Nothing Special   »   [go: up one dir, main page]

CN108499361B - Preparation method of nano-porous polymer film with adjustable pore size - Google Patents

Preparation method of nano-porous polymer film with adjustable pore size Download PDF

Info

Publication number
CN108499361B
CN108499361B CN201810317098.1A CN201810317098A CN108499361B CN 108499361 B CN108499361 B CN 108499361B CN 201810317098 A CN201810317098 A CN 201810317098A CN 108499361 B CN108499361 B CN 108499361B
Authority
CN
China
Prior art keywords
membrane
pore size
pore
solution
separation 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
Application number
CN201810317098.1A
Other languages
Chinese (zh)
Other versions
CN108499361A (en
Inventor
李建荣
束伦
赵翠
王乃鑫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Technology
Original Assignee
Beijing University of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing University of Technology filed Critical Beijing University of Technology
Priority to CN201810317098.1A priority Critical patent/CN108499361B/en
Publication of CN108499361A publication Critical patent/CN108499361A/en
Application granted granted Critical
Publication of CN108499361B publication Critical patent/CN108499361B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • 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
    • B01D61/002—Forward osmosis or direct osmosis
    • 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
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • 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
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • 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
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • 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
    • B01D61/362—Pervaporation
    • 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
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0013—Casting processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
    • 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
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • B01D71/14—Esters of organic acids
    • B01D71/16—Cellulose acetate
    • 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
    • B01D71/26—Polyalkenes
    • 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
    • B01D71/30—Polyalkenyl halides
    • 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
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • 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
    • 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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Manufacturing & Machinery (AREA)
  • Nanotechnology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dispersion Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

一种孔径可调节的纳米多孔聚合物膜的制备方法，属于膜分离领域。本发明使用分子基配位化合物分子作为造孔剂制备具有纳米孔径的分离膜。通过使用不同分子大小的分子基配位化合物，控制分离膜的孔径大小，可实现对纳米多孔聚合物膜孔径在纳米尺度的调节。本发明提供了一种简易的孔径可调节纳米多孔聚合物膜的制备方法，工艺简单且成本较低，材料易得便于扩大化生产，且制备的分离膜孔径可在纳米尺度进行调节，因此其在分子筛分方面具有潜在的应用前景。A preparation method of a nanoporous polymer membrane with adjustable pore size belongs to the field of membrane separation. The present invention uses the molecule-based coordination compound molecule as a pore-forming agent to prepare a separation membrane with nano-pore size. By using molecular-based coordination compounds with different molecular sizes to control the pore size of the separation membrane, the pore size of the nanoporous polymer membrane can be adjusted at the nanoscale. The invention provides a simple method for preparing a nanoporous polymer membrane with adjustable pore size, the process is simple, the cost is low, the material is easy to obtain and facilitates enlarged production, and the pore size of the prepared separation membrane can be adjusted at the nanometer scale, so its It has potential application prospects in molecular sieving.

