CN116059852B - Method for facilitating interfacial polymerization of hollow fiber organic filter membrane into polyamide membrane - Google Patents
Method for facilitating interfacial polymerization of hollow fiber organic filter membrane into polyamide membrane Download PDFInfo
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- CN116059852B CN116059852B CN202310148234.XA CN202310148234A CN116059852B CN 116059852 B CN116059852 B CN 116059852B CN 202310148234 A CN202310148234 A CN 202310148234A CN 116059852 B CN116059852 B CN 116059852B
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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
- B01D71/56—Polyamides, e.g. polyester-amides
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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
- 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
- B01D61/147—Microfiltration
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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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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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
- B01D69/02—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
- 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
- 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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- 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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- 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 provides a method for facilitating interfacial polymerization of hollow fiber organic filter membrane into polyamide membrane, which is characterized in that hydrophilic nano modified particles are doped in liquid paraffin, paraffin phase conversion and characteristics of the hollow fiber organic filter membrane are utilized to plug holes in a paraffin manner, so that the hydrophilicity of a support membrane in the process of coating polyamine is improved, the hydrophilicity of the membrane can be adjusted at any time through the amount of nano modified particles in the liquid paraffin with holes, and the subsequent paraffin removal can ensure that the support membrane has no hydrophilic improvement in multiple applications, thereby reducing the production cost of membrane production enterprises and having remarkable application potential.
Description
Technical Field
The invention relates to a preparation method of a membrane material, in particular to a method for facilitating interfacial polymerization of a hollow fiber organic filter membrane into a polyamide membrane.
Background
Polyamide membranes are relatively common TFC membranes which have wide applications in nanofiltration, reverse osmosis, forward osmosis, etc. As the separation of nanometer level, the polyamide nanometer membrane in the prior art is formed by interfacial polymerization on a porous organic filter membrane, namely, firstly, a layer of polyamine layer is coated on the porous organic filter membrane, and then the polyamide nanometer membrane is placed in a polybasic acyl chloride phase to enable the polyamine and the polybasic acyl chloride to form a membrane at the interface. For this reason, physicochemical parameters of the porous organic filter membrane, such as hydrophilicity, pore size of the organic filter membrane, etc., have a critical effect on the performance of the polyamide membrane formed by interfacial polymerization.
For the hydrophilic property, the organic filter membrane with good hydrophilic property is favorable for spreading the aqueous phase monomer on the organic filter membrane, so that the organic filter membrane is hydrophilic in the prior art, for example, hydrophilic particles such as molecular sieve, graphene, silicon dioxide and the like are blended or grafted into a porous supporting layer, but the modification method of the organic filter membrane is a permanent modification. However, for nanofiltration, reverse osmosis membrane applications, the porous support layer is typically placed on the near-feed side and the separation layer is placed on the far-feed side. Therefore, if the hydrophilicity of the support layer side is greater than that of the support layer, it becomes a mass transfer barrier of moisture through the membrane layer, thereby reducing the water flux. Thus, a stronger hydrophilic modification of the separation is often required, leading to cost pressurization and excessive membrane modification.
Moreover, for industrial production of the nano-scale separation membrane, the support material is often purchased and commercialized ultrafiltration or microfiltration membrane products are used as the organic filter membrane, so that hydrophilic modification of the organic filter membrane often needs to be improved from the source, the nano-scale separation membrane production enterprises are required to produce the organic filter membrane by themselves or cooperate with the organic filter membrane production enterprises to produce customized organic filter membrane products, and the cost is necessarily increased.
Disclosure of Invention
Therefore, the invention takes the existing hollow fiber microfiltration membrane as the organic filter membrane, and improves the interfacial polymerization method of the organic filter membrane, so that the organic filter membrane has temporary hydrophilicity during coating, thereby avoiding the problems of obviously increasing the preparation cost of a separation layer and the like.
