with pH of 2-5 with dilute hydrochloric acid as coagulating bath;
e) pouring the casting solution obtained in the step c) on a dry and clean glass plate, scraping the glass plate by using a glass rod with two ends wound with copper wires with the diameter of 10-1000 mu m, immediately putting the glass plate and the scraped film into the coagulating bath obtained in the step d) for soaking for 5-120min, and washing residual zinc chloride and unreacted monomers by deionized water to obtain a hollow microsphere reinforced high-flux polyacrylonitrile filter membrane; the pore walls of the silicon dioxide hollow microspheres allow water and inorganic salt to pass through, and because the silicon dioxide hollow microspheres are discontinuous, and a polyacrylonitrile-based filter membrane prepared by taking a zinc chloride aqueous solution as a solvent is homogeneous and does not have finger-shaped pores and a dense layer of a traditional high-molecular filter membrane, the interception performance of the membrane is not influenced by the introduction of the silicon dioxide hollow microspheres, and the flux of the membrane is also improved by 5-100%.
The double-bond functional group silane is any one or a mixture of two or more of gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane and vinyltrimethoxysilane; the second comonomer is any one or a mixture of two or more of acrylamide, vinyl pyrrolidone, methyl acrylate and hydroxyethyl methacrylate; the initiator is any one or a mixture of two or more of potassium persulfate, sodium persulfate, ammonium persulfate, sodium bisulfite, ferrous sulfate and ferrous chloride.
The preparation method is simple, the process is green and environment-friendly, the membrane has high retention rate on body type dyes and the retention rate on inorganic salts is lower than 5%, and the membrane has wide application prospects in the field of protein and dye desalination and purification.
Detailed Description
Specific examples of the present invention will be described below, but the present invention is not limited to the examples.
Example 1.
a) Preparing a gamma-methacryloxypropyl trimethoxy silane aqueous solution with the mass percentage concentration of 0.01%, and soaking the activated silicon dioxide hollow microspheres in the silane aqueous solution for 24 hours to obtain the silicon dioxide hollow microspheres with the surfaces containing double-bond functional groups;
b) preparing a zinc chloride aqueous solution with the mass percentage concentration of 60%, weighing the silica hollow microspheres with the surface containing double bond functional groups obtained in the step a) and accounting for 0.01% of the mass percentage of the aqueous solution, dispersing the silica hollow microspheres in the zinc chloride aqueous solution, introducing nitrogen to discharge oxygen, and adding acrylonitrile accounting for 2% of the mass percentage of the aqueous solution and acrylamide accounting for 1% of the mass percentage of the aqueous solution under stirring;
c) dropwise adding potassium persulfate-sodium sulfite accounting for 0.1 percent of the total mass of the acrylonitrile and the acrylamide under stirring to initiate the graft polymerization of the acrylonitrile and the acrylamide on the silicon dioxide hollow microspheres with double-bond functional groups on the surfaces, wherein the reaction time is 240min, and obtaining a casting solution;
d) preparing aqueous solution with pH of 2 by using dilute hydrochloric acid as coagulating bath;
e) pouring the casting solution obtained in the step c) on a dry and clean glass plate, strickling the glass plate by using a glass rod with two ends wound with copper wires with the diameter of 10 mu m, immediately putting the glass plate and the strickled film into the coagulating bath obtained in the step d) for soaking for 5min, and washing residual zinc chloride and unreacted monomers by deionized water to obtain a hollow microsphere reinforced high-flux polyacrylonitrile filter membrane; the pore walls of the silicon dioxide hollow microspheres allow water and inorganic salt to pass through, and because the silicon dioxide hollow microspheres are discontinuous, and a polyacrylonitrile-based filter membrane prepared by taking a zinc chloride aqueous solution as a solvent is homogeneous and does not have finger-shaped pores and a dense layer of a traditional high-molecular filter membrane, the interception performance of the membrane is not influenced by the introduction of the silicon dioxide hollow microspheres, and the flux of the membrane is also improved by 5%.
