CN110314559B - Preparation method of interfacial polymerization composite membrane - Google Patents
Preparation method of interfacial polymerization composite membrane Download PDFInfo
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- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention provides a preparation method of an interfacial polymerization composite membrane, which comprises the steps of firstly dissolving water-soluble monomers in a polymer solution (or a membrane casting solution), scraping the membrane casting solution onto non-woven fabrics by using a membrane scraping machine, then immersing the non-woven fabrics into a coagulating bath for carrying out a phase inversion process, and controlling the concentration of the monomers in a polymerization membrane by controlling the phase inversion time to form a polymer base membrane containing the water-soluble monomers. And taking out the polymer film, removing residual liquid on the surface of the film by using filter paper, pouring the oil phase solution onto the surface of the polymer film, and drying after reaction. The invention can simplify the process flow of the existing polyamide or polyester amide composite membrane preparation to a great extent, and the obtained composite membrane has high flux and high selectivity, and compared with the traditional preparation method, the performance is obviously improved. In addition, the method is suitable for conventional polymers, the using amount of the water-soluble monomer is reduced to a great extent, and the method has the advantages of simple process, easy preparation, low raw material price and good industrial practicability of preparation.
Description
Technical Field
The invention relates to the field of preparation of separation membranes, in particular to a preparation method of an interfacial polymerization composite membrane.
Background
Nanofiltration membranes and reverse osmosis membranes are common composite films, and currently commercialized nanofiltration membranes and reverse osmosis membranes are mainly prepared by an interfacial polymerization method. Such composite membranes are generally composed of a nonwoven fabric, a porous base membrane, and an ultra-thin polyamide or polyesteramide separation layer formed by interfacial polymerization.
Interfacial polymerization refers to a rapid, irreversible polymerization of water phase monomers and oil phase monomers at the water-oil interface. The porous support base membrane generally belongs to an ultrafiltration membrane and plays a role in supporting the composite membrane in the interfacial polymerization process. In addition, ultrafiltration membranes are mostly made of low-cost polymer materials such as polyimide, polysulfone, polyethersulfone, polyacrylonitrile and the like. In the current composite film preparation process, a polymer ultrafiltration base film supported by non-woven fabric is prepared by a phase inversion method, and then the composite polyamide film is prepared on the surface of the base film by an interfacial polymerization method. For the preparation of ultrafiltration membrane bases, polymers are generally dissolved in polar solvents to form uniform membrane casting solutions, then the membrane casting solutions are scraped onto non-woven fabrics by a scraper with a certain thickness, and finally the non-woven fabrics are immersed in a water bath to obtain ultrafiltration membrane bases with a certain aperture. Since the physicochemical properties of the surface of the ultrafiltration membrane, such as pore diameter, roughness, porosity and hydrophilicity, have a great influence on interfacial polymerization, many researches on the preparation process of the membrane have been made, and meanwhile, the influence of the membrane properties on interfacial polymerization is also researched.
In addition, interfacial polymerization belongs to a reaction-diffusion process, and the main factors influencing the interfacial polymerization process are the diffusion rate of aqueous phase monomers, the pH of the aqueous phase, the monomer concentration and the like, but these factors have been widely studied and mature interfacial polymerization process systems exist. Although there are many modification methods such as preparing high-performance polyamide or polyester amide composite films by adding nanoparticles, interposing an intermediate layer, and controlling the diffusion rate of monomers, these steps are complicated, high in cost, and difficult to scale up.
Although primarily produced by interfacial polymerization, the support provided by the base film is essential for commercial polyamide composite films. Therefore, the whole process is completed by preparing the polymer-based membrane and then sequentially soaking the water phase and the oil phase, and the steps are time-consuming and complicated. The interfacial polymerization composite membrane obtained by the method generally has a very thick selective layer, and is difficult to reach the level of a high-performance separation membrane. In addition, the conventional impregnation method requires a large amount of aqueous monomer to prepare the aqueous solution, and thus is costly. The current commercial interfacial polymerization composite membrane continuously simplifies the preparation process flow based on the prior process, reduces the cost, and has great challenges for improving the separation performance of the composite membrane.
