CN117000059A - A blended co-deposition modified bifunctional separation membrane and its preparation method - Google Patents
A blended co-deposition modified bifunctional separation membrane and its preparation method Download PDFInfo
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Abstract
The application provides a blending and co-deposition modified dual-function separation membrane and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, synthesizing two types of monofunctional primary amine-containing copolymers, including an anti-pollution primary amine-containing copolymer and a bactericidal primary amine-containing copolymer, and then blending and adding the two types of monofunctional primary amine-containing copolymers in an accurate proportion, and preparing a blending and co-deposition solution with a polyphenol compound; and finally, modifying the surface of the separation membrane by using the prepared blending co-deposition solution, namely directionally preparing the co-deposition modified dual-function biological pollution resistant separation membrane. Compared with the prior art, the preparation process of the method is simpler and milder, the industrial application is easy, and the prepared separation membrane has the advantages of good anti-pollution effect, long service period and the like.
Description
Technical Field
The application relates to the technical field of membranes, in particular to a blending and co-deposition modified dual-function separation membrane and a preparation method thereof.
Background
As a 21 st century water treatment technology, the membrane separation technology has the advantages of good quality of produced water, relatively low energy consumption and cost, and the like, and the application field of the membrane separation technology relates to a plurality of industries such as sea water desalination, industrial sewage treatment, ultrapure water preparation, medicine and food processing, and the like. The separation membrane is the core of membrane separation technology and can be divided into four types of reverse osmosis membrane, nanofiltration membrane, ultrafiltration membrane and microfiltration membrane according to the pore size, but in the actual use process, pollutants such as suspended particles, colloid, organic matters, microorganisms and the like existing in raw material liquid are easy to adsorb and deposit on the surface of the membrane to form a pollution layer, so that membrane pollution is caused. The cause of biological contamination is more complex and difficult to remove than organic contamination. Biological pollution is simply the complex action of adsorbing organic matters and biological macromolecules. The adherent bacteria and other organisms grow to form a biological film, so that the chemical cleaning frequency and the chemical dosing can be improved, the running cost can be increased, and the service life of the film can be reduced. Thus, reducing the biological contamination of the membrane is critical to its long-term effective use.
Hydrophilic materials such as polyethylene glycol, zwitterionic polymers and the like are modified on the surface of the membrane, so that the membrane is the most commonly used membrane modification mode for effectively reducing bacterial adhesion and improving the anti-pollution performance of the membrane. Such hydrophilic materials may delay or prevent the approach and adhesion of microorganisms, but may not be effective in killing bacteria and preventing biological contamination. Thus, unlike the simple "defense" mechanism, i.e., the reduction of the adhesion contamination of microorganisms such as bacteria by the anti-contamination properties of the surface hydrophilic polymer material, studies have begun to propose bilayer functionalization modifications combining the "defense" mechanism and the "attack" mechanism. The "attack" mechanism relies mainly on materials with strong bactericidal properties, inhibiting bacterial growth, commonly used cationic quaternary ammonium compounds, and various nano-materials with biotoxicity. The concept of combining "defense" and "attack" mechanisms is becoming an effective solution against surface biological contamination.
In order to solve the problem caused by membrane pollution and improve the operation efficiency of the separation membrane, the preparation of the novel dual-function anti-biological pollution separation membrane and the research of the anti-pollution performance of the separation membrane have important significance. The existing membrane surface dual-function modification method has the defects of strict requirements on reaction conditions and equipment and the like, and greatly limits the industrialized application of the method for realizing modification on the surface of the separation membrane. Therefore, the method overcomes the defects of severe conditions, large damage to the surface structure of the membrane, complex and tedious operation process and the like of the modification means while ensuring the anti-biological pollution performance and stable chemical structure of the dual-function separation membrane, and is a problem which needs to be faced in realizing large-scale production of the current anti-pollution separation membrane. The application is based on the technical background and is developed and improved for solving the current problems.
Disclosure of Invention
The application aims to solve the technical problems and provide the blending and blending deposition modified dual-function separation membrane and the preparation method thereof.