Example 2.
a) Preparing an isobutylene propoxy trimethoxy silane aqueous solution with the mass percentage concentration of 5%, and soaking the activated silicon dioxide hollow microspheres in the silane aqueous solution for 12 hours to obtain the silicon dioxide hollow microspheres with the surfaces containing double-bond functional groups;
b) preparing a zinc chloride aqueous solution with the mass percentage concentration of 60%, weighing the silica hollow microspheres with the surface containing double bond functional groups obtained in the step a) and accounting for 10% of the mass percentage of the aqueous solution, dispersing the silica hollow microspheres in the zinc chloride aqueous solution, introducing nitrogen to discharge oxygen, and adding acrylonitrile accounting for 50% of the mass percentage of the aqueous solution and vinyl pyrrolidone accounting for 20% of the mass percentage of the aqueous solution under stirring;
c) dropwise adding ammonium persulfate-sodium bisulfite accounting for 0.1 percent of the total mass of the acrylonitrile and the vinyl pyrrolidone under stirring to initiate the graft polymerization of the acrylonitrile and the vinyl pyrrolidone on the silicon dioxide hollow microspheres with double-bond functional groups on the surfaces, wherein the reaction time is 10min, and obtaining a casting solution;
d) preparing an aqueous solution with pH of 5 by using dilute hydrochloric acid as a coagulating bath;
e) pouring the casting solution obtained in the step c) on a dry and clean glass plate, strickling the glass plate by using a glass rod with two ends wound with copper wires with the diameter of 100 mu m, immediately putting the glass plate and the strickled film into the coagulating bath obtained in the step d) for soaking for 60min, and washing residual zinc chloride and unreacted monomers by deionized water to obtain a hollow microsphere reinforced high-flux polyacrylonitrile filter membrane; the pore walls of the silicon dioxide hollow microspheres allow water and inorganic salt to pass through, and because the silicon dioxide hollow microspheres are discontinuous, and a polyacrylonitrile-based filter membrane prepared by taking a zinc chloride aqueous solution as a solvent is homogeneous and does not have finger-shaped pores and a dense layer of a traditional high-molecular filter membrane, the interception performance of the membrane is not influenced by the introduction of the silicon dioxide hollow microspheres, and the flux of the membrane is also improved by 100%.
Example 3.
a) Preparing a vinyltriethoxysilane aqueous solution with the mass percentage concentration of 0.5%, and soaking the activated silicon dioxide hollow microspheres in the silane aqueous solution for 12h to obtain the silicon dioxide hollow microspheres with the surface containing double-bond functional groups;
b) preparing a zinc chloride aqueous solution with the mass percentage concentration of 60%, weighing the silica hollow microspheres with the surface containing double bond functional groups obtained in the step a) and accounting for 5% of the mass percentage of the aqueous solution, dispersing the silica hollow microspheres in the zinc chloride aqueous solution, introducing nitrogen to discharge oxygen, and adding acrylonitrile accounting for 10% of the mass percentage of the aqueous solution and methyl acrylate accounting for 10% of the mass percentage of the aqueous solution under stirring;
c) dropwise adding sodium persulfate-ferrous sulfate accounting for 0.5 percent of the total mass of the acrylonitrile and the methyl acrylate under stirring to initiate the graft polymerization of the acrylonitrile and the methyl acrylate on the silicon dioxide hollow microspheres with double-bond functional groups on the surfaces, wherein the reaction time is 120min, and obtaining a casting solution;
d) preparing an aqueous solution with pH of 3 by using dilute hydrochloric acid as a coagulating bath;
e) pouring the casting solution obtained in the step c) on a dry and clean glass plate, strickling the glass plate by using a glass rod with two ends wound with copper wires with the diameter of 600 mu m, immediately putting the glass plate and the strickled film into the coagulating bath obtained in the step d) for soaking for 30min, and washing residual zinc chloride and unreacted monomers by deionized water to obtain a hollow microsphere reinforced high-flux polyacrylonitrile filter membrane; the pore walls of the silicon dioxide hollow microspheres allow water and inorganic salt to pass through, and because the silicon dioxide hollow microspheres are discontinuous, and a polyacrylonitrile-based filter membrane prepared by taking a zinc chloride aqueous solution as a solvent is homogeneous and does not have finger-shaped pores and a dense layer of a traditional high-molecular filter membrane, the interception performance of the membrane is not influenced by the introduction of the silicon dioxide hollow microspheres, and the flux of the membrane is improved by 60%.
