CN114870644A - Semipermeable membrane composite material and preparation method thereof - Google Patents
Semipermeable membrane composite material and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 169
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 179
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 89
- 238000010521 absorption reaction Methods 0.000 claims abstract description 34
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 73
- 238000005266 casting Methods 0.000 claims description 60
- 239000000835 fiber Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 38
- 230000008569 process Effects 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 17
- 238000012695 Interfacial polymerization Methods 0.000 claims description 12
- 238000011033 desalting Methods 0.000 claims description 11
- 229920002492 poly(sulfone) Polymers 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 6
- 239000004677 Nylon Substances 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 230000001112 coagulating effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
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- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 35
- 238000010612 desalination reaction Methods 0.000 abstract description 5
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- RUOKPLVTMFHRJE-UHFFFAOYSA-N benzene-1,2,3-triamine Chemical compound NC1=CC=CC(N)=C1N RUOKPLVTMFHRJE-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
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- 210000002189 macula lutea Anatomy 0.000 description 1
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- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
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Classifications
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- 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
- B01D69/10—Supported membranes; Membrane supports
-
- 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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a semipermeable membrane composite material and a preparation method thereof. The semipermeable membrane composite material comprises a supporting material and a semipermeable membrane; the supporting material is provided with a surface to be coated and a non-coating surface, and the semi-permeable membrane is arranged on the surface to be coated of the supporting material; the water absorption height h of the supporting material is more than or equal to 5 and less than 70mm, and when 20 +/-10 mu L of water drop is dripped on the surface to be coated of the supporting material, the water seepage time t of the water drop is more than 30s and less than or equal to 30 min. The stable and uniform semipermeable membrane can be quickly formed on the support material, the obtained semipermeable membrane composite material has high desalination rate and proper water flux, and the semipermeable membrane composite material is not yellowed; during the coating process, the situation of liquid permeation can be effectively avoided.
Description
Technical Field
The invention relates to the technical field of membrane materials, in particular to a semipermeable membrane composite material and a preparation method thereof.
Background
Semipermeable membranes are used as a high-efficiency filtering material, and are increasingly concerned, applied and popularized due to higher filtering efficiency and lower operation and maintenance cost. According to the aperture size of the semipermeable membrane, the semipermeable membrane can be divided into microfiltration, ultrafiltration, nanofiltration, reverse osmosis membrane and the like. These semipermeable membranes are generally made of synthetic resins such as cellulose-based resins, polyester-based resins, polysulfone-based resins, polyamide-based resins, and fluororesins, and these materials have low bulk strength when used as semipermeable membranes, and are difficult to stably operate for a long period of time under rated operating conditions of the semipermeable membranes, and cannot be used alone.
A technique of applying a semipermeable membrane to one surface of a fibrous substrate such as a nonwoven fabric as a support is commonly used. The semi-permeable membrane support body of Mitsubishi and other companies is manufactured by using main fiber and adhesive fiber as raw materials, adopting a wet papermaking process and then carrying out hot pressing treatment.
The prior art mainly focuses on researching the permeation condition of the polysulfone solution and does not carry out quantitative specification on the hydrophilicity of the semipermeable membrane support. In the actual coating process, the hydrophilicity of the semipermeable membrane support has great influence on washing off amine monomers of the porous polysulfone layer and the subsequent desalting layer, so that yellowing or liquid permeation of the semipermeable membrane occurs in the preparation process.
Disclosure of Invention
The invention mainly aims to provide a semipermeable membrane composite material and a preparation method thereof, and aims to solve the problem that a semipermeable membrane in the prior art is easy to yellow or have liquid permeability.
In order to achieve the above object, according to one aspect of the present invention, there is provided a semipermeable membrane composite, including a support material and a semipermeable membrane; the supporting material is provided with a surface to be coated and a non-coating surface, and the semi-permeable membrane is arranged on the surface to be coated of the supporting material; the water absorption height h of the supporting material is more than or equal to 5 and less than 70mm, and when 20 +/-10 mu L of water drop is dripped on the surface to be coated of the supporting material, the water seepage time t of the water drop is more than 30s and less than or equal to 30 min.
Further, the supporting material comprises main body fibers and adhesive fibers, wherein the mass ratio of the main body fibers to the adhesive fibers is 2-3: 1.
further, the gram weight of the supporting material is 60-100 g/m 2 Preferably, the gram weight of the supporting material is 70-80 g/m 2 (ii) a The thickness of the support material is 80-120 μm, and preferably 90-120 μm.
