CN113289499B - Internal pressure type hollow fiber ultrafiltration membrane and preparation method and application thereof - Google Patents
Internal pressure type hollow fiber ultrafiltration membrane and preparation method and application thereof Download PDFInfo
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- CN113289499B CN113289499B CN202110653069.4A CN202110653069A CN113289499B CN 113289499 B CN113289499 B CN 113289499B CN 202110653069 A CN202110653069 A CN 202110653069A CN 113289499 B CN113289499 B CN 113289499B
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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
- B01D69/08—Hollow fibre membranes
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- 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
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- 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
- B01D67/0016—Coagulation
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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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses an internal pressure hollow fiber ultrafiltration membrane, a preparation method and application thereof. According to the invention, a mixed system of polyether sulfone and sulfonated polyether sulfone is used as a film-forming polymer, and the introduction of sulfonic acid groups improves the hydrophilicity and the anti-pollution capability of the hollow fiber ultrafiltration membrane; the carboxylic ester with hydroxyl is used as an additive, so that the hydrophilicity of the polyether sulfone hollow fiber ultrafiltration membrane is adjusted, and the pore structure can be adjusted; the phenolic hydroxyl structure in the additive can also improve the antibacterial property of the hollow fiber ultrafiltration membrane, and the step of antibacterial treatment of the membrane filaments is omitted. The internal pressure type hollow fiber ultrafiltration membrane has excellent acid and alkali resistance, adjustable pore diameter and simple preparation process, and can realize industrial production.
Description
Technical Field
The invention relates to the field of hollow fiber membranes, in particular to an internal pressure type hollow fiber ultrafiltration membrane and a preparation method and application thereof.
Background
With the development of membrane technology, the membrane process gradually replaces the traditional process and becomes the main water production method in the water treatment industry at present. The ultrafiltration belongs to a porous membrane, realizes the required mechanical separation by screening, can remove turbidity, pathogenic microorganisms and macromolecular organic matters in water, and also has the advantages of low operating pressure, small occupied area, flexible construction mode and the like. Hollow fiber ultrafiltration membranes can be classified into internal pressure type and external pressure type depending on whether the separation layer of the membrane is on the inner surface or the outer surface of the hollow fiber. The internal and external pressure type hollow fiber ultrafiltration membranes have certain differences in filtration mode, membrane material, installation mode and the like. The external pressure type ultrafiltration membrane element is characterized in that the space outside the membrane filaments is large, the membrane surface area is large, and the water flux is large, so that the membrane element has large pollutant carrying capacity, is resistant to blockage during operation, has low requirement on the water quality of raw water, has wide applicable water quality range, and is applicable to sewage treatment or a system with large fluctuation of the water quality of the raw water; the internal pressure type ultrafiltration membrane element is characterized in that the internal pore channel of the membrane wire is small, the membrane surface area and the water flux are small, the requirement on the content of the inflow suspended matters is strict, and the internal pressure type ultrafiltration membrane element is suitable for a water treatment system with good raw water quality.
Currently, hollow fiber ultrafiltration membranes available on the market are mainly made of Polyethersulfone (PES) in the internal pressure type and polyvinylidene fluoride (PVDF) in the external pressure type. Most of the manufacturers engaged in the production of the ultrafiltration membrane in China add a hydrophilic pore-forming agent into a membrane casting solution and carry out membrane formation by a non-solvent induced phase separation method, and the prepared ultrafiltration membrane is widely applied to water treatment.
Disclosure of Invention
The invention aims to provide an internal pressure type hollow fiber ultrafiltration membrane which has the advantages of high porosity, large water flux and controllable and adjustable pore diameter.
The internal pressure hollow fiber ultrafiltration membrane is prepared by spinning, washing, post-treating and airing a membrane casting solution consisting of polyether sulfone, sulfonated polyether sulfone, an additive and a solvent.
The invention also aims to provide a preparation method of the internal pressure type hollow fiber ultrafiltration membrane.
The preparation method of the internal pressure type hollow fiber ultrafiltration membrane comprises the following steps:
1) Mixing, stirring, dissolving, filtering and defoaming the polyether sulfone casting solution which comprises the following components in a mass ratio of 10-30;
2) Extruding the core liquid and the polyether sulfone casting film liquid prepared in the step 1) through a spinneret plate to form a hollow liquid film, allowing the liquid film to pass through a water vapor air gap, and then allowing the liquid film to enter an external coagulation bath solution for curing and forming to prepare a polyether sulfone hollow fiber film;
3) Washing, post-treating and airing the polyether sulfone hollow fiber membrane prepared in the step 2) to prepare the internal pressure type hollow fiber ultrafiltration membrane.