Description

Preparation method of nano-porous polymer film with adjustable pore size
Technical Field
The invention relates to a preparation method of a nano porous polymer membrane with adjustable pore diameter, belonging to the field of membrane separation.
Background
The membrane separation technology is a technology for realizing selective separation when a mixture of molecules with different particle sizes passes through a semipermeable membrane at the molecular level, has the characteristics of simple operation, low energy consumption, good separation effect, no secondary pollution and the like, and is receiving more and more attention. Compared with the traditional processes of rectification, absorption, extraction and the like, the membrane separation technology has the advantages of high efficiency, energy conservation, environmental protection, simple molecular filtration and filtration process, easy control and the like. The membrane material mainly comprises organic high molecular polymer, but the aperture of the separation membrane prepared by the high molecular polymer is lack of nano-scale adjustment, and the 'trade-off' effect between permeability and selectivity exists, so that the further improvement of the performance of the polymer membrane is limited, and the cost of the membrane separation technology is increased.
Coordination compounds such as Metal Organic Polyhedra (MOPs) and metal clusters are molecular-based nanomaterials. The material not only has a regular and uniform structure, but also can change the size by using different metal ions and ligands, and meanwhile, the material can be removed under the conditions of water, acid and alkali, so that the adjustment of the pore diameter of the polymer membrane separation layer on a nanometer scale can be realized by using molecular-based coordination compounds with different molecular sizes as pore forming agents, and the separation membrane with adjustable nanometer pore diameter is prepared. The invention provides a simple preparation method of the nano porous polymer membrane with adjustable pore diameter, the process is simple, the cost is lower, the material is easy to obtain, the expanded production is convenient, and the prepared separation membrane has better separation effect and stability and has potential application prospect.
Disclosure of Invention
The invention aims to provide a preparation method of a nano-porous polymer film with adjustable pore size.
A preparation method of a nano-porous polymer film with adjustable pore size is characterized by comprising the following steps:
(1) dissolving a pore-forming agent in an organic solvent to prepare a transparent solution;
(2) dissolving a polymer in the solution prepared in the step (1) to obtain a casting solution, and standing at a certain temperature to remove air bubbles in the prepared casting solution;
(3) preparing the membrane casting solution prepared in the step (2) into a membrane, then soaking the obtained membrane in a proper solvent, and fully removing the pore-forming agent in the polymer membrane; the proper solvent is a solvent which can wash away the pore-forming agent and simultaneously keep the structure of the polymer film;
(4) and (4) taking the polymer membrane obtained in the step (3) out of the proper solvent to obtain the separation membrane with adjustable pore size.
The pore-forming agent in the invention is a molecular-based coordination compound, such as a molecular-based coordination compound selected from Metal Organic Polyhedrons (MOPs), formate and acetate.
The solvent in the step (1) of the invention can be one or more of methanol, ethanol, acetone, dichloromethane, N-hexane, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and the like.
The polymer selected in the step (2) can be one or more of acetate fiber, aromatic polyamide, polypiperazine amide, sulfonated polyethersulfone, polyvinylidene fluoride polyethersulfone, polysulfone, polyvinyl chloride, polyvinyl alcohol, polyethylene, polypropylene and the like.
The concentration of the pore-forming agent in the membrane casting solution is 0.01-20.00 wt.%, and the concentration of the polymer is 1.00-50.00 wt.%.
The temperature used in the step (2) in the invention is 0-150 ℃.
In the invention, the standing time in the step (2) is 0-5 days.
The method for preparing the membrane in the step (3) in the invention comprises any methods such as a phase inversion method, a coating method, an interfacial polymerization method, a dynamic membrane method and the like.
Suitable solvents described in step (3) of the present invention may be water, acid solutions (e.g., sulfuric acid, hydrochloric acid, nitric acid, and the like), and alkali solutions (e.g., hydroxides, ammonia, and the like).
The nano porous polymer membrane with adjustable pore diameter prepared by the method is used for separation in the fields of gas separation, pervaporation, reverse osmosis, forward osmosis, nanofiltration, ultrafiltration and the like.
