CN112755798A - Method for preparing oil-water separation membrane with high anti-pollution performance - Google Patents
Method for preparing oil-water separation membrane with high anti-pollution performance Download PDFInfo
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- CN112755798A CN112755798A CN201911001335.4A CN201911001335A CN112755798A CN 112755798 A CN112755798 A CN 112755798A CN 201911001335 A CN201911001335 A CN 201911001335A CN 112755798 A CN112755798 A CN 112755798A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/08—Thickening liquid suspensions by filtration
- B01D17/085—Thickening liquid suspensions by filtration with membranes
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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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The invention provides a method for preparing an oil-water separation membrane with high pollution resistance, which comprises the following steps: s1, preparing a membrane casting solution comprising a zwitterionic polymer containing phosphorylcholine groups and a membrane material; s2, coating the casting film liquid on the surface of a base film, and performing film forming treatment to obtain the oil-water separation film with high anti-pollution performance. The oil-water separation membrane prepared by the invention has the advantages of strong anti-pollution capability, simple preparation method, less flux attenuation of the membrane operating in a long period, easy industrialization and the like, and has great application potential in the aspect of treating oily sewage.
Description
Technical Field
The invention relates to a method for preparing an oil-water separation membrane with high pollution resistance, belonging to the preparation technology of flat membranes.
Background
Along with tertiary oil recovery, polymer injection recovery, edge oil field recovery and the like, the emulsification problem of oily sewage of domestic oil fields and refining enterprises is more serious, the treatment process is more difficult, the existing oily sewage treatment technology has the defects of long time, large equipment volume, high equipment corrosion rate, use of a large amount of chemical agents and the like, and a novel technology needs to be developed for treatment.
The membrane filtration separation method is a novel oil-water separation technology, has the characteristics of simplicity, high efficiency, flexible operation, low environmental pollution, strong universality and the like, and is the main development direction of the oil-water separation technology. However, the conventional hydrophilic and hydrophobic oil-water separation membrane has the defects of poor pollution resistance, fast flux attenuation, poor oil-water separation effect and the like.
Polypropylene, polysulfones and polyvinylidene fluoride are widely applied ultrafiltration membrane materials in the petrochemical industry, have good stability and can be applied to wider water quality environments. However, when the membranes are applied to oil-water separation, the problem of poor pollution resistance exists due to poor hydrophilicity, so that the flux of the membranes is attenuated quickly, and the hydrophilic modification of the membrane materials is particularly important.
The material modification technique comes to the question of how to combine substances with specific properties with the membrane. At present, the membrane is modified hydrophilically by methods such as blending, plasma treatment, surface grafting modification and the like. Plasma treatment and surface modification are mainly carried out on the surface of the membrane material, but the overall hydrophilicity of the membrane material is reduced rapidly along with long-period operation, so that the membrane material is not ideal in the industrial application process.
The phosphorylcholine group is the main component of the outer membrane of the cell, and the phosphorylcholine group can form a firm hydration layer with water molecules on the surface of the cell membrane, and has excellent hydrophilic capacity and anti-pollution performance (Journal of Materials Chemistry A,2018, 6, 3231-3241.). Zwitterionic polymers containing Phosphorylcholine (PC) groups have good resistance to bioadhesion and staining (chinese patents CN 201610485188.2 and CN 201610485203.3). However, the hydrophilic oil-water separation membrane modified by phosphorylcholine groups reported at present is carried out in a surface modification mode, and the modification mode has the defect of poor pollution resistance in the long-term use process. The phosphorylcholine groups are uniformly dispersed in the membrane in a blending mode, the modification mode has no influence on the mechanical property and the thermal stability of the membrane, the pollution resistance of the membrane can be effectively improved, and the preparation method has great application potential particularly in the aspects of biological adhesion resistance and pollution resistance.
Disclosure of Invention
The invention aims to solve the problem of poor anti-pollution capability of an oil-water separation membrane in the prior art, and provides a method for preparing the oil-water separation membrane with high anti-pollution performance. The oil-water separation membrane prepared by the invention has the advantages of strong anti-pollution capability, simple preparation method, less flux attenuation of the membrane operating in a long period, easy industrialization and the like, and has great application potential in the aspect of treating oily sewage.