Disclosure of Invention
The invention provides a preparation method of an interfacial polymerization composite membrane, which simplifies the preparation process flow of the existing polyamide or polyester amide composite separation membrane and further improves the performance of the interfacial polymerization separation membrane. Specifically, a water-phase monomer is dissolved in a membrane casting solution required by membrane scraping, the concentration of the monomer in a polymer membrane is regulated and controlled by controlling the phase inversion time, and then an oil phase (containing the oil-phase monomer) is added to complete the interfacial polymerization reaction. The preparation process can not only save the complicated steps of preparing the ultrafiltration basal membrane in advance, but also save the preparation of the aqueous phase solution in advance, thereby greatly simplifying the preparation process. In addition, in the phase inversion process, part of the aqueous phase monomer can diffuse away from the membrane main body along with the solvent, so that the concentration of the aqueous monomer in the polymer membrane can be effectively reserved and regulated by controlling the diffusion time, and the high-performance polyamide or polyester amide composite membrane is prepared. In addition, the method can greatly reduce the using amount of the aqueous phase monomer, thereby reducing the production cost. The method is improved on the basis of the original process, so that the preparation and the expanded production are easy, the raw materials are low in price, and the method has a good application prospect.
The technical scheme for realizing the invention is as follows:
a preparation method of an interfacial polymerization composite membrane comprises the following steps:
(1) dissolving a water-soluble monomer in a polymer solution to prepare a membrane casting solution, coating the membrane casting solution on a non-woven fabric by using a membrane scraping machine, then immersing the non-woven fabric in a coagulating bath for a phase conversion process, and controlling the concentration of the monomer in a polymer membrane by controlling the phase conversion time to form a polymer base membrane containing the water-soluble monomer;
(2) and (2) taking out the polymer base membrane obtained in the step (1), removing residual liquid on the surface of the polymer base membrane by using filter paper, then pouring the oil phase solution onto the surface of the polymer membrane, taking out after reaction, and drying to obtain the composite membrane.
The water-soluble monomer in the step (1) is at least one of piperazine, alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, m-phenylenediamine, p-phenylenediamine, hyperbranched polyethyleneimine, tannic acid, diaminotoluene, ethylenediamine, propylenediamine, xylylenediamine, 1, 3-diaminocyclohexane or 1, 4-diaminocyclohexane, and the concentration of the water-soluble monomer relative to the total amount of the casting solution is 0.4-4.0 wt%.
In the step (1), the polymer is polyether sulfone, polysulfone, polyacrylonitrile, polyimide, polyvinylidene fluoride, polyarylene sulfide, poly (p-phenylene terephthalamide), chitosan or polyvinyl alcohol, and the polymer is dissolved in dimethyl sulfoxide, dimethylacetamide, dimethylformamide or N-methylpyrrolidone to obtain a polymer solution.
Preferably, the method for preparing the composite membrane by using the polyether sulfone or the polysulfone as the base membrane material comprises the following steps: dissolving a certain amount of water-soluble monomer in 10-25 wt% of polyether sulfone casting solution, scraping the casting solution onto a supporting layer (any porous material capable of increasing strength can be used as the supporting layer, such as non-woven fabric and the like) by using a film scraping machine, then immersing the supporting layer coated with the casting solution into a coagulating bath, and carrying out phase transformation for a certain time to obtain the polyether sulfone film containing a certain amount of monomer.
The coagulating bath in the step (1) is water or a mixed solution of water and any one of an alkali regulator, acetaldehyde, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, dimethylacetamide, phenol, cyclohexanone, phenol or tetrachloroethane; the alkali regulator is at least one of sodium hydroxide, triethylamine, potassium oxide, ammonia water, sodium carbonate and sodium bicarbonate.
The phase conversion process time in the step (1) is 2-30 min.
The oil phase solution in the step (2) is obtained by dissolving a polybasic acyl chloride monomer in an oily solvent, wherein the polybasic acyl chloride monomer is at least one of trimesoyl chloride, terephthaloyl chloride, isophthaloyl chloride, biphenyldicarbonyl chloride, benzenetrisulfonyl chloride, tricarbonyl chloride, butanetriacyl chloride, pentanedioyl chloride, glutaroyl chloride, adipoyl chloride, maleoyl chloride, cyclopropanetriacyl chloride, cyclobutanetriacyl chloride, cyclobutane tetracoyl chloride, cyclopentanedioyl chloride, cyclopentane triacyl chloride, cyclopentane tetracoyl chloride, cyclohexane diacyl chloride, cyclohexane tricarbonyl chloride or cyclohexane tetracoyl chloride, and the concentration of the oil phase solution is 0.04-4.0 wt%.