The technical principle of the invention is as follows: dissolving a molecular-based coordination compound serving as a pore-forming agent in a solvent, enabling the molecular-based coordination compound to be uniformly dispersed in a polymer membrane casting solution and to achieve nano-level mixing and dispersion, then preparing the obtained membrane casting solution into a membrane, and removing the pore-forming agent by using a proper solvent to obtain the polymer membrane with adjustable aperture for dye removal and nanofiltration (the aperture can be further adjusted by adjusting concentration, the type of the pore-forming agent and the like). The polymer membrane prepared by the method has larger porosity, small molecule flow channels are added, the permeation flux of the separation membrane is greatly increased, and meanwhile, the polymer membrane with separation layers with different pore sizes is obtained by adopting pore-forming agents with different molecular sizes. The separation membrane has the advantages of simple preparation method, excellent performance, low cost and easy industrialization.
Detailed Description
The following examples further illustrate the adjustable pore size polymeric nanofiltration membranes of the present invention and their dye retention properties. However, the present invention is not limited to the following examples.
Example 1
The preparation method of the separation membrane comprises the following steps:
(1) 161.5mg of [ Cu ] were weighed24(5-tBu-1,3-BDC)24(S)24]Dissolving (tBu-MOP) powder in 100mL of N-methylpyrrolidone, and ultrasonically stirring until the (tBu-MOP) powder is completely dissolved to obtain a solution containing a pore-forming agent tBu-MOP;
(2) weighing 25.84g of polyvinylidene fluoride powder, adding the polyvinylidene fluoride powder into the solution obtained in the step (1), continuously stirring until the polyvinylidene fluoride powder is dissolved, then placing the obtained solution in a 60 ℃ drying oven, standing and defoaming for 2 days to obtain a polyvinylidene fluoride casting solution;
(3) scraping the casting solution obtained in the step (2) on a clean glass plate by using a scraper with the height of 150 microns, then putting the clean glass plate into a coagulating bath consisting of tap water for curing and film forming, and periodically replacing the coagulating bath to completely remove the pore-forming agent;
(4) and (4) taking the nanofiltration membrane obtained in the step (3) out of the coagulating bath, and airing at room temperature to obtain the polymer separation membrane for dye removal and nanofiltration.
The obtained separation membrane was subjected to a dye removal performance test in a nanofiltration device using an aqueous solution of 0.1g/L of methyl blue (MW 799.8), a test pressure of 0.5MPa, and a test temperature of room temperature.
The removal performance of the separation membrane for methyl blue was measured as follows: the flux was 13.45 L.m-2·h-1·MPa-1The methyl blue retention was 97.81%.
Example 2
The preparation method of the separation membrane comprises the following steps:
(1) 323.5mg of [ Cu ] were weighed24(5-tBu-1,3-BDC)24(S)24]Dissolving (tBu-MOP) powder in 100mL of N-methylpyrrolidone, and ultrasonically stirring until the (tBu-MOP) powder is completely dissolved to obtain a solution containing a pore-forming agent tBu-MOP;
(2) weighing 25.88g of polyvinylidene fluoride powder, adding the polyvinylidene fluoride powder into the solution obtained in the step (1), continuously stirring until the polyvinylidene fluoride powder is dissolved, then placing the obtained solution in a 60 ℃ drying oven, standing and defoaming for 2 days to obtain a polyvinylidene fluoride casting solution;
(3) scraping the casting solution obtained in the step (2) on a clean glass plate by using a scraper with the height of 150 microns, then putting the clean glass plate into a coagulating bath consisting of tap water for curing and film forming, and periodically replacing the coagulating bath to completely remove the pore-forming agent;
(4) and (4) taking the nanofiltration membrane obtained in the step (3) out of the coagulating bath, and airing at room temperature to obtain the polymer separation membrane for dye removal and nanofiltration.
The obtained separation membrane was subjected to a dye removal performance test in a nanofiltration device using an aqueous solution of 0.1g/L of methyl blue (MW 799.8), a test pressure of 0.5MPa, and a test temperature of room temperature.
The removal performance of the separation membrane for methyl blue was measured as follows: flux 41.27 L.m-2·h-1·MPa-1The methyl blue retention was 97.01%.
Example 3
The preparation method of the separation membrane comprises the following steps:
(1) 486.1mg of [ Cu ] was weighed24(5-tBu-1,3-BDC)24(S)24]Dissolving (tBu-MOP) powder in 100mL of N-methylpyrrolidone, and ultrasonically stirring until the (tBu-MOP) powder is completely dissolved to obtain a solution containing a pore-forming agent tBu-MOP;
(2) weighing 25.92g of polyvinylidene fluoride powder, adding the polyvinylidene fluoride powder into the solution obtained in the step (1), continuously stirring until the polyvinylidene fluoride powder is dissolved, then placing the obtained solution in a 60 ℃ drying oven, standing and defoaming for 2 days to obtain a polyvinylidene fluoride casting solution;
(3) scraping the casting solution obtained in the step (2) on a clean glass plate by using a scraper with the height of 150 microns, then putting the clean glass plate into a coagulating bath consisting of tap water for curing and film forming, and periodically replacing the coagulating bath to completely remove the pore-forming agent;
(4) and (4) taking the nanofiltration membrane obtained in the step (3) out of the coagulating bath, and airing at room temperature to obtain the polymer separation membrane for dye removal and nanofiltration.