According to an aspect of the present invention, there is provided a method of preparing an oil-water separation membrane having high contamination resistance, including:
s1, preparing a membrane casting solution comprising a zwitterionic polymer containing phosphorylcholine groups and a membrane material;
s2, coating the casting film liquid on the surface of a base film, and performing film forming treatment to obtain the oil-water separation film with high anti-pollution performance.
According to some embodiments of the invention, the structure of the zwitterionic polymer containing phosphorylcholine groups is as follows:
in the formula I, R1、R2Selected from hydrogen and C1-C20Is preferably selected from hydrogen and substituted or unsubstituted C1-C20Alkyl groups of (a); r3Is selected from C1-C20Is preferably selected from substituted or unsubstituted C4-C20More preferably C containing an amide bond or an ester bond4-C20A long-chain alkyl group of (a); m is an integer of 20 to 200, and n is an integer of 1 to 1000.
According to a preferred embodiment of the present invention, the molecular weight of the phosphorylcholine group-containing zwitterionic polymer is 15000-30000.
According to a preferred embodiment of the present invention, the phosphorylcholine group-containing zwitterionic polymer is prepared by:
(1) reacting the compound shown in the formula A with the compound shown in the formula B to obtain a compound shown in the formula C;
(2) reacting the compound shown in the formula C with dopamine to obtain the zwitterionic polymer containing the phosphorylcholine groups shown in the formula I;
in formula A, B, C, R1、R2、R3Have the same definitions as in formula I.
According to a preferred embodiment of the present invention, in step (1), the reaction temperature is 60 to 80 ℃, preferably 70 ℃; the reaction time is 5-30h, preferably 24 h.
According to a preferred embodiment of the present invention, the reaction solvent in step (1) is preferably tetrahydrofuran.
According to a preferred embodiment of the present invention, 1 to 5% Azobisisobutyronitrile (AIBN) is added to the reaction in step (1).
According to a preferred embodiment of the present invention, the reaction temperature in step (2) is 50 to 80 ℃, preferably 60 ℃; the reaction time is 1-100h, preferably 12-72 h.
According to a preferred embodiment of the present invention, the reaction solvent in step (2) is preferably ethanol.
According to a preferred embodiment of the present invention, the final pH of the reaction in step (2) is adjusted to 3 to 4 to produce the phosphorylcholine group-containing zwitterionic polymer.
According to a preferred embodiment of the present invention, the reaction for preparing the zwitterionic polymer containing phosphorylcholine groups may be carried out under the protection of an inert gas, preferably nitrogen.
According to a preferred embodiment of the present invention, the step S1 includes:
adding the zwitterionic polymer containing the phosphorylcholine groups and a membrane material into an organic solvent, and stirring and dissolving at 40-80 ℃ to obtain a mixed solution, wherein the preferable stirring and dissolving temperature is 40-60 ℃;
and swelling and defoaming the mixed solution to obtain the membrane casting solution.
According to a preferred embodiment of the present invention, the membrane material comprises at least one of polyolefin, polysulfone and fluoropolymer, preferably at least one of polypropylene, polysulfone, polyethersulfone and polyvinylidene fluoride.
According to a preferred embodiment of the present invention, the organic solvent includes at least one of ethanol, methanol, N-dimethylformamide, and dimethylsulfoxide; the organic solvent preferably includes at least one of ethanol and N, N-dimethylformamide.
According to a preferred embodiment of the present invention, the mass ratio of the membrane material, the zwitterionic polymer and the organic solvent is (5-25): (2-10): (65-95); preferably (10-20): (2-8): (80-90).
According to a preferred embodiment of the present invention, the film formation process includes:
and (3) immersing the base membrane coated with the casting membrane liquid into water, washing out impurities which are not firmly combined by water, and enabling hydrophilic groups to migrate from the inside of the membrane to the surface of the membrane to obtain the oil-water separation membrane with high anti-pollution performance.
According to a preferred embodiment of the present invention, the step S2 of applying the casting solution to the surface of the base film may be performed on a film scraper, for example, the speed of the base film is 1-3m/S, preferably 1-1.6m/S, and the thickness between the size between the scraper and the base film is 120-350 μm, preferably 150-300 μm.
According to a preferred embodiment of the present invention, the base film is preferably a polyester nonwoven fabric.
According to another aspect of the present invention, there is provided a method of preparing an oil-water separation membrane having high contamination resistance, and an application of the oil-water separation membrane having high contamination resistance in oil-water separation.
