CN114870644B - Semipermeable membrane composite material and preparation method thereof - Google Patents
Semipermeable membrane composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000010521 absorption reaction Methods 0.000 claims abstract description 34
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims description 77
- 238000005266 casting Methods 0.000 claims description 58
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- 238000000034 method Methods 0.000 claims description 33
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- 238000012695 Interfacial polymerization Methods 0.000 claims description 13
- 238000011033 desalting Methods 0.000 claims description 12
- 229920002492 poly(sulfone) Polymers 0.000 claims description 11
- 239000011248 coating agent Substances 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
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 6
- 239000004677 Nylon Substances 0.000 claims description 5
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- 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—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
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 support material is provided with a surface to be coated and a non-coated surface, and the semipermeable membrane is arranged on the surface to be coated of the support material; the water absorption height h of the support material is in the range of 5-70 mm, and when 20+ -10 mu L of water drops are dripped on the surface to be coated of the support material, the water penetration time t of the water drops is in the range of 30 s-30 min. The stable and uniform semipermeable membrane can be rapidly 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 cannot generate yellowing; in the coating process, the condition 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, which are a highly efficient filter material, are increasingly receiving attention, application and popularization with their higher filtration efficiency and lower operating and maintenance costs. The semipermeable membrane can be divided into microfiltration, ultrafiltration, nanofiltration, reverse osmosis membrane and the like according to the pore size of the semipermeable membrane. These semipermeable membranes are generally composed of synthetic resins such as cellulose-based resins, polyester-based resins, polysulfone-based resins, polyamide-based resins, and fluororesin, and when these materials are used as semipermeable membranes, the bulk strength is low, and it is difficult to stably operate for a long period of time under the rated operating conditions of the semipermeable membranes, and they cannot be used alone.
In the conventional technique, a semipermeable membrane is coated on one surface of a fibrous base material such as nonwoven fabric as a support. The semi-permeable membrane support of Mitsubishi company is prepared from main fibres and adhesive fibres through wet paper-making process and hot pressing.
The prior art is mainly focused on researching the permeation condition of polysulfone solution, and the hydrophilicity of the semipermeable membrane support is not quantified and standardized. In the actual coating process, the hydrophilicity of the semipermeable membrane support has a great influence on the porous polysulfone layer and the subsequent amine monomer washing-off of the 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, which are used for solving the problem that a semipermeable membrane is easy to yellow or permeate liquid in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a semipermeable membrane composite material including a support material and a semipermeable membrane; the support material is provided with a surface to be coated and a non-coated surface, and the semipermeable membrane is arranged on the surface to be coated of the support material; the water absorption height h of the support material is in the range of 5-70 mm, and when 20+ -10 mu L of water drops are dripped on the surface to be coated of the support material, the water penetration time t of the water drops is in the range of 30 s-30 min.
Further, 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.
further, the gram weight of the supporting material is 60-100 g/m 2 Preferably, the support material has a gram weight of 70 to 80g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The thickness of the support material is 80 to 120. Mu.m, preferably 90 to 120. Mu.m.
Further, the thickness of the semipermeable membrane composite material is 90-150 mu m, and the thickness of the semipermeable membrane is 10-30 mu m.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing the semipermeable membrane composite material, comprising: coating the surface to be coated of the support material by using a casting solution, and then forming a porous layer on the surface to be coated of the support material by using a coagulating bath to obtain a composite material with the porous layer; and performing interfacial polymerization on the porous layer to obtain the semipermeable membrane composite material with the desalting layer.
Further, the solute of the 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 thickness of the casting solution immersed in the support material is 10-90 mu m.
Further, the process of interfacial polymerization includes: immersing the composite material with the porous layer in a first solution to obtain a first composite material; immersing the first composite material into the second solution, and performing heating reaction to obtain the semipermeable membrane composite material with the desalting layer.
Further, the temperature of the heating reaction is 70-130 ℃.
Further, the first solution is m-phenylenediamine aqueous solution and/or piperazine aqueous solution; preferably, the second solution is trimesoyl chloride solution.
