CN113499693A - Chemical stimulus response anti-pollution reverse osmosis membrane and preparation method thereof - Google Patents
Chemical stimulus response anti-pollution reverse osmosis membrane and preparation method thereof Download PDFInfo
- Publication number
- CN113499693A CN113499693A CN202110894031.6A CN202110894031A CN113499693A CN 113499693 A CN113499693 A CN 113499693A CN 202110894031 A CN202110894031 A CN 202110894031A CN 113499693 A CN113499693 A CN 113499693A
- Authority
- CN
- China
- Prior art keywords
- reverse osmosis
- osmosis membrane
- solution
- membrane
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a chemical stimulus response anti-pollution reverse osmosis membrane and a preparation method thereof. Constructing a chemical stimulation response shedding anti-fouling coating on the surface of the reverse osmosis membrane by utilizing the self-polymerization characteristic of catechol and the Schiff base or Michael addition reaction of catechol and amino; according to the chemical stimulus response anti-pollution reverse osmosis membrane prepared by the invention, the membrane shows the stimulus response characteristic to a reducing agent, and has excellent anti-pollution performance while keeping good separation performance.
Description
Technical Field
The invention relates to a chemical stimulus response anti-pollution reverse osmosis membrane and a preparation method thereof, belonging to the technical field of membrane separation.
Background
Over one third of the world's population lives in countries and regions with water shortages, and this figure is expected to rise to nearly two thirds by 2025. Water crisis is further aggravated by factors such as population growth, industrialization, pollution of available fresh water resources, climate change and the like. At the same time, people are aware of the wide social and ecological benefits brought by sufficient water resources, which also prompts people to seek technical solutions to solve the water resource shortage. The sea occupies 71 percent of the surface area, the volume of the seawater reaches 13.7 hundred million cubic kilometers, and the total water quantity of the land occupation ball is more than 97 percent. The seawater desalination technology provides stable and high-quality water supply and has little harm to the environment. Most of the existing seawater desalination facilities are based on reverse osmosis membrane technology, and compared with a distillation method, a crystallization method, flash evaporation, an ion exchange method and the like, the reverse osmosis membrane technology has the advantages of high efficiency, energy conservation, high automation, safety, stability and the like. However, in the actual operation process, pollutants are continuously accumulated on the surface of the reverse osmosis membrane, and then a gel layer is formed, so that the permeation flux is greatly reduced, the energy consumption in the separation process is increased, and the desalination cost is increased. Therefore, reverse osmosis membrane fouling has greatly limited the practical application of reverse osmosis membrane materials in seawater desalination.
In order to solve the problems, various methods can be adopted to prepare the high-performance anti-pollution reverse osmosis membrane.
CN104226123A discloses a preparation method of a modified reverse osmosis membrane based on pure amine coating, amino groups are fixed on the membrane surface through reaction with residual acyl chloride groups on the membrane surface and reduce the charge of the membrane surface, and hydroxyl groups increase the hydrophilicity of the membrane. CN102921315A discloses a preparation method of a polyamide desalting layer containing PVA molecules and a reverse osmosis membrane of a PVA cross-linked coating, wherein PVA is added into a water phase solution, then the water phase solution is contacted with an oil phase solution to obtain a PVA polyamide layer, and finally residual hydroxyl is utilized to further cross-link with the PVA coated on the surface of the membrane, so that the PVA coating and the desalting layer are bonded together. However, such coating modification methods that utilize increased hydrophilicity to form a hydrated layer on the membrane surface to resist contamination can only retard contamination but cannot remove contamination. Therefore, an antifouling sacrificial layer with intelligent response shedding is an effective method for maintaining the membrane separation performance and removing the pollutants on the membrane surface.
Disclosure of Invention
In view of the above problems in the prior art, the present invention is to provide a chemical stimulus response anti-pollution reverse osmosis membrane and a preparation method thereof, which solve the technical problems at present.