The obtained separation membrane was subjected to a dye removal performance test in a nanofiltration device using an aqueous solution of 0.1g/L of methyl blue (MW 799.8), a test pressure of 0.5MPa, and a test temperature of room temperature.
The removal performance of the separation membrane for methyl blue was measured as follows: flux 52.72 L.m-2·h-1·MPa-1The methyl blue retention was 95.77%.
Example 4
The preparation method of the separation membrane comprises the following steps:
(1) 315.6mg of [ Cu ] was weighed24(5-tBu-1,3-BDC)24(S)24]Dissolving (tBu-MOP) powder in 100mL of N-methylpyrrolidone, and ultrasonically stirring until the (tBu-MOP) powder is completely dissolved to obtain a solution containing a pore-forming agent tBu-MOP;
(2) weighing 22.72g of polyvinylidene fluoride powder, adding the polyvinylidene fluoride powder into the solution obtained in the step (1), continuously stirring until the polyvinylidene fluoride powder is dissolved, then placing the obtained solution in a 60 ℃ drying oven, standing and defoaming for 2 days to obtain a polyvinylidene fluoride casting solution;
(3) scraping the casting solution obtained in the step (2) on a clean glass plate by using a scraper with the height of 150 microns, then putting the clean glass plate into a coagulating bath consisting of tap water for curing and film forming, and periodically replacing the coagulating bath to completely remove the pore-forming agent;
(4) and (4) taking the nanofiltration membrane obtained in the step (3) out of the coagulating bath, and airing at room temperature to obtain the polymer separation membrane for dye removal and nanofiltration.
The obtained separation membrane was subjected to a dye removal performance test in a nanofiltration device using an aqueous solution of 0.1g/L of methyl blue (MW 799.8), a test pressure of 0.5MPa, and a test temperature of room temperature.
The removal performance of the separation membrane for methyl blue was measured as follows: flux 203.92 L.m-2·h-1·MPa-1The methyl blue retention was 97.82%.
Example 5
The preparation method of the separation membrane comprises the following steps:
(1) 315.6mg of [ Fe ] was weighed2Co(μ3-O)(CH3COO)6](Fe2Co) powder, dissolved in 100mL of N-methylpyrrolidone, and ultrasonically stirred until the solution is completely dissolved to obtain Fe containing pore-forming agent2A solution of Co;
(2) weighing 22.72g of polyvinylidene fluoride powder, adding the polyvinylidene fluoride powder into the solution obtained in the step (1), continuously stirring until the polyvinylidene fluoride powder is dissolved, then placing the obtained solution in a 60 ℃ drying oven, standing and defoaming for 2 days to obtain a polyvinylidene fluoride casting solution;
(3) scraping the casting solution obtained in the step (2) on a clean glass plate by using a scraper with the height of 150 micrometers, firstly putting the casting solution into a coagulating bath consisting of tap water for curing to form a film, then soaking the film into the coagulating bath consisting of a dilute hydrochloric acid solution with the pH value of 4, and periodically replacing the film so that a pore-forming agent can be completely removed;
(4) and (4) taking the nanofiltration membrane obtained in the step (3) out of the coagulating bath, and airing at room temperature to obtain the polymer separation membrane for dye removal and nanofiltration.
The obtained separation membrane was subjected to a dye removal performance test in a nanofiltration device using an aqueous solution of 0.1g/L of methyl blue (MW 799.8), a test pressure of 0.5MPa, and a test temperature of room temperature.
The removal performance of the separation membrane for methyl blue was measured as follows: flux 94.61 L.m-2·h-1·MPa-1The methyl blue retention was 99.38%.
Example 6
The preparation method of the separation membrane comprises the following steps:
(1) weighing 315.6mg of copper acetate powder, dissolving the copper acetate powder in 100mL of N-methylpyrrolidone, and ultrasonically stirring until the copper acetate powder is completely dissolved to obtain a solution containing a pore-forming agent copper acetate;
(2) weighing 22.69g of polyvinylidene fluoride powder, adding the polyvinylidene fluoride powder into the solution obtained in the step (1), continuously stirring until the polyvinylidene fluoride powder is dissolved, then placing the obtained solution in a 60 ℃ drying oven, standing and defoaming for 2 days to obtain a polyvinylidene fluoride casting solution;
(3) scraping the casting solution obtained in the step (2) on a clean glass plate by using a scraper with the height of 150 microns, then putting the clean glass plate into a coagulating bath consisting of tap water for curing and film forming, and periodically replacing the coagulating bath to completely remove the pore-forming agent;
(4) and (4) taking the nanofiltration membrane obtained in the step (3) out of the coagulating bath, and airing at room temperature to obtain the polymer separation membrane for dye removal and nanofiltration.
The obtained separation membrane was subjected to a dye removal performance test in a nanofiltration device using an aqueous solution of 0.1g/L of methyl blue (MW 799.8), a test pressure of 0.5MPa, and a test temperature of room temperature.
The removal performance of the separation membrane for methyl blue was measured as follows: the flux was 93.31 L.m-2·h-1·MPa-1The methyl blue retention was 98.37%.

