CN111871223B - High-flux antibacterial nanofiltration membrane and preparation method thereof - Google Patents

High-flux antibacterial nanofiltration membrane and preparation method thereof Download PDF

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CN111871223B
CN111871223B CN202010719414.5A CN202010719414A CN111871223B CN 111871223 B CN111871223 B CN 111871223B CN 202010719414 A CN202010719414 A CN 202010719414A CN 111871223 B CN111871223 B CN 111871223B
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CN111871223A (en
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赵强
彭华文
罗浩
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Huazhong University of Science and Technology
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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
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • 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
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • 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
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/48—Antimicrobial properties

Abstract

The invention belongs to the technical field of membrane separation, and discloses a high-flux antibacterial nanofiltration membrane and a preparation method thereof. The preparation method comprises the following steps: (1) preparing a piperazine-trimesoyl chloride active layer on a bottom membrane to obtain a primary membrane; (2) carrying out surface modification on the primary membrane by using a quaternary ammonium salt monomer containing amino to obtain a modified membrane; (3) and drying the modified membrane to obtain the high-flux antibacterial nanofiltration membrane. The high-flux antibacterial nanofiltration membrane prepared by the invention is subjected to one-step simple surface modification on the surface of a primary membrane, the modification method is simple and quick, the existing technological process for preparing the nanofiltration membrane is not damaged, and the prepared nanofiltration membrane has the characteristics of high flux and high antibacterial property and shows good application prospect.

Description

High-flux antibacterial nanofiltration membrane and preparation method thereof
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a high-flux antibacterial nanofiltration membrane and a preparation method thereof.
Background
Nanofiltration is a membrane separation technology driven by pressure, the separation precision of the nanofiltration is between ultrafiltration and reverse osmosis, and the nanofiltration is widely applied to the fields of brackish water desalination, heavy metal removal, hard water softening, wastewater retreatment, dairy product desalination concentration and the like. The nanofiltration membrane has higher flux compared with the reverse osmosis membrane, but the nanofiltration membrane still has the problem of low water flux in practical application. In addition, the nanofiltration membrane is often easily polluted by microorganisms such as bacteria in long-term operation, even if water is disinfected and sterilized by hypochlorous acid and the like, the fact that bacteria are not introduced in the later period can not be guaranteed, the bacteria can not only damage the microstructure of the membrane surface and reduce the separation performance of the membrane, but also the accumulation of the bacteria on the membrane surface can increase the mass transfer resistance of the water and reduce the flux. Therefore, the preparation of the nanofiltration membrane with high flux, high selectivity and high antibacterial property is not only an effective method for coping with various complicated separation environments, but also an important guarantee for prolonging the service life of the nanofiltration membrane.
CN108014651A discloses a method for preparing an antibacterial composite nanofiltration membrane by dopamine-assisted deposition, and particularly discloses a method for preparing an antibacterial composite nanofiltration membrane by using a polymer porous ultrafiltration membrane as a supporting layer base membrane and performing a crosslinking reaction on the surface of the base membrane by using a reaction solution, so as to obtain the antibacterial composite nanofiltration membrane; the reaction solution comprises a water phase and an oil phase, wherein the water phase comprises dopamine hydrochloride, chitosan quaternary ammonium salt and Tris buffer solution; the oil phase comprises crosslinking monomers and organic solvents. In the nanofiltration membrane of the technical scheme, the polyamide ultrathin desalting layer is combined with the PVB porous base membrane by chemical bonds, so that the base membrane is firmly combined with the polyamide separation layer, the separation layer is complete and free of defects, the hydrophilicity is good, the water flux is high, the preparation method is complicated, and the sterilization capability is insufficient.
CN106582326B discloses an antibacterial composite nanofiltration membrane, which specifically discloses that the composite nanofiltration membrane comprises a support layer, a cross-linked network structure on the surface of the support layer, and silver nanoparticles attached to the cross-linked network structure, wherein the cross-linked network structure is obtained by performing a cross-linking reaction on a polymer containing hydroxyl groups and a silane coupling agent containing mercapto groups in a solution containing a cross-linking agent. The technical scheme mainly utilizes a cross-linked network structure, and has higher interception effect on divalent ions; on the other hand, the multi-hydroxyl polymer on the surface of the membrane can absorb Ag + and reduce the Ag + into silver nano particles under the heating condition, and the nano ions are utilized for sterilization to improve the sterilization capability of the nanofiltration membrane, but the technical scheme still has the defects in the aspect of high flux.