The purpose of the invention is realized by the following technical scheme:
a chemical stimulus response anti-pollution reverse osmosis membrane is prepared by the following preparation method, and comprises the following steps:
(1) preparation of aqueous phase solution: dissolving water phase monomer in deionized water, placing in an ultrasonic instrument, and performing ultrasonic treatment for 10min to uniformly disperse the monomer; (ii) a
(2) Preparation of oil phase solution: dissolving an oil phase monomer in an organic solvent, and performing ultrasonic treatment for 5min to obtain an oil phase solution;
(3) preparing a Tris solution: placing trihydroxy aminomethane in water, and performing ultrasonic treatment for 10min to uniformly disperse the monomers;
(4) preparation of HCl solution: placing concentrated hydrochloric acid in water, and stirring at normal temperature for 10min to uniformly disperse the monomers;
(5) preparation of Tris-HCl buffer: taking the Tris solution prepared in the step (3) and the HCl solution prepared in the step (4), adding deionized water for dilution, and placing the solution in an ultrasonic instrument for ultrasonic treatment for 10 min;
(6) preparation of codeposition solution: adding catecholamine and a disulfide polymer into the Tris-HCl buffer solution prepared in the step (5), and performing ultrasonic treatment for 1min to uniformly disperse the catecholamine and the disulfide polymer;
(7) preparing a stimulus response reverse osmosis membrane: pouring the water phase solution prepared in the step (1) on the surface of the reverse osmosis base membrane for standing, pouring out redundant solution, then immersing the membrane into the oil phase solution in the step (2) for reaction for a period of time, and after the reaction is finished, putting the membrane into a drying oven for heat treatment to obtain an initial reverse osmosis membrane; and (4) pouring the co-deposition solution prepared in the step (6) onto the surface of the prepared initial reverse osmosis membrane immediately, and depositing for a period of time to obtain the reverse osmosis membrane responding to chemical stimulation.
Wherein the oil phase monomer in the step (2) is one or more of the following: 1,3, 5-benzenetricarboxychloride, 1, 3-benzenedicarbonyl chloride, bridged bicyclic tricyclic tetracarbonyl or biphenylhexacarbonyl; the organic solvent is one or more of n-hexane, heptane, cyclohexane or Isopar-G; the oil phase monomer accounts for 0.1-0.5 wt% of the organic solvent.
And (4) the concentration of the Tris solution in the step (3) is 0.1 mol/L.
And (4) HCl solution is 0.1 mol/L.
And (5) taking 50ml of Tris solution prepared in the step (3) and 14.7ml of HCl solution prepared in the step (4), and adding deionized water to dilute to 100 ml.
The catecholamine in the step (6) is one or more of dopamine, levodopa, tannic acid and norepinephrine, and the mass fraction is 0.1-0.5 wt%; the disulfide polymer is one or more of cystamine and cystine, and the mass fraction is 0.05-1 wt%.
In the step (7), the material of the reverse osmosis basement membrane is one of polysulfone, polyethersulfone, polyacrylonitrile, cellulose acetate and polyamide, and the aperture of the reverse osmosis basement membrane is 0.001-0.002 μm.
The reaction time of the initial reverse osmosis membrane obtained in the step (7) is 30s-5min, the heat treatment temperature is 50-120 ℃, and the heat treatment time is 1-30 min; the time for depositing the blended solution on the surface of the initial reverse osmosis membrane is 2-24 h.
The invention utilizes the self-polymerization characteristic of catechol and can generate Schiff base or Michael addition reaction with amino to construct a layer of anti-fouling coating which is peeled off in response to chemical stimulation on the surface of the reverse osmosis membrane. Because the coating contains a large number of disulfide bonds, the disulfide bonds can be broken in the presence of a reducing agent, and pollutants adhered to the surface of the film are taken away while the coating is decomposed, so that the aim of pollution resistance is fulfilled. In a pollution test, the prepared reverse osmosis membrane has good resistance to Dodecyl Trimethyl Ammonium Bromide (DTAB) and Sodium Alginate (SA).