Claims (1)

1.一种孔径可调节的纳米多孔聚合物膜的应用，作为纳滤膜用于甲基蓝的脱除，多孔聚合物膜的制备包括以下步骤：1. the application of a nanoporous polymer membrane with adjustable pore size, as a nanofiltration membrane for the removal of methyl blue, the preparation of the porous polymer membrane comprises the following steps: 分离膜制备方法：Separation membrane preparation method: 称取315.6 mg的[Fe2Co(μ3-O)(CH3COO)6] (Fe2Co)粉末，溶于100 mL的N-甲基吡咯烷酮中，超声搅拌至完全溶解，得到含有造孔剂Fe2Co的溶液；Weigh 315.6 mg of [Fe 2 Co(μ 3 -O)(CH 3 COO) 6 ] (Fe2Co) powder, dissolve it in 100 mL of N-methylpyrrolidone, stir with ultrasonic until it dissolves completely, and obtain a pore-forming agent containing Fe 2 Co solution; 称取22.72 g聚偏氟乙烯粉末加入到步骤(1)中的溶液中，并不断搅拌至溶解，然后将得到的溶液放置在60 ℃烘箱中，静置脱泡2天，即可得到聚偏氟乙烯铸膜液；Weigh 22.72 g of polyvinylidene fluoride powder into the solution in step (1), and keep stirring until dissolved, then place the obtained solution in a 60 ℃ oven, let it stand for deaeration for 2 days, and then obtain polyvinylidene fluoride. Vinyl fluoride casting liquid; 将步骤（2）得到的铸膜液用高度为150微米的刮刀刮涂在干净的玻璃板上，先放入由自来水组成的凝固浴中固化成膜，然后浸泡在pH为4的稀盐酸溶液组成的凝固浴中，并定期更换，使得造孔剂能够完全去除；The film casting liquid obtained in step (2) is scraped on a clean glass plate with a scraper with a height of 150 microns, first put into a coagulation bath composed of tap water to solidify into a film, and then immersed in a dilute hydrochloric acid solution with a pH of 4. In the coagulation bath composed of, and regularly replaced, so that the pore-forming agent can be completely removed; 将步骤(3)得到的纳滤膜从凝固浴中取出，室温下晾干，即可得到一种用于染料脱除纳滤的聚合物分离膜。The nanofiltration membrane obtained in step (3) is taken out from the coagulation bath and air-dried at room temperature to obtain a polymer separation membrane for dye removal nanofiltration.
CN201810317098.1A 2018-04-10 2018-04-10 Preparation method of nano-porous polymer film with adjustable pore size Active CN108499361B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810317098.1A CN108499361B (en) 2018-04-10 2018-04-10 Preparation method of nano-porous polymer film with adjustable pore size