Example 4.
a) Preparing 1% of vinyl trimethoxy silane aqueous solution by mass percentage, and soaking the activated silicon dioxide hollow microspheres in the silane aqueous solution for 8 hours to obtain the silicon dioxide hollow microspheres with the surfaces containing double-bond functional groups;
b) preparing a zinc chloride aqueous solution with the mass percentage concentration of 60%, weighing the silica hollow microspheres with the surface containing double bond functional groups obtained in the step a) and accounting for 1% of the mass percentage of the aqueous solution, dispersing the silica hollow microspheres in the zinc chloride aqueous solution, introducing nitrogen to discharge oxygen, and adding acrylonitrile accounting for 15% of the mass percentage of the aqueous solution and hydroxyethyl methacrylate accounting for 5% of the mass percentage of the aqueous solution under stirring;
c) dropwise adding ammonium persulfate-ferrous chloride accounting for 2 percent of the total mass of the acrylonitrile and the hydroxyethyl methacrylate under stirring to initiate the graft polymerization of the acrylonitrile and the hydroxyethyl methacrylate on the silicon dioxide hollow microspheres with double-bond functional groups on the surfaces, wherein the reaction time is 60min, and obtaining a casting solution;
d) preparing an aqueous solution with pH of 3 by using dilute hydrochloric acid as a coagulating bath;
e) pouring the casting solution obtained in the step c) on a dry and clean glass plate, strickling the glass plate by using a glass rod with two ends wound with copper wires with the diameter of 500 mu m, immediately putting the glass plate and the strickled film into the coagulating bath obtained in the step d) for soaking for 60min, and washing residual zinc chloride and unreacted monomers by deionized water to obtain a hollow microsphere reinforced high-flux polyacrylonitrile filter membrane; the pore walls of the silicon dioxide hollow microspheres allow water and inorganic salt to pass through, and because the silicon dioxide hollow microspheres are discontinuous, and a polyacrylonitrile-based filter membrane prepared by taking a zinc chloride aqueous solution as a solvent is homogeneous and does not have finger-shaped pores and a dense layer of a traditional high-molecular filter membrane, the interception performance of the membrane is not influenced by the introduction of the silicon dioxide hollow microspheres, and the flux of the membrane is also improved by 55%.