Drawings
FIG. 1(a) SEM image of the surface of a reverse osmosis membrane obtained in comparative example 1 before response to a chemical stimulus;
FIG. 1(b) SEM image of the surface of the reverse osmosis membrane obtained in example 1 before response to chemical stimulus;
FIG. 1(c) SEM image of the surface of the reverse osmosis membrane obtained in example 2 before response to chemical stimulus;
FIG. 1(d) SEM image of the surface of the reverse osmosis membrane obtained in example 3 before response to chemical stimulus;
FIG. 1(e) SEM image of the surface of the reverse osmosis membrane obtained in example 4 before response to chemical stimulus;
FIG. 1(f) SEM image of the surface of the reverse osmosis membrane obtained in example 5 before response to chemical stimulus;
FIG. 1 (a') is a surface SEM image of a reverse osmosis membrane TCEP obtained in comparative example 1 after cleaning;
FIG. 1 (b') SEM image of the surface of a cleaned reverse osmosis membrane TCEP obtained in example 1;
FIG. 1 (c') SEM image of the surface of a cleaned reverse osmosis membrane TCEP obtained in example 2;
FIG. 1 (d') SEM image of the cleaned surface of the TCEP of the reverse osmosis membrane obtained in example 3;
FIG. 1 (e') SEM image of the cleaned surface of the TCEP of the reverse osmosis membrane obtained in example 4;
FIG. 1 (f') SEM image of the surface of the cleaned reverse osmosis membrane TCEP obtained in example 5.
Detailed Description
The invention of this patent is illustrated below with reference to examples, but it is not limited thereto.
Comparative example 1
2.0g of m-phenylenediamine, 2.3g of camphorsulfonic acid and 1.1g of triethylamine are placed in a beaker, 100ml of distilled water is added and ultrasonically dispersed, then the solution is poured on the surface of the basement membrane and stands for 5min, and the excess solution is poured out and naturally dried. 0.1g of 1,3, 5-benzene trimethyl chloride is dissolved in 100ml of normal hexane, the mixture is poured onto the surface of the processed basement membrane after ultrasonic dispersion, the reaction time is 30s, and the prepared initial reverse osmosis membrane is subjected to heat treatment for 1min at the temperature of 50 ℃ after the reaction is finished. The prepared initial reverse osmosis membrane was treated with a 1mM/L TCEP solution for 10min to obtain a TCEP-washed initial reverse osmosis membrane.
Example 1
2.0g of m-phenylenediamine, 2.3g of camphorsulfonic acid and 1.1g of triethylamine are put into 100ml of distilled water, poured on the surface of a basement membrane after being completely dissolved, kept stand for 5min and then poured to remove the redundant solution. 0.12g of 1,3, 5-benzene trimethyl acyl chloride is dissolved in 100ml of n-hexane, after the dissolution is finished, the solution is poured on the surface of a basement membrane for reaction, the reaction time is 60s, and after the reaction is finished, the prepared PA membrane is subjected to heat treatment for 5min at the temperature of 60 ℃. Placing 1.2g trihydroxy aminomethane in 200ml water, and performing ultrasonic treatment for 10min to uniformly disperse the monomers; 1.0g of concentrated hydrochloric acid is put into 200ml of water and stirred for 10min at normal temperature, so that the monomers are uniformly dispersed; taking 50ml of Tris solution and 14.7ml of HCl solution, adding deionized water to dilute to 100ml, and placing in an ultrasonic instrument for ultrasonic treatment for 10 min. Weighing 0.1g of dopamine and 0.05g of cystine, placing the dopamine and the cystine in 100ml of Tris-HCl buffer solution, stirring uniformly, pouring the mixture into the surface of the initial reverse osmosis membrane immediately, then placing the initial reverse osmosis membrane on a shaking table for deposition for 2 hours, repeatedly washing the surface of the membrane by using deionized water after the deposition is finished, and washing off redundant solution to obtain the chemical stimulus response anti-pollution reverse osmosis membrane. The prepared initial reverse osmosis membrane is treated with 5mM/L of TCEP solution for 20min to obtain the reverse osmosis membrane after TCEP chemical stimulation response.
