CN114733373A - Preparation method for preparing composite hollow fiber ultrafiltration membrane by NIPS method - Google Patents
Preparation method for preparing composite hollow fiber ultrafiltration membrane by NIPS method Download PDFInfo
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- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 49
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention discloses a preparation method for preparing a composite hollow fiber ultrafiltration membrane by using a NIPS method, which belongs to the technical field of sewage treatment and comprises the following steps of S1: mixing and stirring high molecular weight polyvinylidene fluoride 1, a pore-forming agent and an organic solvent uniformly to prepare a base membrane spinning casting solution A of the composite hollow fiber membrane; s2: mixing and stirring low-molecular-weight polyvinylidene fluoride 2, a pore-forming agent and an organic solvent uniformly to prepare a composite layer spinning casting solution B of the composite hollow fiber membrane; s3: defoaming and filtering the base membrane spinning membrane casting solution A in the step S1 and the composite layer spinning membrane casting solution B in the step S2, and conveying the base membrane spinning membrane casting solution A and the composite layer spinning membrane casting solution B into a hollow fiber spinning machine through a metering pump to prepare a composite hollow fiber ultrafiltration membrane; the compatibility of the composite material is good, the stripping phenomenon of the membrane yarn caused by different composite materials is basically avoided, and the normal operation of later-maintenance backwashing is ensured; the method can more accurately control the membrane separation aperture.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a preparation method for preparing a composite hollow fiber ultrafiltration membrane by using an NIPS method.
Background
In the field of sewage treatment, a high-efficiency and low-consumption solid-liquid technology plays an important role in developing safe and clean, green and low-carbon, intensive gathering, innovation and high-efficiency sewage treatment. The MBR membrane separation technology is widely applied to the field of solid-liquid separation of sewage treatment due to the advantages of no phase change, small land occupation, low cost, no secondary pollution and the like.
As an important separation filter medium, methods for preparing a hollow fiber membrane mainly include a solution spinning method (also referred to as a solution phase inversion method, a dip precipitation method, or a non-solvent induced phase separation method), a thermally induced phase separation method, a melt spinning-drawing method, and the like. The non-solvent induced phase separation method (NIPS) is a common method for preparing a hollow fiber ultrafiltration membrane, is widely popularized, and does not have a good synergistic effect so far due to a plurality of factors influencing the membrane formation. The membrane-making material suitable for the non-solvent induced phase separation (NIPS) spinning method mainly comprises Polysulfone (PS), polyether sulfone (PES), sulfonated polyether sulfone (SPES), Polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC) and the like, the physical properties and the chemical properties of various membrane-making materials have characteristics, and the cost of different membrane-making materials is different. Therefore, the preparation of hollow fiber membranes with excellent comprehensive performance by utilizing the characteristics of different materials and membrane preparation processes is a hotspot of research in the technical field of membrane preparation.
In practical application, MBR membranes have various limitations due to problems of membrane pollution, membrane yarn strength, operation and maintenance and the like, and restrict the application and popularization range of MBR ultrafiltration membranes in the field of sewage treatment. The hollow fiber ultrafiltration membrane is generally applied to the field of sewage treatment basically in a structural mode of an MBR membrane group device in the application process. Through continuous exploration and comparison, the membrane wire strength is accepted by users at present, the membrane wire cannot be broken under the condition of mud accumulation only by bearing over 10N of pulling force, and the filtration precision of the membrane wire is not easy to cause membrane pollution acceleration only by reaching 10-50 nm. MBR membrane can carry out maintenance nature backwash of certain frequency (including adding the medicine backwash) at the operation in-process, if membrane silk self intensity (including combined strength) is unsatisfactory, causes membrane silk damage or cortex to peel off easily.
Patent document No. CN200610035536.2 entitled "a method for producing composite hollow fiber membrane" discloses a method for producing PVDF/PES (or PS) composite hollow fiber membrane, which is to adopt a solution phase transfer spinning process, dissolve PS or PES, pore-forming agent, etc. in an organic solvent to form a membrane system of a base membrane, dissolve PVDF, pore-forming agent, etc. in an organic solvent to form a membrane system of a composite layer, and synchronously spray the solution and core solution to a coagulating bath through a composite spinning and spinning assembly to obtain the composite hollow fiber membrane with the separation layer being PVDF and the base layer being PS or PES. The patent does not specifically indicate the specific components, temperature and other process parameters of the spinning core solution and the coagulating solution, and the casting solution composed of PVDF and the membrane forming solution composed of PS (or PES) belong to different materials, so that the compatibility is poor, the later-stage use has peeling risk, the strength of the two materials is inconsistent, and the use risk is also brought.