Claims (4)
1. A preparation method of a hollow microsphere reinforced high-flux polyacrylonitrile filter membrane is characterized by comprising the following steps:
a) preparing a silane aqueous solution containing double bond functional groups with the mass percentage concentration of 0.01-5%, and soaking the activated silicon dioxide hollow microspheres in the silane aqueous solution for 0.5-24h to obtain the silicon dioxide hollow microspheres containing double bond functional groups on the surfaces;
b) preparing a zinc chloride aqueous solution with the mass percentage concentration of 60%, weighing the silica hollow microspheres with the surface containing double bond functional groups obtained in the step a) and accounting for 0.01-10% of the mass percentage of the aqueous solution, dispersing the silica hollow microspheres in the zinc chloride aqueous solution, introducing nitrogen for oxygen discharge, and adding acrylonitrile accounting for 2-50% of the mass percentage of the aqueous solution and a second comonomer accounting for 1-20% of the mass percentage of the aqueous solution under stirring;
c) dropwise adding an initiator accounting for 0.1-10% of the total mass of the acrylonitrile and the second comonomer under stirring to initiate the graft polymerization of the acrylonitrile and the second comonomer on the silicon dioxide hollow microspheres with double-bond functional groups on the surfaces, wherein the reaction time is 10-240min, and obtaining a casting solution;
d) preparing aqueous solution with pH of 2-5 with dilute hydrochloric acid as coagulating bath;
e) pouring the casting solution obtained in the step c) on a dry and clean glass plate, scraping the glass plate by using a glass rod with two ends wound with copper wires with the diameter of 10-1000 mu m, immediately putting the glass plate and the scraped film into the coagulating bath obtained in the step d) for soaking for 5-120min, and washing residual zinc chloride and unreacted monomers by deionized water to obtain a hollow microsphere reinforced high-flux polyacrylonitrile filter membrane; the pore walls of the silicon dioxide hollow microspheres allow water and inorganic salt to pass through, and because the silicon dioxide hollow microspheres are discontinuous, and a polyacrylonitrile-based filter membrane prepared by taking a zinc chloride aqueous solution as a solvent is homogeneous and does not have finger-shaped pores and a dense layer of a traditional high-molecular filter membrane, the interception performance of the membrane is not influenced by the introduction of the silicon dioxide hollow microspheres, and the flux of the membrane is also improved by 5-100%.
2. The method for preparing hollow microsphere reinforced high-flux polyacrylonitrile filter membrane according to claim 1, wherein said silane with double bond functional group is one or a mixture of two or more of gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane and vinyltrimethoxysilane.
3. The method for preparing the hollow microsphere reinforced high-flux polyacrylonitrile filter membrane as claimed in claim 1, wherein the second comonomer is any one or a mixture of two or more of acrylamide, vinyl pyrrolidone, methyl acrylate and hydroxyethyl methacrylate.
4. The method for preparing the hollow microsphere reinforced high-flux polyacrylonitrile filter membrane as claimed in claim 1, wherein the initiator is any one or a mixture of two or more of potassium persulfate, sodium persulfate, ammonium persulfate, sodium bisulfite, ferrous sulfate and ferrous chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910269986.5A CN110052177B (en) | 2019-04-04 | 2019-04-04 | Preparation method of hollow microsphere reinforced high-flux polyacrylonitrile filter membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910269986.5A CN110052177B (en) | 2019-04-04 | 2019-04-04 | Preparation method of hollow microsphere reinforced high-flux polyacrylonitrile filter membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110052177A CN110052177A (en) | 2019-07-26 |
| CN110052177B true CN110052177B (en) | 2021-04-30 |
Family