Furthermore, the thickness of the semipermeable membrane composite material is 90-150 μm, and the thickness of the semipermeable membrane is 10-30 μm.
In order to achieve the above object, according to an aspect of the present invention, there is provided a method for preparing the semi-permeable membrane composite as described above, the method comprising: coating the surface to be coated of the support material with the casting solution, and forming a porous layer on the surface to be coated of the support material with the casting solution through a coagulating bath to obtain a composite material with the porous layer; and carrying out interfacial polymerization on the porous layer to obtain the semipermeable membrane composite material with the desalting layer.
Further, the solute of the membrane casting solution is one or more of polysulfone, polyethersulfone, cellulose, nylon, polyvinylidene fluoride and polyvinyl chloride; preferably, the solvent of the casting solution is one or more of N, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide; preferably, the mass fraction of solute in the casting solution is 10-20%.
Further, when the casting solution is used for coating the surface to be coated of the support material, the casting solution is immersed into the support material to be 10-90 μm thick.
Further, the process of interfacial polymerization comprises: immersing the composite material with the porous layer into a first solution to obtain a first composite material; and immersing the first composite material into the second solution for heating reaction to obtain the semipermeable membrane composite material with the desalting layer.
Further, the heating reaction temperature is 70-130 ℃.
Further, the first solution is m-phenylenediamine aqueous solution and/or piperazine aqueous solution; preferably, the second solution is a trimesoyl chloride solution.
By applying the technical scheme of the invention, a stable and uniform semipermeable membrane can be quickly formed on the support material, the obtained semipermeable membrane composite material has high desalination rate and proper water flux, and the semipermeable membrane composite material is not yellowed; during the coating process, the situation of liquid permeation can be effectively avoided.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a view of a semipermeable membrane face of example 1 of the present invention;
FIG. 2 shows a schematic representation of a semipermeable membrane face of comparative example 2 of the present invention;
FIG. 3 shows a membrane face view of a semipermeable membrane according to comparative example 4 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
The water absorption height is the distance that water rises on the pattern by capillary action. The paper pattern in the application refers to the paper pattern which is sampled and selected according to GB/T450 in the supporting material.
As analyzed by the background art of the present application, when the hydrophilicity of the semipermeable membrane supporting material is poor, the problems of nonuniform thickness of the semipermeable membrane, yellowing of the membrane surface of the semipermeable membrane, yellow spots and the like are likely to occur; however, when the semipermeable membrane support material is too hydrophilic, problems such as liquid permeation are likely to occur. In order to solve these problems, the present application provides a semipermeable membrane composite and a method for preparing the same.
In an exemplary embodiment of the present application, a semipermeable membrane composite is provided, the semipermeable membrane composite comprising a support material and a semipermeable membrane; the supporting material is provided with a surface to be coated and a non-coating surface, and the semi-permeable membrane is arranged on the surface to be coated of the supporting material; the water absorption height h of the supporting material is more than or equal to 5 and less than 70mm, and when 20 +/-10 mu L of water drop is dripped on the surface to be coated of the supporting material, the water seepage time t of the water drop is more than 30s and less than or equal to 30 min. The water penetration time is a time during which the water droplets penetrate into the support material.
The inventor finds that the hydrophilicity of the semipermeable membrane supporting material has a great influence on the washing of amine monomers by the semipermeable membrane and the desalting layer through experiments. When the hydrophilicity of the support material is poor, the permeability of the casting solution on the support material is poor in the coating process, and the diffusion and permeation of the casting solution and the water-induced phase inversion process are not uniform, so that the thickness of the finally formed semipermeable membrane is not uniform, and the problems of yellow spots and light-dark connection of the membrane surface of the semipermeable membrane are caused, as shown in fig. 2 and 3; when the hydrophilicity of the support material is too excellent, liquid permeation is easy to occur in the coating process, so that the casting solution is precipitated on the non-coating surface of the support material, the production is influenced, and a uniform and stable semipermeable membrane cannot be obtained. Therefore, in the process of preparing the semipermeable membrane composite material, the selection of the supporting material is very important, the supporting material with proper hydrophilic performance is selected, and in the stage of desalting (namely the interfacial polymerization process), the introduced solvent (amine monomer, such as m-phenylenediamine or benzenetriamine) can be better removed, so that the generation of yellowing is reduced. Meanwhile, the support material with proper hydrophilic performance can enable the membrane casting solution to have better permeation in a shorter time, and generate enough acting force with the support material after the solvent is removed, so that enough powerful acting force is formed between the semipermeable membrane and the support material, and stable operation under the use working condition is ensured.
The hydrophilic performance of the support material is characterized by the two properties of water seepage time and water absorption height. The method for testing the water absorption height of the supporting material comprises the following steps:
(1) the support material prepared by the method is sampled according to GB/T450: taking a roll of the finished support material, removing all the damaged film layer from the outside of the roll, and removing three layers (the fixed quantity is not more than 225 g/m) 2 ) Or one layer (quantitative over 225 g/m) 2 ) And cutting along the full width cutter of the reel, wherein the depth of the cutter can meet the number required by sampling, and the cut paper sample is separated from the roll paper. Several samples were randomly selected, divided into five equal parts in the original width direction (CD direction), and samples 15mm wide and 250mm long were cut in each area in the longitudinal direction (MD direction).
(2) The samples were tested for water absorption height according to the standard GB/T461.1: a vertically suspended paper sample is taken, the lower end of the paper sample is immersed in water, and the capillary water absorption height after a certain time is measured.
The hydrophilicity of the water-absorbing material is judged according to the water absorption height, a gram tester is adopted as an experimental instrument, the length of a ruler of the gram tester is 200mm, and the experimental reagent is distilled water or deionized water.
The method for testing the water seepage time of the support material comprises the following steps:
(1) taking a roll of the finished support material, removing all the damaged film layer from the outside of the roll, and removing three layers (the fixed quantity is not more than 225 g/m) 2 ) Or one layer (quantitative over 225 g/m) 2 ) And cutting along the full width cutter of the reel, wherein the depth of the cutter can meet the number required by sampling, and the cut paper sample is separated from the roll paper. Randomly selecting a plurality of paper patterns, and equally dividing the paper patterns into five equal parts along the original width direction (CD direction) (each part is controlled to be 15-20 cm in width).
(2) The cut sample was suspended and dropped with 20 + -10 μ L of water on the surface, and the time required for complete permeation was recorded.
In general, the environment of the above test is not particularly limited, as in a normal laboratory environment, extreme conditions of excessive (up to 100%) or insufficient (near 0%) air humidity do not occur, and excessive (greater than 40 ℃) or insufficient (less than 5 ℃) air temperature do not occur. Preferably, the test environment temperature is 25 ℃, and the relative air humidity is 30-80%.
The inventor characterizes the water absorption height and the water seepage time of the supporting material according to the test method, and finds that the two have a certain relation although no obvious linear relation exists, as shown in table 1.
TABLE 1
| Water penetration time t | Height h of water absorption |
| 0≤t≤30s | 70≤h≤150mm |
| 30s＜t≤3min | 40≤h＜70mm |
| 3min＜t≤10min | 10≤h＜40mm |
| 10min＜t≤30min | 5≤h＜10mm |
| t>30min | 0≤h＜5mm |
The inventor finds that the water absorption height h of the supporting material is within a range of 5-70 mm, the water seepage time t is within a range of 30 s-30 min, the hydrophilic performance of the supporting material is suitable for preparing the semipermeable membrane supporting material, more preferably, the water absorption height h is within a range of 10-40 mm, and the water seepage time t is within a range of 3 min-10 min.
The support material meeting the conditions has proper hydrophilic performance, a stable and uniform semipermeable membrane composite material can be quickly formed on the support material, the obtained semipermeable membrane composite material has high desalination rate and proper water flux, and the semipermeable membrane composite material is not yellowed; and the occurrence of liquid permeation can be effectively avoided in the process of coating the casting solution.
The application is not particularly limited as to the kind of the semipermeable membrane. In some embodiments, the semipermeable membrane is one or more of polysulfone semipermeable membrane, polyethersulfone, polyvinylidene fluoride, polyvinylchloride, nylon.
Any support material commonly used in the art may be applied to the present application. In some embodiments, the support material of the present application comprises a main fiber and a binder fiber, wherein the mass ratio of the main fiber to the binder fiber is 2-3: 1.
the support material of the present application can be prepared by referring to the methods for preparing support materials in the prior art. In some embodiments, the main fibers and the binder fibers are mixed according to the mass ratio of 2-3: 1 to obtain a mixture; dispersing the mixture in water to obtain slurry; transferring the slurry to a paper machine, and carrying out paper making, forming, squeezing and drying processes to obtain base paper; and carrying out hot pressing on the base paper to obtain the support material.
In the process of preparing the semipermeable membrane composite, the support material needs to have good air permeability and strength in addition to suitable hydrophilic properties. In order to balance the air permeability and the strength of the support material, in some embodiments, the gram weight of the support material is controlled to be 60-100 g/m 2 Preferably, the gram weight of the supporting material is 70-80 g/m 2 For example, the grammage of the support material is 60g/m 2 、65g/m 2 、70g/m 2 、72g/m 2 、75g/m 2 、78g/m 2 、80g/m 2 、85g/m 2 、100g/m 2 . When the gram weight of the supporting material is larger than the range, the air permeability of the supporting material is obviously reduced, and when the gram weight is smaller than the range, the strength of the supporting material is low, so that the strength requirement for preparing the semipermeable membrane composite material is difficult to meet.
In some embodiments, the thickness of the support material is 80-120 μm, preferably 90-120 μm, for example 80 μm, 90 μm, 95 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm. The thickness is less than the range, and the air permeability and the hydrophilic performance of the support are poor; when the thickness is larger than the range, the strength and the flatness of the supporting material are difficult to meet the requirements, and a uniform and stable semipermeable membrane cannot be formed, so that the problem of yellowing is easily caused.
In some embodiments, the semi-permeable membrane composite has a thickness of 90 to 150 μm and the semi-permeable membrane has a thickness of 10 to 30 μm. The semi-permeable membrane has overlarge membrane thickness, can reduce the flux of the semi-permeable membrane, and has undersize membrane thickness, can reduce the desalination rate of the semi-permeable membrane.
In another exemplary embodiment, there is provided a method for preparing the semi-permeable membrane composite as described above, the method comprising: coating the surface to be coated of the support material with the casting solution, and then forming a porous layer on the surface to be coated of the support material with the casting solution through a coagulating bath to obtain a composite material with the porous layer; and carrying out interfacial polymerization on the porous layer to obtain the semipermeable membrane composite material with the desalting layer.
According to the method, the casting solution with a certain concentration is coated on the surface to be coated of the support material meeting the conditions, and as the support material has proper hydrophilic performance, one part of the casting solution is remained on the surface of the surface to be coated of the support material, and the other part of the casting solution is uniformly diffused and permeated into the support material without liquid permeation. After entering the coagulating bath, the casting solution is gradually precipitated on the non-coating surface to form a layer of porous structure, and interfacial polymerization is carried out on the porous layer to obtain the semipermeable membrane composite material. The semipermeable membrane composite material prepared by the preparation method is uniform and stable and does not yellow.
The present application is not particularly limited to casting solutions, and all casting solutions commonly used in the art may be used in the present application. To form a uniform semipermeable membrane during the coating process, in some embodiments, the solute of the membrane casting solution is one or more of polysulfone, polyethersulfone, cellulose, nylon, polyvinylidene fluoride, polyvinyl chloride; preferably, the solvent of the casting solution is one or more of N, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide; the higher the concentration of the casting solution is, the larger the thickness and mechanical strength of the semipermeable membrane are, and in order to ensure that the strength of the semipermeable membrane meets the requirements and avoid the influence of the excessively thick semipermeable membrane on the performance of the semipermeable membrane, the mass fraction of the solute in the casting solution is preferably 10-20%, for example, 10%, 12%, 15%, 17% and 20%.
In order to obtain a semipermeable membrane with satisfactory mechanical strength and good performance, in some embodiments, the thickness of the casting solution penetrating into the support material is 10-90 μm when the casting solution is coated on the surface to be coated of the support material. The support material is too hydrophilic, and the thickness of the casting solution penetrating into the support material is too large, resulting in liquid permeation.
The interfacial polymerization process may be performed by reference to procedures commonly used in the art. In some embodiments, the process of interfacial polymerization comprises: immersing the composite material with the porous layer into a first solution to obtain a first composite material; and immersing the first composite material into the second solution, and carrying out heating reaction to obtain the composite material with the desalting layer. The first solution is m-phenylenediamine aqueous solution and/or piperazine aqueous solution; preferably, the second solution is a trimesoyl chloride solution. In the process of interfacial polymerization, a solvent such as m-phenylenediamine is introduced, and when the support material has proper hydrophilic performance, the amine monomer can be easily removed when the support material is washed by water in a washing tank.
In order to remove the solvent in the semipermeable membrane composite material and not to damage the structure of the semipermeable membrane composite material, in some embodiments, the heating reaction temperature is 70-130 ℃, and the reaction time is 5-10 min.
In some embodiments, the above preparation method further comprises: and cleaning and rolling the semipermeable membrane composite material with the desalting layer to obtain a finished product roll of the semipermeable membrane composite material.
Both coagulation baths and washing steps commonly used in the art may be used in this application. In some embodiments, the coagulation bath employs a water coagulation tank; the desalinated semi-permeable membrane is washed by a washing tank, and a hydrosolvent is adopted in the washing tank.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the present application as claimed.
Example 1
Preparing a support material:
the host fiber (PET) and the binder fiber (PET) were mixed to obtain a mixture. Wherein the mass content of the main body fiber is 70 percent, and the content of the adhesive fiber is 30 percent. The melting temperature of the main body fiber is 247 ℃, and the diameter of the main body fiber is 0.5D; the binder fiber had a melting temperature of 238 ℃ and a diameter of 1.2D.
Dispersing the mixture in water to obtain slurry; transferring the slurry to a paper machine, and carrying out paper making, forming, squeezing and drying processes to obtain base paper; and carrying out hot pressing on the base paper at the temperature of 200 ℃ to obtain the support material.
Controlling the gram of support materialThe weight is 75g/m 2 The thickness is 100 mu m, the water seepage time of the obtained support material is more than 3min and less than or equal to 10min, and the water absorption height is more than or equal to 10 and less than or equal to h and less than 40 mm.
Preparing a semipermeable membrane composite material:
preparing a 15 mass percent dimethyl sulfoxide solution of polysulfone, uniformly coating the solution on the surface to be coated of the support membrane by adopting a coating machine, and solidifying in a solidification tank to form a composite material with a porous layer; immersing the composite material with the porous layer into an m-phenylenediamine aqueous solution with the mass fraction of 1% to obtain a first composite material; immersing the first composite material into a trimesoyl chloride solution with the mass fraction of 0.1%, and carrying out interfacial polymerization for 10min at 100 ℃ to obtain a composite material with a desalting layer; and soaking the desalted composite material into a water cleaning tank to obtain a semipermeable membrane composite material, and then rolling to obtain a finished product roll of the semipermeable membrane composite material.
The thickness of the semipermeable membrane is 15-25 μm through electron microscope observation, and the thickness of the membrane casting solution immersed in the support material is 20-70 μm.
In the coating process, the support material shows good processability, the membrane surface of the prepared semipermeable membrane is flat and smooth and has uniform thickness, the support layer between the semipermeable membrane and the support material has good adhesiveness, the membrane surface has no yellowing sign and has no liquid permeation, and the membrane surface condition is shown in figure 1.
Example 2
Different from the embodiment 1, in the process of preparing the support material, the hot pressing temperature is 220 ℃, the water seepage time of the obtained support material is more than 10min and less than or equal to t and less than or equal to 30min, and the water absorption height is more than or equal to 5 and less than or equal to h and less than 10 mm.
The thickness of the semipermeable membrane is 20-30 μm through electron microscope observation, and the thickness of the membrane casting solution immersed in the support material is 10-20 μm.
The film surface is slightly yellow and has no liquid permeability.
Example 3
Different from the embodiment 1, in the process of preparing the support material, the hot pressing temperature is 180 ℃, the water seepage time of the obtained support material is more than 30s and less than or equal to t and less than or equal to 3min, and the water absorption height is more than or equal to 40 and less than or equal to h and less than 70 mm.
The thickness of the semipermeable membrane is observed to be 5-20 mu m through an electron microscope, and the thickness of the membrane casting solution immersed in the support material is 70-90 mu m.
The film thickness is difficult to control because the film casting liquid is immersed in the support material to a deeper thickness. The film surface showed no sign of yellowing.
Example 4
Unlike example 1, in the preparation of the supporting material, the amount of the main body fiber and the binder fiber was adjusted to control the grammage of the supporting material to 60g/m 2 The water seepage time of the obtained support material is more than 30s and less than or equal to 3min, and the water absorption height is more than or equal to 40 and less than or equal to h and less than 70 mm.
The thickness of the semipermeable membrane is observed to be 5-20 mu m through an electron microscope, and the thickness of the membrane casting solution immersed in the support material is 70-90 mu m.
The film thickness is difficult to control because the film casting liquid is immersed in the support material to a deeper thickness. The film surface showed no sign of yellowing.
Example 5
Unlike example 1, in the preparation of the supporting material, the amount of the main body fiber and the binder fiber was adjusted to control the grammage of the supporting material to 70g/m 2 The water seepage time of the obtained support material is more than 3min and less than or equal to 10min, and the water absorption height is more than or equal to 10 and less than or equal to h and less than 40 mm.
The thickness of the semipermeable membrane is 15-25 μm through electron microscope observation, and the thickness of the membrane casting solution immersed in the support material is 20-70 μm.
No sign of yellowing on the membrane surface was observed, and no liquid was permeated.
Example 6
Unlike example 1, in the preparation of the supporting material, the amounts of the main body fiber and the binder fiber were adjusted to control the grammage of the supporting material to 80g/m 2 The water seepage time of the obtained support material is more than 4min and less than or equal to 10min, and the water absorption height is more than or equal to 10 and less than or equal to h and less than 30 mm.
The thickness of the semipermeable membrane is 15-25 μm through electron microscope observation, and the thickness of the membrane casting solution immersed in the support material is 20-70 μm.
No yellowing on the membrane surface and no liquid permeation.
Example 7
With fruitExample 1 except that in the preparation of the supporting material, the amount of the main body fiber and the binder fiber was adjusted to control the grammage of the supporting material to 100g/m 2 The water seepage time of the obtained support material is more than 10min and less than or equal to t and less than or equal to 30min, and the water absorption height is more than or equal to 5 and less than or equal to h and less than 10 mm.
The thickness of the semipermeable membrane is 20-30 μm through electron microscope observation, and the thickness of the membrane casting solution immersed in the support material is 10-20 μm.
The film surface was slightly yellow and no liquid was permeated.
Example 8
Different from the embodiment 1, in the process of preparing the supporting material, the gap of the hot press is adjusted to ensure that the thickness of the supporting material is 80 mu m, the water seepage time of the obtained supporting material is more than 10min and less than or equal to t and less than or equal to 30min, and the water absorption height is more than or equal to 5 and less than or equal to h and less than 10 mm.
The thickness of the semipermeable membrane is 20-30 μm through electron microscope observation, and the thickness of the membrane casting solution immersed in the support material is 10-20 μm.
The film surface was slightly yellowish and there was no liquid permeation.
Example 9
Different from the embodiment 1, in the process of preparing the supporting material, the gap of the hot press is adjusted to ensure that the thickness of the supporting material is 90 mu m, the water seepage time of the obtained supporting material is more than 5min and less than or equal to t and less than or equal to 10min, and the water absorption height is more than or equal to 10 and less than or equal to h and less than 25 mm.
The thickness of the semipermeable membrane is 15-25 μm through electron microscope observation, and the thickness of the membrane casting solution immersed in the support material is 20-60 μm.
The film surface is not yellowed and has no liquid permeation.
Example 10
Different from the embodiment 1, in the process of preparing the supporting material, the gap of the hot press is adjusted to ensure that the thickness of the supporting material is 120 mu m, the water seepage time of the obtained supporting material is more than 3min and less than or equal to t and less than or equal to 6min, and the water absorption height is more than or equal to 25 and less than or equal to h and less than 40 mm.
The thickness of the semipermeable membrane is 15-25 μm through electron microscope observation, and the thickness of the membrane casting solution immersed in the support material is 30-80 μm.
The film surface has no yellowing and no liquid permeation.
Example 11
Different from the embodiment 1, in the process of preparing the supporting material, the gap of the hot press is adjusted to ensure that the thickness of the supporting material is 150 mu m, the water seepage time of the obtained supporting material is more than 30s and less than or equal to t and less than or equal to 3min, and the water absorption height is more than or equal to 40 and less than or equal to h and less than 70 mm.
The thickness of the semipermeable membrane is observed to be 5-20 mu m through an electron microscope, and the thickness of the membrane casting solution immersed in the supporting material is 80-120 mu m.
The film thickness is difficult to control because the film casting liquid is immersed in the support material to a deeper thickness. The film surface showed no sign of yellowing.
Example 12
Unlike example 1, in the preparation of the support material, the diameter of the main body fiber was 0.3D and the melting temperature of the binder fiber was 230 ℃. The water seepage time of the obtained support material is more than 10min and less than or equal to t and less than or equal to 30min, and the water absorption height is more than or equal to 5 and less than or equal to h and less than 10 mm.
The thickness of the semipermeable membrane is 20-30 μm through electron microscope observation, and the thickness of the membrane casting solution immersed in the support material is 10-20 μm.
The film surface is slightly yellow and has no liquid permeability.
Example 13
Unlike example 1, in the preparation of the support material, the diameter of the main body fiber was 0.7D and the melting temperature of the binder fiber was 230 ℃. The water seepage time of the obtained support material is more than 30s and less than or equal to 3min, and the water absorption height is more than or equal to 40 and less than or equal to h and less than 70 mm.
The thickness of the semipermeable membrane is observed to be 5-20 mu m through an electron microscope, and the thickness of the membrane casting solution immersed in the support material is 70-90 mu m.
The film thickness is difficult to control because the film casting liquid is immersed in the support material to a deeper thickness. The film surface is not yellowed.
Example 14
Unlike example 1, in the preparation of the support material, the diameter of the main body fiber was 1D, and the melting temperature of the binder fiber was 230 ℃. The water seepage time of the obtained support material is more than 30s and less than or equal to 3min, and the water absorption height is more than or equal to 40 and less than or equal to h and less than 70 mm.
The thickness of the semipermeable membrane is observed to be 5-20 mu m through an electron microscope, and the thickness of the membrane casting solution immersed in the support material is 70-90 mu m.
Because the membrane casting solution is immersed in the support material to a greater thickness, the thickness of the membrane layer is difficult to control. The film surface is not yellowed.
Comparative example 1
Different from the embodiment 1, in the process of preparing the support material, the hot pressing temperature is 150 ℃, the water seepage time t of the obtained support material is more than or equal to 0 and less than or equal to 30s, and the water absorption height h is more than or equal to 70 and less than or equal to 150 mm.
The thickness of the semipermeable membrane is observed to be 5-15 mu m through an electron microscope, and the thickness of the membrane casting solution immersed in the support material is 100 mu m.
The film surface was not yellowed, but liquid permeation occurred.
Comparative example 2
Different from the embodiment 1, in the process of preparing the support material, the hot pressing temperature is 250 ℃, the water seepage time of the obtained support material is more than 30min, and the water absorption height h is more than or equal to 0 and less than 5 mm.
The thickness of the semipermeable membrane is 20-30 mu m through electron microscope observation, and the thickness of the membrane casting liquid immersed in the support material is 0-10 mu m.
Because the support material has poor hydrophilicity, the casting solution (polysulfone solution) is difficult to permeate into the support material in the coating process, but the coating process of the polysulfone layer can be still completed, and the method can be used for preparing the semipermeable membrane. However, due to the poor hydrophilicity of the support material, the amine monomer cannot be effectively removed in the interfacial polymerization stage, so that a large amount of macula lutea appears on the membrane surface, but the liquid-permeable condition is absent, and the condition of the membrane surface is shown in fig. 2.
Comparative example 3
Unlike example 1, in the preparation of the support material, the diameter of the binder fiber was 1.5D, the melting temperature of the binder fiber was 230 ℃, and the grammage of the support material was controlled to be 50g/m 2 The water seepage time of the obtained support material is more than or equal to 0 and less than or equal to 30s, and the water absorption height is more than or equal to 70 and less than or equal to h and less than or equal to 150 mm.
The thickness of the semipermeable membrane is observed to be 5-15 mu m through an electron microscope, and the thickness of the membrane casting solution immersed in the support material is 100 mu m.
The film surface is not yellowed, and the liquid permeation situation appears.
Comparative example 4
Unlike example 1, in the process of preparing the supporting material, the diameter of the main body fiber was 0.3D, the melting temperature of the binder fiber was 230 ℃, and the grammage of the supporting material was controlled to be 110g/m 2 The water seepage time of the obtained support material is more than 30min, and the water absorption height is more than or equal to 0 and less than 5 mm.
The thickness of the semipermeable membrane is 20-30 mu m through electron microscope observation, and the thickness of the membrane casting liquid immersed in the support material is 0-10 mu m.
The membrane surface exhibited a large number of maculas without liquid permeation, as shown in fig. 3.
Comparative example 5
Different from the embodiment 1, in the process of preparing the support material, the diameter of the adhesive fiber is 1.5D, the melting temperature is 230 ℃, the thickness of the support material is controlled to be 70 mu m, the water seepage time of the obtained support material is more than 30min, and the water absorption height is more than or equal to 0 and less than 5 mm.
The thickness of the semipermeable membrane is 20-30 mu m through electron microscope observation, and the thickness of the membrane casting liquid immersed in the support material is 0-10 mu m.
The membrane surface had a large number of macula spots without liquid permeation.
Comparative example 6
Different from the embodiment 1, in the process of preparing the supporting material, the diameter of the main body fiber is 0.3D, the melting temperature of the adhesive fiber is 230 ℃, the thickness of the supporting material is controlled to be 170 mu m, the water seepage time of the obtained supporting material is 0-30 s, and the water absorption height is 70-150 mm.
The thickness of the semipermeable membrane is observed to be 5-15 mu m through an electron microscope, and the thickness of the membrane casting solution immersed in the support material is 100 mu m.
The film surface has liquid permeation and no yellowing.
The parameters and the film surface conditions of the above examples and comparative examples are shown in Table 2.
TABLE 2
The symbols used for the yellowing and liquid permeation are shown in Table 3.
TABLE 3
| ◎ | No yellowing occurs | Impermeable liquid |
| ○ | Yellowing/number of spots less than 2 | Slight liquid permeability |
| × | Yellowing/number of spots greater than 5 | Liquid permeable |
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the stable and uniform semipermeable membrane can be quickly formed on the support material, the obtained semipermeable membrane composite material has high desalination rate and proper water flux, and the semipermeable membrane composite material is not yellowed; during the coating process, the situation of liquid permeation can be effectively avoided.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A semipermeable membrane composite, wherein said semipermeable membrane composite comprises a support material and a semipermeable membrane;
the supporting material is provided with a surface to be coated and a non-coating surface, and the semi-permeable membrane is arranged on the surface to be coated of the supporting material;
the range of the water absorption height h of the supporting material is more than or equal to 5 and less than 70mm, and when 20 +/-10 mu L of water drop is dripped on the surface to be coated of the supporting material, the water seepage time t of the water drop is more than 30s and less than or equal to 30 min.
2. The semipermeable membrane composite according to claim 1, wherein the support material comprises a main body fiber and a binder fiber, and the mass ratio of the main body fiber to the binder fiber is 2-3: 1.
3. the semipermeable membrane composite according to claim 1, wherein the grammage of the support material is 60-100 g/m 2 Preferably, the gram weight of the supporting material is 70-80 g/m 2 ；
The thickness of the supporting material is 80-120 mu m, and preferably the thickness of the supporting material is 90-120 mu m.
4. The semipermeable membrane composite according to claim 1, wherein the thickness of the semipermeable membrane composite is 90 to 150 μm, and the thickness of the semipermeable membrane is 10 to 30 μm.
5. A method for manufacturing the semipermeable membrane composite according to any of claims 1 to 4, wherein said manufacturing method comprises:
coating the surface to be coated of the support material with a membrane casting solution, and then forming a porous layer on the surface to be coated of the support material with the membrane casting solution through a coagulating bath to obtain a composite material with the porous layer;
and carrying out interfacial polymerization on the porous layer to obtain the semipermeable membrane composite material with the desalting layer.
6. The preparation method according to claim 5, characterized in that the solute of the membrane casting solution is one or more of polysulfone, polyethersulfone, cellulose, nylon, polyvinylidene fluoride and polyvinyl chloride; preferably, the solvent of the casting solution is one or more of N, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide; preferably, the mass fraction of the solute in the casting solution is 10-20%.
7. The preparation method according to claim 5, wherein when the casting solution is used for coating the surface to be coated of the support material, the casting solution is immersed into the support material to a thickness of 10-90 μm.
8. The method of claim 5, wherein the interfacial polymerization process comprises:
immersing the composite material with the porous layer into a first solution to obtain a first composite material;
and immersing the first composite material into a second solution for heating reaction to obtain the semipermeable membrane composite material with the desalting layer.
9. The method according to claim 8, wherein the temperature of the heating reaction is 70 to 130 ℃.
10. The production method according to claim 8, wherein the first solution is an aqueous solution of m-phenylenediamine and/or an aqueous solution of piperazine; preferably, the second solution is trimesoyl chloride solution.
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| CN112782936A (en) * | 2021-02-04 | 2021-05-11 | 杭州福斯特应用材料股份有限公司 | Photosensitive film and preparation method thereof |
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| GB816572A (en) * | 1954-09-24 | 1959-07-15 | Nat Res Dev | Improvements in and relating to polyamide membranes |
| FI851598A0 (en) * | 1984-04-23 | 1985-04-23 | Gore & Ass | TVAERBINDANDE KEMISK FORMULERING OCH SEMIPERMEABELT KOMPOSITMEMBRAN FRAMSTAELLT DAERAV. |
| CN106823826A (en) * | 2017-02-15 | 2017-06-13 | 北京新源国能科技集团股份有限公司 | A kind of continuous preparation method of the compound forward osmosis membrane of high flux |
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Effective date of registration: 20240119 Address after: 311300, Building 14, 201, No. 8 Foster Street, Jinbei Street, Lin'an District, Hangzhou City, Zhejiang Province (self declared) Patentee after: Hangzhou Foster Functional Membrane Materials Co.,Ltd. Address before: No.8, foster street, Jinbei street, Lin'an District, Hangzhou City, Zhejiang Province Patentee before: HANGZHOU FIRST APPLIED MATERIAL Co.,Ltd. |