The oily solvent is at least one of n-hexane, cyclohexane, heptane, octane, naphtha, Isopar-E, Isopar-G, Isopar-L or mineral oil.
And (3) removing the oil phase solution after reacting for 30 s-10 min in the step (2), then treating the polymer base film at 40-90 ℃ for 0-30 min, and drying to obtain the composite film.
Preferably, in order to enhance the formation of the composite membrane, the high-flux interfacial polymerization composite membrane prepared by the above method may be subjected to a corresponding post-treatment, such as an alkali treatment, an oxidation treatment, a solvent treatment, or the like, as necessary. The alkali treatment process comprises the following steps: and immersing the prepared composite membrane into an alkali solution for 10 min-120 h, and then immersing the composite membrane into an acid or aqueous solution to remove or neutralize the alkali solution in the composite membrane. The alkali solution is potassium hydroxide and sodium hydroxide aqueous solution with the concentration of 1-10%.
The invention has the beneficial effects that:
(1) compared with the prior art, one of the technical characteristics of the invention is that the preparation process of the interfacial polymerization composite membrane is further simplified by dissolving the water-soluble monomer in the polymer solution, and meanwhile, the monomer consumption is greatly reduced, and the effects of simplifying the process flow and reducing the membrane preparation cost are finally achieved;
(2) the method is characterized in that the content of the monomer in the polymer membrane is regulated and controlled by controlling the phase inversion time, so that the high-flux reverse osmosis membrane or the nanofiltration membrane is prepared;
(3) compared with the conventional aqueous monomer immersion method, the polymer base membrane rich in monomers is obtained by directly adding the monomers into the polymer solution, and a composite membrane with higher selectivity can be obtained after interfacial polymerization;
(4) the invention can simplify the process flow of the existing polyamide or polyester amide composite membrane preparation to a great extent, and the obtained composite membrane has high flux and high selectivity, and compared with the traditional preparation method, the performance is obviously improved. In addition, the method is suitable for conventional polymers, the using amount of the water-soluble monomer is reduced to a great extent, and the method has the advantages of simple process, easy preparation, low raw material price and good industrial practicability of preparation.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A preparation method of an interfacial polymerization composite membrane comprises the following steps:
(1) weighing 7.5 g of polyethersulfone and 0.2 g of piperazine, dissolving in 42.3 g of dimethyl sulfoxide solvent, and stirring overnight to obtain a polyethersulfone casting solution with the concentration of 15 wt%;
(2) standing and defoaming the prepared membrane casting solution, coating the membrane casting solution on a non-woven fabric through an automatic membrane scraping machine, wherein the thickness of a scraper is 250 micrometers, then soaking the non-woven fabric coated with the polymer solution into deionized water, and taking out the polyether sulfone membrane after 2min phase inversion;
(3) removing residual liquid on the surface of the membrane by using filter paper, immersing the membrane into 0.04 wt% of trimesoyl chloride n-hexane solution for 1min, and then treating for 10min at 40 ℃ in an oven to obtain the composite nanofiltration membrane.
And (3) testing the performance of the separation membrane:
a separation membrane water flux test, wherein the water flux is the volume (V) of water which permeates a unit membrane area (A) in a unit time (t) under a unit pressure (P) under a certain operation condition; putting the separation membrane into a cross flow device, prepressing for a certain time to stabilize the system, then operating under a certain pressure, and recording the flow of water in unit time; the water flux is finally calculated according to the following formula:
F= V/（A.t.P）
the interception test of the separation membrane, wherein the interception rate is the capacity of the membrane for preventing a certain component in the feed liquid from passing through or intercepting a certain component; the rejection rate was measured by measuring the solute concentration (C) of the filtrate during membrane filtration2) And the concentration of solute in the dope in filtration (C)2) Obtained by the following calculation formula:
R=（1-C2/C1）×100%
the flux of the composite membrane prepared in example 1 is 38L/(m)2 bar h)，Na2SO4Rejection of 97%, MgCl2Trapping 20% of NaCl and 15% of NaCl; the flux of the membrane is 2-3 times that of a conventional commercial membrane at the same rejection.