The invention provides a method for facilitating interfacial polymerization of a hollow fiber organic filter membrane into a polyamide membrane, which is characterized by comprising the following steps:
1) Doping hydrophilic modified particles into molten liquid paraffin to form a pore blocking liquid, wherein the concentration of the hydrophilic modified particles is 5-20wr%;
2) Taking a hollow fiber organic filter membrane with one end sealed as a supporting membrane, sealing the outer surface of the organic filter membrane, continuously injecting hole plugging liquid into the organic filter membrane through the other end to enable liquid paraffin to be filled in the membrane holes of the organic filter membrane, and solidifying at room temperature;
3) Removing the outer surface seal of the organic filter membrane treated in the step 2), immersing the organic filter membrane in aqueous solution containing polyamine for 30-500s, and removing redundant solution on the surface of the organic filter membrane after taking out;
4) Dipping the organic filter membrane in a constant-temperature polybasic acyl chloride oil phase solution for 10-120s to enable the polybasic amine and the polybasic acyl chloride to be subjected to interfacial polymerization to form an amide group;
5) The amide group-forming organic filter membrane is immersed in a nonpolar solvent at 80-100 ℃ for 10-200min to remove liquid paraffin to form a hollow fiber polyamide membrane.
Preferably, the hollow fiber organic filter membrane is an ultrafiltration membrane or a microfiltration membrane, the pore size of which is preferably 2-10 μm.
Preferably, the paraffin is one of No. 70 paraffin and No. 80 paraffin.
Preferably, the hollow fiber organic filter membrane material is selected from one of polyacrylonitrile, polyvinylidene fluoride, polytetrafluoroethylene, polysulfone and polyethersulfone.
Preferably, the polyamine is one of piperazine, ethylenediamine, m-phenylenediamine, p-phenylenediamine, hexamethylenediamine, o-phenylenediamine, triethylamine and diaminotoluene, and the concentration is 0.2-5wt%.
Preferably, the polybasic acyl chloride is one of isophthaloyl dichloride, phthaloyl dichloride and terephthaloyl dichloride, and the concentration is 1-3wt%.
Preferably, the solvent in the multi-component acyl chloride oil phase solution is a polar solvent, and is specifically selected from one of acetone, toluene, N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, the nonpolar solvent is one of chloroform, carbon tetrachloride, naphtha, gasoline, n-hexane and n-heptane.
Preferably, the hydrophilic modified particles are one or more of molecular sieves, silicon dioxide and graphene oxide.
Compared with the prior art, the hydrophilic nano modified particles are doped in the liquid paraffin, the characteristics of paraffin phase inversion and hollow fiber organic filter membranes are utilized to improve the hydrophilicity of the support membrane in the process of coating the polyamine in a paraffin blocking mode, the membrane hydrophilicity can be adjusted at any time through the amount of the nano modified particles in the liquid paraffin with holes, and the subsequent paraffin removal can ensure that the support membrane does not have hydrophilic improvement in application for a plurality of times, so that the production cost of membrane production enterprises is reduced, and the method has remarkable application potential.
Description of the embodiments
The technical scheme of the invention is further described through specific embodiments.
In the present invention, unless otherwise specified, the materials and equipment used are commercially available or are commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Examples
The hollow fiber polyamide membrane prepared in this example was prepared as follows:
1) Doping NaA molecular sieve as hydrophilic modified particles into molten liquid paraffin (70 # paraffin) to form a pore plugging liquid, wherein the concentration of the hydrophilic modified particles is 10 wt%;
2) Taking a hollow fiber organic microfiltration membrane (with the aperture of about 7 mu m) with one end sealed as a support membrane, tightly winding an adhesive tape on the outer surface of the support membrane to seal the support membrane, injecting a hole plugging liquid into the support membrane from the other end through an injector to enable liquid paraffin to fill the membrane holes of the support membrane, and solidifying the support membrane at room temperature;
3) Removing the outer surface seal of the support film treated in the step 1), immersing the support film in an aqueous phase solution (the concentration is 0.5 wt%) containing m-phenylenediamine for 50s, and removing redundant solution on the surface of the support film after taking out;
4) Immersing the support film in isophthaloyl dichloride oil phase solution (the solvent is acetone, the concentration is 1 wt%) at a constant temperature for 20s to form amide groups through interfacial polymerization;
5) The polymer film was treated in a chloroform solution of 80 ℃ for 20min to remove paraffin to form a hollow fiber polyamide film.