According to the invention, the additive in the step 1) is one of 1,2,3,4,6-O-galloylglucose, theaflavin-3' -gallate, octyl gallate, lauryl gallate or p-hydroxybenzoate.
According to the invention, the solvent in the step 1) is one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone or triethyl phosphate.
According to the invention, the core liquid in the step 2) is a mixed solution consisting of 3-20 mass percent.
Further, the polyethylene glycol has an average molecular weight of one of 400, 600, 1000 or 2000.
According to the invention, the conditions of the air gap in step 2) are: the length is 5-20 cm, and the temperature is room temperature.
According to the invention, the external coagulation bath liquid in the step 2) is a mixed solution consisting of 5-20 mass percent of additive, 30-85 mass percent of solvent and water.
According to the invention, the post-treatment method in the step 3) is to soak the polyether sulfone hollow fiber membrane in 10-40% formaldehyde aqueous solution for 5-12 h.
According to the invention, the air drying in the step 3) is to vertically hang the polyether sulfone hollow fiber membrane wires, and the two ends of the polyether sulfone hollow fiber membrane wires are respectively clamped on air drying rods.
The invention further aims to provide application of the internal pressure type hollow fiber ultrafiltration membrane in the fields of reverse osmosis pretreatment, feed liquid concentration, filtration purification, purification and the like.
Compared with the prior art, the invention has the following advantages:
1) According to the invention, a mixed system of polyether sulfone and sulfonated polyether sulfone is used as a film-forming polymer, and the introduction of sulfonic acid groups improves the hydrophilicity and the anti-pollution capability of the hollow fiber ultrafiltration membrane;
2) According to the invention, carboxylic ester with hydroxyl is used as an additive, so that the hydrophilicity of the polyether sulfone hollow fiber ultrafiltration membrane is adjusted, and the pore structure can be adjusted; the phenolic hydroxyl structure in the additive can also improve the antibacterial property of the hollow fiber ultrafiltration membrane, and the step of antibacterial treatment of membrane filaments is omitted;
3) The invention uses a phase separation method combining water vapor and a non-solvent, which is beneficial to forming a membrane pore structure with compact inner surface, large middle layer macroporous support and larger outer surface pore diameter;
4) The core liquid used in the invention is a mixed solution of ethanol, polyethylene glycol, an additive, a solvent and water, and has high phase separation speed, compact inner surface pore structure and smaller pore diameter and porosity due to the existence of ethanol; compared with core liquid, when the mixed solution of the additive, the solvent and water is used as the external coagulation bath liquid, the gel capacity is weak, the phase separation is slow, and the surface pore diameter and the porosity are large; therefore, the hollow fiber membrane prepared by the invention has compact inner surface and large outer surface aperture, and can be used as an internal pressure type membrane;
5) In the process of drying the membrane filaments, certain acting force is applied to the membrane filaments, so that the prepared internal pressure type hollow fiber ultrafiltration membrane is neat and straight;
6) The internal pressure type hollow fiber ultrafiltration membrane has excellent acid and alkali resistance, adjustable pore diameter and simple preparation process, and can realize industrial production.
The specific implementation mode is as follows:
the present invention will be further described with reference to the following examples.
Example 1
1) Mixing 30g of polyether sulfone, 5g of sulfonated polyether sulfone, 10g of p-hydroxybenzoate and 55g of triethyl phosphate at 90 ℃, stirring, dissolving, filtering and defoaming to prepare a polyether sulfone casting solution;
2) Simultaneously extruding a core solution (ethanol, polyethylene glycol 400, p-hydroxybenzoate, triethyl phosphate and water at a mass ratio of 3;
3) And (3) washing the polyether sulfone hollow fiber membrane prepared in the step 2), soaking the membrane in 10% formaldehyde water solution for 12 hours, and airing (membrane wires are vertically hung, and two ends of the membrane wires are respectively clamped on airing rods) to prepare the internal pressure type hollow fiber ultrafiltration membrane. The ultrafiltration membrane has an inner diameter of 0.8mm, an outer diameter of 1.4mm, an alcohol bubble point of 0.68MPa, an r-globulin retention rate of 98.4%, and a water flux of 521.8L/m 2 H, tensile strength at break 3.8N.