Example 2
2.0g of m-phenylenediamine, 2.3g of camphorsulfonic acid and 1.1g of triethylamine are put into 100ml of distilled water, poured on the surface of a basement membrane after being completely dissolved, kept stand for 10min and then poured to remove the redundant solution. 0.15g of 1,3, 5-benzene trimethyl acyl chloride is dissolved in 100ml of n-hexane, after the dissolution is finished, the solution is poured on the surface of a basement membrane for reaction, the reaction time is 2min, and after the reaction is finished, the prepared PA membrane is subjected to heat treatment for 10min at the temperature of 80 ℃. Placing 1.5g trihydroxy aminomethane in 200ml water, and performing ultrasonic treatment for 10min to uniformly disperse the monomers; 1.2g of concentrated hydrochloric acid is put into 200ml of water and stirred for 10min at normal temperature, so that the monomers are uniformly dispersed; taking 50ml of Tris solution and 14.7ml of HCl solution, adding deionized water to dilute to 100ml, and placing in an ultrasonic instrument for ultrasonic treatment for 10 min. Weighing 0.2g of dopamine and 0.4g of cystine, placing the dopamine and the cystine in 100ml of Tris-HCl buffer solution, stirring uniformly, pouring the mixture into the surface of the initial reverse osmosis membrane immediately, then placing the initial reverse osmosis membrane on a shaking table for deposition for 6 hours, repeatedly washing the surface of the membrane by using deionized water after the deposition is finished, and washing off redundant solution to obtain the chemical stimulus response anti-pollution reverse osmosis membrane. The prepared initial reverse osmosis membrane is treated with 8mM/L of TCEP solution for 40min to obtain the reverse osmosis membrane after TCEP chemical stimulation response.
Example 3
2.0g of m-phenylenediamine, 2.3g of camphorsulfonic acid and 1.1g of triethylamine are put into 100ml of distilled water, poured on the surface of a basement membrane after being completely dissolved, kept stand for 5min and then poured to remove the redundant solution. 0.2g of 1,3, 5-benzene trimethyl acyl chloride is dissolved in 100ml of n-hexane, after the dissolution is finished, the solution is poured on the surface of a basement membrane for reaction, the reaction time is 3min, and after the reaction is finished, the prepared PA membrane is subjected to heat treatment for 15min at the temperature of 90 ℃. Placing 1.8g trihydroxy aminomethane in 200ml water, and performing ultrasonic treatment for 10min to uniformly disperse the monomers; 1.5g of concentrated hydrochloric acid is put into 200ml of water and stirred for 10min at normal temperature, so that the monomers are uniformly dispersed; taking 50ml of Tris solution and 14.7ml of HCl solution, adding deionized water to dilute to 100ml, and placing in an ultrasonic instrument for ultrasonic treatment for 10 min. Weighing 0.2g of L-dopamine and 0.2g of cystamine, placing the L-dopamine and the cystamine in 100ml of Tris-HCl buffer solution, stirring uniformly, pouring the mixture into the surface of an initial reverse osmosis membrane immediately, then placing the initial reverse osmosis membrane on a shaking table for deposition for 10 hours, repeatedly washing the surface of the membrane by using deionized water after the deposition is finished, and washing off redundant solution to obtain the chemical stimulus response anti-pollution reverse osmosis membrane. The prepared initial reverse osmosis membrane is treated with 10mM/L of TCEP solution for 60min to obtain the reverse osmosis membrane after TCEP chemical stimulation response.
Example 4
2.0g of m-phenylenediamine, 2.3g of camphorsulfonic acid and 1.1g of triethylamine are put into 100ml of distilled water, poured on the surface of a basement membrane after being completely dissolved, kept stand for 5min and then poured to remove the redundant solution. 0.3g of 1,3, 5-benzene trimethyl acyl chloride is dissolved in 100ml of n-hexane, after the dissolution is finished, the solution is poured on the surface of a basement membrane for reaction, the reaction time is 4min, and after the reaction is finished, the prepared PA membrane is subjected to heat treatment for 20min at the temperature of 100 ℃. 2.4g of trihydroxy aminomethane is put into 200ml of water and is subjected to ultrasonic treatment for 10min, so that the monomers are uniformly dispersed; 2.0g of concentrated hydrochloric acid is put into 200ml of water and stirred for 10min at normal temperature, so that the monomers are uniformly dispersed; taking 50ml of Tris solution and 14.7ml of HCl solution, adding deionized water to dilute to 100ml, and placing in an ultrasonic instrument for ultrasonic treatment for 10 min. Weighing 0.4g of noradrenaline and 0.8g of cystamine, placing the mixture in 100ml of Tris-HCl buffer solution, stirring uniformly, pouring the mixture onto the surface of an initial reverse osmosis membrane immediately, then placing the initial reverse osmosis membrane on a shaking table for deposition for 16 hours, repeatedly washing the surface of the membrane with deionized water after the deposition is finished, and washing off redundant solution to obtain the chemical stimulus response anti-pollution reverse osmosis membrane. The prepared initial reverse osmosis membrane is treated with 15mM/L of TCEP solution for 90min to obtain the reverse osmosis membrane after TCEP chemical stimulation response.