The technical scheme of the application is as follows, and the preparation method of the blending and co-deposition modified dual-function separation membrane comprises the following steps:
step one, synthesizing a high molecular copolymer
(1) Synthesis of anti-pollution Polymer copolymer P anti : under nitrogen atmosphere, adding co-deposition monomer A and anti-pollution monomer B into mixed solvent of dimethyl sulfoxide and deionized water, adding free radical polymerization initiator 2,2' -azobisisobutyronitrile, stirring at 60-100 deg.c for reaction for 6-48 hr, dialyzing the mixed liquid after the reaction, freeze drying to obtain anti-pollution polymer copolymer P anti ；
The dosage of the 2,2' -azobisisobutyronitrile is 0.1% -0.6% of the total mole number of the co-deposition monomer A and the anti-pollution monomer B;
(2) synthetic bactericidal polymer copolymer P kill : under nitrogen atmosphere, adding a co-deposition monomer A and a bactericidal monomer C into a mixed solvent of dimethyl sulfoxide and deionized water, adding a free radical polymerization initiator 2,2' -azobisisobutyronitrile, stirring and reacting for 6-48 hours at 60-100 ℃, dialyzing the mixed solution after the reaction, and freeze-drying to obtain the bactericidal polymer copolymer P kill ；
The dosage of the 2,2' -azobisisobutyronitrile is 0.1% -0.6% of the total mole number of the co-deposition monomer A and the bactericidal monomer C;
the anti-pollution macromolecular copolymer P anti The structure is as follows:the bactericidal polymer copolymer P kill The structure is as follows:Wherein, the value range of m and n is 0-1, and m+n=1;
the volume ratio of dimethyl sulfoxide to deionized water in the mixed solvent in the step one is 4:1-4:3.
Step two, preparing a blending co-deposition solution: the anti-pollution high molecular copolymer P obtained in the step one anti And a bactericidal polymer copolymer P kill Adding the formed blending macromolecule and polyphenol compound into alkaline solution to perform full stirring reaction, thus obtaining blending and depositing solution;
the anti-pollution macromolecular copolymer P anti And a bactericidal polymer copolymer P kill The total concentration in the blending and co-depositing solution is 0.01-20 g/L, wherein the anti-pollution high polymer copolymer P anti With bactericidal polymer copolymer P kill The mass fraction ratio value range of (2) is 0-1;
the concentration of the polyphenol compound in the blending and co-depositing solution is 0.01-15 g/L; the pH value of the alkaline solution is 8-14.
Step three, carrying out blend and blend deposition modification of a separation membrane: pouring the blending co-deposition solution prepared in the second step on the surface of the separation membrane, shaking and coating, pouring off the redundant blending co-deposition solution after coating, and performing oven heat treatment to obtain the co-deposition modified dual-function anti-biological pollution separation membrane.
The coating time of the blending co-deposition solution on the surface of the film in the third step is 10 seconds to 6 hours; the heat treatment temperature of the oven is 30-60 ℃ and the heat treatment time is 0.01-12 hours.
The co-deposition monomer A of the application can be 2-aminoethyl methacrylate or 2-aminoethyl methacrylate hydrochloride, or a combination of the two; the anti-pollution monomer B can be any one or more than two of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, hydroxyethyl methacrylate, N-isopropyl acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, 2-ethanesulfonate sodium salt, 3-sulfonate propyl methacrylate potassium salt, sodium allylsulfonate, sodium acrylate, sodium methacrylate, sodium styrene sulfonate and N- [ (3- (dimethylamino N-oxide) propyl ] methacrylamide, the sterilizing monomer C can be acryloyloxyethyl trimethyl ammonium chloride or methacryloyloxyethyl trimethyl ammonium chloride or a combination of the two, and the step polyphenol compound can be any one of water-soluble phenol, dopamine, tannic acid, catechol, gallic acid, juglone and catechol, and the separation membrane in the step (3) can be a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, a polyvinyl chloride, a forward osmosis membrane or a membrane distillation membrane, and the separation membrane can be a chemical group of polyacrylonitrile, polysulphone, polyvinylidene fluoride, polyethersulfone or polyphenylether.