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810317098.1A CN108499361B (en) 2018-04-10 2018-04-10 Preparation method of nano-porous polymer film with adjustable pore size

Publications (2)

Publication Number Publication Date
CN108499361A CN108499361A (en) 2018-09-07
CN108499361B true CN108499361B (en) 2021-11-12

Family

ID=63381357

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810317098.1A Active CN108499361B (en) 2018-04-10 2018-04-10 Preparation method of nano-porous polymer film with adjustable pore size

Country Status (1)

Country Link
CN (1) CN108499361B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109647221B (en) * 2018-11-07 2020-03-27 天津大学 A kind of preparation method of forward osmosis membrane based on 3D printing technology
CN109551698B (en) * 2019-01-27 2020-11-24 安徽华淮澄膜科技有限公司 Production equipment of membrane material with adjustable pore diameter
CN110479120A (en) * 2019-07-30 2019-11-22 三达膜科技（厦门）有限公司 A kind of preparation method of cellulose acetate flat plate ultrafiltration membrane
CN111701459B (en) * 2020-07-01 2022-10-11 浙江工业大学 A kind of ultra/microfiltration membrane of nitrogen-containing heterocyclic polyaryletherketone/sulfone and its structure control method
CN118949720B (en) * 2024-09-27 2025-02-14 重庆化工职业学院 High-performance composite nanofiltration membrane and preparation method and application thereof

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103191657A (en) * 2013-04-02 2013-07-10 天津工业大学 Hybridized gel film for filtration of organic solvent and preparation method thereof
CN103212302A (en) * 2013-04-03 2013-07-24 北京工业大学 Method for preparing macromolecule hollow porous fiber membrane by using chemical reaction inductive phase conversion method
WO2014043315A1 (en) * 2012-09-14 2014-03-20 Evoqua Water Technologies Llc A polymer blend for membranes
CN103977716A (en) * 2014-05-22 2014-08-13 武汉工程大学 Separating membrane for filtering heavy metal ions as well as preparation method thereof
CN104147945A (en) * 2013-05-15 2014-11-19 北京化工大学 Method for preparing polyvinylidene fluoride microporous film
CN104524988A (en) * 2015-01-22 2015-04-22 联合环境技术（厦门）有限公司 Polyvinylidene fluoride hollow fiber membrane of in-situ pore-forming agent and preparation method of polyvinylidene fluoride hollow fiber membrane
CN104801203A (en) * 2015-01-23 2015-07-29 湖北步洲环保科技有限公司 Separating membrane capable of decomposing surface organic pollutants, and preparation method thereof
CN104923085A (en) * 2015-06-04 2015-09-23 宁波聿丰新材料科技有限公司 Method for preparing high-hydrophobicity polyvinylidene fluoride compound porous membrane
CN105413486A (en) * 2015-12-03 2016-03-23 中国科学院化学研究所 Cellulose acetate commixed nano-filtration membrane and preparation method thereof
CN106000123A (en) * 2016-05-27 2016-10-12 成都易态科技有限公司 Preparation method of porous film