Example 5
2.0g of m-phenylenediamine, 2.3g of camphorsulfonic acid and 1.1g of triethylamine are put into 100ml of distilled water, poured on the surface of a basement membrane after being completely dissolved, kept stand for 5min and then poured to remove the redundant solution. 0.5g of 1,3, 5-benzene trimethyl acyl chloride is dissolved in 100ml of n-hexane, after the dissolution is finished, the solution is poured on the surface of a basement membrane for reaction, the reaction time is 5min, and after the reaction is finished, the prepared PA membrane is subjected to heat treatment for 30min at 120 ℃. Putting 3.6g of trihydroxy aminomethane in 200ml of water, and carrying out ultrasonic treatment for 10min to uniformly disperse the monomers; 3.0g of concentrated hydrochloric acid is put into 200ml of water and stirred for 10min at normal temperature, so that the monomers are uniformly dispersed; taking 50ml of Tris solution and 14.7ml of HCl solution, adding deionized water to dilute to 100ml, and placing in an ultrasonic instrument for ultrasonic treatment for 10 min. Weighing 0.5g of dopamine and 1.0g of cystamine, placing the dopamine and the cystamine in 100ml of Tris-HCl buffer solution, stirring uniformly, pouring the mixture onto the surface of an initial reverse osmosis membrane immediately, then placing the initial reverse osmosis membrane on a shaking table for deposition for 24 hours, repeatedly washing the surface of the membrane by deionized water after the deposition is finished, and washing off redundant solution to obtain the chemical stimulus response anti-pollution reverse osmosis membrane. The prepared initial reverse osmosis membrane is treated with 20mM/L of TCEP solution for 120min to obtain the reverse osmosis membrane after TCEP chemical stimulation response.
Table 1 shows the water flux (J, LMH) and the salt rejection (R,%) of the chemical stimulus-responsive reverse osmosis membranes obtained in the comparative examples and examples. These two data were obtained experimentally by first fixing a reverse osmosis membrane in the membrane cell of a triple high pressure flat sheet membrane test apparatus, each cell having an effective test area of 60cm2And has a flow channel 1mm high. Then pre-pressing the mixture at 5MPa by using deionized water, and then preparing the mixture into a product 3000mL of 2000ppm sodium chloride aqueous solution was used as a feed solution, and the test was performed at 1.6MPa, and the feed solution was kept at 25 ℃ for both pre-pressing and testing, and at a flow rate of 3.6L/min. Collecting water at a permeation end, weighing the water (m) at intervals of specific time (delta t), and calculating by using a formula 1, wherein A is the effective filtration area of the membrane pool, so that the mass of the water passing through a unit membrane area in unit time, namely the water flux can be obtained, and all water flux data need to be recorded after the flux is stable. Since sodium chloride is a strong electrolyte, the conductivity of its aqueous solution can be measured as an indication of its concentration. Testing the water solution of the feed liquid and the penetrating fluid to obtain the conductivity data of the feed liquid and the penetrating fluid, and calculating according to a formula 2 to obtain the salt rejection rate of the reverse osmosis membrane, wherein CpAnd CfConductivity of permeate and feed respectively.