The principle and key technical points of the application are as follows: adding primary amine-containing polymer in the self-polymerization process of polyphenol to make the primary amine-containing polymer and polyphenol produce Michael addition or Schiff base reaction so as to make the primary amine-containing polymer be capable of being fed into and enriched in co-deposited layer, and can utilize regulation and control of primary amine-containing anti-pollution high-molecular copolymer (P anti ) And a primary amine-containing bactericidal polymer copolymer (P) kill ) The blending mass fraction ratio in the blending and co-depositing solution can accurately regulate and control the anti-pollution property and the antibacterial growth property of the surface of the separation membrane, and the co-depositing modified layer has stable structure.
The application has the technical advantages that: 1. the application adopts a double-function blending and co-deposition modification method to prepare the anti-biological pollution separation membrane, namely, the microbial pollution on the surface of the separation membrane is improved by preventing microorganism adhesion and sterilization, and the effect is good; 2. the covalent codeposition modification method between the polyphenol and the primary amine-containing polymer adopted by the application can be adhered to the surfaces of films made of various materials, has no special requirement on a matrix, has a stable structure, and can avoid the problems that a common coating is easy to fall off and can not be used for a long time; 3. the method has the advantages of simple and mild operation process, strong designability and easy industrialization. 4. The application provides a thought for improving the dual-function biological pollution resistance of the surface of the separation membrane and overcomes the functional limitation of the surface of the membrane modified by a single polymer.
Drawings
FIG. 1 is a surface electron microscope (A) of an unmodified polyamide reverse osmosis membrane and a surface electron microscope comparison (B) of a modified polyamide reverse osmosis membrane prepared in example 1.
FIG. 2 is a cross-sectional transmission electron micrograph (A) of an unmodified polyamide reverse osmosis membrane and a cross-sectional transmission electron micrograph (B) of a modified polyamide reverse osmosis membrane prepared in example 1.
FIG. 3 is a cross-sectional transmission electron microscope (C) of an unmodified polyvinylidene fluoride separation membrane, a surface electron microscope (A) of a modified polyvinylidene fluoride separation membrane prepared in example 11, a cross-sectional transmission electron microscope (D) of an unmodified polyvinylidene fluoride separation membrane, and a cross-sectional transmission electron microscope (D) of a modified polyvinylidene fluoride separation membrane prepared in example 11.
Detailed Description
The application will be further described with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not to be construed as limiting the scope of the present application. Further, it will be understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the application, and such equivalents are intended to fall within the scope of the application as defined by the claims.
Before the embodiments of the application are explained in further detail, it is to be understood that the application is not limited in its scope to the particular embodiments described below; it is also to be understood that the terminology used in the examples of the application is for the purpose of describing particular embodiments only, and is not intended to be limiting of the scope of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The test methods in the following examples, in which specific conditions are not noted, are generally conducted under conventional conditions or under conditions recommended by the respective manufacturers. In addition to the specific methods, devices, materials used in the embodiments, any methods, devices, and materials of the prior art similar or equivalent to those described in the embodiments of the present application may be used to practice the present application according to the knowledge of one skilled in the art and the description of the present application.
Example 1
Step one, synthesizing a high molecular copolymer:
(1) synthesis of anti-pollution Polymer copolymer (P) anti ): under nitrogen atmosphere, 4.40g of the co-deposition monomer 2-aminoethyl methacrylate and 7.82g of the anti-contamination monomer [2- (methacryloyloxy) ethyl ] were added to 250mL of dimethyl sulfoxide and 500mL of deionized water]Dimethyl- (3-sulfopropyl) ammonium hydroxide, 0.10g of azodiisobutyronitrile is used as a free radical polymerization initiator, stirring reaction is carried out for 36 hours at 70 ℃, the mixed solution is dialyzed after the reaction is finished, and then the anti-pollution high polymer copolymer (P) is obtained after freeze drying anti ) The chemical structural formula is as follows:
(2) synthetic bactericidal polymer copolymer (P) kill ): under nitrogen atmosphere, adding 4.40g of codeposition monomer methacrylic acid 2-amino ethyl ester and 12.2g of bactericidal monomer methacryloyloxyethyl trimethyl ammonium chloride into 250mL of dimethyl sulfoxide and 500mL of deionized water, stirring and reacting at 70 ℃ for 36h by taking 0.10g of azodiisobutyronitrile as a free radical polymerization initiator, dialyzing the mixed solution after the reaction is finished, and then freeze-drying to obtain the bactericidal polymer copolymer (P) kill ) The chemical structural formula is as follows:
preparing a codeposition modifying solution: 2 wt%o of water-soluble phenol and 3 wt%o of anti-pollution high molecular copolymer (P) anti ) And 3wt% of a bactericidal polymer copolymer (P kill ) Adding the mixture into an alkaline solution with pH of 13, and fully stirring to obtain the codeposition modified solution.