ID=67318264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910269986.5A Active CN110052177B (en) | 2019-04-04 | 2019-04-04 | Preparation method of hollow microsphere reinforced high-flux polyacrylonitrile filter membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110052177B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114425241B (en) * | 2020-09-29 | 2023-07-21 | 中国石油化工股份有限公司 | Preparation method and application of copolymer film material containing silicon dioxide |
| CN113262651B (en) * | 2021-05-24 | 2022-12-20 | 四川蓝海化工（集团）有限公司 | Modified polyacrylonitrile ultrafiltration membrane applied to removal of phosphate in water and preparation method thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0574957A2 (en) * | 1989-04-14 | 1993-12-22 | Membrane Products Kiryat Weizmann Ltd. | Acrylonitrile- and polyvinylidene fluoride-derived membranes |
| CN101434708A (en) * | 2008-12-19 | 2009-05-20 | 成都中科来方能源科技有限公司 | Aqueous polymer modified micropore polyolefin barrier diaphragm, and preparation and use thereof |
| CN105854653A (en) * | 2016-06-12 | 2016-08-17 | 天津工业大学 | Method for preparing fibroin grafted polyacrylonitrile nanofiltration membrane |
| CN105854641A (en) * | 2016-06-12 | 2016-08-17 | 天津工业大学 | Method for preparing narrow-hole-diameter-distribution polyacrylonitrile nano-filtration membrane |
| CN105854642A (en) * | 2016-06-12 | 2016-08-17 | 天津工业大学 | Preparation method of hydrophilic polyacrylonitrile nanofiltration membrane with polyhydroxy |
| CN106000134A (en) * | 2016-07-08 | 2016-10-12 | 天津工业大学 | Temperature-sensitive filtering membrane with small pore size distribution and preparation method thereof |
| CN107281940A (en) * | 2016-03-30 | 2017-10-24 | 天津工业大学 | A kind of polymer/polymer hollow microsphere hybridized film and application |
| CN107335344A (en) * | 2017-08-22 | 2017-11-10 | 天津工业大学 | Preparation method for the hollow-fibre membrane of dye desalination |
| CN108380055A (en) * | 2018-02-28 | 2018-08-10 | 天津大学 | The sodium alginate hybridized film of hollow ZIF-8 nano particles filling and preparation and application |
| CN108704495A (en) * | 2018-05-21 | 2018-10-26 | 天津工业大学 | A kind of preparation method of carboxylation titanium dioxide/calcium alginate compounded hydrogel filter membrane |
| CN108727628A (en) * | 2018-06-14 | 2018-11-02 | 常州大学 | A kind of nano silver tiny balloon/PVDF ultrafiltration membrane and preparation method thereof |
| CN108771983A (en) * | 2018-07-04 | 2018-11-09 | 青岛大学 | Multilayer through-hole high-permeability polymer microfiltration membrane and preparation method thereof |
-
2019
- 2019-04-04 CN CN201910269986.5A patent/CN110052177B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0574957A2 (en) * | 1989-04-14 | 1993-12-22 | Membrane Products Kiryat Weizmann Ltd. | Acrylonitrile- and polyvinylidene fluoride-derived membranes |
| CN101434708A (en) * | 2008-12-19 | 2009-05-20 | 成都中科来方能源科技有限公司 | Aqueous polymer modified micropore polyolefin barrier diaphragm, and preparation and use thereof |
| CN107281940A (en) * | 2016-03-30 | 2017-10-24 | 天津工业大学 | A kind of polymer/polymer hollow microsphere hybridized film and application |
| CN105854653A (en) * | 2016-06-12 | 2016-08-17 | 天津工业大学 | Method for preparing fibroin grafted polyacrylonitrile nanofiltration membrane |
| CN105854641A (en) * | 2016-06-12 | 2016-08-17 | 天津工业大学 | Method for preparing narrow-hole-diameter-distribution polyacrylonitrile nano-filtration membrane |
| CN105854642A (en) * | 2016-06-12 | 2016-08-17 | 天津工业大学 | Preparation method of hydrophilic polyacrylonitrile nanofiltration membrane with polyhydroxy |
| CN106000134A (en) * | 2016-07-08 | 2016-10-12 | 天津工业大学 | Temperature-sensitive filtering membrane with small pore size distribution and preparation method thereof |
| CN107335344A (en) * | 2017-08-22 | 2017-11-10 | 天津工业大学 | Preparation method for the hollow-fibre membrane of dye desalination |
| CN108380055A (en) * | 2018-02-28 | 2018-08-10 | 天津大学 | The sodium alginate hybridized film of hollow ZIF-8 nano particles filling and preparation and application |
| CN108704495A (en) * | 2018-05-21 | 2018-10-26 | 天津工业大学 | A kind of preparation method of carboxylation titanium dioxide/calcium alginate compounded hydrogel filter membrane |