Table 2 shows the flux recovery data of the comparative examples and examples after 24h of contamination with dodecyltrimethylammonium bromide (DTAB) and after the TCEP reducing agent has cleaned the coating and the deionized water has rinsed the surface of the membrane. The flux recovery rate can be obtained by the following steps: DTAB (50ppm) was added to a 2000ppm aqueous NaCl solution as a contaminant solution to simulate contamination of a reverse osmosis membrane with a surfactant under actual conditions. The whole experiment is the same as a water flux salt rejection test system. The specific experimental steps are as follows: all membrane samples were pre-stressed for 30min to stabilize the filtration system, and then the membrane samples were filtered in 2000ppm NaCl aqueous solution for 1h to obtain stable purified water (J)o). Then, an antifouling filtration test was carried out, a. the aqueous NaCl solution in the feed cylinder was replaced by the feed solution of the contaminant, the filtration was circulated for 6 hours, and the water flux (J) of the membrane under the contaminated conditions was measured in real timet) (ii) a b. The pollutant solution in the material cylinder is replaced by pure water or TCEP reducing agent and the membrane is washed for 1 h;c. the aqueous NaCl solution was poured into the feed cylinder again and the recovered water flux (J) was measured after 1 hour of filtrationr) To investigate the long-term antifouling performance of the membranes, the above antifouling filtration test was cycled three times. The water Flux Recovery Rate (FRR) is commonly used for analyzing the anti-pollution performance of a membrane sample, the higher the recovery rate is, the better the anti-pollution effect of the membrane is proved, and the anti-pollution performance can be calculated by a formula 3:
table 3 shows the flux recovery data of the TCEP reducing agent after the coating is cleaned and the deionized water is used for washing the surface of the membrane after the comparative example and the example are polluted by sodium alginate for 36 h. The test method was the same as the DTAB contamination test, but the time to contamination per cycle was 10 h.
TABLE 1
TABLE 2
TABLE 3
FIGS. 1(a) to 1(f) are SEM images of the surface of a reverse osmosis membrane before response to chemical stimulation obtained in comparative example and example:
FIGS. 1(a ') to 1 (f') are SEM images of the surface of the cleaned reverse osmosis membrane TCEP obtained in the comparative example and example:
after being cleaned by the reducing agent solution, the coating is obviously cleaned, and the flux recovery rate can reach 98 percent. The chemical stimulus response anti-pollution reverse osmosis membrane prepared by the invention shows the stimulus response characteristic to a reducing agent, and has excellent anti-pollution performance while keeping good separation performance.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. A preparation method of a chemical stimulus response anti-pollution reverse osmosis membrane is characterized by comprising the following steps:
(1) preparation of aqueous phase solution: dissolving water phase monomer in deionized water, placing in an ultrasonic instrument, and performing ultrasonic treatment for 10min to uniformly disperse the monomer;
(2) preparation of oil phase solution: dissolving an oil phase monomer in an organic solvent, and performing ultrasonic treatment for 5min to obtain an oil phase solution;
(3) preparing a Tris solution: placing trihydroxy aminomethane in water, and performing ultrasonic treatment for 10min to uniformly disperse the monomers;
(4) preparation of HCl solution: placing concentrated hydrochloric acid in water, and stirring at normal temperature for 10min to uniformly disperse the monomers;
(5) preparation of Tris-HCl buffer: taking the Tris solution prepared in the step (3) and the HCl solution prepared in the step (4), adding deionized water for dilution, and placing the solution in an ultrasonic instrument for ultrasonic treatment for 10 min;
(6) preparation of codeposition solution: adding catecholamine and a disulfide polymer into the Tris-HCl buffer solution prepared in the step (5), and performing ultrasonic treatment for 1min to uniformly disperse the catecholamine and the disulfide polymer;
(7) preparing a stimulus response reverse osmosis membrane: pouring the water phase solution prepared in the step (1) on the surface of the reverse osmosis base membrane for standing, pouring out redundant solution, then immersing the membrane into the oil phase solution in the step (2) for reaction for a period of time, and after the reaction is finished, putting the membrane into a drying oven for heat treatment to obtain an initial reverse osmosis membrane; and (4) pouring the co-deposition solution prepared in the step (6) onto the surface of the prepared initial reverse osmosis membrane immediately, and depositing for a period of time to obtain the reverse osmosis membrane responding to chemical stimulation.