The polyamide membrane was tested for separation performance and pure water flux performance of a 0.2% sodium sulfate solution at an operating pressure of 0.5MPa and a temperature of 25 ℃ for 1 hour, with a rejection of 94.5% and a pure water flux of 58.8L/(m 2. H).
Comparative example 1
The preparation method of the polyamide membrane of the comparative example is as follows:
taking a hollow fiber organic micro-filtration membrane (with the aperture of about 7 μm) with one end sealed as an organic filtration membrane;
dipping the organic filter membrane in the step 1) in an aqueous phase solution (the concentration is 0.5 wt%) containing m-phenylenediamine for 50s, taking out, and removing redundant solution on the surface of the organic filter membrane;
the organic filter membrane was again immersed in an isophthaloyl chloride oil phase solution (solvent is acetone, concentration is 1 wt%) at a constant temperature for 20s to form an amide group by interfacial polymerization to form a hollow fiber polyamide membrane.
The membrane was tested for separation performance and pure water flux performance of a 0.2% sodium sulfate solution at an operating pressure of 0.5MPa and a temperature of 25 ℃ for 1 hour, with a rejection of 34.8% and a pure water flux of 208.1L/(m 2. H).
Comparative example 2
The polyamide film of this comparative example was prepared as follows:
taking a hollow fiber organic micro-filtration membrane (with a pore diameter of about 7 mu m) with one end sealed as an organic filtration membrane, tightly winding an outer surface of the organic filtration membrane with an adhesive tape to seal, injecting molten liquid paraffin (with the mark of No. 70 paraffin) into the organic filtration membrane from the other end through a syringe to enable the liquid paraffin to fill the membrane pores of the organic filtration membrane, and solidifying at room temperature;
removing the outer surface seal of the organic filter membrane treated in the step 1), immersing the organic filter membrane in an aqueous phase solution (the concentration is 0.5 wt%) containing m-phenylenediamine for 50s, and removing redundant solution on the surface of the organic filter membrane after taking out;
dipping the organic filter membrane in isophthaloyl dichloride oil phase solution (solvent is normal hexane, the concentration is 1 wt%) at constant temperature for 20s to form amide groups through interfacial polymerization;
the polymer membrane was treated in chloroform solution at 80 ℃ for 20min to remove paraffin to form a high flux hollow fiber polyamide membrane.
The membrane is tested for separation performance and pure water flux performance of a sodium sulfate solution with the concentration of 0.2 percent after the membrane is operated for 1 hour under the conditions of the operating pressure of 0.5MPa and the temperature of 25 ℃, the rejection rate is 68.9 percent, and the pure water flux is 93.6L/(m 2. H).
Comparative example 3
The polyamide film of this comparative example was prepared as follows:
1) Taking a hollow fiber organic microfiltration membrane (with a pore diameter of about 7 mu m) with one end sealed as a support membrane, tightly winding an adhesive tape on the outer surface of the support membrane to seal, injecting molten liquid paraffin (70 # paraffin) into the support membrane from the other end through a syringe to fill the membrane pores of the support membrane with the liquid paraffin, and solidifying at room temperature;
2) Removing the outer surface seal of the support film treated in the step 1), immersing the support film in an aqueous phase solution (the concentration is 0.5 wt%) containing m-phenylenediamine for 50s, and removing redundant solution on the surface of the support film after taking out;
3) Immersing the support film in isophthaloyl dichloride oil phase solution (the solvent is acetone, the concentration is 1 wt%) at a constant temperature for 20s to form amide groups through interfacial polymerization;
4) The polymer film was treated in a chloroform solution of 80 ℃ for 20min to remove paraffin to form a hollow fiber polyamide film.