| CN108727628A (en) * | 2018-06-14 | 2018-11-02 | 常州大学 | A kind of nano silver tiny balloon/PVDF ultrafiltration membrane and preparation method thereof |
| CN108771983A (en) * | 2018-07-04 | 2018-11-09 | 青岛大学 | Multilayer through-hole high-permeability polymer microfiltration membrane and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Antimicrobial and pressure resistant polysulfone blended ultrafiltration membranes with core-shell ZnO microspheres;Zehai Xu et al.;《Desalination and Water Treatment》;20180228;第105卷;第51-61页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110052177A (en) | 2019-07-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106943899B (en) | A kind of hydrophilic polysulfone film and preparation method thereof | |
| CN104587852B (en) | A kind of heavy metal ion adsorbed type PS hollow fiber ultrafiltration membrane and preparation method thereof | |
| CN109621739B (en) | Hydrophilic modification method for high-flux PVDF porous membrane | |
| CN101711952A (en) | Polyvinylidene fluoride hollow fiber ultrafiltration membrane with permanent hydrophilcity and preparation method thereof | |
| US4252652A (en) | Process of using a semi-permeable membrane of acrylonitrile copolymers | |
| CN110052177B (en) | Preparation method of hollow microsphere reinforced high-flux polyacrylonitrile filter membrane | |
| CN101239283B (en) | Convenient for cleaning hollow fiber membrane, preparation of the same and products produced thereby | |
| US11623183B2 (en) | Synthesis of imidazolium-based functional ionic liquid copolymer and preparation method of alloy ultra-filtration membrane | |
| CN105817146B (en) | A kind of CNT is modified the preparation method of NF membrane | |
| CN105617882A (en) | Chitosan modified graphene oxide nano composite positive osmotic membrane and preparation method thereof | |
| CN110813103A (en) | Preparation method of antibacterial and anti-pollution hollow fiber membrane | |
| CN113797763B (en) | Cellulose gel layer modified loose nanofiltration membrane for high-flux dye separation and preparation method and application thereof | |
| CN109260970B (en) | Preparation method of high-strength inorganic doped calcium alginate hydrogel filtering membrane | |
| CN110038454A (en) | A kind of high-intensitive, high modified PVDF supermicro filtration membrane of water flux graphene and preparation method thereof | |
| CN101773794A (en) | Three-component five-hole hollow fibrous membrane and preparation method thereof | |
| CN104190264A (en) | Preparation method for hollow fiber ultrafiltration membrane with chelation function | |
| CN110975650A (en) | Method for preparing super-hydrophilic PVDF ultrafiltration membrane by one-pot method | |
| CN105854642A (en) | Preparation method of hydrophilic polyacrylonitrile nanofiltration membrane with polyhydroxy | |
| CN102389718A (en) | Preparation method of acetyl cellulose hollow fiber nano filter membrane | |
| CN104587848A (en) | A PVDF hollow fiber ultrafiltration membrane and a preparing method thereof | |
| CN106621837B (en) | A kind of hydrophilic modifying network cross-linked object perforated membrane and preparation method thereof | |
| CN110605033B (en) | Preparation method of temperature-resistant hollow fiber ultrafiltration membrane, temperature-resistant hollow fiber ultrafiltration membrane and components thereof | |
| CN110743383B (en) | Modification method for improving permeation flux of polyamide composite membrane | |
| CN109304101B (en) | Zwitterionic high-strength pollution-resistant forward osmosis membrane and preparation method thereof | |
| CN109865501A (en) | A kind of compound membrane preparation method for organic dyestuff in Adsorption water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230602 Address after: 509 Kangrui Times Square, Keyuan Business Building, 39 Huarong Road, Gaofeng Community, Dalang Street, Longhua District, Shenzhen, Guangdong Province, 518000 Patentee after: Shenzhen lizhuan Technology Transfer Center Co.,Ltd. Address before: 300387 School of materials science and engineering, 399 West Pennsylvania Road, Xiqing, Tianjin Patentee before: TIANJIN POLYTECHNIC University |
|
| TR01 | Transfer of patent right |