2. The method of claim 1 for preparing a chemically stimuli-responsive anti-fouling reverse osmosis membrane, wherein the method comprises the following steps: the oil phase monomer in the step (2) is one or more of the following monomers: 1,3, 5-benzenetricarboxychloride, 1, 3-benzenedicarbonyl chloride, bridged bicyclic tricyclic tetracarbonyl or biphenylhexacarbonyl; the organic solvent is one or more of n-hexane, heptane, cyclohexane or Isopar-G; the oil phase monomer accounts for 0.1-0.5 wt% of the organic solvent.
3. The method of claim 1 for preparing a chemically stimuli-responsive anti-fouling reverse osmosis membrane, wherein the method comprises the following steps: and (4) the concentration of the Tris solution in the step (3) is 0.1 mol/L.
4. The method of claim 3 for preparing a chemically stimuli-responsive anti-fouling reverse osmosis membrane, wherein the method comprises the following steps: and (4) HCl solution is 0.1 mol/L.
5. The method of claim 4 for preparing a chemically stimuli-responsive anti-fouling reverse osmosis membrane, wherein the method comprises the following steps: and (5) taking 50ml of Tris solution prepared in the step (3) and 14.7ml of HCl solution prepared in the step (4), and adding deionized water to dilute to 100 ml.
6. The method of claim 1 for preparing a chemically stimuli-responsive anti-fouling reverse osmosis membrane, wherein the method comprises the following steps: the catecholamine in the step (6) is one or more of dopamine, levodopa, tannic acid and norepinephrine, and the mass fraction is 0.1-0.5 wt%;
the disulfide polymer is one or more of cystamine and cystine, and the mass fraction is 0.05-1 wt%.
7. The method of claim 1 for preparing a chemically stimuli-responsive anti-fouling reverse osmosis membrane, wherein the method comprises the following steps: in the step (7), the material of the reverse osmosis basement membrane is one of polysulfone, polyethersulfone, polyacrylonitrile, cellulose acetate and polyamide, and the aperture of the reverse osmosis basement membrane is 0.001-0.002 μm.
8. The method of claim 1 for preparing a chemically stimuli-responsive anti-fouling reverse osmosis membrane, wherein the method comprises the following steps: the reaction time of the initial reverse osmosis membrane obtained in the step (7) is 30s-5min, the heat treatment temperature is 50-120 ℃, and the heat treatment time is 1-30 min; the time for depositing the blended solution on the surface of the initial reverse osmosis membrane is 2-24 h.
9. A chemical stimulus responsive anti-fouling reverse osmosis membrane produced by the process of any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110894031.6A CN113499693B (en) | 2021-08-05 | 2021-08-05 | Chemical stimulus response anti-pollution reverse osmosis membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110894031.6A CN113499693B (en) | 2021-08-05 | 2021-08-05 | Chemical stimulus response anti-pollution reverse osmosis membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113499693A true CN113499693A (en) | 2021-10-15 |
| CN113499693B CN113499693B (en) | 2023-03-21 |
Family
ID=78015614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110894031.6A Active CN113499693B (en) | 2021-08-05 | 2021-08-05 | Chemical stimulus response anti-pollution reverse osmosis membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113499693B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110189469A1 (en) * | 2008-08-05 | 2011-08-04 | Polymers Crc Limited | Functionalized thin film polyamide membranes |
| US20180056248A1 (en) * | 2016-08-29 | 2018-03-01 | The Penn State Research Foundation | Membrane surface activation to eliminate fouling and concentration polarization in water purification systems |
| CN108097059A (en) * | 2018-01-15 | 2018-06-01 | 哈尔滨工业大学 | A kind of method of modifying that aquaporin reinforced polyamide reverse osmosis membrane water flux is established using molybdenum disulfide |
| CN109126477A (en) * | 2018-09-13 | 2019-01-04 | 浙江工业大学 | A kind of preparation method of chiral separation film |
| CN111318190A (en) * | 2018-12-17 | 2020-06-23 | 中国石油化工股份有限公司 | Graphene composite material filtering membrane |
