CN112023728A - PBI hydrophobic microporous membrane for acid-resistant and oxidation-resistant membrane distillation and preparation method thereof - Google Patents
PBI hydrophobic microporous membrane for acid-resistant and oxidation-resistant membrane distillation and preparation method thereof Download PDFInfo
- Publication number
- CN112023728A CN112023728A CN202010793483.0A CN202010793483A CN112023728A CN 112023728 A CN112023728 A CN 112023728A CN 202010793483 A CN202010793483 A CN 202010793483A CN 112023728 A CN112023728 A CN 112023728A
- Authority
- CN
- China
- Prior art keywords
- membrane
- pbi
- temperature
- film
- hydrophobic microporous
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
-
- 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
- B01D69/08—Hollow fibre membranes
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/08—Thin film evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a preparation method of PBI hydrophobic microporous membrane for acid-resistant and oxidation-resistant membrane distillation, which comprises the steps of mixing PBI polymer with auxiliary oil and pore-forming agent; storing and curing the uniformly mixed raw materials; extruding the cured raw materials to form a compact columnar blank; extruding the uniformly mixed pre-formed blank through a die in a screw machine, and forming a film through tape casting; the obtained film is on
Blowing and curing the inside of the passage by hot air to form a film; the solidified film enters a stretching system; gradually cooling the film in the stretching state in a drying room, and cooling to room temperature for high-temperature shaping; extracting to remove the auxiliary oil in the membrane, eluting the pore-forming agent in the membrane, and drying to obtain the PBI hydrophobic microporous membrane. The PBI hydrophobic microporous membrane for membrane distillation is successfully prepared by a thermally induced phase separation-stretching method, and has high porosity under the condition of high enough mechanical strength. The prepared PBI hydrophobic microporous membrane has higher mechanical stability in a high-acidity solution environment.
Description
Technical Field
The invention belongs to the field of membrane materials, relates to a membrane distillation technology, and particularly relates to a PBI (Poly-p-phenylene benzobisoxazole) hydrophobic microporous membrane for high-acid-resistance and oxidation-resistance membrane distillation and a preparation method thereof.
Background
The key point of the high acidity heavy metal wastewater treatment technology is to keep the concentration of heavy metals in discharged water as low as possible and to keep the volume of heavy metal concentrated solution as small as possible. As a novel membrane technology combining traditional evaporation and a membrane technology, when a high-acidity heavy metal solution is concentrated, an important technical problem exists at present, and how to ensure that a membrane distillation membrane material can stably operate in a high-acidity high-oxidizability environment for a long time is guaranteed. At present, the most commonly used membrane materials in the membrane distillation process are polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE) and polypropylene (PP), and novel membrane materials such as Polyethylene (PE), polyvinyl chloride (PVC) and Polystyrene (PS) are also reported correspondingly. In the current research situation, PVDF and PTFE materials have good film forming performance, but the processing requirements of high-acidity and high-oxidation solutions are difficult to meet.
Polybenzimidazole (PBI) refers to a linear heterocyclic polymer containing benzimidazole groups in a repeating unit, and has excellent thermal stability, mechanical strength and chemical resistance. At present, PBI is mainly applied to the fields of proton exchange membranes of fuel cells and redox flow batteries and diaphragms of lithium batteries. PBI is used for proton exchange membranes, and is mainly prepared by a solution casting method, and the prepared PBI membrane is a non-porous membrane; part of PBI microporous proton exchange membranes and lithium battery diaphragms mainly adopt a non-solvent induced phase separation method, but the prepared microporous membranes have low porosity and low mechanical tensile strength and are difficult to meet the requirements of membrane distillation operation.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the PBI hydrophobic microporous membrane for the high-acid-resistance and oxidation-resistance membrane distillation and the preparation method thereof.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a preparation method of a PBI hydrophobic microporous membrane for high-acid-resistance and oxidation-resistance membrane distillation comprises the following steps:
firstly, the PBI membrane material is ensured to have higher mechanical strength, the melting point temperature of the PBI membrane material is reduced, the membrane preparation energy consumption is reduced, and PBI polymer with higher weight-average molecular weight of 10000-1000000 is selected to be mixed with an oil assisting agent and a pore forming agent for membrane preparation; in order to promote the PBI polymer to be melted at high temperature to form a uniform membrane casting solution, a proper amount of auxiliary oil is added in the membrane making process, and the auxiliary oil is volatile solvent oil with good compatibility with the polymer, such as: petroleum ether, solvent oil, aviation kerosene, and the like; in order to increase the porosity of the membrane and improve the flux of the membrane, a small amount of pore-forming agent can be added in the membrane preparation process, and the pore-forming agent is easily soluble and difficultly decomposable inorganic salt, such as sodium chloride, potassium chloride, sodium sulfate and the like; the PBI, the auxiliary oil and the pore-foaming agent are respectively used in the following mixing proportion by weight percent: 20% -50%, 50% -80% and 0% -8%. Secondly, storing and curing the uniformly mixed raw materials for 6 to 24 hours at the temperature 20 to 100 ℃ higher than the melting point temperature of the polymer PBI to ensure that the polymer is fully melted, wetted and absorbed. Thirdly, extruding the cured raw materials to discharge air among the powder materials to form a compact structureThe columnar shaped billet (columnar pellet). Extruding the uniformly mixed preformed blank through a die in a screw machine, and forming a film through tape casting, wherein the hollow fiber film is extruded and tape-cast through a double-tube type neck mold, and hot nitrogen with the temperature 10-50 ℃ higher than the melting point temperature of the polymer PBI is introduced into the central tube to form a fiber internal cavity in order to prevent the surface of the central tube in the film from being separated too fast and influence the structure of a mold hole; the flat membrane is directly extruded and cast on a template to obtain the flat membrane. Fifthly, the obtained hollow fiber membrane or flat membrane is placed in
And blowing hot air with the temperature 0-30 ℃ higher than the melting point temperature of the polymer PBI for 10-60 s in the channel to solidify and form a film, adjusting the phase separation rate by controlling the blowing temperature of the hot air, and adjusting and controlling the structure and porosity of the die hole. Sixthly, the solidified hollow fiber membrane or flat sheet membrane enters a stretching system to carry out unidirectional stretching on the hollow fiber membrane or carry out bidirectional stretching on the flat sheet membrane, the stretching speed is controlled to be 1 cm/min-4 cm/min, the stretching temperature is 10-40 ℃ lower than the melting point temperature of polymer PBI, the final deformation amount is 3-8 times of the initial deformation amount, and the mechanical strength and the porosity of the membrane are further coordinated and controlled through the stretching speed and the deformation amount. Seventhly, gradually cooling the hollow fiber membrane or the flat membrane in the stretching state in a drying room, and cooling to room temperature for 4-24 hours to carry out high-temperature shaping. Extracting assistant oil in the membrane by using alcohol, halogenated olefin or alkane, eluting an inorganic salt pore-forming agent in the membrane by using hot water at 70-90 ℃, and drying to prepare the PBI hydrophobic microporous hollow fiber membrane or the flat membrane.
The invention has the advantages and positive effects that:
the PBI hydrophobic microporous membrane for membrane distillation is successfully prepared by a thermally induced phase separation-stretching method, and has high porosity (60%) and average pore diameter of 0.1-0.3 mu m under the condition of high enough mechanical strength (tensile strength >10 MPa).
The prepared PBI hydrophobic microporous membrane has higher mechanical stability in a high-acidity solution environment, and the mechanical strength retention rate of the membrane is more than 90 percent after the PBI hydrophobic microporous membrane is soaked in a 0.8mol/L nitric acid solution for 10 days.
③ P madeThe BI hydrophobic microporous membrane has higher concentration and separation performance on high-acidity (0.2-1.0 mol/L) heavy metal solution and heavy metal retention rate>99.0% flux>12L·m-2·h-1。
The PBI hydrophobic microporous membrane prepared by the method has good stability to high-acidity heavy metal solution, the membrane flux change rate is less than 20% after the PBI hydrophobic microporous membrane continuously operates in acidic heavy metal solution with acidity of 0.2-1.0 mol/L for 15 days, and heavy metal interception can still be kept above 99.0%.
Drawings
FIG. 1 is a graph comparing the porosity and membrane flux of PBI membranes prepared by the methods of example 1 and comparative example 1;
fig. 2 is a graph comparing vacuum membrane distillation performance of the PBI hydrophobic microporous membrane prepared in example 3 with commercial PTFE and PP membranes.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, which are illustrative only and not limiting, and the scope of the present invention is not limited thereby.