Example 2
A preparation method of an interfacial polymerization composite membrane comprises the following steps:
(1) weighing 7.5 g of polyethersulfone and 2 g of piperazine, dissolving in 42.3 g of dimethylformamide solvent, and stirring overnight to obtain a polyethersulfone casting solution with the concentration of 15 wt%;
(2) standing and defoaming the prepared membrane casting solution, coating the membrane casting solution on a non-woven fabric through an automatic membrane scraping machine, wherein the thickness of a scraper is 250 micrometers, then soaking the non-woven fabric coated with the polymer solution into deionized water, and taking out the polyether sulfone membrane after 30min of phase inversion;
(3) removing residual liquid on the surface of the membrane by using filter paper, immersing the membrane into a trimesoyl chloride n-hexane solution with the concentration of 4 wt% for 30s, and then treating for 10min at 40 ℃ in an oven to obtain the composite nanofiltration membrane.
The flux of the composite membrane prepared in example 1 was 22L/(m)2 bar h)，Na2SO4Rejection of 99%, MgCl250% of interception and 40% of interception of NaCl; the membrane can achieve high salt rejection performance and water flux twice that of commercial membranes.
Comparative example 1
The method comprises the steps of carrying out interfacial polymerization by using a commercial polyether sulfone (PES) ultrafiltration membrane as a base membrane, immersing the PES ultrafiltration membrane into a 0.1 wt% piperazine water solution for 5min, removing residual liquid on the surface of the membrane by using filter paper, immersing the base membrane into a 0.1 wt% trimesoyl chloride n-hexane solution for 1min, and then treating the base membrane in an oven at 40 ℃ for 10min to obtain the composite nanofiltration membrane.
The prepared composite membrane has water flux of 12L/(m)2 bar h)，Na2SO4Rejection of 96%, MgCl212% retention and 10% retention of NaCl. In the case where similar salt rejection was obtained, the pure water flux of the membrane prepared in comparative example 1 was much smaller than that of the membrane prepared in example 2.
Example 3
A preparation method of an interfacial polymerization composite membrane comprises the following steps:
(1) weighing 8 g of polysulfone and 0.4 g of piperazine, dissolving the polysulfone and the 0.4 g of piperazine in 41.6 g N-methyl pyrrolidone, and stirring overnight to obtain 16 wt% polysulfone membrane casting solution containing piperazine monomers;
(2) standing and defoaming the prepared membrane casting solution, coating the membrane casting solution on a non-woven fabric through an automatic membrane scraping machine, wherein the thickness of a scraper is 250 micrometers, then immersing the non-woven fabric coated with the polymer solution into a deionized water solution, and taking out the polysulfone membrane after 2min of phase inversion;
(3) removing residual liquid on the surface of the membrane by using filter paper, immersing the membrane into 0.2 wt% of trimesoyl chloride n-hexane solution for 1min, and then treating the membrane in an oven at 90 ℃ for 1min to obtain the composite nanofiltration membrane.
The water flux of the prepared composite membrane is 30L/(m)2 bar h)，Na2SO4Rejection of 99%, MgCl240% of the NaCl solution is retained, and 30% of the NaCl solution is retained. The pure water flux and salt rejection of the membrane prepared by the method are both higher than those of the membrane in comparative example 1.
Example 4
A preparation method of an interfacial polymerization composite membrane comprises the following steps:
(1) weighing 8 g of polyacrylonitrile and 0.3g of piperazine, dissolving in 41.7 g of dimethylacetamide, and stirring overnight to obtain a 16 wt% polyacrylonitrile membrane casting solution containing piperazine monomers;
(2) standing and defoaming the prepared membrane casting solution, coating the membrane casting solution on a non-woven fabric through an automatic membrane scraping machine, wherein the thickness of a scraper is 250 micrometers, then immersing the non-woven fabric coated with the polymer solution into a deionized water solution, and taking out the polyacrylonitrile membrane after 5min of phase conversion;
(3) removing residual liquid on the surface of the membrane by using filter paper, immersing the membrane into a 1 wt% m-phthaloyl chloride n-hexane solution for 1min, and then treating for 2min at 90 ℃ in an oven to obtain the composite nanofiltration membrane.