Step three, co-deposition modification of separation membranes: pouring the codeposition modified liquid prepared in the second step on the surface of the polyamide reverse osmosis membrane, and shaking for 40s. After the coating is completed, the redundant codeposition modifying liquid is poured off, and the codeposition modified pollution-resistant separation membrane is obtained after the codeposition modifying liquid is treated for 12 hours at the temperature of 30 ℃ in an oven.
Example 2
In this example 2, the step-removed second anti-fouling polymer copolymer (P anti ) And a bactericidal polymer copolymer (P) kill ) The other steps were the same as those in example 1 except that the mass fraction ratio of (a) was different;
preparing a codeposition modifying solution: 2 wt% of water-soluble phenol and 1.5 wt% of anti-pollution high molecular copolymer (P) anti ) And 4.5 wt% of a bactericidal polymer (P) kill ) Adding the mixture into an alkaline solution with pH of 13, and fully stirring to obtain the codeposition modified solution.
Example 3
In this example 3, the bactericidal polymer copolymer (P) in the first step kill ) The rest of the steps were the same as in example 1, except for the synthesis steps of (a);
(2) bactericidal polymer copolymer (P) kill ) Is synthesized by the following steps: under nitrogen atmosphere, adding 4.40g of codeposition monomer methacrylic acid 2-amino ethyl ester and 5.42g of bactericidal monomer acryloyloxyethyl trimethyl ammonium chloride into 250mL of dimethyl sulfoxide and 500mL of deionized water, stirring and reacting at 70 ℃ for 36h by taking 0.10g of azodiisobutyronitrile as a free radical polymerization initiator, dialyzing the mixed solution after the reaction is finished, and then freeze-drying to obtain the bactericidal polymer copolymer (P) kill ) The chemical structural formula is as follows:
example 4
In this example 4, the anti-fouling polymer copolymer (P) in the first step was removed anti ) The rest of the steps were the same as in example 1, except for the synthesis steps of (a);
(1) anti-pollution high molecular copolymer (P) anti ) Is synthesized by the following steps: under nitrogen atmosphere, 250mL of dimethyl sulfoxide and 500mL of deionized water were usedAdding 4.40g of codeposition monomer methacrylic acid 2-amino ethyl ester and 3.64g of anti-pollution monomer hydroxyethyl methacrylate into ionized water, stirring and reacting for 36h at 70 ℃ by taking 0.10g of azodiisobutyronitrile as a free radical polymerization initiator, dialyzing the mixed solution after the reaction is finished, and freeze-drying to obtain the anti-pollution high polymer copolymer (P) anti ) The chemical structural formula is as follows:
example 5
In this example 5, the anti-fouling polymer copolymer (P) in the first step was removed anti ) The rest of the steps were the same as in example 1, except for the synthesis steps of (a);
(1) anti-pollution high molecular copolymer (P) anti ) Is synthesized by the following steps: under nitrogen atmosphere, adding 4.40g of codeposition monomer methacrylic acid 2-amino ethyl ester and 3.17g of anti-pollution monomer N-isopropyl acrylamide into 250mL of dimethyl sulfoxide and 500mL of deionized water, stirring and reacting for 24h at 80 ℃ by taking 0.10g of azodiisobutyronitrile as a free radical polymerization initiator, dialyzing the mixed solution after the reaction is finished, and freeze-drying to obtain the anti-pollution high polymer copolymer (P) anti ) The chemical structural formula is as follows:
example 6
In this example 6, the anti-fouling polymer copolymer (P) in the first step was removed anti ) The rest of the steps were the same as in example 1, except for the synthesis steps of (a);
(1) anti-pollution high molecular copolymer (P) anti ) Is synthesized by the following steps: under nitrogen atmosphere, adding 4.40g of codeposition monomer methacrylic acid 2-amino ethyl ester and 6.05g of anti-pollution monomer methacrylic acid 2-ethane sulfonate sodium salt into 250mL of dimethyl sulfoxide and 500mL of deionized water, and taking 0.10g of azodiisobutyronitrile as free radical polymerization primerThe hair-growing agent is stirred at 80 ℃ for 24 hours, the mixed solution is dialyzed after the reaction is finished, and then the anti-pollution high polymer copolymer (P) is obtained after freeze drying anti ) The chemical structural formula is as follows:
example 7
In this example 7, the step one (1) of the anti-fouling polymer copolymer (P anti ) The procedure was the same as in example 1 except that the synthesis procedure was different from that of (1) the anti-fouling polymer copolymer (P anti ) The synthesis steps of (a) are as follows:
(1) anti-pollution high molecular copolymer (P) anti ) Is synthesized by the following steps: under nitrogen atmosphere, adding 4.40g of codeposition monomer methacrylic acid 2-amino ethyl ester and 3.03g of anti-pollution monomer sodium methacrylate into 250mL of dimethyl sulfoxide and 500mL of deionized water, stirring and reacting at 80 ℃ for 24 hours by taking 0.10g of azodiisobutyronitrile as a free radical polymerization initiator, dialyzing the mixed solution after the reaction is finished, and freeze-drying to obtain the anti-pollution high polymer copolymer (P) anti ) The chemical structural formula is as follows:
example 8
In this example 8, the step one (1) of the anti-fouling polymer copolymer (P anti ) The procedure was the same as in example 1 except that the synthesis procedure was different from that of (1) the anti-fouling polymer copolymer (P anti ) The synthesis steps of (a) are as follows:
(1) anti-pollution high molecular copolymer (P) anti ) Is synthesized by the following steps: under nitrogen atmosphere, 4.40g of the co-deposited monomer 2-aminoethyl methacrylate and 5.23g of the anti-contaminating monomer N- [ (3- (dimethylamino N-oxide) propyl) were added to 250mL of dimethyl sulfoxide and 500mL of deionized water]Methacrylamide and 0.10g of azobisisobutyronitrileStirring at 90deg.C for 12 hr as free radical polymerization initiator, dialyzing the mixed solution, and lyophilizing to obtain anti-pollution polymer copolymer (P) anti ) The chemical structural formula is as follows:
example 9
In example 9, the bactericidal polymer copolymer (P) of step (2) was removed kill ) The procedure was the same as in example 1 except that the procedure for synthesizing (A) was different from that of (B) except that the bactericidal polymer (P) kill ) The synthesis steps of (a) are as follows:
(2) bactericidal polymer copolymer (P) kill ) Is synthesized by the following steps: under nitrogen atmosphere, adding 4.40g of codeposition monomer methacrylic acid 2-amino ethyl ester and 5.42g of bactericidal monomer acryloyloxyethyl trimethyl ammonium chloride into 250mL of dimethyl sulfoxide and 500mL of deionized water, stirring and reacting for 12h at 90 ℃ by taking 0.10g of azodiisobutyronitrile as a free radical polymerization initiator, dialyzing the mixed solution after the reaction is finished, and then freeze-drying to obtain the bactericidal polymer copolymer (P) kill ) The chemical structural formula is as follows:
example 10
In this example 10, the steps were the same as those in example 1 except for the second step;
preparing a codeposition modifying solution: 0.3wt% of dopamine and 3wt% of antipollution high molecular copolymer (P) anti ) And 3wt% of a bactericidal polymer copolymer (P kill ) Adding the mixture into a tris buffer solution with pH of 8.5, and fully stirring to obtain a codeposition modified solution.
Example 11
In this example 11, the steps were the same as those in example 1 except for the third step;
and step three, codeposition modification of a separation membrane: pouring the codeposition modified liquid prepared in the second step on the surface of the polyvinylidene fluoride separation membrane, and shaking for 40s. After the coating is completed, the redundant codeposition modifying liquid is poured off, and the codeposition modified pollution-resistant separation membrane is obtained after the codeposition modifying liquid is treated for 12 hours at the temperature of 30 ℃ in an oven.