In summary, a nanofiltration membrane with high flux and high antibacterial property is still lacking in the prior art.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a simple preparation method of the high-flux antibacterial nanofiltration membrane without destroying the prior production process, and the high flux and high antibacterial property of the nanofiltration membrane can be realized. The detailed technical scheme of the invention is as follows.
A preparation method of a high-flux antibacterial nanofiltration membrane comprises the following steps:
(1) preparing a piperazine-trimesoyl chloride active layer on a bottom membrane to obtain a primary membrane;
(2) carrying out surface modification on the primary membrane by using a quaternary ammonium salt monomer containing amino to obtain a modified membrane;
(3) and drying the modified membrane to obtain the high-flux antibacterial nanofiltration membrane.
Preferably, the number of amino groups in the quaternary ammonium salt monomer is 2 or more.
Preferably, the surface modification is primary modification, specifically, the quaternary ammonium salt monomer is prepared into a modified aqueous solution, the modified aqueous solution is subjected to primary infiltration on the surface of the primary membrane, and the mass concentration of the quaternary ammonium salt monomer in the modified aqueous solution is 1-7 wt%.
Preferably, the modified aqueous solution is also added with a phase transfer catalyst, the phase transfer catalyst comprises one or more of 4-dimethylaminopyridine, tetrabutylammonium bromide and dodecylammonium bromide, and the mass concentration of the phase transfer catalyst in the modified aqueous solution is 3-6 wt%.
Preferably, the pH of the aqueous modifying solution is from 11 to 13.
Preferably, the wetting time of the modified aqueous solution on the surface of the primary membrane is 2-20 minutes.
Preferably, the quaternary ammonium salt monomer is one of 2, 6-diaminocyanomethylpyridine bromide salt, 1-aminoethyl-2, 6-diaminopyridine bromide salt, N, N, N-triaminoethylmethylbromide salt, 1, 7-diaminoethyl-1, 1,4,7, 7-pentamethyldiethylenetriamine dibromoammonium salt, 1, 3-bis (2-aminoethyl) -1,3,5, 7-tetraazaadamantane bromide salt, 1, 4-diaminoethyl-methylbromide ammonium salt, 1,4, 4-tetraaminoethylpiperazine bromide salt, 1, 4-bis (2-aminoethyl) -1, 4-diazabicyclo [2.2.2] octane bromide salt, preferably, the quaternary ammonium salt monomer is 1, 3-bis (2-aminoethyl) -1,3,5, 7-tetraazaadamantane bromide salt, 1,4, 4-tetraaminoethylpiperazine bromide salt, 1, 4-bis (2-aminoethyl) -1, 4-diazabicyclo [2.2.2] octane bromide salt.
Preferably, the base membrane in step (1) comprises one or more of polyvinylidene fluoride, polysulfone, polyethersulfone or polyacrylonitrile membrane.
Preferably, the drying in step (3) is to air-dry the modified film naturally, and dry the modified film at 30-70 ℃ for 10-30 minutes after no obvious water drops on the surface.
The invention also provides a high-flux antibacterial nanofiltration membrane prepared by the preparation method.
The invention has the following beneficial effects:
(1) the high-flux antibacterial nanofiltration membrane prepared by the invention is subjected to one-step simple surface modification on the primary membrane surface, the modification method is simple and quick, the existing process flow for preparing the nanofiltration membrane is not damaged, and the high-flux antibacterial nanofiltration membrane has a good application prospect.
(2) The high-flux antibacterial nanofiltration membrane prepared by the invention has very obvious modification effect, and can reach 100L/m in flux compared with most modification methods2h above, the method has very obvious advantages, and meanwhile, the nanofiltration membrane prepared by the method also has excellent antibacterial performance, which is not possessed by many modification methods.
(3) According to the high-flux antibacterial nanofiltration membrane prepared by the invention, the modified monomer is connected with the surface of the membrane through a chemical bond (amido bond), so that the membrane has excellent long-term stability, and the used strong electrolyte monomer has strong designability and wide applicability.