Example 1
Molecular weight 115000 formula
The aromatic ether type PBI polymer (the melting point is 350 ℃), the auxiliary oil petroleum ether and the pore-forming agent sodium chloride are uniformly mixed according to the proportion of 30 percent, 67 percent and 3 percent respectively by mass, and the mixture is stored and cured for 12 hours at the temperature of 380 ℃; extruding the cured raw materials to discharge air among powder materials, and then extruding and casting the air onto a template through a screw machine to obtain a flat membrane; the flat sheet is covered with
Blowing hot air at 360 ℃ for 30s in the way to solidify and form a film, and then, entering a stretching system for biaxial stretching after solidification, wherein the stretching speed is controlled to be 2cm/min, the stretching temperature is 320 ℃, and the final deformation amount is 4 times of the initial deformation amount; holdingAnd (5) in a final stretching state, gradually cooling in a drying room, and cooling to room temperature for 12 hours to carry out high-temperature shaping. Extracting the shaped membrane in normal hexane, rinsing the membrane with hot water at 80 ℃, and drying to obtain the PBI hydrophobic microporous flat membrane.
The PBI hydrophobic microporous flat membrane prepared by the embodiment has the following properties: the average pore diameter is 0.15 mu m, the porosity is 70 percent, the mechanical tensile strength is 13.5MPa, and the mechanical tensile strength of the membrane is 12.6MPa after the membrane is soaked in a nitric acid solution of 0.8mol/L for 10 days; vacuum membrane distillation is carried out by taking solution with 0.3mol/L nitric acid concentration and 60g/L aluminum nitrate concentration as simulated acidic heavy metal solution, and membrane flux is 17.6 L.m-2·h-1The retention rate of aluminum nitrate is 99.7 percent, and the membrane flux is 15.3 L.m after continuous operation for 15 days-2·h-1The retention rate of aluminum nitrate was 99.4%.
Comparative example 1
The PBI polymer used in the embodiment is prepared by a solution casting method, polyethylene glycol (PEG) is used as a pore-foaming agent, the PBI polymer and the PEG are mixed according to the mass ratio of 1:5 in the membrane preparation, the mixed material is dissolved in dimethyl sulfoxide (DMSO) solvent to prepare a 10% uniform blending solution, and then the uniform blending solution is cast into a membrane and dried at 80 ℃ to prepare the PBI/PEG blending membrane. The membrane was then soaked in 60 ℃ water for 48h (water was changed every 6 h), then removed and dried under vacuum at 100 ℃ for 10h to give a PBI microporous membrane.
The prepared PBI membrane has the porosity of 43 percent, the mechanical tensile strength of 10.4MPa, the vacuum membrane distillation test is carried out by taking a solution with the nitric acid concentration of 0.3mol/L and the aluminum nitrate concentration of 60g/L as a simulated acidic heavy metal solution, and the membrane flux is 4.6 L.m-2·h-1And the retention rate of aluminum nitrate is 99.5%, and compared with the PBI hydrophobic microporous membrane prepared by the method, as shown in figure 1, the membrane porosity is greatly reduced, so that the membrane flux is sharply reduced, which is only 26% of the embodiment.
Example 2
Molecular weight 115000 formula
The aromatic ether type PBI polymer (the melting point is 350 ℃), the auxiliary oil petroleum ether and the pore-forming agent sodium chloride are uniformly mixed according to the proportion of 40 percent, 57 percent and 3 percent respectively by mass, and the mixture is stored and cured for 12 hours at the temperature of 380 ℃; extruding the cured raw materials to discharge air among powder materials, then extruding and casting by using a double-tube type neck mold, and introducing nitrogen gas at 370 ℃ into a central tube to form a fiber inner cavity; the hollow fiber is filmed in
Blowing hot air at 360 ℃ for 30s in the way to solidify and form a film, and after solidification, entering a stretching system to carry out unidirectional stretching, wherein the stretching speed is controlled to be 2cm/min, the stretching temperature is 320 ℃, and the final deformation amount is 4 times of the initial deformation amount; keeping the final stretching state, gradually cooling in a drying room, and cooling to room temperature for 12h to carry out high-temperature shaping. Extracting the shaped membrane in normal hexane, rinsing the membrane with hot water at 80 ℃, and drying to obtain the PBI hydrophobic microporous hollow fiber membrane.