The water flux of the prepared composite membrane is 39L/(m)2 bar h)，Na2SO4Rejection of 97%, MgCl232% was retained and 25% was retained by NaCl. The pure water flux and salt rejection of the membrane prepared by the method are both higher than those of the membrane in comparative example 1.
Example 5
A preparation method of an interfacial polymerization composite membrane comprises the following steps:
(1) weighing 7.5 g of polyether sulfone and 1.2 g of beta-cyclodextrin, dissolving in 42.3 g of dimethyl sulfoxide solvent, and stirring overnight to obtain a polyether sulfone casting solution with the concentration of 15 wt% and containing a cyclodextrin monomer;
(2) standing and defoaming the prepared membrane casting solution, coating the membrane casting solution on a non-woven fabric through an automatic membrane scraping machine, wherein the thickness of a scraper is 250 mu m, then soaking the non-woven fabric coated with the polymer solution into 0.5wt% of sodium hydroxide solution, and taking out the polyether sulfone membrane after 6min phase conversion;
(3) removing residual liquid on the surface of the membrane by using filter paper, immersing the membrane into 0.75 wt% of trimesoyl chloride n-hexane solution for 10min, and then treating for 3min at 50 ℃ in an oven to obtain the composite nanofiltration membrane.
The water flux of the prepared composite membrane is 40L/(m)2 bar h)，Na2SO4Rejection of 96%, MgCl230% of interception and 20% of interception of NaCl; the flux of the membrane is 2-3 times that of a conventional commercial membrane at the same rejection.
Example 6
A preparation method of an interfacial polymerization composite membrane comprises the following steps:
(1) weighing 7.5 g of polyethersulfone and 1.2 g of gamma-cyclodextrin, dissolving the polyethersulfone and the gamma-cyclodextrin in 42.3 g of dimethyl sulfoxide solvent, and stirring overnight to obtain a polyethersulfone casting solution with the concentration of 15 wt% and containing cyclodextrin monomers;
(2) standing and defoaming the prepared membrane casting solution, coating the membrane casting solution on a non-woven fabric through an automatic membrane scraping machine, wherein the thickness of a scraper is 250 mu m, then soaking the non-woven fabric coated with the polymer solution into 0.5wt% of sodium hydroxide solution, and taking out the polyether sulfone membrane after 6min phase conversion;
(3) removing residual liquid on the surface of the membrane by using filter paper, immersing the membrane into 0.15 wt% of trimesoyl chloride n-hexane solution for 6min, and then treating for 3min at 60 ℃ in an oven to obtain the composite nanofiltration membrane.
The water flux of the prepared composite membrane is 35L/(m)2 bar h)，Na2SO4Rejection of 98%, MgCl240% of interception and 25% of interception of NaCl; the flux of the membrane is 2-3 times that of a conventional commercial membrane at the same rejection.
Comparative example 2
The method comprises the steps of adopting a commercial polyether sulfone (PES) ultrafiltration membrane as a base membrane to carry out interfacial polymerization, firstly immersing the PES ultrafiltration membrane into a mixed aqueous solution containing 2.0 wt% of beta-cyclodextrin and 0.5wt% of sodium hydroxide for 5min, removing residual liquid on the surface of the membrane by using filter paper, then immersing the base membrane into a 0.75 wt% trimesoyl chloride n-hexane solution for 10min, and then treating for 3min at 60 ℃ in an oven to obtain the composite nanofiltration membrane.
The water flux of the prepared composite membrane is 20L/(m)2 bar h)，Na2SO4Rejection of 89%, MgCl210% of the NaCl solution is retained, and 9% of the NaCl solution is retained. The separation performance of the membrane prepared in comparative example 2 was much less than that of the membrane prepared in example 5, with similar salt rejection.
Example 7
A preparation method of an interfacial polymerization composite membrane comprises the following steps:
(1) weighing 12.5 g of polyethersulfone and 1.0 g of m-phenylenediamine and dissolving the polyethersulfone and the 1.0 g of m-phenylenediamine in 41.5 g of dimethyl sulfoxide solvent, and stirring overnight to obtain a polyethersulfone casting solution with the concentration of 25 wt% and containing the m-phenylenediamine monomer;
(2) standing and defoaming the prepared membrane casting solution, coating the membrane casting solution on a non-woven fabric through an automatic membrane scraping machine, wherein the thickness of a scraper is 250 micrometers, then immersing the non-woven fabric coated with the polymer solution into a deionized water bath, and taking out the polyether sulfone membrane after 3min phase conversion;
(3) removing residual liquid on the surface of the membrane by using filter paper, immersing the membrane into 0.2 wt% of trimesoyl chloride n-hexane solution for 30s, and then treating for 1.5min at 90 ℃ in an oven to obtain the composite reverse osmosis membrane.