Example 2
1) Mixing 18g of polyether sulfone, 8g of sulfonated polyether sulfone, 8g of octyl gallate and 66g of N, N-dimethylacetamide at 70 ℃, stirring, dissolving, filtering and defoaming to prepare a polyether sulfone casting solution;
2) Simultaneously extruding a core solution (ethanol, polyethylene glycol 1000, octyl gallate, N-dimethylacetamide and water in a mass ratio of 10;
3) And (3) washing the polyether sulfone hollow fiber membrane prepared in the step 2), soaking the membrane in 40% formaldehyde water solution for 5 hours, and airing (membrane wires are vertically hung, and two ends of the membrane wires are respectively clamped on airing rods) to prepare the internal pressure type hollow fiber ultrafiltration membrane. The ultrafiltration membrane has an inner diameter of 0.9mm, an outer diameter of 1.5mm, an alcohol bubble point of 0.64MPa, a gamma-globulin retention rate of 96.5%, and a water flux of 587.2L/m 2 H, tensile strength at break 3.4N.
Example 3
1) Mixing 24g of polyether sulfone, 5g of sulfonated polyether sulfone, 2g of lauryl gallate and 69gN, and carrying out stirring, dissolving, filtering and defoaming on N-dimethylformamide at the temperature of 80 ℃ to prepare a polyether sulfone casting solution;
2) Simultaneously extruding a core solution (ethanol, polyethylene glycol 2000, lauryl gallate, N-dimethylformamide and water at a mass ratio of 20;
3) And (3) washing the polyether sulfone hollow fiber membrane prepared in the step 2), soaking the membrane in a 30% formaldehyde aqueous solution for 8 hours, and airing (membrane wires are vertically hung, and two ends of the membrane wires are respectively clamped on airing rods) to prepare the internal pressure type hollow fiber ultrafiltration membrane. The ultrafiltration membrane has an inner diameter of 0.9mm, an outer diameter of 1.5mm, an alcohol bubble point of 0.65MPa, an r-globulin retention rate of 97.8%, and a water flux of 559.7L/m 2 H, tensile strength at break 3.6N.
Example 4
1) Mixing 10g of polyethersulfone, 10g of sulfonated polyethersulfone, 5g of theaflavin-3' -gallate and 75g of N-methyl pyrrolidone at 60 ℃, stirring, dissolving, filtering and defoaming to prepare a polyethersulfone membrane casting solution;
2) Simultaneously extruding a core solution (ethanol, polyethylene glycol 600, N-methyl pyrrolidone and water at a mass ratio of 15;
3) And (3) washing the polyether sulfone hollow fiber membrane prepared in the step 2), soaking the membrane in 20% formaldehyde water solution for 7 hours, and airing (membrane wires are vertically hung, and two ends of the membrane wires are respectively clamped on airing rods) to prepare the internal pressure type hollow fiber ultrafiltration membrane. The ultrafiltration membrane has an inner diameter of 0.8mm, an outer diameter of 1.4mm, an alcohol bubble point of 0.62MPa, an r-globulin retention rate of 95.2%, and a water flux of 630.4L/m 2 H, tensile strength at break 3.1N.
Claims (6)
1. The preparation method of the internal pressure type hollow fiber ultrafiltration membrane is characterized by comprising the following steps:
1) Mixing, stirring, dissolving, filtering and defoaming the polyether sulfone casting solution with the mass ratio of 10-30;
the additive is one of 1,2,3,4,6-O-galloylglucose, theaflavin-3' -gallate, octyl gallate, lauryl gallate or p-hydroxybenzoate;
2) Extruding the core liquid and the polyether sulfone casting film liquid prepared in the step 1) through a spinneret plate to form a hollow liquid film, allowing the liquid film to pass through a water vapor air gap, and then allowing the liquid film to enter an external coagulation bath liquid for curing and forming to prepare a polyether sulfone hollow fiber film;
the core liquid is a mixed solution consisting of 3-20 mass percent of ethanol, 10-86 mass percent of polyethylene glycol, additive, solvent and water;
the external coagulation bath liquid is a mixed solution consisting of additives, solvents and water with the mass percentage of 5-20;
3) Washing, post-treating and airing the polyether sulfone hollow fiber membrane prepared in the step 2) to prepare the internal pressure type hollow fiber ultrafiltration membrane.
2. The method according to claim 1, wherein the solvent in the step 1) is one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, or triethylphosphate.
3. The method of claim 1, wherein the air gap in step 2) is provided by: the length is 5-20 cm, and the temperature is room temperature.
4. The preparation method according to claim 1, characterized in that the post-treatment method in the step 3) is to soak the polyethersulfone hollow fiber membrane in 10-40% formaldehyde aqueous solution for 5-12 h.
5. The preparation method according to claim 1, wherein the air drying in the step 3) is to vertically hang the polyethersulfone hollow fiber membrane wires, and the two ends of the polyethersulfone hollow fiber membrane wires are respectively clamped on an air drying rod.
6. An internal pressure type hollow fiber ultrafiltration membrane produced by the production method according to any one of claims 1 to 5.
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