Comparative example 1
(1) Anti-pollution high molecular copolymer (P) anti ) Is synthesized by the following steps: under nitrogen atmosphere, 4.40g of the co-deposition monomer 2-aminoethyl methacrylate and 7.82g of the anti-contamination monomer [2- (methacryloyloxy) ethyl ] were added to 250mL of dimethyl sulfoxide and 500mL of deionized water]Dimethyl- (3-sulfopropyl) ammonium hydroxide, 0.10g of azodiisobutyronitrile is used as a free radical polymerization initiator, stirring reaction is carried out for 24 hours at 70 ℃, the mixed solution is dialyzed after the reaction is finished, and then the anti-pollution high polymer copolymer (P) is obtained after freeze drying anti ) The chemical structural formula is as follows:
(2) Preparing a codeposition modifying solution: 2 wt%o of water-soluble phenol and 6 wt%o of anti-pollution high molecular copolymer (P) anti ) Adding the mixture into an alkaline solution with pH of 13, and fully stirring to obtain the codeposition modified solution.
(3) Co-deposition modification of separation membranes: pouring the codeposition modified solution prepared in the step (2) on the surface of the polyamide reverse osmosis membrane, and shaking for 40s. After the coating is completed, the redundant codeposition modifying liquid is poured off, and the codeposition modified pollution-resistant separation membrane is obtained after the codeposition modifying liquid is treated for 12 hours at the temperature of 30 ℃ in an oven.
Comparative example 2
Step (1) sterilizing Polymer copolymer (P) kill ) Is synthesized by the following steps: under nitrogen atmosphere, 4.40g of the co-deposition monomer 2-aminoethyl methacrylate and 5.42g of the bactericidal monomer [2- (methacryloyloxy) ethyl ] were added to 250mL of dimethyl sulfoxide and 500mL of deionized water]Dimethyl- (3-sulfopropyl) ammonium hydroxide in an amount of 0.10g azobisisobutyronitrileStirring at 70deg.C for 24 hr as free radical polymerization initiator, dialyzing the mixed solution, and lyophilizing to obtain bactericidal polymer (P) kill ) The chemical structural formula is as follows:
preparing a codeposition modifying solution in the step (2): 2 wt% of water-soluble phenol and 6 wt% of bactericidal polymer copolymer (P kill ) Adding the mixture into an alkaline solution with pH of 13, and fully stirring to obtain the codeposition modified solution.
And (3) codeposition modification of the separation membrane: pouring the codeposition modified solution prepared in the step (2) on the surface of the polyamide reverse osmosis membrane, and shaking for 40s. And after the coating is finished, pouring off redundant codeposition modifying liquid, and treating for 12 hours at the temperature of 30 ℃ in an oven to obtain the codeposition modified pollution-resistant polyamide composite reverse osmosis membrane.
Comparative example 3
In comparative example 3, the procedure was the same as in comparative example 1 except that the film used in step (3) was different, and the different step (3) was as follows:
and (3) codeposition modification of the separation membrane: pouring the codeposition modified solution prepared in the step (2) on the surface of the polyvinylidene fluoride ultrafiltration membrane, and shaking for 40s. After the coating is completed, the redundant codeposition modifying liquid is poured off, and the codeposition modified pollution-resistant separation membrane is obtained after the codeposition modifying liquid is treated for 12 hours at the temperature of 30 ℃ in an oven.
Comparative example 4
In comparative example 4, the procedure was the same as in comparative example 2 except that the film used in step (3) was different, and the different step (3) was as follows:
and (3) codeposition modification of the separation membrane: pouring the codeposition modified solution prepared in the step (2) on the surface of the polyvinylidene fluoride ultrafiltration membrane, and shaking for 40s. And after the coating is finished, pouring off redundant codeposition modifying liquid, and treating for 12 hours at the temperature of 30 ℃ in an oven to obtain the codeposition modified pollution-resistant polyamide composite reverse osmosis membrane.