Drawings
FIG. 1 is a schematic view of the preparation process of surface modification in example 9 of the present invention.
FIG. 2 is an optical picture of the film tested for antibacterial performance after surface modification in example 9 of the present invention and the relative survival rate of bacteria.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Examples
Example 1
A high-flux antibacterial nanofiltration membrane is prepared by the following steps:
(1) soaking a piperazine water solution with the weight concentration of 0.3 wt% on the surface of the polysulfone support membrane for 3 minutes, then splashing the surface solution, soaking a n-hexane solution of trimesoyl chloride with the weight concentration of 0.3 wt% for 1 minute after obvious water drops do not exist on the surface, and then splashing the surface solution to obtain a primary membrane;
(2) 1-aminoethyl pyridine bromide aqueous solution with the weight concentration of 5 wt% is soaked on the surface of the primary membrane, NaOH is added to adjust the pH value to 12, 4-dimethylamino pyridine with the weight concentration of 5 wt% is mixed in the aqueous solution, and the soaking time is 10 minutes.
(3) And splashing the solution on the surface of the modified membrane, naturally drying, and drying the modified membrane at 50 ℃ for 10 minutes after no obvious water drops exist on the surface to obtain the high-flux antibacterial nanofiltration membrane.
Examples 2-9 differ from example 1 in the modifying monomers and are detailed in table 1.
Examples 10 to 12 differ from example 9 in the base film.
Examples 13-15 differ from example 9 in the monomer concentration.
Examples 16-18 differ from example 9 in the phase transfer catalyst.
Examples 19-21 differ from example 9 in the wetting time of the modifying monomer. Examples 10-21 are detailed in Table 2.
Comparative example
Comparative example 1
Comparative example 1 is different from example 1 in that surface modification was not performed using a quaternary ammonium salt monomer having an amino group.
Table 1 table of parameters of examples
Figure BDA0002599416950000051
Figure BDA0002599416950000061
TABLE 2 continuation of the parameters of the examples
Examples Monomer concentration Base film Phase transfer catalyst Soaking time
9 5wt％ Polysulfone 4-dimethylaminopyridine 10min
10 5wt％ Polyvinylidene fluoride 4-dimethylaminopyridine 10min
11 5wt％ Polyether sulfone 4-dimethylaminopyridine 10min
12 5wt％ Polyacrylonitrile 4-dimethylaminopyridine 10min
13 1wt％ Polysulfone 4-dimethylaminopyridine 10min
14 3wt％ Polysulfone 4-dimethylaminopyridine 10min
15 7wt％ Polysulfone 4-dimethylaminopyridine 10min
16 5wt％ Polysulfone Is free of 10min
17 5wt％ Polysulfone Tetrabutylammonium bromide 10min
18 5wt％ Polysulfone Dodecyl ammonium bromide 10min
19 5wt％ Polysulfone 4-dimethylaminopyridine 2min
20 5wt％ Polysulfone 4-dimethylaminopyridine 5min
21 5wt％ Polysulfone 4-dimethylaminopyridine 20min
Comparative example 1 Is free of Polysulfone Is free of Is free of
Test examples
The high-flux antibacterial nanofiltration membranes prepared in examples 1 to 21 and comparative example 1 were subjected to a nanofiltration performance test and an antibacterial test.
Nanofiltration Performance test
Flux (F) and solvent rejection (R) are two important parameters that measure the separation performance of nanofiltration membranes. In the invention, a cross-flow nanofiltration test is carried out by a nanofiltration instrument, the separation performances such as the sodium sulfate removal rate, the flux and the like of the high-flux antibacterial nanofiltration membrane are evaluated, and the sodium sulfate concentration of the feeding liquid in the above embodiments is 1g L-1The test was completed at 25 ℃.
The solute rejection rate refers to the proportion of the solute that is trapped by the membrane after passing through the nanofiltration membrane. The specific calculation formula is as follows:
Figure BDA0002599416950000071
wherein, CfAnd CpFeed solution and permeate solution solute concentrations, respectively. The salt concentration was determined by conductivity meter.