The pure water flux of the prepared reverse osmosis membrane is 4.3L/(m)2bar h), the rejection of NaCl 98.5%.
Comparative example 3
Adopting a commercial Polyethersulfone (PES) ultrafiltration membrane as a base membrane to carry out interfacial polymerization, and firstly soaking the PES ultrafiltration membrane in an aqueous phase solution containing 2 wt% of m-phenylenediamine for 5 min; removing residual liquid on the membrane surface by using filter paper, immersing the membrane into 0.1 wt% of trimesoyl chloride n-hexane solution for 30s, and treating for 1.5min at 80 ℃ in an oven to obtain the composite reverse osmosis nanofiltration membrane
The flux of the prepared composite reverse osmosis pure water membrane is 1.9L/(m)2bar h), the NaCl rejection was 97%. The pure water flux and salt rejection were both less than the performance of the membrane prepared in example 7; the reverse osmosis membrane with more excellent performance is obtained after the simplified interfacial polymerization method is adopted.
Example 8
A preparation method of an interfacial polymerization composite membrane comprises the following steps:
(1) weighing 9 g of polyethersulfone and 1.2 g of m-phenylenediamine and dissolving the polyethersulfone and the 1.2 g of m-phenylenediamine in 39.8 g of dimethyl sulfoxide solvent, and stirring the solution overnight to obtain a polyethersulfone casting solution with the concentration of 18 wt% and containing the m-phenylenediamine monomer;
(2) standing and defoaming the prepared membrane casting solution, coating the membrane casting solution on a non-woven fabric through an automatic membrane scraping machine, wherein the thickness of a scraper is 250 micrometers, then immersing the non-woven fabric coated with the polymer solution into a deionized water bath, and taking out the polyether sulfone membrane after 2min phase inversion;
(3) removing residual liquid on the surface of the membrane by using filter paper, immersing the membrane into 0.2 wt% of trimesoyl chloride n-hexane solution for 1min, and then treating for 3min at 80 ℃ in an oven to obtain the composite reverse osmosis membrane.
The pure water flux of the prepared reverse osmosis membrane is 3.5L/(m)2bar h), the rejection of NaCl was 99.1%.
Example 9
A preparation method of an interfacial polymerization composite membrane comprises the following steps:
(1) weighing 7.5 g of polyethersulfone and 0.2 g of highly branched polyethyleneimine (with the molecular weight of 600 Da) and dissolving the polyethersulfone and the highly branched polyethyleneimine in 42.3 g of dimethyl sulfoxide solvent, and stirring the solution overnight to obtain a polyethersulfone casting solution with the concentration of 15 wt%;
(2) standing and defoaming the prepared membrane casting solution, coating the membrane casting solution on a non-woven fabric through an automatic membrane scraping machine, wherein the thickness of a scraper is 250 micrometers, then immersing the non-woven fabric coated with the polymer solution into a deionized water solution, and taking out the polyether sulfone membrane after 3min phase conversion;
(3) removing residual liquid on the surface of the membrane by using filter paper, immersing the membrane into 0.1 wt% of trimesoyl chloride n-hexane solution for 1min, and then treating for 2min at 70 ℃ in an oven to obtain the composite nanofiltration membrane.
The water flux of the prepared composite nanofiltration membrane is 16L/(m)2 bar h)，MgCl297% of Na was retained2SO4The retention rate is 40 percent, and the NaCl retention rate is 31 percent.