Compared with the prior art, the method for preparing the oil-water separation membrane with high anti-pollution performance provided by the invention has the following advantages:
(1) the oil-water separation membrane with high anti-pollution performance prepared by the blending method has the advantages of simple method, simple and convenient operation process and easy industrialization.
(2) The invention uses the amphoteric ion polymer containing phosphorylcholine groups with strong hydrophilicity and biological pollution resistance, not only contains the amphoteric ion groups with pollution resistance, but also contains the catechol groups, so the amphoteric ion polymer can easily adhere to the membrane-making polymer, and has the advantages of stable structure, strong pollution resistance, high oil-water separation efficiency and large water flux.
Drawings
FIG. 1 is a scheme showing the preparation of a zwitterionic polymer containing phosphorylcholine groups (PMEND).
FIG. 2 is a scheme showing the preparation of a zwitterionic polymer containing phosphorylcholine groups (PMEN 12D).
Detailed Description
The present invention will be further illustrated by the following examples, but is not limited to these examples.
[ example 1 ]
The preparation process of the zwitterionic Polymer (PMEND) containing phosphorylcholine groups is shown in figure 1, and the specific preparation steps are as follows:
(1) anhydrous ethanol (20mL) was first added to a 250mL three-necked round bottom flask and the temperature was adjusted to 70 ℃ for 0.5hr under a nitrogen blanket. To keep the temperature constant, 0.1040g of Azobisisobutyronitrile (AIBN) were weighed into 10mL of Tetrahydrofuran (THF) solution and 1mL of this solution was transferred to the three-necked flask described above with vigorous magnetic stirring. NPCEMA (1.2g), MPC (4g) and 8mL AIBN in THF were then dissolved in 130mL absolute ethanol and added dropwise to a three-neck round-bottom flask using a constant pressure dropping funnel. After the addition was complete, the remaining 1mL of AIBN in THF was added. Stirring for reaction for 6hr, stopping introducing nitrogen gas, sealing for reaction for 18hr, rotary steaming, and dialyzing to obtain phosphorylcholine-containing polymer PMEN.
(2) Weighing 2g of the polymer PMEN synthesized in the step (1), adding the polymer PMEN into a three-neck round-bottom flask, adding 50mL of ethanol, and introducing N2The reaction temperature was increased to 60 ℃. 0.5g dopamine hydrochloride was weighed, dissolved in 20mL ethanol, added to a three-necked round bottom flask in N2And regulating the pH value to 7 by using Triethylamine (TEA) under protection, continuously reacting for 12h, regulating the pH value to 4 by using hydrochloric acid, and dialyzing for 72h to obtain the zwitterionic polymer PMEND containing the phosphorylcholine groups.
[ example 2 ]
The preparation process of the zwitterionic polymer containing phosphorylcholine groups (PMEN12D) is shown in FIG. 2, and the specific preparation steps are as follows:
(1) anhydrous ethanol (30mL) was first added to a 500mL three-necked round bottom flask and the temperature was adjusted to 70 ℃ for 0.5hr under a nitrogen blanket. To keep the temperature constant, 0.2080g of Azobisisobutyronitrile (AIBN) were weighed into 10mL of Tetrahydrofuran (THF) solution and 1mL of this solution was transferred to the three-necked flask described above with vigorous magnetic stirring. NPCEMA12(2.4g), MPC (8g) and 16mL of AIBN in THF were then dissolved in 230mL of absolute ethanol and added dropwise to a three-necked round-bottom flask using a constant pressure dropping funnel. After the addition was complete, the remaining 2mL of AIBN in THF was added. Stirring for reaction for 6hr, stopping introducing nitrogen gas, sealing for reaction for 12hr, rotary steaming, and dialyzing to obtain phosphorylcholine-containing polymer PMEN 12.
(2) 2g of the polymer PMEN12 synthesized in step (1) was weighed into a three-necked round-bottomed flask, 100mL of ethanol and 20mL of chloroform were added, and N was introduced2The reaction temperature was increased to 60 ℃. 1.0g dopamine hydrochloride was weighed, dissolved in 20mL ethanol, added to a three-necked round bottom flask in N2And regulating the pH value to 7 by using Triethylamine (TEA) under protection, continuously reacting for 12h, regulating the pH value to 4 by using hydrochloric acid, and dialyzing for 48h to obtain the zwitterionic polymer PMEN12D containing phosphorylcholine groups.