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014043315A1 (en) * 2012-09-14 2014-03-20 Evoqua Water Technologies Llc A polymer blend for membranes
CN103191657A (en) * 2013-04-02 2013-07-10 天津工业大学 Hybridized gel film for filtration of organic solvent and preparation method thereof
CN103212302A (en) * 2013-04-03 2013-07-24 北京工业大学 Method for preparing macromolecule hollow porous fiber membrane by using chemical reaction inductive phase conversion method
CN104147945A (en) * 2013-05-15 2014-11-19 北京化工大学 Method for preparing polyvinylidene fluoride microporous film
CN103977716A (en) * 2014-05-22 2014-08-13 武汉工程大学 Separating membrane for filtering heavy metal ions as well as preparation method thereof
CN104524988A (en) * 2015-01-22 2015-04-22 联合环境技术（厦门）有限公司 Polyvinylidene fluoride hollow fiber membrane of in-situ pore-forming agent and preparation method of polyvinylidene fluoride hollow fiber membrane
CN104801203A (en) * 2015-01-23 2015-07-29 湖北步洲环保科技有限公司 Separating membrane capable of decomposing surface organic pollutants, and preparation method thereof
CN104923085A (en) * 2015-06-04 2015-09-23 宁波聿丰新材料科技有限公司 Method for preparing high-hydrophobicity polyvinylidene fluoride compound porous membrane
CN105413486A (en) * 2015-12-03 2016-03-23 中国科学院化学研究所 Cellulose acetate commixed nano-filtration membrane and preparation method thereof
CN106000123A (en) * 2016-05-27 2016-10-12 成都易态科技有限公司 Preparation method of porous film

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Fabrication of Porous Matrix Membrane (PMM) Using Metal-Organic Framework as Green Template for Water Treatment;Jian-Yuan Lee et al.;《SCIENTIFIC REPORTS》;20140117;第4卷;第4页 *

Also Published As

Publication number Publication date
CN108499361A (en) 2018-09-07

Similar Documents

Publication Publication Date Title
CN108499361B (en) Preparation method of nano-porous polymer film with adjustable pore size
CN104209022B (en) A kind of high throughput polyamide/ZIF-8 Nano filtering composite membranes and preparation method thereof
CN103977718B (en) Positive osmosis composite membrane of a kind of high water flux and preparation method thereof
CN103861472B (en) A kind of preparation method of amino modified graphene oxide compound forward osmosis membrane
CN102836644B (en) Method for synchronously preparing hollow fiber compound nanofiltration membrane through immersion precipitation phase inversion/interface crosslinking
CN107158978B (en) Preparation method of self-assembled nanofiltration membrane of polyamine nanoparticles
WO2018120476A1 (en) Supramolecular composite nano-filtration membrane and preparation method therefor and use thereof
CN105413486A (en) Cellulose acetate commixed nano-filtration membrane and preparation method thereof
CN101513593B (en) Hydrophilic polyvinyl chloride membrane and preparation method thereof
CN102728247B (en) A kind of preparation method of composite forward osmosis membrane
EP2722100A2 (en) Reverse osmosis membrane having superior salt rejection and permeate flow, and method for manufacturing same
CN107029555A (en) A kind of solvent resistant NF membrane and preparation method thereof
CN103386258A (en) Preparation method of polyamide composite nanofiltration membrane containing modified carbon nano tube
CN102114391A (en) Method for preparing polyisophthaloyl metaphenylene diamide nanofiltration membrane
CN106823854A (en) A kind of preparation method of polymer-based metal organic backbone hybridized film
CN106215720A (en) Preparation method, prepared ultrafilter membrane and the application of this ultrafilter membrane of a kind of doped graphene quantum dot organic solvent-resistant ultrafilter membrane
CN104147943A (en) Preparation method and application of high-molecular forward osmosis membrane
CN114028947A (en) A reverse osmosis membrane modified by amino functionalized ZIFs nanomaterials and preparation method thereof
CN105597552A (en) Forward osmosis membrane with high water flux and high salt rejection rate and method for preparing forward osmosis membrane with one-step method
CN106693706A (en) Nanofiltration membrane, and preparation method and application thereof
CN114345140A (en) A kind of preparation method of high-performance composite nanofiltration membrane with intermediate layer structure
CN110960987A (en) High-performance nano hybrid reverse osmosis membrane and preparation method thereof
CN105582816A (en) Preparation method of forward osmosis membrane modified with oxidized graphene
CN105233703A (en) Preparation method of high flux cellulose microfiltration membrane
CN107213796A (en) A kind of preparation method of the novel polyetherimide NF membrane containing modified graphene oxide

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