By applying the technical scheme of the invention, a stable and uniform semipermeable membrane can be rapidly formed on the supporting material, the obtained semipermeable membrane composite material has high desalination rate and proper water flux, and the semipermeable membrane composite material cannot generate yellowing; in the coating process, the condition of liquid permeation can be effectively avoided.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 shows a semi-permeable membrane according to example 1 of the present invention;
FIG. 2 shows a semi-permeable membrane face view of comparative example 2 of the present invention;
FIG. 3 shows a semi-permeable membrane of comparative example 4 of the present invention.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
The water absorption height is the rising distance of water on the paper sample by capillary action. The paper pattern in the application refers to a paper pattern which is sampled and selected according to GB/T450 in a supporting material.
As analyzed by the background technology of the application, under the condition that the semipermeable membrane supporting material has poor hydrophilicity, the problems of uneven semipermeable membrane thickness, yellowing of the semipermeable membrane surface, yellow spots and the like are easy to occur; in the case where the semipermeable membrane support material is too excellent in hydrophilicity, problems such as liquid permeation tend to occur. In order to solve the problems, the application provides a semipermeable membrane composite material and a preparation method thereof.
In one exemplary embodiment of the present application, a semipermeable membrane composite is provided that includes a support material and a semipermeable membrane; the support material has a surface to be coated and a non-coated surface, and the semipermeable membrane is arranged on the surface to be coated of the support material; the water absorption height h of the support material is in the range of 5-70 mm, and when 20+ -10 mu L of water drops are dripped on the surface to be coated of the support material, the water penetration time t of the water drops is in the range of 30 s-30 min. The water penetration time refers to the time for the water drops to penetrate into the support material.
The inventor finds that the hydrophilicity of the semipermeable membrane supporting material has a great influence on the washing-off 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-shade connection on the 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 likely to occur during the coating process, so that the casting solution is precipitated on the non-coated surface of the support material, thereby affecting the production and failing to obtain a uniform and stable semipermeable membrane. Therefore, in the process of preparing the semipermeable membrane composite material, the selection of the support material is very important, the support material with proper hydrophilic performance is selected, and the introduced solvent (amine monomer such as m-phenylenediamine or trimellitamine) can be better removed in the desalting stage (i.e. the interfacial polymerization process) stage, so that the generation of yellowing is reduced. Meanwhile, the support material with proper hydrophilic performance can enable the casting solution to generate better permeation in a shorter time, and generate enough acting force with the support material after the solvent is removed, so that enough strong acting force is formed between the semipermeable membrane and the support material, and stable operation under the use condition is ensured.
The application characterizes the hydrophilic performance of the support material by two properties of water penetration time and water absorption height. The method for testing the water absorption height of the supporting material in the application is as follows:
(1) The support material prepared in the application is sampled according to GB/T450: taking a roll of the support material, removing all damaged film layers from the outside of the roll, and removing three more layers (with a basis weight of not more than 225g/m 2 ) Or a layer (basis weight of more than 225g/m 2 ) And cutting a cutter along the full-width cutter of the winding drum, wherein the depth of the cutter can meet the number of sheets required by sampling, and separating the cut paper pattern from the roll paper. Several paper patterns are randomly selected, equally divided into five equal parts along the original width direction (CD direction), and samples with the width of 15mm and the length of 250mm are cut in each area along the longitudinal direction (MD direction).
(2) The samples were subjected to a water absorption height test according to standard GB/T461.1: and (3) taking a vertically suspended paper sample, immersing the lower end of the paper sample in water, and measuring the capillary water absorption height after a certain time.
The hydrophilicity of the water is judged according to the water absorption height, a gram tester is adopted as an experimental instrument, the length of a scale is 200mm, and the experimental reagent is distilled water or deionized water.
The test method for the water seepage time of the support material is as follows:
(1) Taking a roll of the support material, removing all damaged film layers from the outside of the roll, and removing three more layers (with a basis weight of not more than 225g/m 2 ) Or a layer (basis weight of more than 225g/m 2 ) And cutting a cutter along the full-width cutter of the winding drum, wherein the depth of the cutter can meet the number of sheets required by sampling, and separating the cut paper pattern from the roll paper. Several paper patterns are randomly selected, and the paper patterns are equally divided into five equal parts along the original width direction (CD direction) (each part is controlled to be 15-20 cm).
(2) The cut sample is suspended, 20+ -10 μl of water is dripped on the surface, and the time required for complete permeation is recorded.
In general, the environment of the above test is not particularly limited, since in a normal laboratory environment, an extreme condition of excessively large air humidity (up to 100%) or excessively small air humidity (near 0%) or an excessive temperature (more than 40 ℃) or excessively small air humidity (less than 5 ℃) does not occur. Preferably, the test environment temperature is 25 ℃ and the relative humidity of air is 30-80%.
The inventors characterized the water absorption height and water penetration time of the support material according to the above test method, and found that there is a certain relationship between the two, although there is no obvious linear relationship, as shown in table 1.
TABLE 1
| Time t of water seepage | Water absorption height h |
| 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 support material is more than or equal to 5 and less than or equal to 70mm, the water seepage time t is more than or equal to 30s and less than or equal to 30min, the hydrophilic performance of the support material is suitable for preparing the semipermeable membrane support material, the water absorption height h is more preferably more than or equal to 10 and less than or equal to 40mm, and the water seepage time t is more than or equal to 3min and less than or equal to 10min.
The support material meeting the conditions has proper hydrophilic performance, and the stable and uniform semipermeable membrane composite material can be rapidly formed on the support material, so that the obtained semipermeable membrane composite material has high desalination rate and proper water flux, and the semipermeable membrane composite material cannot generate yellowing; and the occurrence of the condition of liquid permeation can be effectively avoided in the process of coating the casting film liquid.
The type of semipermeable membrane is not particularly limited in the present application. In some embodiments, the semipermeable membrane is one or more of polysulfone semipermeable membrane, polyethersulfone, polyvinylidene fluoride, polyvinyl chloride, nylon.
Support materials commonly used in the art may be used in this application. In some embodiments, the support material of the present application comprises a host fiber and a binder fiber in a mass ratio of 2 to 3:1.
the support material of the present application may be prepared with reference to the methods of preparing support materials in the prior art. In some embodiments, the host fiber and the binder fiber are mixed in a 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 performing papermaking forming, squeezing and drying procedures to obtain base paper; and (3) hot-pressing the base paper to obtain the support material.
In the process of preparing semipermeable membrane composites, the support material requires good air permeability and strength in addition to suitable hydrophilic properties. In order to balance the breathability and strength of the support material, in some embodiments, the grammage of the support material is controlled to be 60 to 100g/m 2 Preferably, the support material has a gram weight of 70 to 80g/m 2 For example, the supporting material has a grammage of 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 . Of supporting materialThe gram weight exceeding this range results in a significant decrease in the air permeability of the support material, and the gram weight falling below this range results in a low strength of the support material, thereby making it difficult to meet the strength requirements for preparing semipermeable membrane composites.
In some embodiments, the thickness of the support material is 80 to 120 μm, preferably the thickness of the support material is 90 to 120 μm, for example the thickness of the support material is 80 μm, 90 μm, 95 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm. The thickness is smaller than the range, and the air permeability and the hydrophilic performance of the support are poor; when the thickness is larger than this range, the strength and flatness of the support material are both difficult to satisfy the requirements, and a uniform and stable semipermeable membrane cannot be formed, so that yellowing is liable to occur.
In some embodiments, the semipermeable membrane composite material has a thickness of 90 to 150 μm and the semipermeable membrane has a thickness of 10 to 30 μm. The thickness of the semipermeable membrane layer is too large, so that the flux of the semipermeable membrane can be reduced, and the desalination rate of the semipermeable membrane can be reduced due to the too small thickness of the membrane layer.
In another exemplary embodiment, a method for preparing the semipermeable membrane composite material described above is provided, the method comprising: coating the surface to be coated of the support material by using a casting solution, and then forming a porous layer on the surface to be coated of the support material by using a coagulating bath to obtain a composite material with the porous layer; and performing interfacial polymerization on the porous layer to obtain the semipermeable membrane composite material with the desalting layer.
The casting solution with a certain concentration is coated on the surface to be coated of the supporting material meeting the conditions, and as the supporting material has proper hydrophilic performance, a part of the casting solution is left on the surface of the surface to be coated of the supporting material, and a part of the casting solution uniformly diffuses and permeates into the supporting material without permeating liquid. After entering into the coagulating bath, the casting solution is gradually precipitated on the non-coating surface to form a layer of porous structure, and the porous layer is subjected to interfacial polymerization to obtain the semipermeable membrane composite material. The semipermeable membrane composite material prepared by the preparation method is uniform and stable and does not generate yellowing.
The casting solution is not particularly limited, and any casting solution commonly used in the prior 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 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 greater 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 excessive thickness of the semipermeable membrane on the performance of the semipermeable membrane, the mass fraction of solute in the casting solution is preferably 10-20%, such as 10%, 12%, 15%, 17% and 20%.
In order to obtain a semipermeable membrane with satisfactory mechanical strength and good properties, in some embodiments, the casting solution, when coating the surface to be coated of the support material, penetrates into the support material to a thickness of 10-90 μm. The support material is too hydrophilic, and the thickness of the casting solution penetrating into the support material is too large, thereby resulting in liquid permeation.
The interfacial polymerization process may be referred to as procedures commonly used in the art. In some embodiments, the process of interfacial polymerization comprises: immersing the composite material with the porous layer in a first solution to obtain a first composite material; 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 trimesoyl chloride solution. The solvent such as m-phenylenediamine is introduced during the interfacial polymerization, and amine monomers can be easily removed during washing with water in a washing tank when the support material has proper hydrophilic properties.
In order to remove the solvent from the semipermeable membrane composite material without destroying the structure of the semipermeable membrane composite material, in some embodiments, the reaction is heated to a temperature of 70 to 130 ℃ for a reaction time of 5 to 10 minutes.
In some embodiments, the above preparation method further comprises: and cleaning the semipermeable membrane composite material with the desalting layer, and rolling 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 the present application. In some embodiments, the coagulation bath employs a water coagulation tank; the desalted semipermeable membrane is cleaned by a cleaning tank, and an aqueous solvent is adopted in the cleaning tank.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Example 1
Preparing a supporting material:
the main fiber (PET) and the binder fiber (PET) are mixed to obtain a mixture. Wherein the mass content of the main body fiber is 70%, and the content of the binder fiber is 30%. The melting temperature of the main fiber is 247 ℃, and the diameter 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 performing papermaking forming, squeezing and drying procedures to obtain base paper; and (3) hot-pressing the base paper at the temperature of 200 ℃ to obtain the support material.
Controlling the gram weight of the supporting material to be 75g/m 2 The thickness is 100 mu m, the water seepage time of the obtained support material is 3min less than t less than or equal to 10min, and the water absorption height is 10 less than or equal to h less than 40mm.
Preparing a semipermeable membrane composite material:
preparing a dimethyl sulfoxide solution of polysulfone with the mass fraction of 15%, uniformly coating the solution on the surface to be coated of the support film by using 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 aqueous solution containing 1% by mass of m-phenylenediamine to obtain a first composite material; immersing the first composite material into a trimesic acid chloride solution with the mass fraction of 0.1%, and performing interfacial polymerization at 100 ℃ for 10min to obtain a composite material with a desalting layer; immersing the composite material with desalination into a water washing tank to obtain a semi-permeable membrane composite material, and then rolling to obtain a semi-permeable membrane composite material finished product roll.
The thickness of the semi-permeable membrane is 15-25 μm by electron microscopy, and the thickness of the casting solution immersed into the supporting material is 20-70 μm.
In the coating process, the support material has good processability, the prepared semipermeable membrane surface is flat and smooth, the thickness is uniform, the support layer between the semipermeable membrane and the support material has good adhesive property, no yellowing sign exists on the membrane surface, no liquid permeation exists on the membrane surface, and the membrane surface is shown in figure 1.
Example 2
Unlike example 1, the hot pressing temperature is 220 ℃, the water seepage time of the obtained support material is 10min less than or equal to t less than or equal to 30min, and the water absorption height is 5 less than or equal to h less than 10mm.
The thickness of the semi-permeable membrane is 20-30 μm when observed by an electron microscope, and the thickness of the casting solution immersed into the supporting material is 10-20 μm.
The membrane surface is slightly yellow, and no liquid permeation exists.
Example 3
Unlike example 1, the hot pressing temperature is 180 ℃ during the preparation of the support material, the water seepage time of the support material is 30s < t < 3min, and the water absorption height is 40 < h < 70mm.
The thickness of the semi-permeable membrane is 5-20 μm by electron microscopy, and the thickness of the casting solution immersed into the supporting material is 70-90 μm.
The thickness of the film is difficult to control because the casting solution is immersed into the supporting material to a deeper thickness. The film side showed no signs of yellowing.
Example 4
Unlike example 1, the amount of the main fiber and the binder fiber was adjusted to control the gram weight of the support material to 60g/m during the preparation of the support material 2 The water seepage time of the obtained support material is 30s < t < 3min, and the water absorption height is 40 < h < 70mm.
The thickness of the semi-permeable membrane is 5-20 μm by electron microscopy, and the thickness of the casting solution immersed into the supporting material is 70-90 μm.
The thickness of the film is difficult to control because the casting solution is immersed into the supporting material to a deeper thickness. The film side showed no signs of yellowing.
Example 5
And the actual onesExample 1 differs in that the amount of host fiber and binder fiber is adjusted during the preparation of the support material, and the grammage of the support material is controlled to be 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 40mm.
The thickness of the semi-permeable membrane is 15-25 μm by electron microscopy, and the thickness of the casting solution immersed into the supporting material is 20-70 μm.
The film surface showed no signs of yellowing, nor was it liquid permeable.
Example 6
Unlike example 1, the amount of the host fiber and the binder fiber was adjusted to control the grammage of the support material to 80g/m during the preparation of the support material 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 30mm.
The thickness of the semi-permeable membrane is 15-25 μm by electron microscopy, and the thickness of the casting solution immersed into the supporting material is 20-70 μm.
The film surface showed no signs of yellowing, nor was it liquid permeable.
Example 7
Unlike example 1, the amount of the main fiber and the binder fiber was adjusted to control the grammage of the support material to 100g/m during the preparation of the support material 2 The water seepage time of the obtained support material is more than 10min and less than or equal to 30min, and the water absorption height is more than or equal to 5 and less than 10mm.
The thickness of the semi-permeable membrane is 20-30 μm when observed by an electron microscope, and the thickness of the casting solution immersed into the supporting material is 10-20 μm.
The membrane surface turns slightly yellow and is not permeable.
Example 8
Unlike example 1, in the process of preparing the support material, the gap of the hot press was adjusted so that the thickness of the support material was 80. Mu.m, the water permeation time of the obtained support material was 10min < t.ltoreq.30 min, and the water absorption height was 5.ltoreq.h < 10mm.
The thickness of the semi-permeable membrane is 20-30 μm when observed by an electron microscope, and the thickness of the casting solution immersed into the supporting material is 10-20 μm.
The membrane surface turns slightly yellow and is not permeable.
Example 9
Unlike example 1, in the process of preparing the support material, the gap of the hot press was adjusted so that the thickness of the support material was 90. Mu.m, the water permeation time of the obtained support material was 5min < t.ltoreq.10 min, and the water absorption height was 10.ltoreq.h < 25mm.
The thickness of the semi-permeable membrane is 15-25 μm by electron microscopy, and the thickness of the casting solution immersed into the supporting material is 20-60 μm.
The membrane surface has no yellowing and no liquid permeation.
Example 10
Unlike example 1, in the process of preparing the support material, the gap of the hot press was adjusted so that the thickness of the support material was 120. Mu.m, the water permeation time of the obtained support material was 3min < t.ltoreq.6 min, and the water absorption height was 25.ltoreq.h < 40mm.
The thickness of the semi-permeable membrane is 15-25 μm by electron microscopy, and the thickness of the casting solution immersed into the supporting material is 30-80 μm.
The membrane surface has no yellowing and no liquid permeation.
Example 11
Unlike example 1, in the process of preparing the support material, the gap of the hot press was adjusted so that the thickness of the support material was 150. Mu.m, the water permeation time of the obtained support material was 30s < t < 3min, and the water absorption height was 40 < h < 70mm.
The thickness of the semi-permeable membrane is 5-20 μm when observed by an electron microscope, and the thickness of the casting solution immersed into the supporting material is 80-120 μm.
The thickness of the film is difficult to control because the casting solution is immersed into the supporting material to a deeper thickness. The film side showed no signs of yellowing.
Example 12
Unlike example 1, the diameter of the host fiber during the preparation of the support material 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 30min, and the water absorption height is more than or equal to 5 and less than 10mm.
The thickness of the semi-permeable membrane is 20-30 μm when observed by an electron microscope, and the thickness of the casting solution immersed into the supporting material is 10-20 μm.
The membrane surface is slightly yellow, and no liquid permeation exists.
Example 13
Unlike example 1, the diameter of the host fiber during the preparation of the support material 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 70mm.
The thickness of the semi-permeable membrane is 5-20 μm by electron microscopy, and the thickness of the casting solution immersed into the supporting material is 70-90 μm.
The thickness of the film is difficult to control because the casting solution is immersed into the supporting material to a deeper thickness. The film surface has no yellowing.
Example 14
Unlike example 1, the diameter of the host fiber during the preparation of the support material 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 70mm.
The thickness of the semi-permeable membrane is 5-20 μm by electron microscopy, and the thickness of the casting solution immersed into the supporting material is 70-90 μm.
The thickness of the film is difficult to control because the casting solution is immersed into the supporting material to a deeper thickness. The film surface has no yellowing.
Comparative example 1
Unlike example 1, the hot pressing temperature was 150℃during the preparation of the support material, and the water permeation time of the support material obtained was 0.ltoreq.t.ltoreq.30 s, and the water absorption height was 70.ltoreq.h.ltoreq.150 mm.
The thickness of the semi-permeable membrane is 5-15 μm by electron microscopy, and the thickness of the casting solution immersed in the support material is 100 μm.
The film surface was free from yellowing, but liquid permeation occurred.
Comparative example 2
Different from example 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 is more than or equal to 0 and less than 5mm.
The thickness of the semi-permeable membrane is 20-30 μm when observed by an electron microscope, and the thickness of the casting solution immersed into the supporting material is 0-10 μm.
Because the hydrophilicity of the support material is poor, 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 finished, and the method can be used for preparing the semipermeable membrane. However, because the support material has poor hydrophilicity, amine monomers cannot be effectively removed in the interfacial polymerization stage, so that a large number of macula lutea appear on the membrane surface, but the membrane surface is shown in fig. 2 without liquid permeation.
Comparative example 3
Unlike example 1, the diameter of the binder fiber was 1.5D, the melting temperature of the binder fiber was 230℃and the gram weight of the support material was controlled to be 50g/m in the preparation of the support material 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 150mm.
The thickness of the semi-permeable membrane is 5-15 μm by electron microscopy, and the thickness of the casting solution immersed in the support material is 100 μm.
The membrane surface has no yellowing and has liquid penetration condition.
Comparative example 4
Unlike example 1, the diameter of the host fiber during the preparation of the support material was 0.3D, the melting temperature of the binder fiber was 230℃and the gram weight of the support 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 5mm.
The thickness of the semi-permeable membrane is 20-30 μm when observed by an electron microscope, and the thickness of the casting solution immersed into the supporting material is 0-10 μm.
The membrane surface showed a large number of macula and was not permeable to liquid, as shown in fig. 3.
Comparative example 5
Unlike example 1, in the process of preparing the support material, the diameter of the binder fiber was 1.5D, the melting temperature was 230℃and the thickness of the support material was controlled to 70. Mu.m, and the water permeation time of the resulting support material was more than 30 minutes, and the water absorption height was 0.ltoreq.h < 5mm.
The thickness of the semi-permeable membrane is 20-30 μm when observed by an electron microscope, and the thickness of the casting solution immersed into the supporting material is 0-10 μm.
The membrane surface has a large number of macula and is not permeable to liquid.
Comparative example 6
Unlike example 1, in the process of preparing the support material, the diameter of the main fiber is 0.3D, the melting temperature of the binder fiber is 230 ℃, the thickness of the support material is 170 μm, the water seepage time of the obtained support material is 0.ltoreq.t.ltoreq.30s, and the water absorption height is 70.ltoreq.h.ltoreq.150mm.
The thickness of the semi-permeable membrane is 5-15 μm by electron microscopy, and the thickness of the casting solution immersed in the support material is 100 μm.
The membrane surface has the condition of liquid permeation and no yellowing.
The parameters and film surface conditions of the above examples and comparative examples are shown in Table 2.
TABLE 2
The marks used for the yellowing and liquid penetration are shown in Table 3.
TABLE 3 Table 3
| ◎ | No yellowing occurs | Liquid-impermeable |
| ○ | The number of yellowing/spots is less than 2 | Slightly permeable to liquid |
| × | The number of yellowing/spots is greater than 5 | Liquid permeable |
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: the stable and uniform semipermeable membrane can be rapidly 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 cannot generate yellowing; in the coating process, the condition of liquid permeation can be effectively avoided.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A semipermeable membrane composite material, characterized in that the semipermeable membrane composite material comprises a support material and a semipermeable membrane;
the support material has a surface to be coated and a non-coated surface, and the semipermeable membrane is arranged on the surface to be coated of the support material; the preparation method of the semipermeable membrane composite material comprises the following steps: coating the surface to be coated of the support material by using a casting solution, and then forming a porous layer on the surface to be coated of the support material by using a coagulating bath to obtain a composite material with the porous layer; performing interfacial polymerization on the porous layer to obtain the semipermeable membrane composite material with the desalting layer; the solute of the membrane casting solution is one or more of polysulfone, polyethersulfone, cellulose, nylon, polyvinylidene fluoride and polyvinyl chloride;
the water absorption height h of the supporting material is in the range of 5-70 mm, and when water drops with the concentration of 20+/-10 mu L are dripped on the surface to be coated of the supporting material, the water seepage time t of the water drops is in the range of 30 s-30 min;
the support material comprises main body fibers and binder fibers, wherein the mass ratio of the main body fibers to the binder fibers is 2-3: 1, a step of;
the gram weight of the supporting material is 60-100 g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The thickness of the supporting material is 80-120 mu m;
the thickness of the semipermeable membrane composite material is 90-150 mu m, and the thickness of the semipermeable membrane is 10-30 mu m.
2. The semipermeable membrane composite material according to claim 1, wherein the gram weight of the support material is 70-80 g/m 2 。
3. The semipermeable membrane composite material according to claim 1, wherein said support material has a thickness of 90-120 μm.
4. A method of preparing the semipermeable membrane composite material according to any of claims 1-3, comprising:
coating the surface to be coated of the support material by using a casting solution, and then forming a porous layer on the surface to be coated of the support material by using a coagulating bath to obtain a composite material with the porous layer; the solute of the membrane casting solution is one or more of polysulfone, polyethersulfone, cellulose, nylon, polyvinylidene fluoride and polyvinyl chloride;
and performing interfacial polymerization on the porous layer to obtain the semipermeable membrane composite material with the desalting layer.
5. The method according to claim 4, wherein the solvent of the casting solution is one or more of N, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide.
6. The preparation method of claim 5, wherein the mass fraction of the solute in the casting solution is 10-20%.
7. The method according to claim 4, wherein the casting solution is immersed in the support material to a thickness of 10 to 90 μm when the surface to be coated of the support material is coated with the casting solution.
8. The method of claim 4, 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, and performing heating reaction to obtain the semipermeable membrane composite material with the desalting layer.
9. The method according to claim 8, wherein the heating reaction is carried out at a temperature of 70 to 130 ℃.
10. The method according to claim 8, wherein the first solution is an aqueous solution of m-phenylenediamine and/or an aqueous solution of piperazine.
11. The method of claim 8, wherein the second solution is trimesoyl chloride solution.
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| CN109316974A (en) * | 2018-11-23 | 2019-02-12 | 浙江福斯特新材料研究院有限公司 | A kind of semipermeable membrane support material material |
| 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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