CN110201545B - Preparation method of antibacterial high-flux nanofiltration membrane - Google Patents
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- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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Abstract
The invention provides a preparation method of an antibacterial high-flux nanofiltration membrane, which comprises the steps of firstly treating a polysulfone ultrafiltration membrane by a first aqueous phase solution and an oil phase solution to carry out primary interfacial polymerization reaction, then pouring a second aqueous phase solution containing cucurbituril and 1, 2-benzisothiazolin-3-one on the surface of a nascent state membrane to carry out secondary interfacial polymerization, pouring the second aqueous phase solution out, carrying out heat treatment, and finally taking out a membrane and washing the membrane by water to obtain the composite nanofiltration membrane. The 1, 2-benzisothiazolin-3-one is wrapped in the cucurbituril cavity by utilizing stronger host-guest interaction with cucurbituril, and then is introduced into the polyamide layer by a secondary interface polymerization method, so that the antibacterial performance and water flux of the nanofiltration membrane can be obviously improved, the antibacterial effect is lasting and effective, the influence on the desalination rate of the membrane is small, and the method is simple, effective, safe and environment-friendly and is convenient for realizing industrial production.
Description
Technical Field
The invention belongs to the technical field of nanofiltration, and particularly relates to a preparation method of an antibacterial high-flux nanofiltration membrane.
Background
Nanofiltration is a pressure-driven membrane separation process between reverse osmosis and ultrafiltration, and the core of the nanofiltration technology is a nanofiltration membrane. The greatest application field of the nanofiltration membrane is softening of drinking water and removal of organic matters, and people are more concerned about the quality of drinking water along with the improvement of living standard and the increasing severity of environmental pollution. The traditional drinking water treatment mainly removes suspended matters and bacteria in water through flocculation, sedimentation, sand filtration and chlorination, but has low removal rate of various soluble substances. The nanofiltration membrane can intercept microorganisms, suspended solids, bacteria, pathogens and trace organic pollutants in water, and can effectively reduce the hardness of water and remove inorganic pollutants such as nitrate, arsenic, fluoride, heavy metal and the like harmful to human bodies in drinking water. Therefore, people pay more attention to the 'drinking water advanced treatment technology' taking the nanofiltration membrane as a core.
However, in the practical application process, the problem of membrane pollution restricts the wide application and further development of the nanofiltration membrane, and particularly, the membrane separation performance is reduced and the cleaning is very difficult due to the microbial pollution on the surface of the membrane caused by the adsorption of bacteria, fungi and other microorganisms in water, so that the economical efficiency of the application of the nanofiltration technology is reduced, and the safety of the treated drinking water is threatened. The conventional method is to sterilize the membrane periodically and use a medicament to clean the membrane, but the most effective method is to improve the antibacterial property of the surface of the nanofiltration membrane in order to solve the problem fundamentally.
For a long time, methods such as introducing inorganic antibacterial nanoparticles or antibacterial groups and coating antibacterial agents on the surface of a nanofiltration membrane are generally adopted to improve the antibacterial performance of the membrane surface. Chinese patent CN 104548951A discloses a preparation method of a high salt rejection rate antibacterial composite nanofiltration membrane, which is characterized in that after the interface polymerization is completed, the membrane is contacted with attapulgite modified by chitosan quaternary ammonium salt to prepare the antibacterial nanofiltration membrane. In the Chinese patent CN 107983158A, polyethyleneimine is used as a water-phase monomer to prepare a composite nanofiltration membrane with a large number of amino groups on the surface, and the composite nanofiltration membrane is complexed with antibacterial metal ions, so that the antibacterial performance of the composite nanofiltration membrane is improved. The Chinese patent CN 103263862A prepares the composite nanofiltration membrane with antibacterial organic groups on the surface by adding antibacterial triclosan formyl chloride into an oil phase.
Although the methods can improve the antibacterial property of the surface of the nanofiltration membrane, the methods have many defects, such as poor dispersibility of the introduced inorganic antibacterial particles, easy loss in the actual use process, long treatment time required in the antibacterial modification process, general antibacterial effect of the membrane and the like.
