CN113304626A - High-molecular separation membrane and composite phase separation preparation method and device thereof - Google Patents
High-molecular separation membrane and composite phase separation preparation method and device thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation of polymer separation membranes, and particularly relates to a polymer separation membrane and a composite phase separation preparation method and device thereof, wherein the method comprises the following steps: s1: taking the casting solution, uniformly coating the casting solution on a substrate, and forming a liquid film on the substrate; s2: placing the liquid film in an environment with stable temperature and humidity for 5-300s to obtain a semi-finished membrane; s3: placing the semi-finished membrane into a gel tank, soaking and curing to obtain a finished membrane; s4: and taking a finished membrane and carrying out post-treatment to obtain the polymer separation membrane. The method can realize the control of the membrane structure and performance without excessive additives in the formula of the casting membrane, and can process the polymer separation membranes with various structures without adjusting the formula.
Description
Technical Field
The invention belongs to the technical field of preparation of polymer separation membranes, and particularly relates to a polymer separation membrane and a composite phase separation preparation method and device thereof.
Background
The polymer separation membrane comprises a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, a reverse osmosis membrane and the like, wherein the microfiltration membrane is a separation membrane with the average membrane pore diameter of more than or equal to 0.1 mu m; the pore diameter of the ultrafiltration membrane is larger than that of the microfiltration membrane, is used for removing particles including bacteria, viruses, heat sources, other foreign matters and the like, and consists of a skin layer for separation and a sponge-shaped or finger-shaped layer for supporting, wherein the thickness of the skin layer is usually only 0.1-1 μm, and the thickness of the porous layer is usually 125 μm; the base membrane for nanofiltration and reverse osmosis usually employs a hydrophilic ultrafiltration membrane; membrane distillation typically uses hydrophobic microfiltration membranes.
The preparation method of the polymer separation membrane mainly comprises a phase transformation method, a stretching method, a sintering method, an interface polymerization method and the like, wherein the phase transformation method has the widest application and comprises a solvent evaporation method, a steam-induced phase separation method, a non-solvent induced phase separation method (NIPS) and a thermally induced phase separation method (TIPS). At present, the industry mostly adopts NIPS to prepare ultrafiltration/microfiltration membrane materials, i.e. polymers are dissolved in a solvent to form a homogeneous solution, a casting solution is uniformly coated on a substrate and enters a gel tank formed by a non-solvent, the solvent and the non-solvent are mutually diffused, the solution is subjected to phase splitting due to thermodynamic instability, and finally, the solution is coagulated and cured to form a porous high-molecular separation membrane along with the gradual development of exchange. The solvent evaporation method is to slowly phase-separate the casting solution during the evaporation process of the solvent to form a membrane, and usually to obtain a microporous membrane with a compact surface. In the VIPS process, water vapor and solvent vapor in the air are slowly exchanged, thereby obtaining relatively large epidermal and sub-epidermal pores.
When a single NIPS method is adopted for membrane preparation in industry, dense pores are easily formed on the surface layer, water in a gel bath has great resistance to penetrate through the surface layer, delayed phase separation is carried out under the surface layer, a large amount of polymer lean phases are formed, and finger-shaped pores and macroporous structures are easily formed on the section, so that the membrane has poor mechanical property and low flux. In order to solve the problems, research has been carried out to reduce macropores by increasing the content of a non-solvent in a casting solution, but the casting solution has poor stability, is easy to phase separate in advance, and is difficult to popularize in industrial production. There are also studies on the use of a high concentration of a gel bath solution or multiple gel baths to achieve phase separation control of membrane pores, but this presents great difficulties in solvent recovery processing.
Chinese patent document CN111266016A discloses a preparation method of a separation membrane with a spongy structure capable of regulating and controlling pore size. The membrane aperture is accurately regulated and controlled by controlling the composition of a membrane casting solution and the vapor gelation treatment conditions, a formula is debugged by depending on the proper composition of the membrane casting solution, a membrane or a membrane wire stays in an environment with the humidity of 50-100% RH and the temperature of 30-100 ℃ in a dry process for 0-300S to evaporate and split phase, and the membrane or the membrane wire enters a coagulating bath to be solidified and formed into a membrane. The dry process does not mention how to control the uniformity of the temperature and the humidity in the environment, and the existence of temperature and humidity gradient cannot be avoided, so that the effective control of the size of the membrane pore cannot be ensured, and continuous and stable production cannot be carried out.