Flux refers to the volume (V) of water passing through the membrane per unit area (S) per unit time (t) at a certain operating pressure. The operation pressure of the embodiment of the invention is 0.6MPa, and the specific calculation formula is as follows:
Figure BDA0002599416950000072
antibacterial testing
The survival rate (Q) of bacteria on the surface of the membrane is an important parameter for measuring the antibacterial performance of the nanofiltration membrane. In the invention, common escherichia coli and staphylococcus aureus are used as strains for antibacterial test. Specifically, the nanofiltration membrane was first irradiated with ultraviolet rays for 30 minutes to kill bacteria on the membrane surface, and then the membrane was cut into 5cm × 5cm size and placed in a 24-well plate, and 20 μ L of bacteria was addedSuspension (concentration: 1X 10)5CFU mL-1) Dropped on the surface and coated evenly, and incubated at 37 ℃ for 2 hours. Subsequently, 1980. mu.L of the bacterial nutrient solution was added to the well plate and the membrane was washed repeatedly, 60. mu.L of the solution was applied uniformly to the agar plate, and cultured at 37 ℃ for 12 hours, on which the bacteria grew and white spots were visible to the naked eye. The number of bacteria on the surface of the film was recorded as the number of surviving bacteria, as compared with the number of bacteria (M) in the control example0) For reference, the bacteria in the examples (M)1) The survival rate Q is calculated by the formula:
Figure BDA0002599416950000081
the test results are shown in table 3 below.
TABLE 3 test results table
Figure BDA0002599416950000082
Figure BDA0002599416950000091
The reaction principle of the present invention is exemplified by example 9, and as shown in fig. 1, since the interfacial polymerization reaction has time dependency, piperazine and trimesoyl chloride have not completely reacted at the beginning and the degree of crosslinking is not high, a large amount of unreacted acyl chloride groups remain on the surface of the primary membrane, as shown in the left diagram. The right side is a modified membrane, and a quaternary ammonium salt monomer is introduced to the surface of the primary membrane by utilizing the reaction of amino and acyl chloride groups.
Example 9 the number of bacteria on agar plates is shown in FIG. 2, where the graphs a, b show the antibacterial results of Staphylococcus aureus and Escherichia coli, respectively, with the primary membrane on the left and the modified membrane on the right, it can be seen that there is substantially no bacteria present on the modified membrane, and a large amount of bacteria are grown on the primary membrane. The c picture shows the specific survival rates of the two bacteria, compared with the primary membrane, the survival rates of staphylococcus aureus and escherichia coli on the membrane modified by strong electrolyte are respectively 0.9% and 0.7%, and the excellent antibacterial performance is shown. This is mainly due to the high efficiency and broad spectrum of sterilization of quaternary ammonium nitrogen ions on the strong electrolyte molecules.
By analyzing the data in the table 3, the modified membrane of the invention can be seen to make great technical progress in three aspects of water flux, escherichia coli sterilization rate and staphylococcus aureus sterilization rate.
First, it is known from the comparison between examples 1-9 and comparative example 1 that the flux of the membrane after surface modification by quaternary ammonium salt monomer is significantly improved compared with the comparative example on the premise of maintaining high salt rejection rate, and at the same time, the membrane has good antibacterial performance. Further, the effect of 1 amino technical improvement in example 1 is the worst, the effect of 2 or more amino technical improvements in examples 2 to 9 is generally more remarkable, and the effect of 4 amino technical improvements in example 8 is the most remarkable, which indicates that the water flux of the membrane gradually increases as the number of reactive amino groups of the modified monomer increases, the number of charge sites increases, and the steric hindrance increases. This is because, the larger the number of reactive amino groups, the more strong electrolyte is grafted to the membrane surface; the greater the number of charge sites, the better the hydrophilicity of the strong electrolyte monomer, and thus the better the hydrophilicity of the membrane surface; the larger the steric hindrance of the monomer structure is, the larger the free volume of the system is when the monomer structure is added into the interfacial polymerization of the system, and the water transmission is more facilitated.