Disclosure of Invention
The invention aims to provide a preparation method of an antibacterial high-flux nanofiltration membrane aiming at the defects in the membrane modification technology, which can obviously improve the antibacterial performance and water flux of the nanofiltration membrane, has small influence on the desalination rate of the membrane, is simple, effective, safe and environment-friendly, and is convenient for realizing industrial production.
The invention adopts the following technical scheme:
a preparation method of an antibacterial high-flux nanofiltration membrane comprises the following steps:
(1) fixing a polysulfone ultrafiltration membrane supported by non-woven fabrics, pouring the prepared first aqueous phase solution on the surface of the ultrafiltration membrane, soaking for 1-5 min, pouring the first aqueous phase solution, and removing the residual solution on the surface of the ultrafiltration membrane;
(2) pouring the prepared trimesoyl chloride oil phase solution onto the surface of an ultrafiltration membrane to perform primary interfacial polymerization reaction for 20-60 s, and directly and uniformly blowing by using an air knife or an air knife after pouring the oil phase solution until no residual solvent exists on the surface of the membrane;
(3) then pouring the prepared second aqueous phase solution on the surface of the nascent membrane formed in the step (2) for secondary interfacial polymerization, wherein the reaction time is 10-30 s,
(4) and after the secondary reaction is finished, pouring the second water phase solution, putting the membrane into an oven with the temperature of 80-100 ℃ for heat treatment, wherein the heat treatment time is 5-10 min, and finally taking out the membrane and washing the membrane with water to obtain the composite nanofiltration membrane.
Preferably, the first aqueous solution in the step (1) comprises piperazine and an acid acceptor, wherein the acid acceptor is preferably trisodium phosphate, the concentration of the piperazine is 0.2-2.0 wt%, and the concentration of the acid acceptor is 0.5-3.0 wt%.
Preferably, the oil phase solution in the step (2) comprises trimesoyl chloride and an organic solvent, wherein the concentration of the trimesoyl chloride is 0.1-0.4 wt%.
Preferably, the organic solvent is selected from isoparaffin with boiling point higher than 160 ℃, and more preferably is one or more mixed solvent of Isopar G, Isopar H and Isopar L.
Preferably, the second aqueous solution in step (3) comprises piperazine, cucurbituril and 1, 2-benzisothiazolin-3-one.
Preferably, the cucurbituril used in the second aqueous phase solution in the step (3) is cucurbit [5] urea, cucurbit [6] urea, cucurbit [7] urea or cucurbit [8] urea, and more preferably cucurbit [7] urea.
Preferably, the cucurbituril has a concentration of 0.1 to 2.0 wt%, more preferably 0.1 to 1.0 wt%.
Preferably, the concentration of the 1, 2-benzisothiazolin-3-one in the second aqueous solution in the step (3) is 0.01 to 0.2 wt%, and more preferably 0.01 to 0.1 wt%.
Preferably, the mass ratio of the 1, 2-benzisothiazolin-3-one to the cucurbituril in the second aqueous phase solution in the step (3) is 1: 5-1: 50, and more preferably 1: 10.
Preferably, in the step (3), the concentration of piperazine in the second aqueous phase solution is 0.1 to 1.0 wt%, and an acid acceptor is not added to the second aqueous phase solution.