[ example 3 ]
(1) 10 parts by mass of dried polyethersulfone and 2 parts by mass of the phosphorylcholine group-containing zwitterionic polymer PMEND prepared in example 1 were added to 88 parts by mass of N, N-dimethylformamide, and the mixture was dissolved by stirring at 60 ℃ and subjected to vacuum degassing to form a casting solution.
(2) Fix the polyester non-woven fabrics after the preliminary treatment on the film scraping machine, make the membrane according to the following parameter, base film speed: 1.2m/s, the thickness between the scraper and the base film is 250 mu m, after the casting solution is scraped on the surface of the base film, the base film containing the casting solution is immersed in water, and the oil-water separation membrane with high anti-pollution performance can be obtained after washing.
[ example 4 ]
(1) Adding 15 parts by mass of dried polyvinylidene fluoride and 2 parts by mass of zwitterionic polymer PMEND containing phosphorylcholine groups into 60 parts by mass of N, N-dimethylformamide and 21 parts by mass of ethanol solution, stirring and dissolving at 40 ℃, and vacuumizing and degassing to form the casting solution.
(2) Fix the polyester non-woven fabrics after the preliminary treatment on the film scraping machine, make the membrane according to the following parameter, base film speed: 1.3m/s, and the thickness between the scraper and the base film is 200 μm, after the casting solution is scraped on the surface of the base film, the base film containing the casting solution is immersed in water, and the oil-water separation membrane with high anti-pollution performance can be obtained after washing.
[ example 5 ]
(1) Adding 15 parts by mass of dried polyvinylidene fluoride and 4 parts by mass of zwitterionic polymer PMEND containing phosphorylcholine groups into 60 parts by mass of N, N-dimethylformamide and 21 parts by mass of ethanol solution, stirring and dissolving at 40 ℃, and vacuumizing and degassing to form the casting solution.
(2) Fix the polyester non-woven fabrics after the preliminary treatment on the film scraping machine, make the membrane according to the following parameter, base film speed: 1.3m/s, and the thickness between the scraper and the base film is 200 μm, after the casting solution is scraped on the surface of the base film, the base film containing the casting solution is immersed in water, and the oil-water separation membrane with high anti-pollution performance can be obtained after washing.
[ example 6 ]
(1) Adding 15 parts by mass of dried polyvinylidene fluoride and 2 parts by mass of zwitterionic polymer PMEN12D containing phosphorylcholine groups into 60 parts by mass of N, N-dimethylformamide and 21 parts by mass of ethanol solution, stirring and dissolving at 40 ℃, and vacuumizing and degassing to form the casting solution.
(2) Fix the polyester non-woven fabrics after the preliminary treatment on the film scraping machine, make the membrane according to the following parameter, base film speed: 1.3m/s, and the thickness between the scraper and the base film is 200 μm, after the casting solution is scraped on the surface of the base film, the base film containing the casting solution is immersed in water, and the oil-water separation membrane with high anti-pollution performance can be obtained after washing.
[ example 7 ]
(1) Adding 15 parts by mass of dried polyvinylidene fluoride and 4 parts by mass of zwitterionic polymer PMEN12D containing phosphorylcholine groups into 60 parts by mass of N, N-dimethylformamide and 21 parts by mass of ethanol solution, stirring and dissolving at 40 ℃, and vacuumizing and degassing to form the casting solution.
(2) Fix the polyester non-woven fabrics after the preliminary treatment on the film scraping machine, make the membrane according to the following parameter, base film speed: 1.3m/s, and the thickness between the scraper and the base film is 200 μm, after the casting solution is scraped on the surface of the base film, the base film containing the casting solution is immersed in water, and the oil-water separation membrane with high anti-pollution performance can be obtained after washing.
[ example 8 ]
(1) Adding 18 parts by mass of dried polysulfone and 8 parts by mass of zwitterionic polymer PMEND containing phosphorylcholine groups into 84 parts by mass of N, N-dimethylformamide solution, stirring and dissolving at 60 ℃, and vacuumizing and degassing to form membrane casting solution.
(2) Fix the polyester non-woven fabrics after the preliminary treatment on the film scraping machine, make the membrane according to the following parameter, base film speed: 1.5m/s, the thickness between the scraper and the base film is 160 mu m, after the casting solution is scraped on the surface of the base film, the base film containing the casting solution is immersed in water, and the oil-water separation membrane with high anti-pollution performance can be obtained after washing.
[ example 9 ]
(1) Adding 15 parts by mass of dried polyvinylidene fluoride and 0.5 part by mass of zwitterionic polymer PMEND containing phosphorylcholine groups into 60 parts by mass of N, N-dimethylformamide and 21 parts by mass of ethanol solution, stirring and dissolving at 40 ℃, and vacuumizing and degassing to form the casting solution.
(2) Fix the polyester non-woven fabrics after the preliminary treatment on the film scraping machine, make the membrane according to the following parameter, base film speed: 1.3m/s, and the thickness between the scraper and the base film is 200 μm, after the casting solution is scraped on the surface of the base film, the base film containing the casting solution is immersed in water, and the oil-water separation membrane with high anti-pollution performance can be obtained after washing.
[ example 10 ]
(1) Adding 15 parts by mass of dried polyvinylidene fluoride and 12 parts by mass of zwitterionic polymer PMEND containing phosphorylcholine groups into 60 parts by mass of N, N-dimethylformamide and 21 parts by mass of ethanol solution, stirring and dissolving at 40 ℃, and vacuumizing and degassing to form the casting solution.
(2) Fix the polyester non-woven fabrics after the preliminary treatment on the film scraping machine, make the membrane according to the following parameter, base film speed: 1.3m/s, and the thickness between the scraper and the base film is 200 μm, after the casting solution is scraped on the surface of the base film, the base film containing the casting solution is immersed in water, and the oil-water separation membrane with high anti-pollution performance can be obtained after washing.
Comparative example 1
(1) Adding 10 parts by mass of dried polyether sulfone into 90 parts by mass of N, N-dimethylformamide, stirring and dissolving at 60 ℃, and vacuumizing and degassing to form a membrane casting solution.
(2) Fix the polyester non-woven fabrics after the preliminary treatment on the film scraping machine, make the membrane according to the following parameter, base film speed: 1.2m/s, the thickness between the scraper and the base film is 250 mu m, after the casting solution is scraped on the surface of the base film, the base film containing the casting solution is immersed in water, and the oil-water separation membrane with high anti-pollution performance can be obtained after washing.
Comparative example 2
(1) Adding 15 parts by mass of dried polyvinylidene fluoride into 64 parts by mass of N, N-dimethylformamide and 21 parts by mass of ethanol solution, stirring and dissolving at 40 ℃, and vacuumizing and degassing to form a casting solution.
(2) Fix the polyester non-woven fabrics after the preliminary treatment on the film scraping machine, make the membrane according to the following parameter, base film speed: 1.3m/s, and the thickness between the scraper and the base film is 200 μm, after the casting solution is scraped on the surface of the base film, the base film containing the casting solution is immersed in water, and the oil-water separation membrane with high anti-pollution performance can be obtained after washing.
Comparative example 3
(1) Adding 18 parts by mass of dried polysulfone into 92 parts by mass of N, N-dimethylformamide solution, stirring and dissolving at 60 ℃, and vacuumizing and degassing to form a membrane casting solution.
(2) Fix the polyester non-woven fabrics after the preliminary treatment on the film scraping machine, make the membrane according to the following parameter, base film speed: 1.5m/s, the thickness between the scraper and the base film is 160 mu m, after the casting solution is scraped on the surface of the base film, the base film containing the casting solution is immersed in water, and the oil-water separation membrane with high anti-pollution performance can be obtained after washing.
The oil-water separation membranes prepared in examples 3 to 10 and comparative examples 1 to 3 were subjected to static contact angle (WCA) and underwater oil drop contact angle (OCA) tests, Bovine Serum Albumin (BSA) was selected as a typical contaminant to conduct anti-bio-contamination studies, and kerosene-simulated oil-water mixtures were selected to conduct oil-water separation performance tests. The specific test process is as follows:
(I) membrane anti-BSA protein contamination test and analysis process
Preparing 1mg/mL BSA solution;
② the membrane sample to be measured (the effective filtration area is 50 cm)2) The BSA was placed in an ultrafiltration cup and tested for flux (J, in L.m) at a pressure of 100kPa-2·h-1) The calculation is performed as follows:
wherein V is the volume of filtrate passing through the effective area A within delta t time.
The BSA retention (R) was calculated as follows:
wherein, cIntoIs the concentration of BSA protein added (mg/mL), cGo outThe BSA protein concentration in the transmittance (mg/mL) was used.
(II) oil-water separation Performance test Process and method
Preparation of emulsion: span-80 is used as an emulsifier to prepare the kerosene emulsion. The preparation method comprises the following steps: 10mL of oil and 2.5g of span-80 emulsifier were added to 1L of deionized water, and stirred with a magnetic stirrer at 1500rpm for 24 hr.
Fixing the micro-filtration membranes with different modifications on a terminal filtration system (an ultrafiltration cup), and adding the oil-water emulsion into the filtration cup. Prepressing under the condition of 0.1MPa until the water flux is constant, then carrying out the experiment under the condition of 0.08MPa, measuring the mass change of the filtrate at regular intervals, and stopping the experiment until the emulsion is reduced by 80%.
The oil content in the water was measured with an infrared oil tester.
The separation efficiency R (%) of the membrane is calculated as:
wherein C ispFor the oil content in the separated water, C0Is the oil content of the water before separation.
TABLE 1
The results in table 1 show that the oil-water separation membrane prepared from the zwitterionic polymer adopted by the invention has the advantages of strong pollution resistance, high oil-water separation efficiency, low oil content in the separated water and the like. In addition, it can be seen from examples 5 and 10 that the increase in the amount of the phosphorylcholine group-containing zwitterionic polymer does not significantly improve the performance of the oil-water separation membrane, but the amount of the phosphorylcholine group-containing zwitterionic polymer within the range of the present invention is preferred from the economical viewpoint.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A method for preparing an oil-water separation membrane having high anti-contamination performance, comprising:
s1, preparing a membrane casting solution comprising a zwitterionic polymer containing phosphorylcholine groups and a membrane material;
s2, coating the casting film liquid on the surface of a base film, and performing film forming treatment to obtain the oil-water separation film with high anti-pollution performance.
2. The method of claim 1, wherein the zwitterionic polymer comprising phosphorylcholine groups has the following structure:
in the formula I, R1、R2Selected from hydrogen and C1-C20Is preferably selected from hydrogen and substituted or unsubstituted C1-C20Alkyl groups of (a); r3Is selected from C1-C20Is preferably selected from substituted or unsubstituted C4-C20Alkyl groups of (a); m is an integer of 20 to 200, and n is an integer of 1 to 1000.
3. The method according to claim 1 or 2, characterized in that the molecular weight of the zwitterionic polymer is 15000-30000.
4. The method according to any one of claims 1 to 3, wherein the phosphorylcholine group-containing zwitterionic polymer is prepared by:
(1) reacting the compound shown in the formula A with the compound shown in the formula B to obtain a compound shown in the formula C;
(2) reacting the compound shown in the formula C with dopamine to obtain the zwitterionic polymer containing the phosphorylcholine groups shown in the formula I;
in formula A, B, C, R1、R2、R3Have the same definitions as in formula I.
5. The method according to any one of claims 1 to 4, wherein the step S1 includes:
adding the zwitterionic polymer containing phosphorylcholine groups and a membrane material into an organic solvent, and stirring and dissolving at 40-80 ℃ to obtain a mixed solution;
and swelling and defoaming the mixed solution to obtain the membrane casting solution.
6. The method according to any one of claims 1-5, wherein the membrane material comprises at least one of a polyolefin, a polysulfone, and a fluoropolymer, preferably at least one of a polypropylene, a polysulfone, a polyethersulfone, and a polyvinylidene fluoride.
7. The method of any one of claims 1-6, wherein the organic solvent comprises at least one of ethanol, methanol, N-dimethylformamide, and dimethylsulfoxide.
8. The method according to any one of claims 1 to 7, wherein the mass ratio of the membrane material, the zwitterionic polymer and the organic solvent is (5-25): (2-10): (65-95).
9. The method according to any one of claims 1 to 8, wherein the film formation process comprises:
and (3) immersing the base membrane coated with the casting solution into water, and washing to obtain the oil-water separation membrane with high anti-pollution performance.
10. Use of the oil-water separation membrane with high contamination resistance prepared by the method according to any one of claims 1 to 9 in oil-water separation.
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