The patent No. CN201210081941.3, patent name "preparation method of hollow fiber composite membrane" discloses a preparation method of composite hollow fiber membrane using different polymers as base membrane and composite layer, preparing different polymerization, pore-forming agent and organic solvent into membrane casting solution of spinning membrane forming system I and II, spinning the membrane casting solution of solution spinning membrane forming system I by solution spinning method, immersing into the membrane casting solution of solution spinning membrane forming system II under the condition of spinning formation and filling hollow cavity with core solution for coating, then quickly immersing into coagulating bath for full solidification to obtain hollow fiber composite membrane consisting of core layer formed by membrane casting solution I and skin layer formed by membrane casting solution II. The patent also proposes that the bore fluid consists of an organic solvent and water, the water content being not less than 50%, but does not indicate the temperature parameters of the bore fluid. The method is difficult to operate in the practical implementation process, and because the nascent membrane filaments of the membrane casting solution I have core liquid and are not fixed in shape, the nascent membrane filaments are difficult to draw and dip into the membrane casting solution II, the core liquid is easy to leak and pollute the membrane casting solution II due to improper operation. The method has little practical operation significance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method for preparing a composite hollow fiber ultrafiltration membrane by using a NIPS method.
The technical scheme of the invention is as follows: a preparation method for preparing a composite hollow fiber ultrafiltration membrane by using an NIPS method comprises the following steps:
s1: mixing and stirring high molecular weight polyvinylidene fluoride 1, a pore-forming agent and an organic solvent uniformly to prepare a base membrane spinning casting solution A of the composite hollow fiber membrane; the spinning casting solution A comprises the following components in percentage by mass: 10-20% of high molecular weight polyvinylidene fluoride, 50-80% of organic solvent and 10-30% of pore-forming agent;
s2: mixing and stirring low-molecular-weight polyvinylidene fluoride 2, a pore-forming agent and an organic solvent uniformly to prepare a composite layer spinning casting solution B of the composite hollow fiber membrane; the spinning membrane casting solution B comprises the following components in percentage by mass: 7-20% of low molecular weight polyvinylidene fluoride 2, 50-80% of organic solvent and 10-30% of pore-forming agent;
s3: defoaming and filtering the base membrane spinning casting solution A in the step S1 and the composite layer spinning casting solution B in the step S2, conveying the base membrane spinning casting solution A and the composite layer spinning casting solution B into a spinning nozzle of a hollow fiber spinning machine and core liquid in a central tube hole of the spinning nozzle through a metering pump, simultaneously extruding, feeding extruded membrane filaments into an external coagulation bath, enabling the membrane filaments to perform vertical stroke in the external coagulation bath, enabling the vertical stroke of the membrane filaments in the external coagulation bath to be 1-3m, then drawing the membrane filaments into a cleaning water tank for cleaning, enabling the solution in the cleaning water tank to be water, enabling the temperature of the water in the cleaning water tank to be 30-70 ℃, obtaining a composite hollow fiber ultrafiltration membrane after cleaning, enabling the solvents and the pore-forming agents in the two spinning casting solutions prepared in the steps S1 and S2 to enter a coagulation liquid phase, and enabling polymers serving as composite layer and base membrane materials to precipitate into a polymer hollow fiber membrane due to phase transfer, thus, the composite hollow fiber membrane which is synchronously formed and comprises the composite layer and the base membrane is spun, and the composite hollow fiber membrane is cleaned in a cleaning water tank and secondarily cured and then wound on the filament winding fiber of the filament winding machine.
Furthermore, the molecular weight of the high molecular weight polyvinylidene fluoride 1 is 50-120 ten thousand, the molecular weight of the low molecular weight polyvinylidene fluoride 2 is 20-60 ten thousand, and the molecular weights are compounded with the process requirements of the composite hollow fiber ultrafiltration membrane.
Further, the composite hollow fiber ultrafiltration membrane obtained in the step S3 has an outer diameter of 0.5-2.5mm, a wall thickness of 0.08-0.9mm, a porosity of 70-90%, a membrane filtration precision pore diameter of 0.01-0.05 μm, a rupture strength of 0.6-1.2MPa, a membrane filament tensile strength of 8.0-12N, and a pure water permeation flux of 400-2·h。
Furthermore, the thickness ratio of the composite layer of the composite hollow fiber ultrafiltration membrane to the base membrane is 1: 20-2: 1.
Further, the organic solvent in step S1 and step S2 is a mixture of one or more of the following solvents: the solvent used by the Dimethylformamide (DMF), the Dimethylacetamide (DMAC), the N-methylpyrrolidone and the dimethyl sulfoxide is a polar solvent with good solubility on the PVDF and the pore-forming agent and strong solubility, and the boiling point of the solvent is far higher than the dissolution temperature of the membrane casting solution.
Further, the pore-forming agent in the steps S1 and S2 is composed of the following components in percentage by mass: 86-90% of water-soluble high molecular polymer, 8-12% of surfactant and 0.5-2% of non-solvent, wherein the water-soluble high molecular polymer is a mixture of one or more of the following components: polyethylene glycol, polyoxyethylene, polyvinylpyrrolidone, polyvinyl alcohol and methyl cellulose, wherein the surfactant is a mixture of one or more of the following components: triton X-100, Tween-20 and Tween-80, wherein the non-solvent is a mixture of one or more of the following components: water, alcohols, ketones.
Further, the spinning jet in the step S3 is provided with three concentric nozzles, which are a core liquid port, a base film spinning casting solution a port, and a composite layer spinning casting solution B port from inside to outside, respectively, the outer diameter of the core liquid port is 0.3-1.2mm, the inner diameter of the base film spinning casting solution a port is 0.8-1.8mm, and the inner diameter of the composite layer spinning casting solution B port is 1.0-2.0mm, and the composite hollow fiber ultrafiltration membrane prepared according to the parameters has the best effect.
Furthermore, the spinning nozzle is provided with a circular material port and is in a stepped invagination, the horizontal line of a port B of the composite layer spinning membrane casting solution is consistent with the bottom of the spinneret plate, the horizontal line of a port A of the base membrane spinning membrane casting solution is 0.2-0.5mm lower than the port B of the composite layer spinning membrane casting solution, and the horizontal line of a core liquid port is 0.2-0.5mm lower; the design ensures that the casting solution A is firstly contacted with core solution to obtain certain precure, then is contacted with the casting solution B, and simultaneously enters a coagulating bath to carry out solvent and non-solvent exchange, so that phase transfer separation is carried out, and the composite hollow fiber membrane wire is generated.
Further, the core liquid is a mixed liquid of a solvent and a non-solvent, the non-solvent is water, the mass percent of the water in the core liquid is 30-75%, the temperature of the core liquid is 30-70 ℃, and the performance of the core liquid prepared at the temperature is good.
Further, the solution in the external coagulation bath is water, other non-solvent or the mixed solution of water, other non-solvent and solvent, when the external coagulation bath is the mixed solution of water and solvent, the mass percent of the solvent is 0-30%, the temperature of the external coagulation bath is 30-70 ℃, the content of the solvent in the coagulation bath is high, the mechanical strength of the membrane yarn is reduced, the concentration is low, the exchange speed of the solvent and the non-solvent is accelerated, subcutaneous finger-shaped holes are easy to form, and the generation of a sponge structure is not facilitated.
The invention has the beneficial effects that:
(1) the preparation method of the composite hollow fiber membrane adopts the same material composite membrane technology, and can spin the homogeneous composite hollow fiber membrane with stable performance, high filtering precision, high flux and high strength. The high molecular weight polyvinylidene fluoride polymer has a molecular weight of about 80-110 ten thousand, which is three times of the low molecular weight polyvinylidene fluoride polymer (about 30-35 ten thousand), and the high molecular weight polyvinylidene fluoride polymer is used as a base membrane material, so that the mechanical strength of the membrane yarn is effectively improved. The polyvinylidene fluoride with low molecular weight is used as a composite layer, and a compact separation layer with low filtration aperture (high filtration precision) is obtained by adjusting the formula of the casting solution. The polyvinylidene fluoride has excellent anti-pollution performance and shows excellent performance in high-pollution separation systems such as sewage treatment, biochemical and pharmaceutical industries, printing and dyeing wastewater treatment and the like. In addition, although the two kinds of polyvinylidene fluoride with different molecular weights have different molecular weights, the polyvinylidene fluoride serving as a similar substance has very outstanding compatibility, and the polyvinylidene fluoride can not be peeled off basically after being compounded by the same process.
(2) The method can effectively improve the strength of the membrane yarn; the compatibility of the composite material is good, the stripping phenomenon of the membrane yarn caused by different composite materials is basically avoided, and the normal operation of later-maintenance backwashing is ensured; the method can more accurately control the membrane separation aperture; the method has simple compounding process, is easy to control the compounding filament, and adopts the common NIPS method to produce; the method of the invention has high and controllable membrane separation precision. The hollow fiber composite membrane with certain filter aperture and mechanical strength can be obtained by changing the formula of the composite membrane material, the formula of the base membrane material, the spinning process parameters, the post-treatment conditions of the hollow fiber and the like.
Drawings
FIG. 1 is a schematic cross-sectional view of a composite hollow fiber ultrafiltration membrane according to example 3.
FIG. 2 is an electron micrograph of the composite hollow fiber ultrafiltration membrane of example 3.
Detailed Description
Example 1:
a preparation method for preparing a composite hollow fiber ultrafiltration membrane by using an NIPS method comprises the following steps:
s1: mixing and stirring high molecular weight polyvinylidene fluoride 1, a pore-forming agent and an organic solvent uniformly to prepare a base membrane spinning casting solution A of the composite hollow fiber membrane; the spinning membrane casting solution A comprises the following components in percentage by mass: 10% of high molecular weight polyvinylidene fluoride, 60% of organic solvent and 30% of pore-forming agent;
s2: mixing and stirring low-molecular-weight polyvinylidene fluoride 2, a pore-forming agent and an organic solvent uniformly to prepare a composite layer spinning casting solution B of the composite hollow fiber membrane; the spinning membrane casting solution B comprises the following components in percentage by mass: 7% of low molecular weight polyvinylidene fluoride 2, 63% of organic solvent and 30% of pore-forming agent;
s3: defoaming and filtering the base membrane spinning casting solution A in the step S1 and the composite layer spinning casting solution B in the step S2, conveying the base membrane spinning casting solution A and the composite layer spinning casting solution B into a spinning nozzle of a hollow fiber spinning machine and core liquid in a central tube hole of the spinning nozzle through a metering pump, extruding at the same time, feeding extruded membrane filaments into an external coagulation bath, enabling the membrane filaments to perform vertical stroke in the external coagulation bath, drawing the membrane filaments into a cleaning water tank for cleaning, wherein the solution in the cleaning water tank is water, the temperature of the water in the cleaning water tank is 30 ℃, obtaining a composite hollow fiber ultrafiltration membrane after cleaning, enabling the solvents and pore-forming agents in the two spinning casting solutions prepared in the steps S1 and S2 to enter the coagulation liquid phase, and precipitating the polymer serving as the composite layer and the base membrane material into a polymer hollow fiber membrane due to phase transfer, thereby spinning the synchronously formed composite hollow fiber membrane comprising the composite layer and the base membrane, and the composite hollow fiber membrane is cleaned in a cleaning water tank and secondarily cured and then wound on a filament winding fiber of a filament winding machine.
The molecular weight of the high molecular weight polyvinylidene fluoride 1 is 50 ten thousand, the molecular weight of the low molecular weight polyvinylidene fluoride 2 is 20 ten thousand, and the molecular weights are compounded with the process requirements of the composite hollow fiber ultrafiltration membrane.
The composite hollow fiber ultrafiltration membrane obtained in the step S3 has an outer diameter of 0.5mm, a wall thickness of 0.08mm, a porosity of 70%, a membrane filtration precision pore diameter of 0.01 μm, a rupture strength of 0.6MPa, a membrane filament tensile strength of 8.0N, and a pure water permeation flux of 400L/m under the test conditions of 0.1MPa and 25 DEG C2·h。
The thickness ratio of the composite layer to the base membrane of the composite hollow fiber ultrafiltration membrane is 1: 20.
The organic solvent in the step S1 and the step S2 is dimethyl formamide (DMF), the solvent used by the base film spinning membrane liquid A and the composite layer spinning membrane liquid B is a polar solvent with good dissolving performance on PVDF and pore-forming agent and strong dissolving performance, and the boiling point of the solvent is far higher than the dissolving temperature of the membrane liquid.
The pore-forming agent in the step S1 and the step S2 comprises the following components in percentage by mass: 86% of water-soluble high molecular polymer, 12% of surfactant and 2% of non-solvent, wherein the water-soluble high molecular polymer is polyethylene glycol, the surfactant is triton X-100, and the non-solvent is alcohol.
The spinning jet in the step S3 is provided with three concentric nozzles, which are a core liquid port, a base film spinning casting solution a port, and a composite layer spinning casting solution B port from inside to outside, the outer diameter of the core liquid port is 0.3mm, the inner diameter of the base film spinning casting solution a port is 0.8mm, and the inner diameter of the composite layer spinning casting solution B port is 1.0mm, and the composite hollow fiber ultrafiltration membrane prepared according to the parameters has the best effect.
The spinning nozzle is provided with a circular material port and is sunken in a step shape, the horizontal line of a port B of the composite layer spinning membrane casting liquid is consistent with the bottom of a spinneret plate, the horizontal line of a port A of the base membrane spinning membrane casting liquid is 0.2mm lower than the port B of the composite layer spinning membrane casting liquid, and the horizontal line of a core liquid port is 0.2mm lower than the horizontal line of the core liquid port; the design ensures that the casting solution A is firstly contacted with core solution to obtain certain precure, then is contacted with the casting solution B, and simultaneously enters a coagulating bath to carry out solvent and non-solvent exchange, so that phase transfer separation is carried out, and the composite hollow fiber membrane wire is generated.
The core liquid is a mixed liquid of a solvent and a non-solvent, the non-solvent is water, the mass percent of the water in the core liquid is 30%, the temperature of the core liquid is 30 ℃, and the performance of the preparation at the temperature is good.
The solution in the external coagulation bath is water, other non-solvent or the mixed solution of water and other non-solvent and solvent, when the external coagulation bath is the mixed solution of water and solvent, the mass percent of the solvent is 7%, the temperature of the external coagulation liquid is 30 ℃, the content of the solvent in the coagulation liquid is high, the mechanical strength of the membrane yarn can be reduced, the concentration is low, the exchange speed of the solvent and the non-solvent is accelerated, subcutaneous finger-shaped holes are easy to form, and the generation of a sponge structure is not facilitated.
Example 2:
a preparation method for preparing a composite hollow fiber ultrafiltration membrane by using an NIPS method comprises the following steps:
s1: mixing and stirring high molecular weight polyvinylidene fluoride 1, a pore-forming agent and an organic solvent uniformly to prepare a base membrane spinning casting solution A of the composite hollow fiber membrane; the spinning membrane casting solution A comprises the following components in percentage by mass: 18% of high molecular weight polyvinylidene fluoride, 59.1% of organic solvent and 22.9% of pore-forming agent;
s2: mixing and stirring low-molecular-weight polyvinylidene fluoride 2, a pore-forming agent and an organic solvent uniformly to prepare a composite layer spinning casting solution B of the composite hollow fiber membrane; the spinning membrane casting solution B comprises the following components in percentage by mass: 12% of low molecular weight polyvinylidene fluoride 2, 65% of organic solvent and 23% of pore-forming agent;
s3: defoaming and filtering the base membrane spinning casting solution A in the step S1 and the composite layer spinning casting solution B in the step S2, conveying the base membrane spinning casting solution A and the composite layer spinning casting solution B into a spinning nozzle of a hollow fiber spinning machine and core liquid in a central tube hole of the spinning nozzle through a metering pump, extruding at the same time, feeding extruded membrane filaments into an external coagulation bath, enabling the membrane filaments to perform vertical stroke in the external coagulation bath, drawing the membrane filaments into a cleaning water tank for cleaning, wherein the solution in the cleaning water tank is water, the temperature of the water in the cleaning water tank is 53 ℃, obtaining a composite hollow fiber ultrafiltration membrane after cleaning, enabling the solvents and pore-forming agents in the two spinning casting solutions prepared in the steps S1 and S2 to enter the coagulation liquid phase, and precipitating the polymer serving as the composite layer and the base membrane material into a polymer hollow fiber membrane due to phase transfer, thereby spinning the synchronously formed composite hollow fiber membrane comprising the composite layer and the base membrane, and the composite hollow fiber membrane is cleaned in a cleaning water tank and secondarily cured and then wound on a filament winding fiber of a filament winding machine.
The molecular weight of the high molecular weight polyvinylidene fluoride 1 is 100 ten thousand, the molecular weight of the low molecular weight polyvinylidene fluoride 2 is 50 ten thousand, and the molecular weights are compounded with the process requirements of the composite hollow fiber ultrafiltration membrane.
The composite hollow fiber ultrafiltration membrane obtained in the step S3 has an outer diameter of 1.4mm, a wall thickness of 0.25mm, a porosity of 71%, a membrane filtration precision pore diameter of 0.03 mu m, a rupture strength of 1.08MPa, a membrane wire tensile strength of 9.4N, and a pure water permeation flux of 600L/m under the test conditions of 0.1MPa and 25 DEG C2·h。
The thickness ratio of the composite layer to the base membrane of the composite hollow fiber ultrafiltration membrane is 1: 1.
The organic solvent in the step S1 and the step S2 is a solvent used by a Dimethylacetamide (DMAC) base membrane spinning membrane solution A and a composite layer spinning membrane solution B, the solvent is a polar solvent with good dissolving performance on PVDF and a pore-forming agent and the boiling point of the solvent is far higher than the dissolving temperature of the membrane solution.
The pore-forming agent in the step S1 and the step S2 comprises the following components in percentage by mass: 91.5% of water-soluble high molecular polymer, 8% of surfactant and 0.5% of non-solvent, wherein the water-soluble high molecular polymer is polyoxyethylene, the surfactant is Tween-20, and the non-solvent is water.
The spinning jet in the step S3 is provided with three concentric nozzles, which are respectively a core liquid port, a base film spinning casting liquid a port, and a composite layer spinning casting liquid B port from inside to outside, wherein the outer diameter of the core liquid port is 1.0mm, the inner diameter of the base film spinning casting liquid a port is 1.0mm, and the inner diameter of the composite layer spinning casting liquid B port is 1.5mm, and the composite hollow fiber ultrafiltration membrane prepared according to the parameters has the best effect.
The spinning nozzle is provided with a circular material port and is sunken in a step shape, the horizontal line of a port B of the composite layer spinning membrane casting liquid is consistent with the bottom of a spinneret plate, the horizontal line of a port A of the base membrane spinning membrane casting liquid is 0.8mm lower than the port B of the composite layer spinning membrane casting liquid, and the horizontal line of a core liquid port is 0.3mm lower; the design ensures that the casting solution A is firstly contacted with core solution to obtain certain precure, then is contacted with the casting solution B, and simultaneously enters a coagulating bath to carry out solvent and non-solvent exchange, so that phase transfer separation is carried out, and the composite hollow fiber membrane wire is generated.
The core liquid is a mixed liquid of a solvent and a non-solvent, the non-solvent is water, the mass percent of the water in the core liquid is 50%, the solvent is DMAC, the temperature of the core liquid is 53 ℃, and the performance of the core liquid prepared at the temperature is good.
The solution in the external coagulation bath is water, other non-solvent or the mixed solution of water, other non-solvent and solvent, when the external coagulation bath is the mixed solution of water and solvent, the mass percent of the solvent is 5%, the solvent is DMAC, the temperature of the external coagulation bath is 50 ℃, the content of the solvent in the coagulation bath is high, the mechanical strength of the membrane yarn can be reduced, the concentration is low, the exchange speed of the solvent and the non-solvent is accelerated, subcutaneous finger-shaped holes are easily formed, and the generation of a sponge structure is not facilitated.
Example 3:
a preparation method for preparing a composite hollow fiber ultrafiltration membrane by using an NIPS method comprises the following steps:
s1: mixing and stirring high molecular weight polyvinylidene fluoride 1, a pore-forming agent and an organic solvent uniformly to prepare a base membrane spinning casting solution A of the composite hollow fiber membrane; the spinning membrane casting solution A comprises the following components in percentage by mass: 10% of high molecular weight polyvinylidene fluoride, 80% of organic solvent and 10% of pore-forming agent;
s2: mixing and stirring low-molecular-weight polyvinylidene fluoride 2, a pore-forming agent and an organic solvent uniformly to prepare a composite layer spinning casting solution B of the composite hollow fiber membrane; the spinning membrane casting solution B comprises the following components in percentage by mass: 7% of low molecular weight polyvinylidene fluoride 2, 80% of organic solvent and 23% of pore-forming agent;
s3: defoaming and filtering the base membrane spinning casting solution A in the step S1 and the composite layer spinning casting solution B in the step S2, conveying the base membrane spinning casting solution A and the composite layer spinning casting solution B into a spinning nozzle of a hollow fiber spinning machine and core liquid in a central tube hole of the spinning nozzle through a metering pump, extruding at the same time, feeding extruded membrane filaments into an external coagulation bath, enabling the membrane filaments to perform vertical stroke in the external coagulation bath, enabling the vertical stroke of the membrane filaments in the external coagulation bath to be 3m, then drawing the membrane filaments into a cleaning water tank for cleaning, enabling the solution in the cleaning water tank to be water, enabling the temperature of the water in the cleaning water tank to be 70 ℃, obtaining a composite hollow fiber ultrafiltration membrane after cleaning, enabling the solvents and pore-forming agents in the two spinning casting solutions prepared in the steps S1 and S2 to enter the coagulation liquid phase, and enabling polymers serving as composite layers and base membrane materials to precipitate into a polymer hollow fiber membrane due to phase transfer, so that the composite hollow fiber membrane comprising the composite layers and the base membrane which are synchronously formed is spun, and the composite hollow fiber membrane is cleaned in a cleaning water tank and secondarily cured and then wound on a filament winding fiber of a filament winding machine.
The molecular weight of the high molecular weight polyvinylidene fluoride 1 is 120 ten thousand, the molecular weight of the low molecular weight polyvinylidene fluoride 2 is 60 ten thousand, and the molecular weights are compounded with the process requirements of the composite hollow fiber ultrafiltration membrane.
The composite hollow fiber ultrafiltration membrane obtained in the step S3 has an outer diameter of 2.5mm, a wall thickness of 0.9mm, a porosity of 90%, a membrane filtration precision pore diameter of 0.05 μm, a rupture strength of 1.2MPa, and a membrane filament tensile strength of12N, and the water permeability of pure water is 800L/m under the test conditions of 0.1MPa and 25 DEG C2·h。
The thickness ratio of the composite layer of the composite hollow fiber ultrafiltration membrane to the base membrane is 2: 1.
The organic solvent in the step S1 and the step S2 is N-methyl pyrrolidone, the solvent used by the base film spinning membrane liquid A and the composite layer spinning membrane liquid B is a polar solvent with good dissolving performance and strong dissolving performance on PVDF and pore-forming agent, and the boiling point of the solvent is far higher than the dissolving temperature of the membrane liquid.
The pore-forming agent in the step S1 and the step S2 comprises the following components in percentage by mass: 90% of water-soluble high molecular polymer, 8% of surfactant and 2% of non-solvent, wherein the water-soluble high molecular polymer is polyvinylpyrrolidone, the surfactant is Tween-80, and the non-solvent is ketone.
The spinning jet in the step S3 is provided with three concentric nozzles, which are respectively a core liquid port, a base film spinning casting liquid a port, and a composite layer spinning casting liquid B port from inside to outside, wherein the outer diameter of the core liquid port is 1.2mm, the inner diameter of the base film spinning casting liquid a port is 1.8mm, and the inner diameter of the composite layer spinning casting liquid B port is 2.0mm, and the composite hollow fiber ultrafiltration membrane prepared according to the parameters has the best effect.
The spinning nozzle is provided with a circular material port and is sunken in a step shape, the horizontal line of a port B of the composite layer spinning membrane casting liquid is consistent with the bottom of a spinneret plate, the horizontal line of a port A of the base membrane spinning membrane casting liquid is 0.5mm lower than the port B of the composite layer spinning membrane casting liquid, and the horizontal line of a core liquid port is 0.5mm lower; the design ensures that the casting solution A is firstly contacted with core solution to obtain certain precure, then is contacted with the casting solution B, and simultaneously enters a coagulating bath to carry out solvent and non-solvent exchange, so that phase transfer separation is carried out, and the composite hollow fiber membrane wire is generated.
The core liquid is a mixed liquid of a solvent and a non-solvent, the non-solvent is water, the mass percent of the water in the core liquid is 75%, the temperature of the core liquid is 70 ℃, and the performance of the core liquid prepared at the temperature is good.
The solution in the external coagulation bath is water, other non-solvent or the mixed solution of water and other non-solvent and solvent, when the external coagulation bath is the mixed solution of water and solvent, the mass percent of the solvent is 30%, the temperature of the external coagulation bath is 70 ℃, the content of the solvent in the coagulation bath is high, the mechanical strength of the membrane yarn can be reduced, the concentration is low, the exchange speed of the solvent and the non-solvent is accelerated, subcutaneous finger-shaped holes are easy to form, and the generation of a sponge structure is not facilitated.
Comparative example 1 to example 3, example 3 is the best example.
As shown in fig. 1, fig. 1 is a real sectional view of the composite hollow fiber ultrafiltration membrane of example 3;
as shown in fig. 2, fig. 2 is a surface electron microscope image of the composite hollow fiber ultrafiltration membrane of example 3.
Claims (10)
1. A preparation method for preparing a composite hollow fiber ultrafiltration membrane by using an NIPS method is characterized by comprising the following steps:
s1: mixing and stirring high molecular weight polyvinylidene fluoride 1, a pore-forming agent and an organic solvent uniformly to prepare a base membrane spinning casting solution A of the composite hollow fiber membrane; the spinning membrane casting solution A comprises the following components in percentage by mass: 10-20% of high molecular weight polyvinylidene fluoride, 50-80% of organic solvent and 10-30% of pore-forming agent;
s2: mixing and stirring low-molecular-weight polyvinylidene fluoride 2, a pore-forming agent and an organic solvent uniformly to prepare a composite layer spinning casting solution B of the composite hollow fiber membrane; the spinning membrane casting solution B comprises the following components in percentage by mass: 7-20% of low molecular weight polyvinylidene fluoride 2, 50-80% of organic solvent and 10-30% of pore-forming agent;
s3: and (2) defoaming and filtering the base membrane spinning membrane casting solution A in the step S1 and the composite layer spinning membrane casting solution B in the step S2, conveying the base membrane spinning membrane casting solution A and the composite layer spinning membrane casting solution B into a spinning nozzle of a hollow fiber spinning machine and core liquid in a central tube hole of the spinning nozzle through a metering pump, extruding the core liquid simultaneously, feeding the extruded membrane filaments into an external coagulation bath, enabling the membrane filaments to perform vertical stroke in the external coagulation bath, enabling the vertical stroke of the membrane filaments in the external coagulation bath to be 1-3m, then drawing the membrane filaments into a cleaning water tank for cleaning, enabling the solution in the cleaning water tank to be water, enabling the temperature of the water in the cleaning water tank to be 30-70 ℃, and obtaining the composite hollow fiber ultrafiltration membrane after cleaning.
2. The method of preparing a composite hollow fiber ultrafiltration membrane according to claim 1, wherein the molecular weight of the high molecular weight polyvinylidene fluoride 1 is 50 to 120 ten thousand, and the molecular weight of the low molecular weight polyvinylidene fluoride 2 is 20 to 60 ten thousand.
3. The method for preparing a composite hollow fiber ultrafiltration membrane using the NIPS process according to claim 1, wherein the composite hollow fiber ultrafiltration membrane obtained in the step S3 has an outer diameter of 0.5 to 2.5mm and a wall thickness of 0.08 to 0.9 mm.
4. The method of claim 1, wherein the thickness ratio of the composite layer to the base membrane of the composite hollow fiber ultrafiltration membrane is 1: 20 to 2: 1.
5. The method for preparing a composite hollow fiber ultrafiltration membrane using the NIPS process according to claim 1, wherein the organic solvent used in the steps S1 and S2 is a mixture of one or more of the following solvents: dimethylformamide (DMF), Dimethylacetamide (DMAC), N-methylpyrrolidone, dimethylsulfoxide.
6. The method for preparing a composite hollow fiber ultrafiltration membrane by using the NIPS method according to claim 1, wherein the pore-forming agent in the steps S1 and S2 comprises the following components in percentage by mass: 86-90% of water-soluble high molecular polymer, 8-12% of surfactant and 0.5-2% of non-solvent, wherein the water-soluble high molecular polymer is a mixture of one or more of the following components: polyethylene glycol, polyoxyethylene, polyvinylpyrrolidone, polyvinyl alcohol and methyl cellulose, wherein the surfactant is a mixture of one or more of the following components: triton X-100, Tween-20 and Tween-80, wherein the non-solvent is a mixture of one or more of the following components: water, alcohols, ketones.
7. The method for preparing a composite hollow fiber ultrafiltration membrane by using the NIPS process according to claim 1, wherein the spinneret in step S3 is provided with three concentric nozzles, which are respectively a core liquid opening, a base film spinning membrane casting solution opening A and a composite layer spinning membrane casting solution opening B from inside to outside, the outer diameter of the core liquid opening is 0.3-1.2mm, the inner diameter of the base film spinning membrane casting solution opening A is 0.8-1.8mm, and the inner diameter of the composite layer spinning membrane casting solution opening B is 1.0-2.0 mm.
8. The method for preparing the composite hollow fiber ultrafiltration membrane by the NIPS process according to claim 7, wherein the spinneret has a circular opening and is stepped, the horizontal line of the B opening of the composite layer spinning membrane casting solution is consistent with the bottom of the spinneret plate, the horizontal line of the A opening of the base membrane spinning membrane casting solution is 0.2-0.5mm lower than that of the B opening of the composite layer spinning membrane casting solution, and the horizontal line of the core solution opening is 0.2-0.5mm lower.
9. The method for preparing the composite hollow fiber ultrafiltration membrane by using the NIPS method according to claim 1, wherein the bore fluid is a mixed liquid of a solvent and a non-solvent, the non-solvent is water, the mass percent of the water in the bore fluid is 30-75%, and the temperature of the bore fluid is 30-70 ℃.
10. The method for preparing a composite hollow fiber ultrafiltration membrane according to claim 7, wherein the bore fluid is a mixed fluid of a solvent and a non-solvent, the non-solvent is water, and the mass percentage of the water in the bore fluid is 30-75%.
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