CN110354701B - Preparation method of high pollution-resistant oil-water separation ultrafiltration membrane - Google Patents
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Abstract
The invention provides a preparation method of a high pollution resistance oil-water separation ultrafiltration membrane, which comprises the steps of adopting perfluorocarbon nonionic surfactant Zonyl FSO macromolecules to carry out functional group modification to prepare a macromolecule initiator, then utilizing an Atom Transfer Radical Polymerization (ATRP) method to synthesize polymers with perfluoro groups in main chains and branched chains, introducing fluorine-containing groups with low surface energy in a maximum amount, dissolving the main and branched fluorine-containing polymers and a film forming material in a solvent, stirring in a constant-temperature water bath for 6-12 h, and standing at room temperature until bubbles in a casting solution are completely removed; the oil-water separation ultrafiltration membrane prepared by adopting a non-solvent induced phase inversion method (NIPS) has extremely high self-cleaning performance and high pollution resistance, reduces the relative flux attenuation rate of the membrane, improves the relative flux recovery rate of the membrane, and is beneficial to reducing the operation cost in the membrane separation process.
Description
Technical Field
The invention relates to the technical field of membranes, in particular to a preparation method of a high-pollution-resistance oil-water separation ultrafiltration membrane.
Background
The oily wastewater mainly comes from industrial enterprises of petroleum exploitation, petrochemical industry, steel smelting, mechanical manufacturing and the like, and according to statistics, about 200 to 300 million tons of oily wastewater are discharged into a water body every year all over the world. The traditional separation method of the oily wastewater mainly comprises a gravity separation method, an ultrasonic separation method, a centrifugal separation method, an electric field method, a flocculation method and a biological treatment method, but the separation methods have low separation efficiency and can cause the problem of secondary pollution. The membrane separation technology has the advantages of low energy consumption, high single-stage separation efficiency, flexible and simple process, low environmental pollution and the like, thereby showing unique advantages and application prospects in the field of oil-water separation.
However, due to the potential lipophilicity of the membrane material, oil droplets and other impurities are easily and irreversibly adsorbed on the surface of the membrane, so that the permeation flux of the membrane is greatly attenuated, and the selectivity is greatly reduced. The membrane module must be cleaned physically or chemically in the process of membrane separation operation, and frequent cleaning can damage the membrane body, cause the reduction of membrane separation performance, lead to the shortening of membrane life and the increase of membrane operation cost. Membrane fouling has become a technical bottleneck in the development of membrane separation technology.
The development of the anti-pollution material is a fundamental way to solve the membrane pollution, and the molecular weight of the polymer prepared by the living radical polymerization is controllable, so that the structure of the polymer can be accurately designed, and the method becomes a research hotspot in the modification aspect of the material. Reversible addition-fragmentation chain transfer radical polymerization (RAFT) usually requires adding a dithioester derivative as a chain transfer agent in a reaction system, and the RAFT reagent has a complex structure and a complex preparation process, so that a commercial finished product is difficult to buy, and the practical application of RAFT is greatly limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a high pollution resistance oil-water separation ultrafiltration membrane.
The invention provides a preparation method of a high pollution resistance oil-water separation ultrafiltration membrane, which is characterized by comprising the following steps:
(1) synthesis of main and branched fluoropolymers:
the main chain fluorine-containing polymer and the branched chain fluorine-containing polymer are synthesized by adopting an Atom Transfer Radical Polymerization (ATRP) method, which comprises the following specific steps:
a. dissolving perfluorocarbon nonionic surfactant Zonyl FSO, triethylamine and toluene in a round-bottom flask, heating, slowly adding dibromo isobutyryl bromide into the round-bottom flask, and carrying out reflux reaction; removing toluene from the reaction solution, dissolving the reaction solution in dichloromethane, purifying by using sodium bicarbonate solution, HCl solution and concentrated brine respectively, and distilling under reduced pressure to obtain a perfluorocarbon nonionic surfactant Zonyl FSO macroinitiator; b. adding a low-surface-energy perfluoropolymer, Cu (I) Br, pentamethyl diethylenetriamine (PMDETA) and methyl ethyl ketone into a dry three-neck round-bottom flask which is filled with nitrogen, then adding the macroinitiator, reacting in an oil bath, then precipitating in hexane, and drying in vacuum for 12 hours; dissolving with chloroform, and removing catalyst with aluminum peroxide column to obtain main and branched chain fluorine-containing polymers;
(2) preparing a casting solution: dissolving the main chain fluorine-containing polymer and the branched chain fluorine-containing polymer and the film forming material in a solvent, stirring for 6-12 h in a constant-temperature water bath at the temperature of (25 +/-5) DEG C-80 ℃, standing at room temperature until bubbles in the film casting solution are completely removed, wherein the minimum temperature of (25 +/-5) DEG C means that the minimum temperature can float up and down at the temperature of 25 ℃ by 5 ℃;
(3) preparing an oil-water separation ultrafiltration membrane by a non-solvent induced phase inversion method (NIPS): firstly scraping the membrane into a flat membrane, or preparing a hollow fiber membrane by using a wet method or a dry-wet method for spinning, quickly immersing the membrane into a gel bath, changing a liquid membrane into a solid membrane through the exchange of a solvent and a non-solvent, immersing the solid membrane into deionized water for 24-48 h, and replacing the deionized water every 6 h.
Preferably, in the step (3), a non-woven fabric is used as a support layer and is fixed on the glass plate.
Preferably, the low surface energy perfluoropolymer in the step (1) is a perfluoroalkyl (meth) acrylate compound, specifically 2- (perfluorooctyl) ethyl methacrylate.
Preferably, the solvent in the step (2) is one of tetrahydrofuran, Methyl Ethyl Ketone (MEK), trimethyl phosphate, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), Dimethylacetamide (DMAC), N-methyl-2-pyrrolidone or isophorone.
Preferably, the film forming material in the step (2) is one or a blend of more than two of polyvinylidene fluoride (PVDF), Polysulfone (PS), Polyethersulfone (PES), Polyacrylonitrile (PAN), Polycarbonate (PC), polyethylene terephthalate (PET), polypropylene (PP), and Polyamide (PA).
Preferably, the mass concentration of the film-forming material in the film-casting solution in the step (2) is 5-30 wt.%.
Preferably, the mass concentration of the main-chain fluoropolymer and the branched-chain fluoropolymer in the casting solution in the step (2) is 0.2-5 wt.%.
Preferably, the membrane casting solution in the step (2) contains an inorganic or organic small-molecule pore-forming agent for regulating and controlling the interception performance of the ultrafiltration membrane.
Preferably, the gel bath in step (3) is non-solvent water or a mixture of water and small molecule organic matter, wherein the small molecule organic matter is methanol, ethanol, propanol, isopropanol, acetone or petroleum ether.
Compared with the prior art, 1) the perfluorocarbon nonionic surfactant Zonyl FSO macromolecule is subjected to functional group modification to prepare a macromolecule initiator, then a polymer with a perfluoro group in a main chain and a branched chain is synthesized by an Atom Transfer Radical Polymerization (ATRP) method, and a low-surface-energy fluorine-containing group is introduced in a maximum amount; 2) the oil-water separation ultrafiltration membrane prepared by the method has extremely high self-cleaning performance and high pollution resistance, reduces the relative flux attenuation rate of the membrane, improves the relative flux recovery rate of the membrane, and is beneficial to reducing the operation cost in the membrane separation process.
Detailed Description
The invention will be further described with reference to specific examples:
EXAMPLE 1 preparation of Main and branched fluoropolymers
a. Synthesis of perfluorocarbon nonionic surfactant Zonyl FSO macroinitiator:
dissolving 0.05mol of perfluorocarbon nonionic surfactant Zonyl FSO, 0.05mol of triethylamine and 100ml of toluene in a round-bottom flask, and heating to 110 ℃; slowly adding 0.05mol of dibromo isobutyryl bromide into a round-bottom flask, and carrying out reflux reaction for 20 hours; removing toluene from the reaction solution, dissolving the reaction solution in dichloromethane, respectively purifying with sodium bicarbonate solution, 0.1N HCl solution and concentrated brine, and distilling under reduced pressure to obtain perfluorocarbon nonionic surfactant Zonyl FSO macroinitiator;
b. synthesis of main and branched fluoropolymers:
11.63mmol of 2- (perfluorooctyl) ethyl methacrylate, 1.163mmol of Cu (I) Br, 1.163mmol of PMDETA and 20ml of methyl ethyl ketone were taken and added to a dry three-necked round bottom flask with nitrogen, 1.163mmol of the macroinitiator was added, the mixture was reacted in an oil bath at 80 ℃ for 2 hours, then precipitated in hexane, dried under vacuum for 12 hours, and an aluminum peroxide column was dissolved with chloroform to remove the catalyst.
The formula 1 is a synthesized perfluorocarbon nonionic surfactant Zonyl FSO macroinitiator, wherein m is 0-15; n is 1-7; formula 2 is a synthetic main, branched fluoropolymer wherein z is 7.
EXAMPLE 2 preparation of Main and branched fluoropolymers
a. Synthesis of perfluorocarbon nonionic surfactant Zonyl FSO macroinitiator:
0.05mol of perfluorocarbon nonionic surfactant Zonyl FSO, 0.05mol of triethylamine and 100ml of toluene are dissolved in a round-bottom flask and heated to 120 ℃; slowly adding 0.05mol of dibromo isobutyryl bromide into a round-bottom flask, and carrying out reflux reaction for 24 hours; removing toluene from the reaction solution, dissolving the reaction solution in dichloromethane, respectively purifying with sodium bicarbonate solution, 0.1N HCl solution and concentrated brine, and distilling under reduced pressure to obtain perfluorocarbon nonionic surfactant Zonyl FSO macroinitiator;
b. synthesis of main and branched fluoropolymers:
11.63mmol of 2- (perfluorooctyl) ethyl methacrylate, 1.163mmol of Cu (I) Br, 1.163mmol of PMDETA and 20ml of methyl ethyl ketone were taken and charged into a dry three-necked round bottom flask charged with nitrogen, 1.163mmol of the macroinitiator was added, the mixture was reacted in an oil bath at 85 ℃ for 3 hours, then precipitated in hexane, dried under vacuum for 12 hours, and an aluminum peroxide column was dissolved with chloroform to remove the catalyst.
EXAMPLE 3 this example uses the main and branched fluoropolymers prepared in example 1 to prepare an oil and water separation flat ultrafiltration membrane
0.6g of main-chain fluoropolymer and branched-chain fluoropolymer, 5.4g of PVDF and 25ml of N, N-dimethylformamide are put into a flask, stirred for 6 hours at 80 ℃ to obtain a uniform membrane casting solution, and then the uniform membrane casting solution is stood at room temperature until bubbles are completely removed. And casting the cooled and defoamed casting solution on one end of a clean glass plate, and scraping the liquid film on the glass plate at a constant speed by using a scraper. The glass plate with the liquid film attached is quickly placed into a gel bath, and the liquid film is changed into a solid film through the exchange of a solvent and a non-solvent. The membrane was soaked in deionized water for 24h to remove residual organic solvent, with the deionized water being replaced every 6 h.
EXAMPLE 4 this example uses the main and branched fluoropolymers prepared in example 1 to prepare a flat ultrafiltration membrane for oil-water separation
1.2g of main-chain fluoropolymer and branched-chain fluoropolymer, 4.8g of PVDF and 25ml of N, N-dimethylformamide are placed in a flask, stirred at 80 ℃ for 6 hours to obtain a uniform membrane casting solution, and then the solution is kept stand at room temperature until bubbles are completely removed. And casting the cooled and defoamed casting solution on one end of a clean glass plate, and scraping the liquid film on the glass plate at a constant speed by using a scraper. The glass plate with the liquid film is put into the gel bath water quickly, and the liquid film is changed into a solid film through the exchange of the solvent and the non-solvent. The membrane was soaked in deionized water for 24h to remove residual organic solvent, with the deionized water being replaced every 6 h.
EXAMPLE 5 this example uses the main and branched fluoropolymers prepared in example 1 to prepare a flat ultrafiltration membrane for oil-water separation
1.5g of main-chain fluoropolymer and branched-chain fluoropolymer, 4.5g of PVDF and 25ml of N, N-dimethylformamide are put into a flask, stirred for 6 hours at 80 ℃ to obtain a uniform membrane casting solution, and then the uniform membrane casting solution is stood at room temperature until bubbles are completely removed. And casting the cooled and defoamed casting solution on one end of a clean glass plate, and scraping the liquid film on the glass plate at a constant speed by using a scraper. The glass plate with the liquid film is put into the gel bath water quickly, and the liquid film is changed into a solid film through the exchange of the solvent and the non-solvent. The membrane was soaked in deionized water for 24h to remove residual organic solvent, with the deionized water being replaced every 6 h.
Example 6 this example uses PEG 600 instead of the main and branched fluoropolymer prepared in example 1 to prepare a decanter ultrafiltration flat membrane
1.5g of PEG 600, 4.5g of PVDF and 25ml of N, N-dimethylformamide are placed in a flask, stirred at 80 ℃ for 6 hours to obtain a uniform casting solution, and then kept stand at room temperature until bubbles are completely removed. And casting the cooled and defoamed casting solution on one end of a clean glass plate, and scraping the liquid film on the glass plate at a constant speed by using a scraper. The glass plate with the liquid film is put into the gel bath water quickly, and the liquid film is changed into a solid film through the exchange of the solvent and the non-solvent. The membrane was soaked in deionized water for 24h to remove residual organic solvent, with the deionized water being replaced every 6 h.
Example 7 this example uses the main and branched fluoropolymers prepared in example 1 to prepare a flat ultrafiltration membrane for oil-water separation
1g of main-chain fluoropolymer and branched-chain fluoropolymer, 5g of PES and 26ml of DMAC are put into a flask, stirred for 6 hours at 85 ℃ to obtain uniform membrane casting liquid, and kept stand at room temperature until bubbles are completely removed. And casting the cooled and defoamed casting solution on one end of a clean glass plate, and scraping the liquid film on the glass plate at a constant speed by using a scraper. The glass plate with the liquid film is put into the gel bath water quickly, and the liquid film is changed into a solid film through the exchange of the solvent and the non-solvent. The membrane was soaked in deionized water for 36h to remove residual organic solvent, with the deionized water being replaced every 6 h.
Example 8 this example uses the main and branched fluoropolymers prepared in example 1 to prepare a flat ultrafiltration membrane for oil and water separation
1.2g of main-chain and branched-chain fluorine-containing polymers, 4.8g of PAN and 25ml of N-methyl-2-pyrrolidone are put into a flask, stirred for 12 hours at 80 ℃ to obtain uniform membrane casting liquid, and then the uniform membrane casting liquid is stood at room temperature until bubbles are completely removed. And (3) casting the cooled and defoamed membrane casting solution at one end of a clean glass plate, scraping a liquid membrane on the glass plate at a constant speed by using a scraper, staying in the air for 5s, quickly putting the glass plate attached with the liquid membrane into gel bath water, and changing the liquid membrane into a solid membrane through the exchange of a solvent and a non-solvent. The membrane was soaked in deionized water for 24h to remove residual organic solvent, with the deionized water being replaced every 6 h.
Example 9 this example uses the main and branched fluoropolymers prepared in example 1 to prepare a hollow fiber membrane for oil-water separation
Putting 1.5g of main-chain and branched-chain fluorine-containing polymers, 4.5g of PAN, 0.9g of pore-forming agent polyvinylpyrrolidone PVP (M is 10000) and 25ml of N, N-dimethylformamide into a flask, stirring at 80 ℃ for 6 hours to obtain a uniform membrane casting solution, adding the prepared polymer solution into a charging bucket of spinning equipment, and standing to remove bubbles. Under the action of external pressure, the casting solution is sprayed out of a spinning nozzle through a filtering device of spinning equipment, enters coagulating bath water through a section of air gap, is subjected to phase inversion to form a hollow fiber membrane, and is placed into deionized water to be soaked for 36 hours, and the deionized water is replaced every 12 hours.
In order to verify the pollution resistance effect of the oil-water separation ultrafiltration membrane prepared by the preparation method disclosed by the invention, a dead-end filtering device is adopted to test the organic pollution resistance of the prepared oil-water separation ultrafiltration membrane. The organic contaminant used in the test procedure was an emulsion of n-hexadecane.
The relative flux decay Rate (RFD) calculation formula is as follows: RFD [ (J) ]0-JP)/J0]*100％；
The Relative Flux Recovery (RFR) calculation formula is as follows: RFR ═ J1/J0)*100％。
Wherein the pure water flux (J)0): to record the flux at 0.5h, when the flow was stabilized;
JPthe ratio of the change of permeation flux to time after filtering organic pollutants for 2 hours by the membrane;
J1after membrane cleaning, the flux at steady flow was recorded for 0.5 h.
The separation membranes of examples 3-8 were tested on a dead-end filtration unit to obtain the flux in three stages, and the RFD and RFR were calculated.
Table 1: relative flux decay Rate (RFD) and relative flux recovery Rate (RFR) of examples 3-8
The results of examples 3 to 6 in table 1 show that the relative flux attenuation rate of the PEG 600 modified ultrafiltration membrane in example 6 is 87%, and the relative flux recovery rate after cleaning is only 25%, indicating that the membrane is severely and mostly irreversibly contaminated. On the contrary, in the embodiments 3-5, the main-chain fluoropolymer and branched-chain fluoropolymer modified ultrafiltration membranes increase with the addition of the fluoropolymer, the relative flux attenuation rate of the ultrafiltration membranes is reduced from 49% to 32%, and the relative flux recovery rate is increased from 62% to 100%, which indicates that the introduction of the main-chain fluoropolymer and branched-chain fluoropolymer greatly improves the organic pollution resistance of the ultrafiltration membranes, and the prepared ultrafiltration membranes have pollution resistance and self-cleaning capability and can effectively reduce the operation cost in the membrane separation process.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (8)
1. A preparation method of a high pollution resistance oil-water separation ultrafiltration membrane is characterized by comprising the following steps:
(1) synthesis of main and branched fluoropolymers:
the main chain fluorine-containing polymer and the branched chain fluorine-containing polymer are synthesized by adopting an Atom Transfer Radical Polymerization (ATRP) method, which comprises the following specific steps: a. dissolving perfluorocarbon nonionic surfactant Zonyl FSO, triethylamine and toluene in a round-bottom flask, heating, slowly adding dibromo isobutyryl bromide into the round-bottom flask, and carrying out reflux reaction; removing toluene from the reaction solution, dissolving the reaction solution in dichloromethane, purifying by using sodium bicarbonate solution, HCl solution and concentrated brine respectively, and distilling under reduced pressure to obtain a perfluorocarbon nonionic surfactant Zonyl FSO macroinitiator; b. adding a low-surface-energy perfluoropolymer, Cu (I) Br, pentamethyl diethylenetriamine (PMDETA) and methyl ethyl ketone into a dry three-neck round-bottom flask which is filled with nitrogen, then adding the macroinitiator, reacting in an oil bath, then precipitating in hexane, and drying in vacuum for 12 hours; dissolving with chloroform, and removing catalyst with aluminum peroxide column to obtain main and branched chain fluorine-containing polymers; the low-surface-energy perfluoropolymer in the step (1) is a (methyl) acrylate perfluoroalkyl ester compound;
(2) preparing a casting solution:
dissolving the main chain fluorine-containing polymer, the branched chain fluorine-containing polymer and the film forming material in a solvent, stirring for 6-12 h in a constant-temperature water bath at the temperature of (25 +/-5) DEG C-80 ℃, and standing at room temperature until bubbles in the film casting solution are completely removed;
(3) preparing an oil-water separation ultrafiltration membrane by a non-solvent induced phase inversion method (NIPS):
firstly scraping the membrane into a flat membrane, or preparing a hollow fiber membrane by using wet method or dry-wet method spinning, quickly immersing the membrane into a gel bath, changing a liquid membrane into a solid membrane through exchange of a solvent and a non-solvent, immersing the solid membrane into deionized water for 24-48 h, and replacing the deionized water every 6 h; in the step (3), a non-woven fabric is used as a supporting layer and is fixed on the glass plate.
2. The method for preparing the oil-water separation ultrafiltration membrane with high pollution resistance according to claim 1, wherein the perfluoroalkyl (meth) acrylate compound in the step (1) is 2- (perfluorooctyl) ethyl methacrylate.
3. The method for preparing the oil-water separation ultrafiltration membrane with high pollution resistance according to claim 2, wherein the membrane forming material in the step (2) is one or a blend of more than two of polyvinylidene fluoride (PVDF), Polysulfone (PS), Polyethersulfone (PES), Polyacrylonitrile (PAN), Polycarbonate (PC), polyethylene terephthalate (PET), polypropylene (PP) and Polyamide (PA).
4. The method for preparing the oil-water separation ultrafiltration membrane with high contamination resistance according to any one of claims 1 to 3, wherein the mass concentration of the main-chain fluoropolymer and the branched-chain fluoropolymer in the membrane casting solution in the step (2) is 0.2 to 5 wt.%.
5. The method for preparing the oil-water separation ultrafiltration membrane with high contamination resistance according to claim 4, wherein the mass concentration of the membrane forming material in the membrane casting solution in the step (2) is 5 to 30 wt.%.
6. The method for preparing the oil-water separation ultrafiltration membrane with high contamination resistance according to claim 5, wherein the membrane casting solution in the step (2) contains an inorganic or organic micromolecular pore-forming agent.
7. The method for preparing the oil-water separation ultrafiltration membrane with high contamination resistance according to claim 1, wherein the solvent in the step (2) is one of tetrahydrofuran, Methyl Ethyl Ketone (MEK), trimethyl phosphate, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), Dimethylacetamide (DMAC), N-methyl-2-pyrrolidone or isophorone.
8. The method for preparing the oil-water separation ultrafiltration membrane with high contamination resistance according to claim 1, wherein the gel bath in the step (3) is non-solvent water or a mixture of water and a small molecule organic substance, wherein the small molecule organic substance is methanol, ethanol, propanol, isopropanol, acetone or petroleum ether.
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Denomination of invention: A Preparation Method of High Pollution Resistance Oil Water Separation Ultrafiltration Membrane Effective date of registration: 20230314 Granted publication date: 20211214 Pledgee: Yantai Xincai Haohan Investment Center (L.P.) Pledgor: YANTAI JINZHENG ECO-TECHNOLOGY Co.,Ltd. Registration number: Y2023370000052 |