The properties of the PBI hydrophobic microporous hollow fiber membrane prepared in this example were: the average pore diameter is 0.19 mu m, the porosity is 74 percent, the mechanical tensile strength is 12.4MPa, and the mechanical tensile strength of the membrane is 11.9MPa after the membrane is soaked in a nitric acid solution of 0.8mol/L for 10 days; vacuum membrane distillation is carried out by taking solution with 0.3mol/L nitric acid concentration and 60g/L aluminum nitrate concentration as simulated acidic heavy metal solution, and membrane flux is 15.8 L.m-2·h-1The retention rate of aluminum nitrate is 99.5 percent, and the membrane flux is 13.9 L.m after continuous operation for 15 days-2·h-1The retention rate of aluminum nitrate was 99.3%.
Example 3
Molecular weight 223000 formula
PBI polymer (melting point 470 ℃), auxiliary oil petroleum ether and pore-forming agent sodium chloride are uniformly mixed according to the mass ratio of 35 percent, 60 percent and 5 percent respectively, and are stored and cured for 18 hours at the temperature of 490 ℃; extruding the cured raw materialsAir among the powder materials is discharged, then a double-tube type neck mold is used for extrusion casting, and nitrogen gas with the temperature of 480 ℃ is introduced into a central tube to form a fiber inner cavity; the hollow fiber is filmed in
Blowing hot air with the temperature of 485 ℃ for 40s in the channel to solidify and form a film, and after solidification, entering a stretching system to perform unidirectional stretching, wherein the stretching speed is controlled to be 3cm/min, the stretching temperature is 450 ℃, and the final deformation amount is 5 times of the initial deformation amount; keeping the final stretching state, gradually cooling in a drying room, and cooling to room temperature for 20h to carry out high-temperature shaping. Extracting the shaped membrane in normal hexane, rinsing the membrane with hot water at 80 ℃, and drying to obtain the PBI hydrophobic microporous hollow fiber membrane.
The properties of the PBI hydrophobic microporous hollow fiber membrane prepared in this example were: the average pore diameter is 0.17 mu m, the porosity is 79 percent, the mechanical tensile strength is 15.2MPa, and the mechanical tensile strength of the membrane is 14.1MPa after the membrane is soaked in a nitric acid solution of 0.8mol/L for 10 days; vacuum membrane distillation is carried out by taking solution with 0.3mol/L nitric acid concentration and 60g/L aluminum nitrate concentration as simulated acidic heavy metal solution, and membrane flux is 18.6 L.m-2·h-1The retention rate of aluminum nitrate is 99.8 percent, and the membrane flux is 16.7 L.m after continuous operation for 15 days-2·h-1The retention rate of aluminum nitrate was 99.5%.
The PBI hydrophobic microporous membrane prepared in example 3 was compared with commercial PTFE membrane and PP membrane in terms of vacuum membrane distillation performance, and as a result, the flux of the PTFE membrane in the initial stage was 20.3 L.m, as shown in FIG. 2-2·h-1The retention rate of the aluminum nitrate is 99.9%; the PP membrane flux is 19.5 L.m-2·h-1The retention rate of the aluminum nitrate is 99.8%; it can be seen that the flux of both the initial commercial PTFE membrane and the PP membrane is slightly higher than the PBI hydrophobic microporous membrane produced in this example. However, in the process of long-term stable operation, after the continuous operation time of the PTFE membrane and the PP membrane respectively exceeds 48h and 36 h, the flux of the membranes is remarkably increased, the retention rate of aluminum nitrate is remarkably reduced, and according to the phenomenon, the membranes are wetted or broken due to the chemical corrosion action of high-concentration acid solution on the PTFE membrane and the PP membrane, so that the PTFE membrane and the PP membrane are difficult to meet the high acidityLong-term stable operation of the membrane distillation treatment of the solution is required. The PBI hydrophobic microporous membrane prepared in this example 3 does not undergo membrane wetting and rupture after 15 days of operation, and the membrane flux is slightly reduced due to a certain pollution effect of heavy metal salts in the treatment solution on the membrane, but the change rate is less than 20%, and the retention rate of aluminum nitrate is maintained at 99.5% or more.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept, and these changes and modifications are all within the scope of the present invention.