Chinese patent document CN108525531A discloses a method for preparing a polymer blend membrane by a non-solvent induced gel phase separation method. The permanent hydrophilicity and the pollution resistance of the membrane are realized by introducing sulfonated polymer blending modification. According to the scheme, the content of a non-solvent in the casting solution is increased, so that large pores and finger-shaped pores on the cross section of the membrane can be avoided, and the blended membrane with a sponge structure is obtained.
Chinese patent document CN105396470A discloses a preparation method of a hollow fiber composite nanofiltration membrane. The relative humidity of a water inlet gap is controlled to be 30-80% RH, so that a hollow fiber ultrafiltration membrane without a macroporous structure and with good mechanical strength is obtained, and a separation layer is further prepared on the surface of the ultrafiltration membrane through interfacial polymerization to obtain the hollow fiber composite nanofiltration membrane. The relative humidity of the water inlet gap is 30-80% RH, but how to control the temperature is not mentioned, the difference of water content at different temperatures is extremely large, and therefore the mass transfer and heat transfer brought by the method are extremely different, and therefore the stability of the membrane pore structure cannot be guaranteed through the control of the water inlet gap.
Therefore, in view of the above disadvantages, the present invention provides a polymer separation membrane and a method and an apparatus for preparing the same, which realize stable and effective control of the surface pore structure and the cross-section pore structure of the polymer separation membrane by a composite phase separation method in which solvent evaporation, VIPS and NIPS are sequentially performed to gradually promote phase separation.
Disclosure of Invention
The invention aims to provide a polymer separation membrane and a composite phase separation preparation method and device thereof, and aims to solve the problem that processing equipment is mixed to be large due to different formulas and different working procedures of different polymer separation membranes in the prior art.
In one aspect, the composite phase separation preparation method of the polymer separation membrane provided by the invention comprises the following steps: s1: taking the casting solution, uniformly coating the casting solution on a substrate, and forming a liquid film on the substrate; s2: placing the liquid film in an environment with stable temperature and humidity for 5-300s to obtain a semi-finished membrane; s3: placing the semi-finished membrane into a gel tank, soaking and curing to obtain a finished membrane; s4: and taking a finished membrane and carrying out post-treatment to obtain the polymer separation membrane.
In the method for preparing a composite phase separation membrane according to the above, it is further preferable that, in step S2, the environment is a semi-closed environment, the stable temperature and humidity of the semi-closed environment are provided by clean air having a stable temperature and humidity, the humidity of the clean air is 20 to 80% RH, the temperature is 30 to 90 ℃, and the pressure is greater than atmospheric pressure.
The composite phase separation preparation method of the polymer separation membrane described above is further preferably that, in step S2, the liquid membrane is placed in a semi-closed environment with a humidity of 20-50% RH and a temperature of 60-90 ℃ for 2-200S to obtain a reaction membrane, and then the reaction membrane is placed in a semi-closed environment with a humidity of 50-80% RH and a temperature of 30-70 ℃ for 2-200S to obtain a semi-finished membrane.
In the method for producing a composite phase separation of a polymer separation membrane as described above, it is more preferable that the casting solution is prepared by mixing and defoaming a polymer resin, a solvent, and an additive in step S1.
In the method for preparing a composite phase separation membrane as described above, it is further preferable that in step S3, the liquid in the gel tank is water, the temperature environment is 20 to 80 ℃, and the immersion time is 5 to 30S.
In the method for preparing a composite phase separation membrane as described above, it is further preferable that the post-treatment in step S4 includes a cleaning step, a protective solution adding step, and a drying step.
The invention also discloses a composite phase separation preparation device of the polymer separation membrane, and further preferably, the composite phase separation preparation device is used for realizing the method of any one of the above methods, and comprises the following steps: the winding and unwinding mechanism comprises a winding machine, an unwinding machine and a steering roller; the number of the turning rollers is multiple, the turning rollers are arranged between the winding machine and the unwinding machine and used for winding and changing the transmission direction of the film between the winding machine and the unwinding machine; film processing mechanism, film processing mechanism includes coating machine, accuse temperature and humidity ware, gel groove and aftertreatment subassembly, coating machine, accuse temperature and humidity ware, gel groove and aftertreatment subassembly are located in proper order between rolling machine and the unreeling machine to through steering roll control and membrane contact processing.
In the above-mentioned apparatus for preparing a composite phase separation of a polymer separation membrane, it is further preferred that the post-treatment assembly includes a cleaning tank, a protective solution tank, and a drying mechanism, and the cleaning tank, the protective solution tank, and the drying mechanism are sequentially disposed in a membrane transmission direction and sequentially used for cleaning, adding a protective solution, and drying.
In the above-mentioned composite phase separation apparatus for preparing a polymer separation membrane, it is further preferred that the temperature and humidity controller provides at least one reaction space having a semi-closed environment with a specified humidity and temperature, and when the number of the reaction spaces is more than one, the reaction spaces are arranged in sequence for the membranes to pass in sequence.
The invention also discloses a high-molecular separation membrane which is prepared by the composite phase separation method and is used as a base membrane of an ultrafiltration membrane, a microfiltration membrane, a flat membrane, a hollow fiber membrane or nanofiltration/reverse osmosis.
Compared with the prior art, the invention has the following advantages:
the invention discloses a polymer separation membrane and a composite phase separation preparation method and device thereof, and provides a new implementation method and device for preparation, structure control and performance regulation of the polymer separation membrane. The method specifically comprises the steps that an environment with stable temperature and humidity is manufactured in a dry process stage before a gel bath, water vapor in the environment is utilized to react with a primary membrane, so that the primary membrane can be separated by evaporation phase separation and steam induction phase separation before entering a gel tank, and further a skin layer and a sub-skin layer which are stable and uniform in structure can be formed, and further good thermodynamic stability is achieved;
further, the environment in the invention is a semi-closed environment, the stable temperature and humidity are provided by clean air with stable temperature and humidity, specifically, the clean air with stable temperature and humidity is introduced into the semi-closed environment at uniform speed, and air flow generated by air supply can form convection to weaken the contact boundary between the primary membrane and the semi-closed environment, so that water molecules can better react with the primary membrane; in addition, the clean air flows out from the gap of the semi-closed environment, so that other substances displaced in the liquid film can be taken away, the membrane is prevented from being blocked due to accumulation on the surface of the membrane, stable heat and mass transfer is realized, and the processed polymer separation membrane is stable in structure, uniform and consistent in internal structure of a finished product and good in thermodynamic stability;
the method can directly obtain surface holes with different sizes and section network structure holes with different gradient sizes by adjusting the temperature, the humidity and the reaction time of the semi-closed environment, so that the processing of membrane products with different pore diameter requirements can be realized without adjusting the formula, and the switching cost of production is greatly reduced;
the method provides enough air water content and driving force for airflow by providing two semi-closed environments with different temperature and humidity and increasing the relative humidity, and promotes the exchange of the solvent of the liquid film sublayer and water vapor in the air.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a flow chart of a composite phase separation method for preparing a polymeric separation membrane according to the present invention;
FIG. 2 is a schematic diagram of an apparatus for producing a polymer separation membrane by composite phase separation according to the present invention.
Description of reference numerals:
the method comprises the following steps of 1-unreeling machine, 2-reeling machine, 3-turning roll, 4-coating machine, 5-temperature and humidity control device, 6-gel tank, 7-cleaning tank, 8-protective liquid tank and 9-drying mechanism.
Detailed Description
As shown in fig. 1, this embodiment provides a composite phase separation preparation method of a polymer separation membrane, including:
s1: taking the casting solution, uniformly coating the casting solution on a substrate, and forming a liquid film on the substrate;
s2: taking the liquid film and placing the liquid film in an environment with stable temperature and humidity for 5-300s to obtain a semi-finished product film;
s3: taking the semi-finished membrane and putting the semi-finished membrane into a gel tank for soaking and curing to obtain a finished membrane;
s4: and taking a finished membrane and carrying out post-treatment to obtain the polymer separation membrane.
In step S1, the casting solution is prepared by mixing and defoaming a polymer resin, a solvent, and an additive. Specifically, the casting solution is coated on a substrate through a coating head to form a liquid film with a certain thickness. The base material can be non-woven fabric, the coating thickness can be adjusted according to actual needs, and generally, the coating thickness can be 40-160 mu m.
Further, in the step S2, the environment is a semi-closed environment, the stable temperature and humidity of the semi-closed environment are provided by clean air with stable temperature and humidity, the humidity of the clean air is 20-80% RH, and the temperature of the clean air is 30-90 ℃. The semi-closed environment is arranged to facilitate the liquid film to enter and penetrate out, so that the liquid film can be treated in batches. To ensure that the semi-enclosed environment has stable temperature and humidity, clean air with stable temperature and humidity needs to be continuously introduced, and specifically, the flow rate of the clean air is controlled to enable the semi-enclosed environment to form a pressure of 1-10Pa compared with the external environment.
Specifically, the primary membrane is placed in a semi-closed environment with constant temperature and humidity, and is subjected to evaporation phase separation and/or steam induced phase separation with steam in the semi-closed environment, and because air flows in the semi-closed environment, the air flows can be used as power to drive air in the semi-closed environment to enter the primary membrane, so that the contact boundary between the air and the primary membrane is weakened, stable heat and mass transfer is realized, and a polymer membrane product with uniform aperture and stable structure is obtained; in addition, clean air flows out from the gap of semi-closed environment, can take away other materials that replace in the liquid film, and then avoids it to gather at the surface of diaphragm and block up the diaphragm.
Further, in step S2, the liquid film is placed in a semi-closed environment with a humidity of 20-50% RH and a temperature of 60-90 ℃ for 2-200S to obtain a reaction membrane, and then the reaction membrane is placed in a semi-closed environment with a humidity of 50-80% RH and a temperature of 30-70 ℃ for 2-200S to obtain a semi-finished membrane.
Specifically, in the reaction membrane processing stage, i.e., the first stage, in a relatively low humidity and relatively high temperature environment, evaporation phase separation and steam-induced phase separation occur simultaneously in the skin layer, i.e., the solvent in the liquid membrane evaporates or exchanges with water vapor, so that the polymer material in the primary membrane is gathered on the surface of the primary membrane and then evaporates or exchanges with water vapor, and then the skin layer with fixed membrane pores is formed on the surface of the primary membrane. In specific application, the thickness of the epidermal layer can be controlled to be 0.5-1 μm and the pore diameter of the membrane pores in the epidermal layer can be controlled to be 0.01-0.3 μm by adjusting the relative humidity and the relative temperature.
Semi-manufactured goods diaphragm process stage, the second stage promptly, through adjusting relative humidity and temperature, make the semi-closed environment of second stage have more sufficient air water content and driving force for the semi-closed environment in the first stage, and then promote the steam exchange in solvent in the liquid membrane cortex and the air, the humid air of higher water content sees through the epidermis layer promptly and gets into the cortex, and exchange each other with the steam in the cortex, and then form the cortex that has fixed membrane hole below the epidermis layer of primary diaphragm. When the method is specifically applied, the thickness of the subcortical layer can be controlled to be 1-20 mu m by adjusting the relative humidity and the relative temperature, and the aperture of the membrane pores in the subcortical layer is controlled to be 0.1-0.5 mu m.
The semi-closed environment is set as the first stage and the second stage, which are the preferred embodiments of this embodiment, in addition, the semi-closed environment can be set as one first stage or two first stages are connected in sequence, and when the two first stages are connected in sequence, the temperature and humidity parameters can be the same or different.
Further, in order to accurately control the reaction type in the semi-closed environment, the constant temperature and humidity steam can be clean air or saturated solvent steam. When the vapour is solvent vapour, only vapour-induced phase separation occurs and no evaporative phase separation reaction occurs.
Further, in step S3, the liquid in the gel tank is water, the temperature environment is 20 to 80 ℃, and the immersion time is 5 to 30S. After the step S2, the epidermis layer and the sub-cortex layer of the liquid film are fixed and formed, the resistance of water in the gel bath entering the liquid film is obviously reduced, and after the liquid film enters the gel bath, the solvent and the water in the liquid film are subjected to rapid migration exchange and solidification to form a film, so that the separation film with different gradient sponge holes or network structures can be obtained. Specifically, the thickness of the separation film layer can be controlled to be 40-160 μm by controlling the temperature parameter of the gel bath, and the pore diameter of the film hole of the separation film layer is controlled to be 0.5-5 μm. Specifically, the temperature of the gel bath can be changed between 20 ℃ and 80 ℃.
After the reaction, the membrane structure is formed, and the post-treatment including the steps of cleaning, adding a protective solution and drying is carried out on the membrane structure after the reaction, so that the polymer separation membrane can be obtained.
Further, in step S1, the casting solution is prepared from a polymer resin, an additive and a solvent, wherein the polymer resin is 10-25 wt%, the additive is 0-20 wt%, and the solvent is 60-80 wt%; all the components are stirred and dissolved at the temperature of 60-120 ℃ and are defoamed for 2-24 hours. Wherein, the polymer resin can be one or more of polyvinylidene fluoride (PVDF), Polysulfone (PSF), Polyethersulfone (PES), Sulfonated Polysulfone (SPSF), Polyacrylonitrile (PAN) and other polymer materials; the solvent may be one or more of dimethylacetamide (DMAc), Dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), etc. The additive can be one or more of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), ethylene glycol, acetone, LiCl, Tween 80, etc.
Example 1:
this example further illustrates a method for preparing a composite phase separation membrane by using a casting solution formulation as an example, wherein the method comprises:
the formula of the casting solution is as follows: the polymer resin adopts polyvinylidene fluoride (PVDF) with the brand model number of solef 6020, and the content of the PVDF in the casting solution is 20 wt%; the additive adopts polyvinylpyrrolidone (PVP) with the molecular weight of 300kDa and polyethylene glycol (PEG) with the molecular weight of 8kDa, wherein the contents of the polyvinylpyrrolidone and the polyethylene glycol in the casting solution are both 8 wt%; the solvent used was dimethylformamide (DMAc), and the content in the casting solution was 64%. Stirring and dissolving at 90 deg.c for 8 hr. The speed of the film casting vehicle is 8m/min, and the width of the obtained liquid film is 1 m. Firstly, placing a liquid film in a semi-closed environment with the temperature of 70 ℃, the humidity of 30% RH and the pressure of 1-10Pa for 10 s; then placing the mixture in a semi-closed environment with the temperature of 40 ℃, the humidity of 60% RH and the pressure of 5-20 Pa for 10 s; then placing the membrane into a gel tank with the temperature of 60 ℃ for soaking and curing, and finally carrying out post-treatment to obtain the polymer separation membrane.
And (3) carrying out quality measurement on the obtained polymer separation membrane, specifically:
in the polymer separation membrane, the membrane thickness is: 60 mu m, the pore diameter of a surface pore is 0.05-0.1 mu m, the pore diameter of a sub-layer membrane pore is 0.1-0.3 mu m, and the membrane flux is 3000 LMHB.
Example 2:
the formulation of the casting solution in this example was the same as that in example 1, and the method of preparing the casting solution, the vehicle speed of the casting vehicle, and the width of the obtained liquid film were also the same. The method is characterized in that firstly, a liquid film is placed in a semi-closed environment with the temperature of 70 ℃, the humidity of 30% RH and the pressure of 1-10Pa for 20 s; then placing the mixture in a semi-closed environment with the temperature of 60 ℃, the humidity of 40% RH and the pressure of 5-20 Pa for 20 s; then placing the membrane into a gel tank with the temperature of 60 ℃ for soaking and curing, and finally carrying out post-treatment to obtain the polymer separation membrane.
And (3) carrying out quality measurement on the obtained polymer separation membrane, specifically:
in the high molecular separation membrane, the membrane thickness is 60 mu m, the pore diameter of a surface pore is 0.1-0.2 mu m, the pore diameter of a sub-layer membrane pore is 0.2-0.5 mu m, and the membrane flux is 5000 LMHB.
Example 3:
the formulation of the casting solution in this example was the same as that in example 1, and the method of preparing the casting solution, the vehicle speed of the casting vehicle, and the width of the obtained liquid film were also the same. The method is characterized in that firstly, a liquid film is placed in a semi-closed environment with the temperature of 70 ℃, the humidity of 30% RH and the pressure of 1-10Pa for 20 s; then placing the membrane into a gel tank with the temperature of 60 ℃ for soaking and curing, and finally carrying out post-treatment to obtain the polymer separation membrane.
And (3) carrying out quality measurement on the obtained polymer separation membrane, specifically:
in the polymer separation membrane, the membrane thickness is 60 mu m, the pore diameter of a surface pore is 0.1-0.2 mu m, the pore diameter of a sub-layer membrane pore is 0.05-0.4 mu m, and the membrane flux is 2500-4000 LMHB.
Example 4:
the embodiment also provides a composite phase separation preparation device of a polymer separation membrane, which is used for implementing the method described in the embodiments 1 to 3, and specifically includes:
the winding and unwinding mechanism 1 comprises a winding machine 2, an unwinding machine 1 and a steering roller 3; the number of the turning rollers 3 is multiple, the turning rollers are arranged between the winding machine 2 and the unreeling machine 1 and are used for winding and changing the transmission direction of the film between the winding machine 2 and the unreeling machine 1;
film processing mechanism, film processing mechanism includes coating machine 4, accuse temperature and humidity ware 5, gel groove 6 and aftertreatment subassembly, coating machine 4, accuse temperature and humidity ware 5, gel groove 6 and aftertreatment subassembly are located in proper order between rolling machine 2 and the unreeling machine 1 to through 3 control of steering roll and the processing of membrane contact.
Further, the post-processing assembly comprises a cleaning tank 7, a protective liquid tank 8 and a drying mechanism 9, wherein the cleaning tank 7, the protective liquid tank 8 and the drying mechanism 9 are sequentially arranged in the film flowing transmission direction and are sequentially used for cleaning, adding protective liquid and drying.
Further, the temperature and humidity controller 5 at least provides a reaction space with a semi-closed environment with specified humidity, temperature and pressure, and when the number of the reaction spaces is more than one, the reaction spaces are arranged in sequence for the membranes to pass in sequence. Specifically, the semi-closed environment is provided by a group of box-shaped structures with gaps on opposite sides, and the gaps are suitable for liquid films coated on the substrate to transmit and pass through and are also used for gas flow. The steam nozzle is arranged on one surface of the box-packed structure, and the spraying direction faces to the liquid film.
In the structure, the winding machine 2 is used for winding, and is specifically used for folding the prepared polymer separation membrane into a coiled material; the unreeling machine 1 is used for unreeling, and specifically, the coiled material on the unreeling machine 1 is a base material, such as a non-woven fabric. The plurality of steering rollers 3 are arranged between the winding machine 2 and the unwinding machine 1 and used for guiding the non-woven fabric in the transmission direction between the unwinding machine 1 and the winding machine 2, so that the non-woven fabric sequentially passes through the film coating machine 4, the temperature and humidity controller 5, the gel tank 6, the cleaning tank 7, the protective liquid tank 8 and the drying mechanism 9, and then passes through all the process steps in the preparation process of the polymer separation membrane, and the processing of the polymer separation membrane is realized.
The coating machine 4 is provided with a coating head for coating the prepared casting solution on a substrate. The temperature and humidity controller 5 is used to provide a space with a specified humidity and temperature environment, specifically, in this embodiment, the temperature and humidity controller 5 generally provides two spaces with specified humidity and temperature environment, which are sequentially arranged, or one or more than two spaces are sequentially arranged, so as to provide a reaction condition for the coating substrate. And because the winder 2 and the unreeling machine 1 all have certain speed for the substrate also with certain speed transmission, in order to guarantee sufficient reaction time, can set up several more spaces that have appointed humidity temperature environment on the dry process through accuse temperature and humidity ware 5, or provide several spaces that have appointed humidity temperature environment through a plurality of accuse temperature and humidity ware 5.
Example 5:
this example discloses a polymeric separation membrane prepared using the composite phase separation method described in example 1 and the composite phase separation preparation apparatus of the polymeric separation membrane of example 2, and used as a base membrane for ultrafiltration membrane, microfiltration membrane, flat membrane, hollow fiber membrane, or nanofiltration/reverse osmosis.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A composite phase separation preparation method of a polymer separation membrane is characterized by comprising the following steps:
s1: taking the casting solution, uniformly coating the casting solution on a substrate, and forming a liquid film on the substrate;
s2: placing the liquid film in an environment with stable temperature and humidity for 5-300s to obtain a semi-finished membrane;
s3: placing the semi-finished membrane into a gel tank, soaking and curing to obtain a finished membrane;
s4: and taking a finished membrane and carrying out post-treatment to obtain the polymer separation membrane.
2. The composite phase separation preparation method of a polymer separation membrane according to claim 1, wherein in step S2, the environment is a semi-closed environment, the stable temperature and humidity of the semi-closed environment are provided by clean air having a stable temperature and humidity, the humidity of the clean air is 20-80% RH, and the temperature is 30-90 ℃.
3. The composite phase separation preparation method of a polymer separation membrane according to claim 2, wherein in step S2, the liquid membrane is placed in a semi-closed environment with a humidity of 20 to 50% RH and a temperature of 60 to 90 ℃ for 2 to 200S to obtain a reaction membrane, and then the reaction membrane is placed in a semi-closed positive pressure environment with a humidity of 50 to 80% RH and a temperature of 30 to 70 ℃ for 2 to 200S to obtain a semi-finished membrane.
4. The composite phase separation method for producing a polymer separation membrane according to claim 3, wherein in step S1, the casting solution is prepared by mixing and defoaming a polymer resin, a solvent, and an additive.
5. The composite phase separation method for producing a polymeric separation membrane according to claim 4, wherein in step S3, the liquid in the gel tank is water, the temperature environment is 20 to 80 ℃, and the immersion time is 5 to 30S.
6. The composite phase separation method for producing a polymeric separation membrane according to claim 5, wherein the post-treatment in step S6 includes a washing step, a protective solution adding step, and a drying step.
7. A composite phase separation preparation device of a polymer separation membrane, which is used for realizing the method of any one of claims 1 to 6 and comprises the following steps:
the winding and unwinding mechanism comprises a winding machine, an unwinding machine and a steering roller; the number of the turning rollers is multiple, the turning rollers are arranged between the winding machine and the unwinding machine and used for winding and changing the transmission direction of the film between the winding machine and the unwinding machine;
film processing mechanism, film processing mechanism includes coating machine, accuse temperature and humidity ware, gel groove and aftertreatment subassembly, coating machine, accuse temperature and humidity ware, gel groove and aftertreatment subassembly are located in proper order between rolling machine and the unreeling machine to through steering roll control and membrane contact processing.
8. The apparatus for preparing a composite phase separation of polymer separation membranes according to claim 7, wherein the post-treatment module comprises a cleaning tank, a protective solution tank and a drying mechanism, which are sequentially disposed in the membrane transmission direction for cleaning, adding protective solution and drying.
9. The apparatus for preparing a composite phase separation of polymer separation membranes according to claim 8, wherein the temperature and humidity controller provides at least one reaction space having a semi-closed environment with a predetermined humidity and temperature, and when the number of the reaction spaces is more than one, the reaction spaces are arranged in sequence for the membrane sheets to pass in sequence.
10. A polymeric separation membrane, characterized by being prepared by the composite phase separation method according to any one of claims 1 to 5, and being used as a base membrane for an ultrafiltration membrane, a microfiltration membrane, a flat membrane, a hollow fiber membrane, or nanofiltration/reverse osmosis.
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| CN113601775A (en) * | 2021-09-10 | 2021-11-05 | 宁波威克丽特功能塑料有限公司 | Production device of environment-friendly composite polymer membrane material |
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Application publication date: 20210827 |