Preferably, the preparation process of the second aqueous phase solution is as follows: dissolving cucurbituril in pure water, adding 1, 2-benzisothiazolin-3-one liquid while stirring, and finally dissolving piperazine in an aqueous solution to prepare a second aqueous phase solution; wherein the 1, 2-benzisothiazolin-3-one liquid is added slowly.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a simple, effective, safe and environment-friendly preparation method of an antibacterial high-flux nanofiltration membrane, which is convenient for realizing industrial production. The cucurbituril has a hydrophobic inner cavity and two symmetrical polar carbonyl ports, so that the cucurbituril can generate strong host-guest interaction with 1, 2-benzisothiazolin-3-one of the antibacterial agent, a hydrophobic aromatic ring in a molecule of the 1, 2-benzisothiazolin-3-one enters the cavity of the cucurbituril, a secondary amino group in the molecule and the port carbonyl form a hydrogen bond, the 1, 2-benzisothiazolin-3-one can be wrapped in the cucurbituril with a special structure, and the cucurbituril is retained on the surface of the polyamide layer through secondary interface polymerization and is not easy to run off. The cucurbituril uniformly dispersed in the polyamide layer has a larger cavity structure, a new water channel is constructed, the water flux of the nanofiltration membrane is improved, the included 1, 2-benzisothiazolin-3-one can effectively kill microorganisms such as bacteria, fungi and the like in contact with the surface by destroying DNA molecules in biological cells by means of the active part on the heterocycle, the antibacterial performance of the nanofiltration membrane is obviously improved, and the desalination rate of the membrane cannot be greatly influenced.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples, but the scope of the present invention is not limited thereto.
1. The separation performance of the prepared composite nanofiltration membrane is evaluated and mainly characterized by two characteristic parameters, namely the water flux and the salt rejection rate of the membrane.
Water flux (LMH) is defined as: the volume of water per unit time that permeates the active membrane area under certain operating pressure conditions.
Salt rejection calculation formula: r ═ 1-Cp/Cf) X 100%, wherein R represents the rejection rate, CfAnd CpThe concentrations of the salts (ppm) in the permeate and in the feed, respectively.
The test conditions of the separation performance of the membrane are as follows: the feed liquid is 2000ppm magnesium sulfate water solution, the temperature of the feed liquid is 25 ℃, and the operating pressure is 0.4 MPa.
2. Quantitatively detecting the antibacterial effect of the membrane:
the antibacterial detection standard refers to national standard GB/T37206-2018, which is specifically to shear an antibacterial nanofiltration membrane into a sample of 40mm multiplied by 40mm, contact the sample with 100 mu L of escherichia coli (ATCC 25922) bacterial liquid, culture for 2h in a constant temperature incubator at 37 ℃, repeatedly wash the sample with 10mL of PBS buffer solution, take washing liquid for proper dilution, perform viable bacteria culture counting, and perform a comparative test on a common nanofiltration membrane (without antibacterial components). The sterilization rate was calculated as follows:
sterilization rate ((N)B-NA)/NB) X 100%, wherein NBRepresents the activity of a common nanofiltration membrane sampleNumber of bacteria (CFU), NARepresenting the viable Count (CFU) of the antibacterial nanofiltration membrane sample.
Example 1
(1) Fixing a polysulfone ultrafiltration membrane supported by non-woven fabrics, pouring a prepared first aqueous phase solution containing 1.0 wt% of piperazine and 2.0 wt% of trisodium phosphate onto the surface of the ultrafiltration membrane for 2min, and removing a residual solution on the surface of the ultrafiltration membrane by rolling a rubber roller after pouring the first aqueous phase solution;
(2) then pouring the prepared Isopar L oil phase solution containing 0.2 wt% of trimesoyl chloride on the surface of the ultrafiltration membrane for primary interfacial polymerization reaction, wherein the reaction time is 40s, after pouring the oil phase solution, no heat treatment is carried out, and air knife or air knife is adopted for even blowing until no residual solvent is left on the surface of the membrane;
(3) then pouring a prepared second aqueous phase solution containing 0.3 wt% of piperazine, 0.4 wt% of cucurbit [7] urea and 0.04 wt% of 1, 2-benzisothiazolin-3-one on the surface of the film for secondary interfacial polymerization for 20s, wherein the preparation process of the second aqueous phase solution is as follows: dissolving cucurbit [7] uril in pure water, slowly dropwise adding 1, 2-benzisothiazolin-3-one liquid while stirring, and finally dissolving piperazine in an aqueous solution to prepare a second aqueous phase solution;
(4) and after the secondary reaction is finished, pouring the second water phase solution, putting the membrane into a 90 ℃ oven for heat treatment for 5-10 min, and finally taking out the membrane and washing with water to obtain the composite nanofiltration membrane.