Claims (6)
1. A preparation method of a PBI hydrophobic microporous membrane for acid-resistant and oxidation-resistant membrane distillation comprises the following steps:
firstly, mixing PBI polymer with weight-average molecular weight of 10000-1000000 with auxiliary oil and pore-forming agent;
secondly, storing and curing the uniformly mixed raw materials for 6 to 24 hours at the temperature which is 20 to 100 ℃ higher than the melting point temperature of the polymer PBI;
extruding the cured raw materials to form a compact columnar blank;
extruding the uniformly mixed preformed blank through a die in a screw machine, and forming a film through tape casting;
fifthly, the obtained film is
Blowing hot air with the temperature 0-30 ℃ higher than the melting point temperature of the polymer PBI in the channel for 10-60 s to solidify and form a film;
sixthly, the solidified film enters a stretching system, the stretching speed is controlled to be 1-4 cm/min, the stretching temperature is 10-40 ℃ lower than the melting point temperature of the polymer PBI, and the final deformation amount is 3-8 times of the initial deformation amount;
seventhly, gradually cooling the film in the stretching state in a drying room, and cooling to room temperature for 4-24 hours to carry out high-temperature shaping;
extracting auxiliary oil in the membrane by using alcohol, halogenated olefin or alkane, eluting a pore-forming agent in the membrane by using hot water at 70-90 ℃, and drying to obtain the PBI hydrophobic microporous membrane.
2. The method of claim 1, wherein: the auxiliary oil is petroleum ether, solvent oil or aviation kerosene.
3. The method of claim 1, wherein: the pore-forming agent is inorganic salt.
4. The method of claim 1, wherein: the PBI, the additive oil and the pore-foaming agent are respectively calculated according to the weight percentage: 20% -50%, 50% -80% and 0% -8%.
5. The method of claim 1, wherein: step four, casting to form a flat membrane or a hollow fiber membrane.
6. The method of claim 5, wherein: the hollow fiber membrane is extruded and cast through a double-tube type neck mold, and hot nitrogen with the temperature 10-50 ℃ higher than the melting point temperature of the polymer PBI is introduced into a central tube to form a fiber inner cavity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010793483.0A CN112023728B (en) | 2020-08-10 | 2020-08-10 | PBI hydrophobic microporous membrane for high-acid-resistance and oxidation-resistance membrane distillation and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010793483.0A CN112023728B (en) | 2020-08-10 | 2020-08-10 | PBI hydrophobic microporous membrane for high-acid-resistance and oxidation-resistance membrane distillation and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112023728A true CN112023728A (en) | 2020-12-04 |
| CN112023728B CN112023728B (en) | 2022-02-22 |
Family
ID=73576769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010793483.0A Active CN112023728B (en) | 2020-08-10 | 2020-08-10 | PBI hydrophobic microporous membrane for high-acid-resistance and oxidation-resistance membrane distillation and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112023728B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240079A (en) * | 2008-02-28 | 2008-08-13 | 武汉理工大学 | Porous proton exchange membrane material and preparation method thereof |
| CN103285739A (en) * | 2013-05-16 | 2013-09-11 | 中国科学院过程工程研究所 | Preparation method of hydrophobic porous separation membrane |
| CN104772049A (en) * | 2014-01-15 | 2015-07-15 | 天津海之凰科技有限公司 | Method for preparing polyvinylidene fluoride hydrophobic microporous membrane by thermally-induced phase separation method |
| US20160243525A1 (en) * | 2016-05-02 | 2016-08-25 | LiSo Plastics, L.L.C. | Multilayer Polymeric Membrane and Process |
| CN106582314A (en) * | 2017-02-26 | 2017-04-26 | 浙江理工大学 | Preparation method of small-pore-size hydrophobic composite membrane used for membrane distillation |
| KR20170131857A (en) * | 2016-05-23 | 2017-12-01 | 한국화학연구원 | Porous Polymer Membranes Fabricated by the Combination Method of Phase Inversion and Roll-Press and Redox-Flow Battery Comprising the Same |