Example 10
A preparation method of an interfacial polymerization composite membrane comprises the following steps:
(1) weighing 1 g of para-aramid fiber, dissolving the para-aramid fiber in a mixed solution system of 0.75 g of potassium hydroxide and 48.25g of dimethyl sulfoxide, and stirring at normal temperature to obtain an aramid nanofiber membrane casting solution with the concentration of 2 wt%; then dissolving 0.3g of piperazine monomer into the membrane casting solution;
(2) standing and defoaming the membrane casting solution, coating the membrane casting solution on a non-woven fabric to a thickness of 250 mu m, then putting the non-woven fabric into water, and taking out the membrane after 6min of phase inversion;
(3) removing residual liquid on the surface of the membrane by using filter paper, immersing the membrane into 0.1 wt% of trimesoyl chloride n-hexane solution for 1min, and then treating for 3min at 60 ℃ in an oven to obtain the composite nanofiltration membrane.
The flux of the prepared composite nanofiltration membrane is 42L/(m)2 bar h)，Na2SO4Rejection of 97.5%, MgCl230% of the NaCl solution is retained, and 25% of the NaCl solution is retained.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A preparation method of an interfacial polymerization composite membrane is characterized by comprising the following steps:
(1) dissolving a water-soluble monomer in a polymer solution to prepare a membrane casting solution, coating the membrane casting solution on a non-woven fabric, and then immersing the non-woven fabric in a coagulating bath for a phase conversion process to form a polymer base membrane containing the water-soluble monomer;
(2) taking out the polymer base membrane obtained in the step (1), removing residual liquid on the surface of the polymer base membrane by using filter paper, then pouring the oil phase solution onto the surface of the polymer membrane, taking out after reaction and drying to obtain a composite membrane;
the oil phase solution in the step (2) is obtained by dissolving a polybasic acyl chloride monomer in an oily solvent, wherein the polybasic acyl chloride monomer is at least one of trimesoyl chloride, terephthaloyl chloride, isophthaloyl chloride, biphenyldicarbonyl chloride, benzenetrisulfonyl chloride, tricarbonyl chloride, butanetriacyl chloride, pentanedioyl chloride, glutaroyl chloride, adipoyl chloride, maleoyl chloride, cyclopropanetriacyl chloride, cyclobutanetriacyl chloride, cyclobutane tetracoyl chloride, cyclopentanedioyl chloride, cyclopentane triacyl chloride, cyclopentane tetracoyl chloride, cyclohexane diacyl chloride, cyclohexane tricarbonyl chloride or cyclohexane tetracoyl chloride, and the concentration of the oil phase solution is 0.04-4.0 wt%.
2. The method of preparing an interfacial polymerization composite film according to claim 1, wherein: the water-soluble monomer in the step (1) is at least one of piperazine, alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, m-phenylenediamine, p-phenylenediamine, hyperbranched polyethyleneimine, tannic acid, diaminotoluene, ethylenediamine, propylenediamine, xylylenediamine, 1, 3-diaminocyclohexane or 1, 4-diaminocyclohexane, and the concentration of the water-soluble monomer relative to the total amount of the casting solution is 0.4-4.0 wt%.
3. The method of preparing an interfacial polymerization composite film according to claim 1, wherein: in the step (1), the polymer is polyether sulfone, polysulfone, polyacrylonitrile, polyimide, polyvinylidene fluoride, polyarylene sulfide sulfone, poly (p-phenylene terephthalamide), chitosan or polyvinyl alcohol, and the polymer is dissolved in dimethyl sulfoxide, dimethylacetamide, dimethylformamide or N-methylpyrrolidone to obtain a polymer solution.
4. The method of preparing an interfacial polymerization composite film according to claim 1, wherein: the coagulating bath in the step (1) is water or a mixed solution of water and any one of an alkali regulator, acetaldehyde, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, dimethylacetamide, phenol, cyclohexanone, phenol or tetrachloroethane; the alkali regulator is at least one of sodium hydroxide, triethylamine, potassium oxide, ammonia water, sodium carbonate and sodium bicarbonate.
5. The method of preparing an interfacial polymerization composite film according to claim 1, wherein: the phase conversion process time in the step (1) is 2-30 min.
6. The method of preparing an interfacial polymerization composite film according to claim 5, wherein: the oily solvent is at least one of n-hexane, cyclohexane, heptane, octane, naphtha, Isopar-E, Isopar-G, Isopar-L or mineral oil.
7. The method of preparing an interfacial polymerization composite film according to claim 1, wherein: and (3) removing the oil phase solution after the reaction is carried out for 10 s-15 min in the step (2), then treating the polymer base film at the temperature of 40-90 ℃ for 0-30 min, and drying to obtain the composite film.
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