| CN112023732A (en) * | 2020-08-05 | 2020-12-04 | 中国科学院青岛生物能源与过程研究所 | Forward osmosis composite membrane and preparation method and application thereof |
-
2021
- 2021-08-05 CN CN202110894031.6A patent/CN113499693B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110189469A1 (en) * | 2008-08-05 | 2011-08-04 | Polymers Crc Limited | Functionalized thin film polyamide membranes |
| US20180056248A1 (en) * | 2016-08-29 | 2018-03-01 | The Penn State Research Foundation | Membrane surface activation to eliminate fouling and concentration polarization in water purification systems |
| CN108097059A (en) * | 2018-01-15 | 2018-06-01 | 哈尔滨工业大学 | A kind of method of modifying that aquaporin reinforced polyamide reverse osmosis membrane water flux is established using molybdenum disulfide |
| CN109126477A (en) * | 2018-09-13 | 2019-01-04 | 浙江工业大学 | A kind of preparation method of chiral separation film |
| CN111318190A (en) * | 2018-12-17 | 2020-06-23 | 中国石油化工股份有限公司 | Graphene composite material filtering membrane |
| CN112023732A (en) * | 2020-08-05 | 2020-12-04 | 中国科学院青岛生物能源与过程研究所 | Forward osmosis composite membrane and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113499693B (en) | 2023-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107670513B (en) | Plant polyphenol modified polymer film and preparation method and application thereof | |
| CN104437111A (en) | Anti-pollution polyamide composite membrane and preparation method thereof | |
| CN110339726B (en) | Polystyrene microsphere/carbon nanotube composite modified hybrid polyethersulfone nanofiltration membrane as well as preparation method and application thereof | |
| CN109794173B (en) | Preparation method of high-performance reverse osmosis membrane for seawater desalination | |
| Liu et al. | High-hydrophilic and salt rejecting PA-g/co-PVP RO membrane via bionic sand-fixing grass for pharmaceutical wastewater treatment | |
| CN104474926A (en) | Preparation method of polyamide reverse osmosis membrane | |
| CN104028110B (en) | A kind of thin layer composite forward osmosis membrane and preparation method thereof | |
| CN108993147B (en) | Chlorine-resistant reverse osmosis composite membrane and preparation method thereof | |
| CN105561801B (en) | A kind of preparation method of the reverse osmosis pollution-resistant membrane of high-performance | |
| WO2019179082A1 (en) | Metal organic frame reverse osmosis membrane and preparation method therefor | |
| CN114471157A (en) | Preparation method of positively charged acid-resistant nanofiltration membrane and positively charged acid-resistant nanofiltration membrane | |
| CN113289498A (en) | Positively charged nanofiltration membrane and preparation method thereof | |
| CN110917891A (en) | Preparation method of modified polyacrylonitrile forward osmosis membrane | |
| CN114887486A (en) | Mannitol-based polyester loose composite nanofiltration membrane and preparation method and application thereof | |
| CN113499693B (en) | Chemical stimulus response anti-pollution reverse osmosis membrane and preparation method thereof | |
| CN111330460B (en) | Method for modifying polysulfone nanofiltration membrane by using DNA/ZIF-8 and obtained membrane | |
| CN114016285A (en) | Preparation method of functional nanofiber membrane for seawater desalination | |
| CN117482758A (en) | Ionic covalent organic framework composite membrane, preparation method and application thereof in separating dye and salt | |
| CN113368699B (en) | Preparation method of anti-pollution composite membrane | |
| CN112870994B (en) | Modification method for improving chlorine resistance of polyacrylonitrile forward osmosis membrane | |
| CN114618313B (en) | High-flux anti-pollution reverse osmosis composite membrane and preparation method thereof | |
| CN113877426B (en) | Super-hydrophobic polypropylene modified ultrafiltration membrane and preparation method and application thereof | |
| CN1631500A (en) | Novel reverse osmosis antioxidant compound membrane of polyamide and its preparing method | |
| CN112844076B (en) | Novel charged nanofiltration membrane for removing organic matters and preparation method thereof | |
| CN115487693A (en) | Polyamide/polyolefin mixed matrix nanofiltration membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |