CN111135726A - Separation membrane with high-strength protective belt and preparation method thereof - Google Patents
Separation membrane with high-strength protective belt and preparation method thereof Download PDFInfo
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- CN111135726A CN111135726A CN201811313799.4A CN201811313799A CN111135726A CN 111135726 A CN111135726 A CN 111135726A CN 201811313799 A CN201811313799 A CN 201811313799A CN 111135726 A CN111135726 A CN 111135726A
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- 229920005597 polymer membrane Polymers 0.000 claims description 15
- 125000000129 anionic group Chemical group 0.000 claims description 14
- 239000004088 foaming agent Substances 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- 125000002091 cationic group Chemical group 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
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- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
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- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical group OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
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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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
Abstract
The invention discloses a separation membrane with a high-strength protective belt, which comprises a membrane layer, the protective belt and a supporting layer which are sequentially arranged from outside to inside. The supporting layer is a supporting pipe woven by cation modified fibers, and the protective belt is a compact layer formed by anion copolymers. The invention also discloses a preparation method of the separation membrane. The invention has the advantages that: the separation membrane with the high-strength protective belt solves the mechanical problems that the separation membrane is easy to break, peel, expand and crush, and the like at one time, and the protective belt can prevent the separation effect of the membrane from being obviously reduced under the condition that a membrane layer is slightly damaged. The membrane liquid and the supporting tube used in the invention do not need any additional chemical and physical treatment, the manufacturing process is simple, the cost is low, and the invention is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of polymer membrane materials, and particularly relates to a separation membrane with a high-strength protective belt and a preparation method thereof.
Background
The hollow fiber membrane module is simple to use, easy to clean and maintain and widely applied to many fields. The traditional high-molecular hollow fiber membrane is simple to manufacture and low in cost, but the membrane with the structure has low mechanical strength, and is easy to break after being used for a long time, and the membrane is easy to flatten or expand and break when being washed by instantaneous high pressure or recoil in the using process. To address these problems, researchers have developed composite membrane structures that are reinforced with other materials without affecting the separation performance of the membrane.
The overall process for membrane enhancement can be divided into two broad categories: one method is to add fibers in the membrane, which improves the defect of easy breaking of membrane yarns to a certain extent, but because the membrane yarns are subjected to high-strength vibration in the using process, the fibers are separated from the membrane layer, and the strength of the membrane yarns is reduced. Moreover, the method cannot fundamentally solve the problems that the membrane material is easy to flatten and expand and break. The other method is to use tubular or bag-shaped support as the support layer and coat the membrane material on the support layer to make the composite membrane with support.
The membrane needs frequent back flushing cleaning in the use process, if the interface bonding strength of the membrane layer and the supporting layer of the lining pipe is not high, the membrane layer can be peeled from the supporting layer in the use process, a peeling phenomenon occurs, and the double image can seriously affect the service performance and the service life of the membrane. Therefore, it is necessary and meaningful to find a preparation method which is simple, does not cause additional pollution, is easy to industrialize, improves the film adhesion, and improves the film swelling resistance and pressure resistance.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a separation membrane having a high-strength guard band and a method for preparing the same, so as to solve the problems of the background art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a separation membrane with a high-strength protective belt comprises a membrane layer, a protective belt and a supporting layer which are sequentially arranged from outside to inside, wherein the supporting layer is a supporting pipe woven by cation modified fibers, and the protective belt is a compact layer formed by an anion copolymer.
Further, the membrane layer is prepared by mixing an anionic copolymer, a high-molecular membrane material and a pore-foaming agent, wherein the anionic copolymer is prepared from the following raw materials in parts by weight: 100 parts of solvent, 5-7 parts of reaction monomer A, 3-5 parts of reaction monomer B and 0.2-0.3 part of initiator; mixing the prepared anionic copolymer with 20-25 parts of polymer membrane material and 2-5 parts of pore-foaming agent to prepare the membrane layer; the reaction monomer A is the emergency methyl acrylate or methyl acrylate, and the reaction monomer B is 2-acrylamide-2-methylpropanesulfonic acid or methacrylic acid.
Further, the thickness of the film layer is 80-120 um.
Further, the polymer membrane material is polyvinylidene fluoride, polyvinyl chloride or polyether sulfone.
Further, the anionic copolymer is P (MMA-co-AMPS) or P (MA-co-MAA) or P (MA-co-AMPS).
Furthermore, the cation modified fiber is cation polyester filament with the specification of low stretch yarn (DTY), the denier number of 150-300D and the count number of 72-288F.
Further, the thickness of the protective belt is 20-30 um.
The preparation method of the separation membrane comprises the following steps:
step 1: preparing a casting solution with anion subset groups: adding the following raw materials in parts by weight into 100 parts of solvent at 60-85 ℃: 5-7 parts of reaction monomer A, 3-5 parts of reaction monomer B and 0.2-0.3 part of initiator, and carrying out polymerization reaction for 4-8 hours under stirring to prepare an anionic copolymer; adding 20-25 parts of membrane material and 2-5 parts of pore-foaming agent into the solvent, stirring for 6-12 hours at 40-80 ℃, stopping stirring after uniform dissolution, standing and defoaming to obtain the membrane casting solution with anionic groups.
Step 2: making a support tube with cationic groups: the hollow supporting tube with the outer diameter of 1-2.5mm and the inner diameter of 0.5-1.5mm is woven by adopting cation modified fibers. The reaction monomer A is the emergency methyl acrylate or methyl acrylate, and the reaction monomer B is 2-acrylamide-2-methylpropanesulfonic acid or methacrylic acid.
And step 3: spraying the anion membrane casting solution on a cation supporting tube, soaking and curing the anion membrane casting solution in water to prepare a separation membrane, cutting the cured separation membrane, soaking the cut separation membrane in a protective solution for 6 to 12 hours, drying the separation membrane for 4 hours at the temperature of between 60 and 80 ℃, and forming a high-strength protective belt in the middle of the separation membrane at the interface between the anion membrane casting solution and the cation supporting tube due to the strong interaction of anions and cations.
Further, the reactive monomer A in the step 1 is methyl methacrylate or methyl acrylate, and the reactive monomer B is 2-acrylamido-2-methylpropanesulfonic acid or methacrylic acid.
Further, the initiator in the step 1 is azobisisobutyronitrile or azobisisoheptonitrile or dibenzoyl peroxide.
Further, the solvent in step 1 is one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Further, the pore-foaming agent used in step 1 is polyvinylpyrrolidone or polyethylene glycol or a mixture of polyvinylpyrrolidone and polyethylene glycol.
Further, the weaving mode in the step 2 is weaving or crocheting.
Further, the protective solution used in the step 3 is a mixed solution of glycerol, alcohol and water, and the weight parts are as follows: glycerol: alcohol: water = 20-35: 5-10:55-75.
The invention has the following beneficial effects: provided are a separation membrane having a high-strength guard band and a method for preparing the same. The protective belt formed by the anionic copolymer in the membrane not only effectively improves the mechanical strength of the membrane in all aspects, but also can keep the filtering performance of the membrane from being greatly changed under the condition that the membrane layer is slightly damaged, and once solves the mechanical problems that the separation membrane is easy to break, peel, expand and break, is easy to flatten and the like. The membrane liquid and the supporting tube used in the invention do not need any additional chemical and physical treatment, the manufacturing process is simple, the cost is low, and the invention is suitable for industrial production.
Drawings
FIG. 1 is a schematic view of the structure of a separation membrane according to the present invention.
Fig. 2 is a schematic diagram of film formation.
Fig. 3 is a flow chart of spinning line.
FIG. 4 is a schematic view of the structure of the spinneret.
FIG. 5 is a schematic diagram of the weaving of cationically modified fibers.
Description of the main component symbols: 11. a film layer; 12. a protective band; 13. a support layer; 2. a support tube supply system; 3. a spinneret; 31. an inner bore; 32. a feed liquid hole; 4. a coagulation bath; 5. a winding machine; 6. a charging bucket; 7. rinsing bath; 8. and (4) supplying to a press.
Detailed Description
The invention is further described with reference to the following drawings and detailed description.
As shown in fig. 1, the separation membrane with a high-strength guard band comprises a membrane layer 11, a guard band 12 and a support layer 13 which are sequentially arranged from outside to inside, wherein the membrane layer 11 is formed by blending a high-molecular membrane material and an anionic copolymer, the support layer 13 is a support tube woven by cationic modified fibers, and the guard band 12 is a dense layer formed by continuously migrating and aggregating the anionic copolymer to the surface of the support tube.
Example one
1) Preparing a casting solution with anionic groups: adding a reaction monomer MMA, an anionic reaction monomer AMPS and an initiator ABVN into a DMF solvent at 60 ℃, and stirring for reaction for 4 hours to prepare an anionic polymer P (MMA-co-AMPS); and then adding a polymer membrane material PES and a pore-forming agent PEG into the solvent, stirring the mixture and an anionic polymer P (MMA-co-AMPS) for 6 hours at 40 ℃, stopping stirring after the mixture is dissolved uniformly, and standing and defoaming to obtain the anionic membrane casting solution. The monomer, the initiator, the solvent, the polymer membrane material and the pore-foaming agent are prepared according to the following mass percent: 100 parts DMF, 5 parts MMA, 5 parts AMPS, 0.2 parts ABVN, 25 parts PES and 5 parts PEG.
2) Making a support tube with cationic groups: the 150D/72F cationic terylene low stretch yarn is made into a hollow supporting tube with the outer diameter of 1.0 mm and the inner diameter of 0.5 mm through the structure of a crochet knitting machine as shown in figure 5.
3) As shown in FIG. 3, the anion membrane casting solution is filtered and put into a charging bucket 6, the cation support tube is put into a supply and lining tube system 2, a supply and pressing machine 8, a support tube supply system 2 and a winding machine 5 are simultaneously started, the membrane casting solution is coated on the support tube through a spinning nozzle 3, and then is collected by the winding machine 5 through water solidification and rinsing. The cured membrane is unloaded from the winding machine 5, cut, soaked in the protective solution for 6 hours, then placed into a vacuum oven for heating, and dried for 4 hours at the temperature of 60 ℃, as shown in figure 2, at the intersection of the anion membrane casting solution and the cation support tube, a high-strength protective belt 12 is formed in the middle of the separation membrane due to the strong interaction of anions and cations.
The process parameters are as follows:
the extrusion temperature of the feed liquid is 40 ℃;
the specification of the spinning nozzle is as follows: the diameter of the inner hole is 1.0 mm, and the diameter of the outer hole is 1.4 mm; the structure of the spinneret is shown in fig. 4;
the coagulating bath is deionized water, the temperature is 20 ℃, and the depth is 1 m;
the linear speed of the winding machine is 5 m/min;
the components of the protective solution are as follows: 75% of water, 25% of glycerol and 5% of alcohol.
The PES hollow composite membrane with the protective belt prepared by the formula and the process has the following properties after tests: the inner diameter is 0.5 mm, the outer diameter is 1.2 mm, the thickness of the film layer is 80 microns, the thickness of the protective belt is 20 microns, the tensile strength is 80N, the bursting pressure for separating the film layer from the supporting layer is 0.5 MPa, the pressure for flattening the composite film is 0.6 MPa, the pure water flux at 25 ℃ under the pressure of 0.1 MPa is 800L/m < 2 > 2h, and the average pore diameter of the surface of the film measured by a pore diameter analyzer is 40 nanometers.
Comparative example 1
The comparative example is completely the same as the film preparation formula and the process of the example 1, except that the supporting tube does not adopt the cationic polyester low stretch yarn, but adopts the common polyester filament yarn, and the process and the result are as follows:
1) preparing a casting solution with anionic groups: adding a reaction monomer MMA, an anionic reaction monomer AMPS and an initiator ABVN into a DMF solvent at 60 ℃, and stirring for reaction for 4 hours to prepare an anionic polymer P (MMA-co-AMPS); and then adding a polymer membrane material PES and a pore-forming agent PEG into the solvent, stirring the mixture and an anionic polymer P (MMA-co-AMPS) for 6 hours at 40 ℃, stopping stirring after the mixture is dissolved uniformly, and standing and defoaming to obtain the anionic membrane casting solution. The monomer, the initiator, the solvent, the polymer membrane material and the pore-foaming agent are prepared according to the following mass percent: 100 parts DMF, 5 parts MMA, 5 parts AMPS, 0.2 parts ABVN, 25 parts PES and 5 parts PEG.
2) Making a support tube with cationic groups: 150D/72F polyester filament is made into a hollow supporting tube with the outer diameter of 1.0 mm and the inner diameter of 0.5 mm through the structure of a crochet loom.
3) Filtering the anion membrane casting solution, putting the anion membrane casting solution into a charging bucket 6, putting a supporting pipe into a lining pipe supplying system 2, simultaneously starting a pressure supplying machine 8, the lining pipe supplying system 2 and a winding machine 5, coating the membrane casting solution on the supporting pipe through a spinning nozzle 3, and then collecting the membrane casting solution by the winding machine 5 after water solidification and rinsing. And unloading the cured film from the winding machine 5, cutting, soaking the protective solution for 6 hours, then putting the film into a vacuum oven for heating, and drying the film for 4 hours at the temperature of 60 ℃.
The process parameters are as follows:
the extrusion temperature of the feed liquid is 40 ℃;
the specification of the spinning nozzle is as follows: the diameter of the inner hole is 1.0 mm, and the diameter of the outer hole is 1.4 mm;
the coagulating bath is deionized water, the temperature is 20 ℃, and the depth is 1 m;
the linear speed of the winding machine is 5 m/min;
the components of the protective solution are as follows: 75% of water; 25% of glycerol; 5% of alcohol.
The PES hollow composite membrane prepared by the formula and the process has the following properties after tests: the inner diameter is 0.5 mm, the outer diameter is 1.2 mm, the thickness of the film layer is 80 microns, no obvious dense layer protective belt is detected, the tensile strength is 70N, the burst pressure for separating the film layer from the supporting layer is 0.15 MPa, the pressure for flattening the composite film is 0.3 MPa, the pure water flux at 25 ℃ under the pressure of 0.1 MPa is 800L/m < 2 > 2h, and the average pore diameter of the surface of the film is 40 nm measured by a pore diameter analyzer.
Comparative example 2
The comparative example is completely the same as the membrane preparation process and the support tube in example 1, except that no anionic polymer is added in the membrane preparation formula, and the membrane casting solution is only composed of a simple high-molecular membrane material and a pore-forming agent, and the process and the result are as follows:
1) preparing a casting solution: adding a polymer membrane material PES and a pore-foaming agent PEG into a DMF solvent at 40 ℃, stirring for 6 hours, stopping stirring after uniform dissolution, standing and defoaming to obtain a membrane casting solution. The solvent, the polymer membrane material and the pore-foaming agent are prepared according to the following mass percentages: 100 parts DMF, 25 parts PES and 5 parts PEG.
2) Making a support tube with cationic groups: 150D/72F cationic polyester low stretch yarn is made into a hollow supporting tube with the outer diameter of 1.0 mm and the inner diameter of 0.5 mm through the structure of a crochet loom.
3) Filtering the casting solution, putting the filtered casting solution into a charging bucket 6, putting a cation supporting tube into a supply and lining tube system 2, simultaneously starting a supply and pressing machine 8, the supply and lining tube system 2 and a winding machine 5, coating the casting solution on the supporting tube through a spinning nozzle 3, and then collecting the casting solution by the winding machine 5 through water solidification and rinsing. And unloading the cured film from the winding machine 5, cutting, soaking the protective solution for 6 hours, then putting the film into a vacuum oven for heating, and drying the film for 4 hours at the temperature of 60 ℃.
The process parameters are as follows:
the extrusion temperature of the feed liquid is 40 ℃;
the specification of the spinning nozzle is as follows: the diameter of the inner hole is 1.0 mm, and the diameter of the outer hole is 1.4 mm;
the coagulating bath is deionized water, the temperature is 20 ℃, and the depth is 1 m;
the linear speed of the winding machine is 5 m/min;
the components of the protective solution are as follows: 75% of water; 25% of glycerol; 5% of alcohol.
The PES hollow composite membrane prepared by the formula and the process has the following properties after tests: the inner diameter is 0.5 mm, the outer diameter is 1.2 mm, the thickness of the film layer is 80 microns, no obvious dense layer protective belt is detected, the tensile strength is 80N, the burst pressure for separating the film layer from the supporting layer is 0.15 MPa, the pressure for flattening the composite film is 0.25 MPa, the pure water flux at 25 ℃ under the pressure of 0.1 MPa is 750L/m < 2 > 2h, and the average pore diameter of the surface of the film is 40 nm measured by a pore diameter analyzer.
Example two
1) Preparing a casting solution with anionic groups: adding a reaction monomer MA, an anionic reaction monomer MAA and an initiator BPO into an NMP solvent at 85 ℃, and stirring for reacting for 8 hours to prepare an anionic polymer P (MA-co-MAA); and then adding a polymer membrane material PVDF and a pore-forming agent PVP into the solvent, stirring the mixture and an anionic polymer P (MA-co-MAA) for 12 hours at the temperature of 80 ℃, stopping stirring after dissolving uniformly, standing and defoaming to obtain the anionic membrane casting solution. The monomer, the initiator, the solvent, the polymer membrane material and the pore-foaming agent are prepared according to the following mass percent: 100 parts NMP, 7 parts MA, 3 parts MAA, 0.3 parts BPO, 23 parts PVDF and 2 parts PVP.
2) Making a support tube with cationic groups: the cationic terylene low stretch yarn of 300D/288F is made into a hollow supporting tube with the outer diameter of 2.5mm and the inner diameter of 1.5mm through the structure of a crochet loom.
3) Filtering the anion membrane casting solution, putting the anion membrane casting solution into a charging bucket, putting a cation supporting tube into a supply and lining tube system 2, simultaneously starting a supply and pressing machine 8, the supply and lining tube system 2 and a winding machine 5, coating the membrane casting solution on the supporting tube through a spinning jet 3, and then collecting the membrane casting solution by the winding machine 5 through water solidification and rinsing. The cured membrane is unloaded from the winding machine 5, is cut and soaked in the protective solution for 12 hours, then is put into a vacuum oven for heating, is dried for 4 hours at the temperature of 80 ℃, and a high-strength protective belt 12 is formed in the middle of the separation membrane at the interface of the anion membrane casting solution and the cation supporting tube due to the strong interaction of anions and cations.
The process parameters are as follows:
the extrusion temperature of the feed liquid is 80 ℃;
the specification of the spinning nozzle is as follows: the diameter of the inner hole is 2.5mm, and the diameter of the outer hole is 3.5 mm;
the coagulating bath is deionized water, the temperature is 40 ℃, and the depth is 2 m;
the linear speed of the winding machine is 10 m/min;
the components of the protective solution are as follows: 55% of water; 35% of glycerol; 10% of alcohol.
The PVDF hollow composite membrane with the protective band prepared by the formula and the process has the following performances after tests: the inner diameter is 1.5mm, the outer diameter is 2.8 mm, the thickness of the film layer is 120 microns, the thickness of the protective belt is 30 microns, the tensile strength is 200N, the bursting pressure for separating the film layer from the supporting layer is 0.4 MPa, the pressure for flattening the composite film is 0.5 MPa, the pure water flux at 25 ℃ under the pressure of 0.1 MPa is 1500L/m < 2 > 2h, and the average pore diameter of the surface of the film measured by a pore diameter analyzer is 100 nanometers.
EXAMPLE III
1) Preparing a casting solution with anionic groups: adding a reaction monomer MA, an anionic reaction monomer AMPS and an initiator AIBN into a DMAC solvent at 75 ℃, and stirring for reacting for 6 hours to prepare an anionic polymer P (MA-co-AMPS); and then adding a high-molecular membrane material PVC, pore-foaming agents PVP and PEG into the solvent, stirring the mixture and an anionic polymer P (MA-co-AMPS) for 9 hours at the temperature of 60 ℃, stopping stirring after dissolving uniformly, and standing and defoaming to obtain the anionic membrane casting solution. The monomer, the initiator, the solvent, the polymer membrane material and the pore-foaming agent are prepared according to the following mass percent: 100 parts of DMAC, 6 parts of MA, 4 parts of AMPS, 0.25 part of AIBN, 20 parts of PVC, 2 parts of PVP and 2 parts of PEG.
2) Making a support tube with cationic groups: the cationic terylene low stretch yarn with the diameter of 200D/144F is weaved by a knitting machine to be made into a hollow supporting tube with the outer diameter of 1.8 mm and the inner diameter of 1.0 mm.
3) Filtering the anion membrane casting solution, putting the anion membrane casting solution into a charging bucket 6, putting a cation supporting tube into a lining tube supply system 2, simultaneously starting a pressure supply machine 8, the lining tube supply system 2 and a winding machine 5, coating the membrane casting solution on the supporting tube through a spinning jet 3, and then collecting the membrane casting solution by the winding machine 5 through water solidification and rinsing. The cured membrane is unloaded from the winding machine 5, is cut and soaked in the protective solution for 9 hours, then is put into a vacuum oven for heating, is dried for 4 hours at the temperature of 70 ℃, and a high-strength protective belt 12 is formed in the middle of the separation membrane at the interface of the anion membrane casting solution and the cation supporting tube due to the strong interaction of anions and cations.
The process parameters are as follows:
the extrusion temperature of the feed liquid is 60 ℃;
the specification of the spinning nozzle is as follows: the diameter of the inner hole is 1.8 mm, and the diameter of the outer hole is 2.5 mm;
the coagulating bath is deionized water, the temperature is 30 ℃, and the depth is 1.5 m;
the linear speed of the winding machine is 8 m/min;
the components of the protective solution are as follows: 62% of water; 30% of glycerol; 8 percent of alcohol.
The PVC hollow composite membrane with the protective belt prepared by the formula and the process has the following properties after tests: the inner diameter is 1.0 mm, the outer diameter is 2.0 mm, the thickness of the film layer is 80 microns, the thickness of the protective belt is 20 microns, the tensile strength is 150N, the bursting pressure for separating the film layer from the supporting layer is 0.45 MPa, the pressure for flattening the composite film is 0.55 MPa, the pure water flux of 1200L/m < 2 > 2h at 25 ℃ under the pressure of 0.1 MPa, and the average pore diameter of the surface of the film measured by a pore diameter analyzer is 80 nanometers.
While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A separation membrane with a high-strength guard band, characterized in that: the protective belt comprises a film layer, a protective belt and a supporting layer which are sequentially arranged from outside to inside, wherein the supporting layer is a supporting pipe woven by cation modified fibers, and the protective belt is a compact layer formed by anion copolymer.
2. The separation membrane having a high strength guard band of claim 1, wherein: the membrane layer is prepared by mixing an anionic copolymer, a high-molecular membrane material and a pore-foaming agent, wherein the anionic copolymer is prepared from the following raw materials in parts by weight: 100 parts of solvent, 5-7 parts of reaction monomer A, 3-5 parts of reaction monomer B and 0.2-0.3 part of initiator; mixing the prepared anionic copolymer with 20-25 parts of polymer membrane material and 2-5 parts of pore-foaming agent to prepare the membrane layer; the reaction monomer A is the emergency methyl acrylate or methyl acrylate, and the reaction monomer B is 2-acrylamide-2-methylpropanesulfonic acid or methacrylic acid.
3. The separation membrane having a high strength guard band of claim 1, wherein: the thickness of the film layer is 80-120 um.
4. The separation membrane having a high strength guard band of claim 1, wherein: the polymer membrane material is polyvinylidene fluoride, polyvinyl chloride or polyether sulfone.
5. The separation membrane having a high strength guard band of claim 1, wherein: the anionic copolymer is P (MMA-co-AMPS) or P (MA-co-MAA) or P (MA-co-AMPS).
6. The separation membrane having a high strength guard band of claim 1, wherein: the cation modified fiber is cation polyester filament.
7. The separation membrane having a high strength guard band of claim 1, wherein: the thickness of the protective belt is 20-30 um.
8. A method of making a separation membrane having a high strength guard band as claimed in any one of claims 1 to 7, comprising the steps of:
step 1: preparing a casting solution with anion subset groups: adding the following raw materials in parts by weight into 100 parts of solvent at 60-85 ℃: 5-7 parts of reaction monomer A, 3-5 parts of reaction monomer B and 0.2-0.3 part of initiator, and carrying out polymerization reaction for 4-8 hours under stirring to prepare an anionic copolymer; adding 20-25 parts of polymer membrane material and 2-5 parts of pore-foaming agent into the solvent, stirring for 6-12 hours at 40-80 ℃, stopping stirring after uniform dissolution, standing and defoaming to obtain a membrane casting solution with anionic groups; the reaction monomer A is the emergency methyl acrylate or methyl acrylate, and the reaction monomer B is 2-acrylamide-2-methylpropanesulfonic acid or methacrylic acid;
step 2: making a support tube with cationic groups: adopting cation modified fiber to weave a hollow supporting tube with the outer diameter of 1-2.5mm and the inner diameter of 0.5-1.5 mm;
and step 3: spraying the anion membrane casting solution on a cation supporting tube, soaking and curing the anion membrane casting solution in water to prepare a separation membrane, cutting the cured separation membrane, soaking the cut separation membrane in a protective solution for 6 to 12 hours, drying the separation membrane for 4 hours at the temperature of between 60 and 80 ℃, and forming a high-strength protective belt in the middle of the separation membrane at the interface between the anion membrane casting solution and the cation supporting tube due to the strong interaction of anions and cations.
9. The method of preparing a separation membrane having a high strength guard band as claimed in claim 8, wherein: the initiator in the step 1 is azobisisobutyronitrile or azobisisoheptonitrile or dibenzoyl peroxide, the solvent is one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, and the pore-forming agent is polyvinylpyrrolidone or polyethylene glycol or a mixture of polyvinylpyrrolidone and polyethylene glycol.
10. The method of preparing a separation membrane having a high strength guard band as claimed in claim 8, wherein: the weaving mode in the step 2 is weaving or crocheting, and the protective solution used in the step 3 is a mixed solution of glycerol, alcohol and water, and the weight parts are as follows: glycerol: alcohol: water = 20-35: 5-10:55-75.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008126199A (en) * | 2006-11-24 | 2008-06-05 | Mitsubishi Rayon Co Ltd | Hollow porous film and its manufacturing method |
| KR20100116257A (en) * | 2009-04-22 | 2010-11-01 | 코오롱인더스트리 주식회사 | Method for manufacturing hollw fiber membrane |
| WO2011046514A2 (en) * | 2009-10-14 | 2011-04-21 | National University Of Singapore | Hollow fiber membrane |
| CN104117289A (en) * | 2014-07-29 | 2014-10-29 | 枫科(北京)膜技术有限公司 | Reinforced composite supported hollow fiber membrane and preparation method thereof |
| CN105080353A (en) * | 2014-04-25 | 2015-11-25 | 中国石油化工股份有限公司 | Method for preparing hydrophilic charged composite ultrafiltration membrane |
| CN108568221A (en) * | 2017-03-08 | 2018-09-25 | 海南立昇净水科技实业有限公司 | A kind of bear electricity type chlorine-containing polymer group compound film and preparation method thereof based on the enhancing of interlayer covalent effect |
| CN108579474A (en) * | 2017-03-08 | 2018-09-28 | 海南立昇净水科技实业有限公司 | A kind of bear electricity type fluoropolymer group compound film and preparation method thereof based on the enhancing of interlayer covalent effect |
-
2018
- 2018-11-06 CN CN201811313799.4A patent/CN111135726A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008126199A (en) * | 2006-11-24 | 2008-06-05 | Mitsubishi Rayon Co Ltd | Hollow porous film and its manufacturing method |
| KR20100116257A (en) * | 2009-04-22 | 2010-11-01 | 코오롱인더스트리 주식회사 | Method for manufacturing hollw fiber membrane |
| WO2011046514A2 (en) * | 2009-10-14 | 2011-04-21 | National University Of Singapore | Hollow fiber membrane |
| CN105080353A (en) * | 2014-04-25 | 2015-11-25 | 中国石油化工股份有限公司 | Method for preparing hydrophilic charged composite ultrafiltration membrane |
| CN104117289A (en) * | 2014-07-29 | 2014-10-29 | 枫科(北京)膜技术有限公司 | Reinforced composite supported hollow fiber membrane and preparation method thereof |
| CN108568221A (en) * | 2017-03-08 | 2018-09-25 | 海南立昇净水科技实业有限公司 | A kind of bear electricity type chlorine-containing polymer group compound film and preparation method thereof based on the enhancing of interlayer covalent effect |
| CN108579474A (en) * | 2017-03-08 | 2018-09-28 | 海南立昇净水科技实业有限公司 | A kind of bear electricity type fluoropolymer group compound film and preparation method thereof based on the enhancing of interlayer covalent effect |
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