CN113842785A - A kind of reinforced hollow fiber separation membrane and preparation method thereof - Google Patents
A kind of reinforced hollow fiber separation membrane and preparation method thereof Download PDFInfo
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Abstract
本发明涉及一种增强型中空纤维分离膜及其制备方法。该方法包括以下步骤：S1，将聚合物原料和液体原料分别进行预混合，然后分别通过固体进料口和液体进料口添加到双螺杆挤出机中，混合并脱泡，获得铸膜液；S2，将所述铸膜液输送至喷丝头，并将增强材料从上向下垂直引入到喷丝头中，使铸膜液渗透进入增强材料，获得初生中空纤维；S3，将所述初生中空纤维传送至一级凝固浴进行初步固化，然后再依次传送至二级凝固浴和清洗槽，清洗后收卷，获得收卷后的膜；S4，对收卷后的膜进行保孔处理，干燥后获得所述增强型中空纤维分离膜。本发明使用双螺杆挤出机配制铸膜液，增强材料主动放卷和膜丝主动输送，并且闭环控制纺丝速度，分离层强度高，工艺稳定。
The invention relates to a reinforced hollow fiber separation membrane and a preparation method thereof. The method includes the following steps: S1, premixing the polymer raw material and the liquid raw material respectively, then adding them to the twin-screw extruder through the solid feeding port and the liquid feeding port respectively, mixing and defoaming to obtain a casting liquid S2, the casting liquid is transported to the spinneret, and the reinforcing material is vertically introduced into the spinneret from top to bottom, so that the casting liquid penetrates into the reinforcing material to obtain primary hollow fibers; S3, the described The nascent hollow fibers are sent to the primary coagulation bath for preliminary curing, and then sequentially sent to the secondary coagulation bath and cleaning tank, and then wound after cleaning to obtain the wound membrane; S4, the wound membrane is subjected to pore preservation treatment , and the reinforced hollow fiber separation membrane is obtained after drying. The invention uses a twin-screw extruder to prepare the casting liquid, the reinforcing material is actively unwinded and the film filaments are actively transported, the spinning speed is controlled in a closed loop, the strength of the separation layer is high, and the process is stable.
Description
Technical Field
The invention belongs to the technical field of material science, and particularly relates to an enhanced hollow fiber separation membrane and a preparation method thereof.
Background
Ultrafiltration is a widely used separation technique, can be applied to industries such as sewage treatment, seawater desalination, drinking water, biological medicine, food and electronics, and occupies more than one third of the membrane process at present. The ultrafiltration membrane has a certain service life, and generally needs to be replaced every 3-5 years, so the demand on the ultrafiltration membrane continuously increases along with the rapid development of the membrane market. The commonly used ultrafiltration membrane materials in the existing petrochemical wastewater reuse membrane process mainly comprise a polyvinylidene fluoride (PVDF) membrane and a polyether sulfone (PES) membrane. The raw material cost of the two types of membrane materials, especially fluorine-containing polymer, is high, and the core technology of the high-performance separation membrane material is mainly mastered in a few companies, so that the one-time investment cost for constructing a membrane method device and the maintenance cost for membrane cleaning, membrane replacement and the like caused by membrane pollution are increased, and further the industrial operation and popularization of the membrane technology are influenced to a certain extent. These hollow fiber membranes are based on the non-solvent induced phase separation (NIPS) process and have few Thermally Induced Phase Separation (TIPS) process products. The traditional NIPS method is a self-supporting product, although the flux is high, the strength is generally low, the yarn is easy to break in sewage treatment, and particularly in a membrane-bioreactor (MBR) process, the strength and the anti-pollution performance of the membrane yarn are extremely high due to the fact that the membrane yarn is in a continuous shaking state in sewage during operation. Although the hollow fiber membrane prepared by the TIPS method can obtain high strength, the process is complex, the modification is difficult, meanwhile, a water-soluble solvent is difficult to adopt in the process, organic liquid is required to be used as a coagulating bath and a core liquid, the treatment and recovery cost of the organic liquid is high, and the environmental protection and safety risks are high. On the basis of the membrane preparation by the NIPS method, the enhanced hollow fiber ultrafiltration membrane is prepared by using the reinforced material, so that a product with good hydrophilicity and high flux can be obtained, the strength of the membrane can be obviously improved, meanwhile, the industrial large-scale continuous membrane preparation can be conveniently realized, and the membrane preparation method is particularly suitable for an MBR process.
In chinese patent CN201811187171, graphene is used as a modifier, generally, graphene has strong hydrophobicity, and in order to be used as a hydrophilic modifier, the graphene needs to be modified in a hydrophilic manner, so that the process is complex, and meanwhile, graphene as a nano material is difficult to be uniformly dispersed in a casting solution with a certain viscosity. Chinese patent CN201810684526 discloses a reinforced hollow fiber ultrafiltration membrane and a preparation method thereof, the reinforced hollow fiber ultrafiltration membrane adopts a hollow fiber membrane as a base membrane, and carries out secondary membrane formation with a membrane casting solution added with a modifier, and the reinforcing effect on membrane filaments is obviously weaker than that of a braided tube.
In the traditional preparation of the enhanced hollow fiber membrane, a reaction kettle is used for preparing a casting solution with a certain viscosity, the casting solution is coated on the surface of an enhanced material, in order to ensure the strength and the pressure resistance of a separation layer, a higher polymer content is needed, the reaction kettle is difficult to stir to obtain a uniform casting solution when the polymer content is higher, the time required by the deaeration of the casting solution is further prolonged, the efficiency of the preparation process is lower, and in addition, the enhanced material is easy to generate the condition of unstable tension of the enhanced material at a higher spinning speed due to the adoption of a passive unwinding mode, so that the stability of membrane yarns is influenced.
Disclosure of Invention
The invention provides a novel preparation method of an enhanced hollow fiber separation membrane, aiming at the problems that in the preparation process of the enhanced hollow fiber separation membrane in the prior art, a traditional reaction kettle is used for preparing a membrane casting solution, a membrane can not be prepared by the membrane casting solution with high viscosity, the compressive strength of a separation layer is poor, the production efficiency is low, the spinning is not uniform due to passive unwinding and the like. According to the method, a double-screw extruder is used for continuously preparing the casting solution and carrying out deaeration extrusion, so that the strength of a functional layer of the separation membrane is increased, and the pressure resistance of the membrane wire is improved; meanwhile, the reinforcing material is conveyed in an active unreeling mode, the tension is controlled and matched with the spinning speed, and the stability of the film yarn production process can be obviously improved through closed-loop control.
To this end, the first aspect of the present invention provides a method for preparing a reinforced hollow fiber separation membrane, comprising the steps of:
s1, respectively premixing a polymer raw material and a liquid raw material, then respectively adding the polymer raw material and the liquid raw material into a double-screw extruder through a solid feed port and a liquid feed port, mixing and defoaming to obtain a casting solution;
s2, conveying the casting solution to a spinning nozzle, vertically introducing a reinforcing material into the spinning nozzle from top to bottom, and enabling the casting solution to penetrate into the reinforcing material to obtain a nascent hollow fiber;
s3, conveying the nascent hollow fiber to a primary coagulation bath for primary solidification, then conveying the nascent hollow fiber to a secondary coagulation bath and a cleaning bath in sequence, cleaning and rolling to obtain a rolled membrane;
and S4, carrying out hole protection treatment on the wound membrane, and drying to obtain the reinforced hollow fiber separation membrane.
In some embodiments of the invention, the premixed polymer feedstock and liquid feedstock are continuously added to the twin screw extruder using a loss-in-weight metering device in a ratio through the solid feed port and the liquid feed port, respectively.
In some embodiments of the present invention, in step S1, the polymer raw material is 20 to 50% by mass, preferably 24 to 45% by mass, and more preferably 26 to 40% by mass, based on the total weight of the polymer raw material and the liquid raw material; the mass percentage of the liquid raw material is 50-80%. Namely, the total raw materials for preparing the enhanced hollow fiber separation membrane comprise a polymer raw material and a liquid raw material, wherein the polymer raw material accounts for 20-50% of the total raw materials by mass, preferably 24-45% of the total raw materials by mass, and more preferably 26-40% of the total raw materials by mass; the liquid raw materials account for 50-80% of the total raw materials by mass. In some embodiments of the invention, the ratio of addition of the polymer feedstock and liquid feedstock is controlled using a loss-in-weight sensor, a feeder screw, and a control system.
In other embodiments of the present invention, in step S1, the premixed liquid raw material is preheated to 25 to 60 ℃ (i.e., room temperature to 60 ℃) and then added to a twin-screw extruder. In some embodiments of the invention, the liquid feedstock after premixing is preheated in a loss-in-weight metering device.
In some embodiments of the invention, the polymer feedstock and liquid feedstock are heated to 60-120 ℃ in a twin screw extruder.
In some embodiments of the invention, the polymer feedstock comprises a host polymer and/or a hydrophilic polymer; preferably, the mass percentage of the main polymer in the polymer raw material is 5-100%, preferably 5-40%.
In some preferred embodiments of the invention, the host polymer is selected from one or more of polyacrylonitrile, polysulfone, cellulose, polyethersulfone, sulfonated polysulfone, polyimide, polyetherimide, polyvinylidene fluoride (PVDF), and polyetherketone; preferably one or more selected from the group consisting of polyvinylidene fluoride, polyethersulfone, and polyacrylonitrile.
In other preferred embodiments of the present invention, the hydrophilic polymer is selected from one or more of polyethylene glycol and polyvinylpyrrolidone; preferably selected from one or more of PEG20000, PVPk17, PVPk30 and PVPk 90.
In some embodiments of the invention, the liquid feedstock comprises a solvent and/or an additive; preferably, the additive comprises an organic additive and/or an inorganic salt additive.
In some preferred embodiments of the present invention, the solvent is selected from one or more of dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, triethylphosphate, trimethyl phosphate, ammonium hexametaphosphate, tetramethylurea, tetrahydrofuran, and acetone; preferably one or more selected from the group consisting of dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
In some preferred embodiments of the invention, the organic additive is selected from one or more of the polyethylene glycol (PEG) series, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethyl acetate, polymaleic anhydride, cyclohexanol, glycerol, triethyl phosphate, tributyl phosphate, polyvinylpyrrolidone, polyacrylic acid, and polyacrylamide; preferably, the polyethylene glycol series is selected from one or more of PEG200, PEG400 and PEG 600.
In other preferred embodiments of the present invention, the inorganic salt additive is selected from one or more of aluminum trichloride, sodium chloride, lithium chloride, calcium chloride, lithium nitrate, calcium nitrate, magnesium chloride, and zinc chloride.
In some embodiments of the invention, the twin screw extruder has a length to diameter ratio of 48 or greater.
In some embodiments of the present invention, the dope solution is delivered to the spinneret by a gear metering pump in step S2.
In other embodiments of the present invention, in step S2, the reinforcing material is unwound by an active unwinding device in an active conveying manner, so as to be vertically introduced into the spinneret from top to bottom; and a tension control device is adopted to stabilize the tension of the reinforced material during unreeling; preferably, the unreeling speed is 0-50 m/min.
In some embodiments of the present invention, in step S2, the temperature of the spinneret is 25 to 70 ℃ (room temperature to 70 ℃).
In other embodiments of the present invention, in step S2, the casting solution penetrates into the reinforcement material to a depth of 50 to 100% of the thickness of the reinforcement material.
In some embodiments of the invention, the reinforcement material is a braided or knitted tube; preferably, the material of the braided tube or the knitted tube is polyester. Specifically, the knitted tube adopts high-strength polyester yarns or fully drawn polyester yarns, and the knitted tube adopts drawn textured polyester yarns or fully drawn polyester yarns.
In other embodiments of the present invention, the braided or knitted tube has an outer diameter of 1.0 to 2.0mm, an inner diameter of 0.6 to 1.3mm, and a density of 30 to 70 cross nodes/inch.
In some embodiments of the invention, in step S3, the temperature of the primary coagulation bath is 25 to 70 ℃; and/or the temperature of the secondary coagulation bath and the cleaning tank is 40-70 ℃.
In some embodiments of the invention, the primary coagulation bath is an aqueous solution of one or more selected from the group consisting of dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, triethylene glycol, diethylene glycol, triethyl phosphate, trimethyl phosphate, ammonium hexametaphosphate, tetramethylurea, tetrahydrofuran, and acetone; preferably an aqueous solution of one or more selected from dimethylformamide, dimethylacetamide, N-methylpyrrolidone, triethylene glycol and diethylene glycol; further preferably, the concentration of the aqueous solution is 3 to 30 wt%.
In other embodiments of the present invention, the secondary coagulation bath is an aqueous solution of one or more selected from the group consisting of dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, triethylene glycol, diethylene glycol, triethyl phosphate, trimethyl phosphate, ammonium hexametaphosphate, tetramethylurea, tetrahydrofuran, and acetone; preferably an aqueous solution selected from the group consisting of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, triethylene glycol and diethylene glycol.
In some embodiments of the invention, the concentration of the aqueous solution of the secondary coagulation bath is lower than the concentration of the aqueous solution of the primary coagulation bath; preferably, the concentration of the aqueous solution of the secondary coagulating bath is 0-10 wt%.
In some embodiments of the invention, the primary coagulation bath, secondary coagulation bath, and wash tank use godets to transport nascent hollow fibers; preferably, the godet wheel is in active transmission, and the transmission speed is matched with the unwinding speed of the reinforcing material and is controlled in a closed loop mode. In the invention, the delivery speed of the godet wheel is matched with the unwinding speed of the reinforcing material, namely the speed of the godet wheel for delivering the nascent hollow fiber is the same as the unwinding speed of the reinforcing material.
In the invention, the reinforcing material is uncoiled in an active conveying mode, the tension of the reinforcing material during uncoiling is stabilized by a tension control device, and the uncoiling speed is matched with the spinning speed (the speed of the godet wheel for conveying the nascent hollow fiber), so that the stability of the film yarn production process can be obviously improved.
In some embodiments of the present invention, in step S4, the hole-keeping process is performed by a hole-keeping method commonly used in a film-making process.
In some embodiments of the present invention, in step S4, the drying method is a drying method commonly used in a film-making process.
In some embodiments of the present invention, the method for preparing the reinforced hollow fiber separation membrane specifically comprises the following steps:
(1) respectively premixing a polymer raw material and a liquid raw material, continuously adding the premixed polymer raw material and the premixed liquid raw material into a double-screw extruder through a solid feed inlet and a liquid feed inlet according to a certain proportion by adopting a weightlessness metering device, and preheating the premixed liquid raw material to 25-60 ℃ (room temperature-60 ℃) in the weightlessness metering device; the polymer material comprises, by weight, 20-50% of a polymer material and 50-80% of a liquid material, wherein the total weight of the polymer material and the liquid material is taken as the basis; heating the premixed polymer raw material and liquid raw material in a double-screw extruder to 60-120 ℃, uniformly mixing and defoaming to obtain a casting solution;
(2) conveying the casting solution obtained in the step (1) to a spinning nozzle through a gear metering pump, and simultaneously, vertically introducing a reinforcing material into the spinning nozzle from top to bottom through an active unwinding device in an active conveying mode to enable the casting solution to penetrate into the reinforcing material to form a nascent hollow fiber; the reinforcing material is a woven tube or a knitted tube, the unreeling speed is 0-50 m/min, the temperature of a spinning nozzle is 25-70 ℃ (room temperature-70 ℃), and the depth of the casting solution penetrating into the reinforcing material accounts for 50-100% of the thickness of the reinforcing material;
(3) the nascent hollow fiber enters a primary coagulation bath after passing through an air gap with a certain distance, enters a secondary coagulation bath and a cleaning tank in sequence after being primarily solidified, and is rolled after being cleaned to obtain a rolled membrane; wherein the temperature of the primary coagulating bath is 25-70 ℃ (room temperature-70 ℃), and the temperature of the secondary coagulating bath and the cleaning tank is 40-70 ℃;
(4) and taking out the wound membrane, and drying the membrane after hole protection treatment to finally obtain the enhanced hollow fiber separation membrane.
Compared with the prior art, the method has the substantial difference that the process flow is shortened by using a double-screw extruder for continuous mixing, defoaming and extruding for batching, the method is suitable for high-viscosity casting solution, and the strength and the pressure resistance of the separating layer of the membrane are improved; meanwhile, the conveying process of the reinforced material and the membrane yarn is improved, the stability of the preparation condition of the separation membrane is improved, and the defects are reduced.
In a second aspect, the present invention provides a reinforced hollow fiber separation membrane prepared according to the method of the first aspect of the present invention.
The invention has the beneficial effects that: in the method, the double-screw extruder is adopted to prepare the membrane casting solution, so that the defoaming time is shortened, and the production efficiency is improved; the separating layer of the membrane has high strength, and the binding force and the compression resistance of the separating layer with a reinforcing material are improved; membrane filaments (primary hollow fibers) obtained after the membrane casting solution and the reinforcing material are introduced into a spinning nozzle enter a coagulating bath, the process flow is simple and efficient, and the hollow fiber separation membrane with uniform pore diameter is simply and conveniently prepared; meanwhile, the reinforced material and the membrane yarn realize stable conveying and speed matching, and the product has high uniformity, so that the obtained reinforced hollow fiber separation membrane is widely used in the fields of water treatment, biology, medicine, energy and the like, and has good application prospect.
Drawings
The invention will be further explained with reference to the drawings.
FIG. 1 is a schematic process flow diagram of an embodiment of the method of the present invention.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description will proceed with reference being made to examples, which are intended to be illustrative only and are not intended to limit the scope of the invention. The starting materials or components used in the present invention may be commercially or conventionally prepared unless otherwise specified.
The starting materials used in the examples which follow are all commercially available.
The pore diameters of the samples (reinforced hollow fiber separation membranes) prepared in the following examples were measured by a 3H-2000PB type pore analyzer (Beijing Besteard), and the fluxes were measured at 0.1 MPa. The density of the reinforcing material is set to the number of cross-nodes per inch of length.
Example 1
(1) Premixing polyvinylidene fluoride and polyethylene glycol to serve as a polymer raw material, premixing dimethyl formamide and triethyl phosphate to serve as a liquid raw material, continuously adding the liquid raw material into a double-screw extruder through a solid feed inlet and a liquid feed inlet according to a certain proportion by adopting a weight loss metering device, and preheating the liquid raw material in the weight loss metering device at the preheating temperature of 40 ℃; the mass percent of the main polymer polyvinylidene fluoride is 10 percent, and the mass percent of the hydrophilic polymer polyethylene glycol is 40 percent; the mass percentages of a solvent dimethylformamide and an organic additive triethyl phosphate are respectively 45% and 5%, the polymer raw material and the liquid raw material are heated to 120 ℃ in a double-screw extruder, and the polymer raw material and the liquid raw material are uniformly mixed and defoamed to obtain a casting solution;
(2) conveying the casting solution obtained in the step (1) to a spinning nozzle through a gear metering pump, and simultaneously vertically introducing a reinforcing material into the spinning nozzle from top to bottom through an active unreeling device to enable the casting solution to penetrate into the reinforcing material to form nascent hollow fibers; wherein the reinforcing material is a polyester braided tube, the outer diameter of the braided tube is 2.0mm, the inner diameter of the braided tube is 1.3mm, the density of the braided tube is 50 cross nodes/inch, the unreeling speed is 20m/min, the temperature of a spinning jet is 70 ℃, and the depth of the casting solution penetrating into the reinforcing material accounts for 50 percent of the thickness of the reinforcing material;
(3) the nascent hollow fiber enters a primary coagulation bath after passing through an air gap with a certain distance, enters a secondary coagulation bath and a cleaning tank in sequence after being primarily solidified, and is rolled after being cleaned to obtain a rolled membrane; the winding speed is 20m/min, wherein the first-stage coagulation bath is a dimethylformamide aqueous solution with the concentration of 3 wt% and the temperature of 70 ℃, the second-stage coagulation bath is a dimethylformamide aqueous solution with the concentration of 0.5 wt%, and the temperatures of the second-stage coagulation bath and the cleaning tank are 40 ℃;
(4) and taking out the wound membrane, and drying the membrane after hole protection treatment to finally obtain the enhanced hollow fiber separation membrane. The properties are shown in table 1.
Example 2
(1) Premixing polyether sulfone and polyvinylpyrrolidone to obtain a polymer raw material, premixing dimethyl acetamide and trimethyl phosphate to obtain a liquid raw material, continuously adding the liquid raw material into a double-screw extruder through a solid feed inlet and a liquid feed inlet according to a certain proportion by adopting a weight loss metering device, and preheating the liquid raw material in the weight loss metering device at a preheating temperature of 60 ℃; the mass percent of the main polymer polyether sulfone is 15 percent, and the mass percent of the hydrophilic polymer polyvinylpyrrolidone is 25 percent; respectively 55% and 5% of dimethylacetamide and trimethyl phosphate, heating the polymer raw material and the liquid raw material to 90 ℃ in a double-screw extruder, uniformly mixing and defoaming to obtain a casting solution;
(2) conveying the casting solution obtained in the step (1) to a spinning nozzle through a gear metering pump, and simultaneously vertically introducing a reinforcing material into the spinning nozzle from top to bottom through an active unreeling device to enable the casting solution to penetrate into the reinforcing material to form nascent hollow fibers; wherein the reinforcing material is a polyester braided tube, the outer diameter of the braided tube is 1.0mm, the inner diameter of the braided tube is 0.6mm, the density of 40 cross nodes/inch is realized, the unreeling speed is 10m/min, the temperature of a spinning nozzle is 60 ℃, and the depth of the casting solution penetrating into the reinforcing material accounts for 100 percent of the thickness of the reinforcing material;
(3) the nascent hollow fiber enters a primary coagulation bath after passing through an air gap with a certain distance, enters a secondary coagulation bath and a cleaning tank in sequence after being primarily solidified, and is rolled after being cleaned to obtain a rolled membrane; the winding speed is 10m/min, wherein the first-stage coagulation bath is an aqueous solution of dimethylformamide, the concentration is 8 wt%, the temperature is 50 ℃, the second-stage coagulation bath is an aqueous solution of dimethylformamide, the concentration is 1 wt%, and the temperatures of the second-stage coagulation bath and the cleaning tank are 40 ℃;
(4) and taking out the wound membrane, and drying the membrane after hole protection treatment to finally obtain the enhanced hollow fiber separation membrane. The properties are shown in table 1.
Example 3
(1) Taking polyacrylonitrile as a polymer raw material, premixing N-methyl pyrrolidone and trimethyl phosphate as liquid raw materials, continuously adding the liquid raw materials into a double-screw extruder through a solid feeding hole and a liquid feeding hole according to a certain proportion by adopting a weight loss metering device, and preheating the liquid raw materials in the weight loss metering device at the preheating temperature of 70 ℃; the mass percentage of the polyacrylonitrile as the main polymer is 40 percent; respectively taking 50% and 10% of solvent N-methyl pyrrolidone and trimethyl phosphate in percentage by mass, heating the polymer raw material and the liquid raw material in a double-screw extruder to 90 ℃, uniformly mixing and defoaming to obtain a casting solution;
(2) conveying the casting solution obtained in the step (1) to a spinning nozzle through a gear metering pump, and simultaneously vertically introducing a reinforcing material into the spinning nozzle from top to bottom through an active unreeling device to enable the casting solution to penetrate into the reinforcing material to form nascent hollow fibers; wherein the reinforcing material is a polyester braided tube, the outer diameter of the braided tube is 1.8mm, the inner diameter of the braided tube is 1.1mm, the density of 37 cross nodes/inch is realized, the unreeling speed is 15m/min, the temperature of a spinning nozzle is room temperature, and the depth of the casting solution penetrating into the reinforcing material accounts for 50 percent of the thickness of the reinforcing material;
(3) the nascent hollow fiber enters a primary coagulation bath after passing through an air gap with a certain distance, enters a secondary coagulation bath and a cleaning tank in sequence after being primarily solidified, and is rolled after being cleaned to obtain a rolled membrane; the rolling speed is 15m/min, wherein the first-stage coagulation bath is a dimethylformamide aqueous solution with the concentration of 5 wt% and the temperature is 50 ℃, the second-stage coagulation bath is a dimethylacetamide aqueous solution with the concentration of 3 wt%, and the temperature of the second-stage coagulation bath and the cleaning tank is room temperature;
(4) and taking out the wound membrane, and drying the membrane after hole protection treatment to finally obtain the enhanced hollow fiber separation membrane. The properties are shown in table 1.
Example 4
(1) Premixing polyvinylidene fluoride and polyvinylpyrrolidone (PVPK) 17 to obtain a polymer raw material, premixing dimethylacetamide and glycerol to obtain a liquid raw material, continuously adding the liquid raw material into a double-screw extruder through a solid feed inlet and a liquid feed inlet according to a certain proportion by adopting a weight loss metering device, and preheating the liquid raw material in the weight loss metering device at the preheating temperature of 40 ℃; the mass percent of the main polymer polyvinylidene fluoride is 15 percent, and the mass percent of the hydrophilic polymer polyvinylpyrrolidone PVPK17 is 15 percent; the mass percentages of the solvent dimethylacetamide and the organic additive glycerol are respectively 60% and 10%, the polymer raw material and the liquid raw material are heated to 95 ℃ in a double-screw extruder, and the polymer raw material and the liquid raw material are uniformly mixed and defoamed to obtain a casting solution;
(2) conveying the casting solution obtained in the step (1) to a spinning nozzle through a gear metering pump, and simultaneously vertically introducing a reinforcing material into the spinning nozzle from top to bottom through an active unreeling device to enable the casting solution to penetrate into the reinforcing material to form nascent hollow fibers; wherein the reinforcing material is a polyester braided tube, the outer diameter of the braided tube is 1.3mm, the inner diameter of the braided tube is 0.7mm, the density of 40 cross nodes/inch is realized, the unreeling speed is 20m/min, the temperature of a spinning nozzle is 50 ℃, and the depth of the casting solution penetrating into the reinforcing material accounts for 90 percent of the thickness of the reinforcing material;
(3) the nascent hollow fiber enters a primary coagulation bath after passing through an air gap with a certain distance, enters a secondary coagulation bath and a cleaning tank in sequence after being primarily solidified, and is rolled after being cleaned to obtain a rolled membrane; the rolling speed is 20m/min, wherein the first-stage coagulation bath is a dimethylformamide aqueous solution, the concentration is 30 wt%, and the temperature is 60 ℃; the second-stage coagulating bath is a dimethylacetamide aqueous solution with the concentration of 10 wt%, and the temperature of the second-stage coagulating bath and the temperature of the cleaning tank are 40 ℃;
(4) and taking out the wound membrane, and drying the membrane after hole protection treatment to finally obtain the enhanced hollow fiber separation membrane. The properties are shown in table 1.
Example 5
(1) Premixing polyvinylidene fluoride and polyvinylpyrrolidone (PVPK 90) to obtain a polymer raw material, premixing dimethyl sulfoxide, triethyl phosphate and sodium chloride to obtain a liquid raw material, continuously adding the liquid raw material into a double-screw extruder through a solid feed inlet and a liquid feed inlet according to a certain proportion by adopting a weight loss metering device, and preheating the liquid raw material in the weight loss metering device at room temperature; the mass percent of the main polymer polyvinylidene fluoride is 5 percent, and the mass percent of the hydrophilic polymer polyvinylpyrrolidone PVPK90 is 40 percent; the mass percentages of a solvent dimethylacetamide, an organic additive triethyl phosphate and an inorganic salt additive sodium chloride are respectively 10%, 44% and 1%, the polymer raw material and the liquid raw material are heated to 60 ℃ in a double-screw extruder, and are uniformly mixed and defoamed to obtain a casting solution;
(2) conveying the casting solution obtained in the step (1) to a spinning nozzle through a gear metering pump, and simultaneously vertically introducing a reinforcing material into the spinning nozzle from top to bottom through an active unreeling device to enable the casting solution to penetrate into the reinforcing material to form nascent hollow fibers; wherein the reinforcing material is a polyester braided tube, the outer diameter of the braided tube is 2.0mm, the inner diameter of the braided tube is 1.3mm, the density of 30 cross nodes/inch is realized, the unreeling speed is 50m/min, the temperature of a spinning nozzle is 50 ℃, and the depth of the casting solution penetrating into the reinforcing material accounts for 90 percent of the thickness of the reinforcing material;
(3) the nascent hollow fiber enters a primary coagulation bath after passing through an air gap with a certain distance, enters a secondary coagulation bath and a cleaning tank in sequence after being primarily solidified, and is rolled after being cleaned to obtain a rolled membrane; the rolling speed is 50m/min, wherein the first-stage coagulation bath is a dimethyl sulfoxide aqueous solution, the concentration is 10 wt%, and the temperature is room temperature; the second-stage coagulation bath is dimethyl sulfoxide aqueous solution with the concentration of 1 wt%, and the temperature of the second-stage coagulation bath and the cleaning tank is 40 ℃;
(4) and taking out the wound membrane, and drying the membrane after hole protection treatment to finally obtain the enhanced hollow fiber separation membrane. The properties are shown in table 1.
Example 6
(1) Premixing polysulfone and PEG20000 to serve as polymer raw materials, premixing dimethylformamide and magnesium chloride to serve as liquid raw materials, continuously adding the liquid raw materials into a double-screw extruder through a solid feeding hole and a liquid feeding hole according to a certain proportion by adopting a weight loss metering device respectively, and preheating the liquid raw materials in the weight loss metering device at room temperature; the mass percent of the main polysulfone is 20 percent, and the mass percent of the hydrophilic polymer PEG20000 is 4 percent; the mass percentages of a solvent dimethylformamide and an inorganic salt additive magnesium chloride are respectively 75.5 percent and 0.5 percent, and a polymer raw material and a liquid raw material are heated to 80 ℃ in a double-screw extruder, uniformly mixed and defoamed to obtain a casting solution;
(2) conveying the casting solution obtained in the step (1) to a spinning nozzle through a gear metering pump, and simultaneously vertically introducing a reinforcing material into the spinning nozzle from top to bottom through an active unreeling device to enable the casting solution to penetrate into the reinforcing material to form nascent hollow fibers; wherein the reinforcing material is a polyester braided tube, the outer diameter of the braided tube is 2.0mm, the inner diameter of the braided tube is 1.3mm, the density of the braided tube is 70 cross nodes/inch, the unreeling speed is 10m/min, the temperature of a spinning jet is 70 ℃, and the depth of the casting solution penetrating into the reinforcing material accounts for 50 percent of the thickness of the reinforcing material;
(3) the nascent hollow fiber enters a primary coagulation bath after passing through an air gap with a certain distance, enters a secondary coagulation bath and a cleaning tank in sequence after being primarily solidified, and is rolled after being cleaned to obtain a rolled membrane; the rolling speed is 10m/min, wherein the first-stage coagulation bath is dimethylformamide and triethylene glycol aqueous solution, the concentration is 5 wt%, and the temperature is 60 ℃; the second-stage coagulation bath is aqueous solution of methyl formamide and triethylene glycol, the concentration is 1 wt%, and the temperature of the second-stage coagulation bath and the cleaning tank is 70 ℃;
(4) and taking out the wound membrane, and drying the membrane after hole protection treatment to finally obtain the enhanced hollow fiber separation membrane. The properties are shown in table 1.
Example 7
(1) Premixing polyvinylidene fluoride and polyvinylpyrrolidone (PVPK) 30 to be used as polymer raw materials, premixing N-methyl pyrrolidone and polyethylene glycol (PEG) 200 to be used as liquid raw materials, continuously adding the liquid raw materials into a double-screw extruder through a solid feed inlet and a liquid feed inlet according to a certain proportion by adopting a weight loss metering device respectively, and preheating the liquid raw materials in the weight loss metering device at the preheating temperature of 40 ℃; the mass percent of the main body polyvinylidene fluoride is 18 percent, and the mass percent of the hydrophilic polymer polyvinylpyrrolidone PVPK30 is 2 percent; the mass percentages of the solvent N-methyl pyrrolidone and the organic additive PEG200 are respectively 70 percent and 10 percent, the polymer raw material and the liquid raw material are heated to 60 ℃ in a double-screw extruder, and the polymer raw material and the liquid raw material are uniformly mixed and defoamed to obtain a casting solution;
(2) conveying the casting solution obtained in the step (1) to a spinning nozzle through a gear metering pump, and simultaneously vertically introducing a reinforcing material into the spinning nozzle from top to bottom through an active unreeling device to enable the casting solution to penetrate into the reinforcing material to form nascent hollow fibers; wherein the reinforcing material is a polyester braided tube, the outer diameter of the braided tube is 2.0mm, the inner diameter of the braided tube is 1.3mm, the density of 30 cross nodes/inch is realized, the unreeling speed is 15m/min, the temperature of a spinning nozzle is 30 ℃, and the depth of the casting solution penetrating into the reinforcing material accounts for 90 percent of the thickness of the reinforcing material;
(3) the nascent hollow fiber enters a primary coagulation bath after passing through an air gap with a certain distance, enters a secondary coagulation bath and a cleaning tank in sequence after being primarily solidified, and is rolled after being cleaned to obtain a rolled membrane; the rolling speed is 15m/min, wherein the primary coagulation bath is N-methyl pyrrolidone and diethylene glycol aqueous solution, the concentration is 6 wt%, and the temperature is room temperature; the second-stage coagulation bath is N-methyl pyrrolidone and diethylene glycol aqueous solution, the concentration is 1 wt%, and the temperature of the second-stage coagulation bath and the cleaning tank is 40 ℃;
(4) and taking out the wound membrane, and drying the membrane after hole protection treatment to finally obtain the enhanced hollow fiber separation membrane. The properties are shown in table 1.
Example 8
(1) Premixing polyvinylidene fluoride and polyvinylpyrrolidone (PVPK) 30 to be used as polymer raw materials, premixing dimethylacetamide and polyethylene glycol (PEG) 400 to be used as liquid raw materials, continuously adding the liquid raw materials into a double-screw extruder through a solid feed inlet and a liquid feed inlet according to a certain proportion by adopting a weight loss metering device respectively, and preheating the liquid raw materials in the weight loss metering device at 60 ℃; the mass percent of the main body polyvinylidene fluoride is 40 percent, and the mass percent of the hydrophilic polymer polyvinylpyrrolidone PVPK30 is 1 percent; the mass percentages of the solvent dimethylacetamide and the organic additive PEG400 are respectively 55% and 4%, the polymer raw material and the liquid raw material are heated to 120 ℃ in a double-screw extruder, and the polymer raw material and the liquid raw material are uniformly mixed and defoamed to obtain a casting solution;
(2) conveying the casting solution obtained in the step (1) to a spinning nozzle through a gear metering pump, and simultaneously vertically introducing a reinforcing material into the spinning nozzle from top to bottom through an active unreeling device to enable the casting solution to penetrate into the reinforcing material to form nascent hollow fibers; wherein the reinforcing material is a polyester braided tube, the outer diameter of the braided tube is 2.0mm, the inner diameter of the braided tube is 1.3mm, the density of 37 cross nodes/inch is realized, the unreeling speed is 10m/min, the temperature of a spinning nozzle is 60 ℃, and the depth of the casting solution penetrating into the reinforcing material accounts for 95 percent of the thickness of the reinforcing material;
(3) the nascent hollow fiber enters a primary coagulation bath after passing through an air gap with a certain distance, enters a secondary coagulation bath and a cleaning tank in sequence after being primarily solidified, and is rolled after being cleaned to obtain a rolled membrane; the rolling speed is 10m/min, wherein the primary coagulation bath is a dimethylacetamide aqueous solution, the concentration is 6 wt%, and the temperature is room temperature; the second-stage coagulating bath is a dimethylacetamide aqueous solution with the concentration of 1 wt%, and the temperature of the second-stage coagulating bath and the temperature of the cleaning tank are 40 ℃;
(4) and taking out the wound membrane, and drying the membrane after hole protection treatment to finally obtain the enhanced hollow fiber separation membrane. The properties are shown in table 1.
Example 9
(1) Premixing polyvinylidene fluoride and polyvinylpyrrolidone (PVPK) 30 to be used as polymer raw materials, premixing dimethylacetamide and polyethylene glycol (PEG) 600 to be used as liquid raw materials, continuously adding the liquid raw materials into a double-screw extruder through a solid feed inlet and a liquid feed inlet according to a certain proportion by adopting a weight loss metering device respectively, and preheating the liquid raw materials in the weight loss metering device at 60 ℃; the mass percent of the main body polyvinylidene fluoride is 20 percent, and the mass percent of the hydrophilic polymer polyvinylpyrrolidone PVPK30 is 6 percent; the mass percentages of the solvent dimethylacetamide and the organic additive PEG600 are respectively 70% and 4%, the polymer raw material and the liquid raw material are heated to 90 ℃ in a double-screw extruder, and the polymer raw material and the liquid raw material are uniformly mixed and defoamed to obtain a casting solution;
(2) conveying the casting solution obtained in the step (1) to a spinning nozzle through a gear metering pump, and simultaneously vertically introducing a reinforcing material into the spinning nozzle from top to bottom through an active unreeling device to enable the casting solution to penetrate into the reinforcing material to form nascent hollow fibers; wherein the reinforcing material is a polyester braided tube, the outer diameter of the braided tube is 2.0mm, the inner diameter of the braided tube is 1.3mm, the density of 37 cross nodes/inch is realized, the unreeling speed is 10m/min, the temperature of a spinning nozzle is 60 ℃, and the depth of the casting solution penetrating into the reinforcing material accounts for 95 percent of the thickness of the reinforcing material;
(3) the nascent hollow fiber enters a primary coagulation bath after passing through an air gap with a certain distance, enters a secondary coagulation bath and a cleaning tank in sequence after being primarily solidified, and is rolled after being cleaned to obtain a rolled membrane; the rolling speed is 10m/min, wherein the primary coagulation bath is a dimethylacetamide aqueous solution, the concentration is 6 wt%, and the temperature is room temperature; the second-stage coagulating bath is a dimethylacetamide aqueous solution with the concentration of 1 wt%, and the temperature of the second-stage coagulating bath and the temperature of the cleaning tank are 40 ℃;
(4) and taking out the wound membrane, and drying the membrane after hole protection treatment to finally obtain the enhanced hollow fiber separation membrane. The properties are shown in table 1.
Table 1: performance parameters of reinforced hollow fiber separation membranes
| Sample (I) | Burst pressure (bar) | Pore size (mum) | Pure water flux (L/m)2·h) |
| Example 1 | 1.6 | 0.15 | 1200 |
| Example 2 | 2.2 | 0.09 | 1050 |
| Example 3 | 2.0 | 0.05 | 360 |
| Example 4 | 2.2 | 0.09 | 1170 |
| Example 5 | 1.5 | 0.17 | 1550 |
| Example 6 | 1.8 | 0.08 | 985 |
| Example 7 | 2.2 | 0.10 | 1087 |
| Example 8 | 2.5 | 0.05 | 280 |
| Example 9 | 2.3 | 0.08 | 926 |
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (18)
1. A preparation method of a reinforced hollow fiber separation membrane comprises the following steps:
s1, respectively premixing a polymer raw material and a liquid raw material, then respectively adding the polymer raw material and the liquid raw material into a double-screw extruder through a solid feed port and a liquid feed port, mixing and defoaming to obtain a casting solution;
s2, conveying the casting solution to a spinning nozzle, vertically introducing a reinforcing material into the spinning nozzle from top to bottom, and enabling the casting solution to penetrate into the reinforcing material to obtain a nascent hollow fiber;
s3, conveying the nascent hollow fiber to a primary coagulation bath for primary solidification, then conveying the nascent hollow fiber to a secondary coagulation bath and a cleaning bath in sequence, cleaning and rolling to obtain a rolled membrane;
and S4, carrying out hole protection treatment on the wound membrane, and drying to obtain the reinforced hollow fiber separation membrane.
2. The method according to claim 1, wherein in step S1, the polymer raw material is 20 to 50% by mass, preferably 24 to 45% by mass, and more preferably 26 to 40% by mass, based on the total weight of the polymer raw material and the liquid raw material; the mass percentage of the liquid raw material is 50-80%.
3. The method according to claim 1 or 2, wherein in step S1, the premixed liquid raw material is preheated to 25 to 60 ℃ and then added to a twin-screw extruder; and/or
The polymer raw material and the liquid raw material are heated to 60-120 ℃ in a double-screw extruder.
4. The method of any one of claims 1-3, wherein the polymer feedstock comprises a host polymer and/or a hydrophilic polymer; preferably, the mass percent of the main polymer in the polymer raw material is 5-100%, preferably 5-40%;
further preferably, the host polymer is selected from one or more of polyacrylonitrile, polysulfone, cellulose, polyethersulfone, sulfonated polysulfone, polyimide, polyetherimide, polyvinylidene fluoride, and polyetherketone; preferably one or more selected from the group consisting of polyvinylidene fluoride, polyethersulfone, and polyacrylonitrile;
still further preferably, the hydrophilic polymer is selected from one or more of polyethylene glycol and polyvinylpyrrolidone; preferably selected from one or more of PEG20000, PVPk17, PVPk30 and PVPk 90.
5. The method according to any one of claims 1 to 4, wherein the liquid feedstock comprises a solvent and/or an additive; preferably, the additive comprises an organic additive and/or an inorganic salt additive.
6. The method of claim 5, wherein the solvent is selected from one or more of dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, triethylphosphate, trimethyl phosphate, ammonium hexametaphosphate, tetramethylurea, tetrahydrofuran, and acetone; preferably one or more selected from the group consisting of dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
7. The method according to claim 5 or 6, wherein the organic additive is selected from one or more of the group consisting of polyethylene glycol series, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethyl acetate, polymaleic anhydride, cyclohexanol, glycerol, triethyl phosphate, tributyl phosphate, polyvinylpyrrolidone, polyacrylic acid, and polyacrylamide; preferably, the polyethylene glycol series is selected from one or more of PEG200, PEG400 and PEG 600.
8. The method of any one of claims 5-7, wherein the inorganic salt additive is selected from one or more of aluminum trichloride, sodium chloride, lithium chloride, calcium chloride, lithium nitrate, calcium nitrate, magnesium chloride, and zinc chloride.
9. The method according to any one of claims 1 to 8, wherein the twin-screw extruder has a length to diameter ratio of 48 or more.
10. The method according to any one of claims 1 to 9, wherein in step S2, the reinforcing material is unwound by an active unwinding device in an active conveying manner, and a tension control device is used to stabilize the tension of the reinforcing material during unwinding; preferably, the unreeling speed is 0-50 m/min.
11. The method according to any one of claims 1 to 10, wherein the temperature of the spinneret is 25 to 70 ℃ in step S2.
12. The method according to any one of claims 1 to 11, wherein in step S2, the casting solution penetrates into the reinforcement material to a depth of 50 to 100% of the thickness of the reinforcement material.
13. The method of any one of claims 1-12, wherein the reinforcement material is a braided or knitted tube; preferably, the material of the braided tube or the knitted tube is polyester; further preferably, the outer diameter of the braided or knitted tube is 1.0-2.0 mm, the inner diameter is 0.6-1.3 mm, and the density is 30-70 cross nodes/inch.
14. The method according to any one of claims 1 to 13, wherein in step S3, the temperature of the primary coagulation bath is 25 to 70 ℃; and/or the temperature of the secondary coagulation bath and the cleaning tank is 40-70 ℃.
15. The method of any one of claims 1-14, wherein the primary coagulation bath is an aqueous solution of one or more selected from the group consisting of dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, triethylene glycol, diethylene glycol, triethyl phosphate, trimethyl phosphate, ammonium hexametaphosphate, tetramethylurea, tetrahydrofuran, and acetone; preferably an aqueous solution of one or more selected from dimethylformamide, dimethylacetamide, N-methylpyrrolidone, triethylene glycol and diethylene glycol; further preferably, the concentration of the aqueous solution is 3 to 30 wt%.
16. The method of any one of claims 1-15, wherein the secondary coagulation bath is an aqueous solution of one or more selected from the group consisting of dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, triethylene glycol, diethylene glycol, triethyl phosphate, trimethyl phosphate, ammonium hexametaphosphate, tetramethylurea, tetrahydrofuran, and acetone; preferably an aqueous solution selected from the group consisting of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, triethylene glycol and diethylene glycol; further preferably, the concentration of the aqueous solution of the secondary coagulation bath is lower than that of the primary coagulation bath; still more preferably, the concentration of the aqueous solution of the secondary coagulation bath is 0 to 10 wt%.
17. The method of any one of claims 1-16, wherein the primary coagulation bath, secondary coagulation bath, and wash tank use godets to deliver nascent hollow fibers; preferably, the godet wheel is in active transmission, and the transmission speed is matched with the unwinding speed of the reinforcing material and is controlled in a closed loop mode.
18. A reinforced hollow fiber separation membrane prepared according to the method of any one of claims 1 to 17.
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Application publication date: 20211228 |