Example 2
This example is mainly different from example 1 in that the concentrations of cucurbit [7] urea and 1, 2-benzisothiazolin-3-one in the second aqueous phase solution in the step (3) are 0.2 wt% and 0.02 wt%, respectively.
Example 3
This example is mainly different from example 1 in that the concentrations of cucurbit [7] urea and 1, 2-benzisothiazolin-3-one in the second aqueous phase solution in the step (3) are 1.0 wt% and 0.1 wt%, respectively.
Example 4
This example is mainly different from example 1 in that the concentrations of cucurbit [7] urea and 1, 2-benzisothiazolin-3-one in the second aqueous phase solution in the step (3) are 1.5 wt% and 0.15 wt%, respectively.
Comparative example 1
The main difference between this comparative example and example 1 is that: the second aqueous phase solution in the step (3) only contains 0.3 wt% of piperazine.
The composite nanofiltration membranes prepared in examples 1 to 4 and comparative example 1 were subjected to separation performance and antibacterial effect tests, and the test results are shown in table 1.
TABLE 1
From the test results of examples 1-5 and comparative example 1, it can be seen that when cucurbit [7] urea and 1, 2-benzisothiazolin-3-one are not added to the second aqueous phase solution, the prepared nanofiltration membrane has no antibacterial property, and when the concentrations of cucurbit [7] urea and 1, 2-benzisothiazolin-3-one are 0.4 wt% and 0.04 wt%, respectively, the water flux of the prepared nanofiltration membrane is obviously improved, the sterilization rate exceeds 90%, and the desalination rate is only reduced by 0.3%.
Example 5
This example is mainly different from example 1 in that the concentration of 1, 2-benzisothiazolin-3-one in the second aqueous phase solution in the step (3) is 0.08 wt%.
Example 6
This example is mainly different from example 1 in that the concentration of 1, 2-benzisothiazolin-3-one in the second aqueous phase solution in the step (3) is 0.02 wt%.
Example 7
This example is mainly different from example 1 in that the concentration of 1, 2-benzisothiazolin-3-one in the second aqueous phase solution in the step (3) is 0.01 wt%.
Comparative example 2
This comparative example differs from example 1 mainly in that 1, 2-benzisothiazolin-3-one is not added to the second aqueous solution in step (3).
The composite nanofiltration membranes prepared in examples 5 to 7 and comparative example 2 were subjected to separation performance and antibacterial effect tests, and the test results are shown in table 2.
TABLE 2
Example 8
The main difference between this embodiment and embodiment 1 is that: the concentration of piperazine in the second aqueous phase solution in the step (3) is 0.1 wt%.
Example 9
The main difference between this embodiment and embodiment 1 is that: the concentration of piperazine in the second aqueous phase solution in the step (3) is 0.6 wt%.
Example 10
The main difference between this embodiment and embodiment 1 is that: the concentration of piperazine in the second aqueous phase solution in the step (3) is 1.0 wt%.
Comparative example 3
The main difference between this comparative example and example 1 is that: and (3) adding no piperazine monomer into the second aqueous phase solution in the step (3).
The composite nanofiltration membranes prepared in examples 8 to 10 and comparative example 3 were subjected to separation performance and antibacterial effect tests, and the test results are shown in table 3.
TABLE 3
From the test results of examples 8-10 and comparative example 3, it can be seen that when no piperazine monomer is added to the second aqueous phase solution, a complete secondary polyamide layer cannot be formed, and the prepared nanofiltration membrane has high water flux but poor desalination rate and antibacterial performance.