Test case one:
dynamic biological pollution experiment: the membrane sample is arranged on the membrane device, and inorganic salt mixed solution (8mM NaCl,0.15mM MgSO) is added to one side of the raw material liquid 4 ,0.5mM NaHCO 3 ,0.4mM NH 4 Cl,0.2mM CaCl 2 ,0.2mM KH 2 PO 4 0.6mM glucose), 16mM ionic strength, pH 7.4, and adjusting the pressure to 1.55MPa (or 0.1 MPa) to obtain the initial water flux. Adding cultured bacteria stock solution, and the concentration of bacteria used for pollution initiation is 10 6 (CFU·mL -1 ) The system temperature is ensured to be 25 ℃ in the whole experimental process. The experimental stage requires monitoring the change in the mass of the draw solution on the balance to calculate the water flux across the membrane. The operation is convenient, and the operation time adopted in the experiment is based on the accumulated water yield of the penetrating fluid reaching 500mL, so that the water flux after pollution is obtained.
Physical cleaning test conditions: physical cleaning is performed to remove contaminants from the contaminated composite membrane. Pure water was circulated in the apparatus for 60 minutes. Reuse of the inorganic salt mixture solution (8mM NaCl,0.15mM MgSO) 4 ,0.5mM NaHCO 3 ,0.4mM NH 4 Cl,0.2mM CaCl 2 ,0.2mM KH 2 PO 4 The water flux after physical washing was tested by running 0.6mM glucose at 25℃for 60 minutes at 1.55MPa (or 0.1 MPa).
The polyamide reverse osmosis membranes prepared in each example and comparative example were subjected to membrane performance test, and the results are shown in table 1. Compared with the anti-pollution copolymer modified reverse osmosis membrane of comparative example 1 and the bactericidal copolymer modified reverse osmosis membrane of comparative example 2, the anti-pollution antibacterial dual-function modified reverse osmosis membranes prepared in examples 1 to 10 can keep higher water flux after pollution and water flux after physical cleaning in a dynamic biological membrane pollution experiment, which shows that the dual-function anti-biological pollution modification of the membrane surface is superior to the single-function anti-biological pollution modification, and can also show the effectiveness of the blending and co-deposition dual-function modified anti-biological pollution strategy.
TABLE 1 Polyamide reverse osmosis membrane Performance test results
The polyvinylidene fluoride separation membranes prepared in each example and comparative example were subjected to membrane performance test, and the results are shown in table 2. Compared with the anti-pollution copolymer modified polyvinylidene fluoride separation membrane of the comparative example 3 and the bactericidal copolymer modified polyvinylidene fluoride separation membrane of the comparative example 4, the anti-pollution antibacterial dual-function modified polyvinylidene fluoride separation membrane prepared in the example 11 also shows excellent water flux after pollution and water flux after physical cleaning, which shows that the blending and co-deposition dual-function modification between the polyphenol compound and the primary amine-containing copolymer can be adhered to substrates of different membrane materials, and has wide material selection.
TABLE 2 polyvinylidene fluoride ultrafiltration membrane Performance test results
Test case two:
the co-deposited modified bifunctional anti-biofouling separation membranes prepared in example 1 and example 11 were subjected to electron microscopy with unmodified membranes, and the results are shown in the accompanying drawings.
As shown in the first graph and the second graph, the surface of the unmodified polyamide reverse osmosis membrane has a typical peak-valley structure, the valley bottom of the surface of the modified polyamide reverse osmosis membrane is obviously filled by a co-deposition modified layer, and the comparison result of the section transmission electron microscope graphs shows that the modified polyamide reverse osmosis membrane is covered with a co-deposition modified layer with the thickness of about 40nm on the skin layer of the unmodified polyamide reverse osmosis membrane.
As shown in fig. three, the surface electron microscope of the unmodified polyvinylidene fluoride separation membrane has an obvious porous structure, the pore structure of the surface electron microscope display surface of the modified polyvinylidene fluoride separation membrane is obviously covered by the co-deposition modified layer, and meanwhile, the cross-section transmission electron microscope image can also show that the polyvinylidene fluoride surface is successfully coated with the co-deposition modified layer with the thickness of about 500 nanometers.
Claims (9)
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| US20160303517A1 (en) * | 2015-01-30 | 2016-10-20 | California Institute Of Technology | Dendrimer particles and related mixed matrix filtration membranes, compositions, methods, and systems |
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