Second, it is clear from the comparison between example 9 and examples 10 to 12 that the four types of primary membranes, i.e., polyvinylidene fluoride, polysulfone, polyethersulfone, and polyacrylonitrile membrane, all have relatively good effects. Therefore, the nanofiltration membranes were prepared on different supporting basement membranes and modified with strong electrolyte monomers, and the separation performance of the nanofiltration membranes was close, indicating that the method can be applied to different commercial basement membranes, and the polysulfone of example 9 has the best effect.
Thirdly, in the embodiment 9 and the embodiments 13 to 16, the strong electrolyte monomer weight concentration has great influence on the flux of the nanofiltration membrane, and the mass concentration is 1 to 7 weight percent, so that different modification effects are obtained. When the concentration is too low, the number of monomers grafted to the membrane surface is small and the flux is relatively small. When the concentration is too high, the crosslinking density of the membrane is increased, so that the mass transfer resistance is increased, the flux is reduced, the water flux and the sterilization rate are integrated, and the effect is optimal when the mass concentration is 5 wt%.
Fourth, as can be seen from the comparison between example 9 and examples 17 to 19, example 16 has poor effect without adding a phase transfer catalyst, but still has a great improvement over comparative example 1, so whether the invention adds a phase transfer catalyst has a great influence on the membrane performance. This is because the strong electrolyte has good hydrophilicity and very low solubility in the organic phase, and thus cannot effectively react with the residual acid chloride, and the film defects are increased. After the phase transfer catalyst is added, the solubility of the strong electrolyte in the organic phase is increased, more monomers participate in the reaction, and therefore the performance is better. In the invention, the 4-dimethylamino pyridine has the most obvious effect on improving the membrane performance.
Fifth, as can be seen from the comparison between example 9 and examples 19 to 21, the soaking time of the strong electrolyte monomer greatly affects the water flux of the film, and when the soaking time is too short, a large amount of the monomer is splashed out without reacting with the acid chloride, and thus the flux is low. When the soaking time is too long, a large amount of monomer reaction increases the crosslinking density of the membrane, and thus the flux decreases. Example 21 soaking time 10min the water flux improvement effect was most pronounced in the present invention.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (5)

1. A preparation method of a high-flux antibacterial nanofiltration membrane is characterized by comprising the following steps:
(1) preparing a piperazine-trimesoyl chloride active layer on a bottom membrane to obtain a primary membrane;
(2) carrying out surface modification on the primary membrane by using a quaternary ammonium salt monomer containing amino to obtain a modified membrane;
(3) drying the modified membrane to obtain the high-flux antibacterial nanofiltration membrane;
the surface modification is primary modification, specifically, the quaternary ammonium salt monomer is prepared into a modified aqueous solution, the modified aqueous solution is subjected to primary infiltration on the surface of the primary membrane, and the mass concentration of the quaternary ammonium salt monomer in the modified aqueous solution is 3-7 wt%;
the modified aqueous solution is also added with a phase transfer catalyst, the phase transfer catalyst comprises one or a mixture of more of 4-dimethylaminopyridine, tetrabutylammonium bromide and dodecylammonium bromide, and the mass concentration of the phase transfer catalyst in the modified aqueous solution is 3-6 wt%;
the soaking time of the modified aqueous solution on the surface of the primary membrane is 10-20 minutes;
the pH value of the modified aqueous solution is 11-13;
the quaternary ammonium salt monomer is 1, 7-diamino ethyl-1, 1,4,7, 7-pentamethyl diethyl triamine dibromo ammonium salt, 1, 3-di (2-aminoethyl) -1,3,5, 7-tetraazaadamantane bromide salt, 1,4, 4-tetraaminoethyl piperazine bromide salt and 1, 4-di (2-aminoethyl) -1, 4-diazabicyclo [2.2.2] octane bromide salt.
2. The method according to claim 1, wherein the number of amino groups in the quaternary ammonium salt monomer is 2 or more.
3. The preparation method according to claim 1, wherein the base membrane in step (1) comprises one or more of polyvinylidene fluoride, polysulfone, polyethersulfone or polyacrylonitrile membrane.
4. The preparation method of claim 1, wherein the drying in step (3) is carried out by naturally air-drying the modified film, and drying at 30-70 ℃ for 10-30 minutes after no obvious water drops on the surface.
5. A high-flux antibacterial nanofiltration membrane, which is prepared by the preparation method according to any one of claims 1 to 4.
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