| CN111495198A (en) * | 2020-04-08 | 2020-08-07 | 江苏巨贤合成材料有限公司 | Preparation method of polymer porous membrane |
-
2020
- 2020-08-10 CN CN202010793483.0A patent/CN112023728B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240079A (en) * | 2008-02-28 | 2008-08-13 | 武汉理工大学 | Porous proton exchange membrane material and preparation method thereof |
| CN103285739A (en) * | 2013-05-16 | 2013-09-11 | 中国科学院过程工程研究所 | Preparation method of hydrophobic porous separation membrane |
| CN104772049A (en) * | 2014-01-15 | 2015-07-15 | 天津海之凰科技有限公司 | Method for preparing polyvinylidene fluoride hydrophobic microporous membrane by thermally-induced phase separation method |
| US20160243525A1 (en) * | 2016-05-02 | 2016-08-25 | LiSo Plastics, L.L.C. | Multilayer Polymeric Membrane and Process |
| KR20170131857A (en) * | 2016-05-23 | 2017-12-01 | 한국화학연구원 | Porous Polymer Membranes Fabricated by the Combination Method of Phase Inversion and Roll-Press and Redox-Flow Battery Comprising the Same |
| CN106582314A (en) * | 2017-02-26 | 2017-04-26 | 浙江理工大学 | Preparation method of small-pore-size hydrophobic composite membrane used for membrane distillation |
| CN111495198A (en) * | 2020-04-08 | 2020-08-07 | 江苏巨贤合成材料有限公司 | Preparation method of polymer porous membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112023728B (en) | 2022-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108807786B (en) | Reinforcing film for battery isolation and preparation method thereof | |
| CN100579638C (en) | Modified polyvinyl chloride hollow fiber microporous memebrane and method for preparing the same | |
| JP2014503946A (en) | Application of porous membrane and its composite membrane in redox flow battery | |
| CN101396641A (en) | Composite thermotropic phase separation film-making method | |
| CN101240079B (en) | Porous proton exchange membrane material and preparation method thereof | |
| CN103897309A (en) | Preparation method of high-temperature-resisting fluorine-containing polymer cellular material | |
| CN111330452A (en) | Polysulfate flat ultrafiltration membrane and preparation method thereof | |
| CN107297156B (en) | Preparation method of composite forward osmosis membrane based on interfacial polymerization | |
| CN101745324A (en) | Preparation method of dry high-hydrophilic polyvinylidene fluoride hollow fibrous membrane | |
| CN112670668B (en) | Ultra-high molecular weight polyethylene lithium battery diaphragm and preparation method thereof | |
| CN110943238B (en) | Ion-conducting membrane for flow battery and preparation and application thereof | |
| CN112023728B (en) | PBI hydrophobic microporous membrane for high-acid-resistance and oxidation-resistance membrane distillation and preparation method thereof | |
| CN110181837B (en) | Production method for controlling aperture of lithium ion secondary battery diaphragm | |
| CN112952295B (en) | Polyolefin-cellulose composite diaphragm and preparation method thereof | |
| CN102512987B (en) | Method for preparing high-flux polyvinylidene fluoride hollow fiber membrane | |
| CN111129557B (en) | Phosphoric acid modified polybenzimidazole proton exchange membrane and preparation method thereof | |
| CN110120532B (en) | Preparation method of composite membrane | |
| CN110350131B (en) | Method for preparing composite polypropylene microporous membrane by phase inversion method, product and application thereof | |
| CN106876631B (en) | A kind of application of amberplex in lithium-sulfur rechargeable battery | |
| CN104356419A (en) | Production process of polytetrafluoroethylene micro-pore membrane reinforced composite proton exchange membrane | |
| CN103537203A (en) | Thermally-induced phase separation polyvinylidene fluoride hollow fiber membrane and preparation method thereof | |
| CN109390601B (en) | Preparation method of ion exchange membrane | |
| CN111777173A (en) | Preparation method of permanent hydrophilic MBR (membrane bioreactor) flat dry film | |
| CN111933873A (en) | Diaphragm with uniform aperture and preparation method thereof | |
| CN104262665A (en) | Preparation method capable of continuously producing perfluorosulfonic proton exchange 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 |