Claims (13)
1. A preparation method of an antibacterial high-flux nanofiltration membrane is characterized by comprising the following steps:
(1) fixing the polysulfone ultrafiltration membrane, pouring the prepared first aqueous phase solution onto the surface of the ultrafiltration membrane, soaking for 1-5 min, pouring the first aqueous phase solution, and removing the residual solution on the surface of the ultrafiltration membrane;
(2) pouring the prepared trimesoyl chloride oil phase solution onto the surface of an ultrafiltration membrane to perform primary interfacial polymerization reaction for 20-60 s, and directly and uniformly blowing by using an air knife or an air knife after pouring the oil phase solution until no residual solvent exists on the surface of the membrane;
(3) pouring the prepared second aqueous phase solution on the surface of the nascent membrane formed in the step (2) for secondary interfacial polymerization, wherein the reaction time is 10-30 s;
(4) after the secondary reaction is finished, pouring the second water phase solution, putting the membrane into an oven with the temperature of 80-100 ℃ for heat treatment, wherein the heat treatment time is 5-10 min, and finally taking out the membrane and washing the membrane with water to obtain the composite nanofiltration membrane;
the second aqueous phase solution in the step (3) comprises piperazine, cucurbituril and 1, 2-benzisothiazolin-3-one;
the concentration of the 1, 2-benzisothiazolin-3-one in the second aqueous phase solution in the step (3) is 0.01-0.2 wt%, the concentration of the cucurbituril is 0.1-2.0 wt%, and the concentration of the piperazine is 0.1-1.0 wt%.
2. The method of claim 1, wherein: the first aqueous phase solution in the step (1) comprises piperazine and an acid acceptor, wherein the concentration of the piperazine is 0.2-2.0 wt%, and the concentration of the acid acceptor is 0.5-3.0 wt%.
3. The method of claim 2, wherein: in the step (1), the acid acceptor is trisodium phosphate.
4. The method of claim 1, wherein: the oil phase solution in the step (2) comprises trimesoyl chloride and an organic solvent, wherein the concentration of the trimesoyl chloride is 0.1-0.4 wt%.
5. The method of claim 4, wherein: the organic solvent is selected from the group consisting of isoparaffins having a boiling point above 160 ℃.
6. The method of claim 5, wherein: the organic solvent is selected from one or more mixed solvents of Isopar G, Isopar H and Isopar L.
7. The method of claim 1, wherein: the cucurbituril used in the second aqueous phase solution in the step (3) is cucurbit [5] urea, cucurbit [6] urea, cucurbit [7] urea or cucurbit [8] urea.
8. The method of claim 7, wherein: the cucurbituril used in the second aqueous phase solution in the step (3) is cucurbit [7] urea.
9. The method of claim 1, wherein: the concentration of the 1, 2-benzisothiazolin-3-one in the second aqueous phase solution in the step (3) is 0.01-0.1 wt%, and the concentration of the cucurbituril is 0.1-1.0 wt%.
10. The method of claim 1, wherein: in the step (3), the mass ratio of the 1, 2-benzisothiazolin-3-one to the cucurbituril in the second aqueous phase solution is 1: 5-1: 50.
11. The method of manufacturing according to claim 10, wherein: in the step (3), the mass ratio of the 1, 2-benzisothiazolin-3-one to the cucurbituril in the second aqueous phase solution is 1: 10.
12. The method of claim 1, wherein: the acid scavenger is not added to the second aqueous phase solution.
13. The method of claim 1, wherein: the preparation process of the second aqueous phase solution comprises the following steps: dissolving cucurbituril in pure water, adding 1, 2-benzisothiazolin-3-one liquid while stirring, and finally dissolving piperazine in an aqueous solution to prepare a second aqueous phase solution.
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| CN111420561B (en) * | 2020-04-30 | 2022-04-22 | 万华化学集团股份有限公司 | Preparation method of antibacterial water-softening nanofiltration membrane and antibacterial water-softening nanofiltration membrane prepared by same |
| CN111871223B (en) * | 2020-07-23 | 2021-10-08 | 华中科技大学 | High-flux antibacterial nanofiltration membrane and preparation method thereof |
| CN112725242B (en) * | 2021-02-10 | 2023-12-05 | 杭州楠大环保科技有限公司 | Special microbial inoculum for strengthening sewage centralized treatment of activated sludge and preparation method thereof |
| CN113968906B (en) * | 2021-11-22 | 2023-03-24 | 四川大学 | Method for endowing collagen with lasting antibacterial function by utilizing outer wall quaternized cucurbituril |
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