The membrane was tested for separation performance and pure water flux performance of a 0.2% sodium sulfate solution at an operating pressure of 0.5MPa and a temperature of 25 ℃ for 1 hour, with a rejection of 85.5% and a pure water flux of 78.6L/(m 2. H).
The present invention is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalent changes and variations in the above-mentioned embodiments can be made by those skilled in the art without departing from the scope of the present invention.
Claims (9)
1. A method for facilitating interfacial polymerization of hollow fiber organic filter membranes into polyamide membranes, characterized in that the method comprises the steps of:
(1) Doping hydrophilic modified particles into molten liquid paraffin to form a pore blocking liquid, wherein the concentration of the hydrophilic modified particles in the pore blocking liquid is 5-20wt%;
(2) Taking a hollow fiber organic filter membrane with one end sealed as a supporting membrane, sealing the outer surface of the organic filter membrane, continuously injecting hole plugging liquid into the organic filter membrane through the other end to enable liquid paraffin to be filled in the membrane holes of the organic filter membrane, and solidifying at room temperature;
(3) Removing the outer surface seal of the organic filter membrane treated in the step 2), immersing the organic filter membrane in aqueous solution containing polyamine for 30-500s, and removing redundant solution on the surface of the organic filter membrane after taking out;
(4) Dipping the organic filter membrane in a constant-temperature polybasic acyl chloride oil phase solution for 10-120s to enable the polybasic amine and the polybasic acyl chloride to be subjected to interfacial polymerization to form an amide group;
(5) The amide group-forming organic filter membrane is immersed in a nonpolar solvent at 80-100 ℃ for 10-200min to remove liquid paraffin to form a hollow fiber polyamide membrane.
2. The method for facilitating interfacial polymerization of hollow fiber organic filter membranes to polyamide membranes according to claim 1, wherein the hollow fiber organic filter membranes are microfiltration membranes having pore diameters of 2-10 μm.
3. The method for facilitating interfacial polymerization of hollow fiber organic filter membranes to polyamide membranes according to claim 1, wherein said paraffin is one of No. 70 paraffin and No. 80 paraffin.
4. The method for facilitating interfacial polymerization of hollow fiber organic filter membrane into polyamide membrane according to claim 1, wherein the hollow fiber organic filter membrane is made of one selected from polyacrylonitrile, polyvinylidene fluoride, polytetrafluoroethylene, polysulfone and polyethersulfone.
5. The method for facilitating interfacial polymerization of hollow fiber organic filter membrane into polyamide membrane according to claim 1, wherein the polyamine is one of piperazine, ethylenediamine, m-phenylenediamine, p-phenylenediamine, hexamethylenediamine, o-phenylenediamine, triethylamine and diaminotoluene, and the concentration is 0.2-5wt%.
6. The method for facilitating interfacial polymerization of hollow fiber organic filter membranes to polyamide membranes according to claim 1, wherein the polyacyl chloride is one of isophthaloyl dichloride, phthaloyl dichloride and terephthaloyl dichloride, and the concentration is 1-3wt%.
7. The method for facilitating interfacial polymerization of hollow fiber organic filter membranes to polyamide membranes according to claim 1, wherein the solvent in the polyacyl chloride oil phase solution is a polar solvent, and specifically selected from one of acetone, toluene, N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide.
8. The method for facilitating interfacial polymerization of hollow fiber organic filter membranes to polyamide membranes according to claim 1, wherein said nonpolar solvent is one of chloroform, carbon tetrachloride, naphtha, gasoline, n-hexane, and n-heptane.
9. The method for facilitating interfacial polymerization of hollow fiber organic filter membranes to polyamide membranes according to claim 1, wherein the hydrophilic modified particles are one or more of molecular sieves, silica, and graphene oxide.
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