CN111974230B - Preparation method of hydrophilic base membrane for preparing high-flux reverse osmosis membrane - Google Patents
Preparation method of hydrophilic base membrane for preparing high-flux reverse osmosis membrane Download PDFInfo
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- CN111974230B CN111974230B CN202010899183.0A CN202010899183A CN111974230B CN 111974230 B CN111974230 B CN 111974230B CN 202010899183 A CN202010899183 A CN 202010899183A CN 111974230 B CN111974230 B CN 111974230B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
- B01D67/0016—Coagulation
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
A preparation method of a hydrophilic basement membrane for preparing a high-flux reverse osmosis membrane relates to the technical field of filter membrane preparation. According to the following steps: preparing sulfonated polyether sulfone, preparing a membrane casting solution, coating the membrane casting solution on a high-strength non-woven fabric, and then putting the non-woven fabric in water for conversion of a solvent phase and a non-solvent phase to obtain a hydrophilic base membrane; the hydrophilic basement membrane for preparing the high-flux reverse osmosis membrane is prepared by adopting sulfonated polyether sulfone as a high polymer material and adding two types of nano particles: the magnetic nano particles and the nano cellulose crystals are combined, the binding force of the additive in the base membrane is enhanced, the hydrophilic modification is carried out on the base membrane to the maximum extent, and the flux of the reverse osmosis membrane is improved on the basis of improving the flux of the base membrane.
Description
Technical Field
The invention relates to the technical field of filter membrane preparation, in particular to a preparation method of a hydrophilic base membrane for preparing a high-flux reverse osmosis membrane.
Background
The membrane separation technology is a very common separation technology in the current water treatment industry, wherein a reverse osmosis membrane becomes an indispensable separation membrane due to the advantages of high efficient desalination rate, high mechanical strength, long service life and the like, and the currently used reverse osmosis base membrane is generally poor in hydrophilicity and low in flux, and is easy to excessively dry in use, so that the problems of poor uniformity, poor parallelism, difficulty in batch experiments and the like of experiments occur.
Many experiments begin with interfacial polymerization, flux is improved by adjusting an oil-water phase process formula, and flux is improved by adding nano-particles into an oil-water phase for wrapping, but the whole operation is difficult to control accurately, and the operation of process parameters is more precise. The membrane can be used as a base membrane as a site of interfacial polymerization reaction and also can be used as an ultrafiltration membrane, and the property of the base membrane is also very important for the performance of the reverse osmosis membrane. The hydrophilic modification of the base membrane can also improve the flux of reverse osmosis, and the existing hydrophilic modification methods of the base membrane can improve the hydrophilicity by adding additives into a membrane casting solution, but the mechanical strength of the membrane is not enough due to the addition of a plurality of materials, the material cost is higher, and the effect of improving the flux by singly adding one additive is not obvious. In the polysulfone membrane material, polyether sulfone (PES) is commonly used as a base membrane material in the prior art due to the characteristic properties of the polyether sulfone (PES), but the pure polyether sulfone base membrane generally has low water flux because the polyether sulfone is a hydrophobic material.
Disclosure of Invention
The present invention has been made in view of the above problems, and provides a method for preparing a hydrophilic base membrane for preparing a high flux reverse osmosis membrane, which further increases the flux of the reverse osmosis membrane by increasing the hydrophilicity of the base membrane.
The technical scheme of the invention is as follows: a method for preparing a hydrophilic base membrane for a high flux reverse osmosis membrane, the method comprising the steps of:
1) preparation of sulfonated polyether sulfone
1.1) adding 240g of polyether sulfone into 1.2L of 98% concentrated sulfuric acid, and stirring and dissolving at room temperature to obtain a mixed solution A;
1.2) slowly dripping 36mL of chlorosulfonic acid into the mixed solution A, and fully reacting to obtain a mixed solution B;
1.3) putting the mixed solution B into ice water, fully stirring to obtain a precipitate, filtering the precipitate by a vacuum filtration device of 0.1Mpa, and washing the precipitate for 3 times by deionized water to obtain the sulfonated polyether sulfone.
2) Preparation of casting solution
2.1) sequentially adding pore-foaming agent with the mass percent ratio of 5-10%, nano cellulose crystal with the mass percent ratio of 1-3%, magnetic nano cobalt particles with the mass percent ratio of 1-3% and sulfonated polyether sulfone with the mass percent ratio of 18-22% into solvent with the mass percent ratio of 62-75%, and stirring at 80 ℃ to fully dissolve the mixture;
2.2) standing and defoaming the casting solution fully dissolved in the step 2.1) at the temperature of 30-40 ℃ for 6-12 hours.
3) And coating the casting solution on a high-strength non-woven fabric, and then putting the non-woven fabric in water for solvent-phase non-solvent-phase conversion to obtain the hydrophilic base film.
The component of the pore-foaming agent in the step 2.1) is one of ethylene glycol monomethyl ether, polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG-400) or a mixture thereof.
In the step 2.1), the solvent is one or a mixture of N, N-Dimethylformamide (DMF) or N-methylpyrrolidone (NMP).
When the casting film liquid is coated on the high-strength non-woven fabric in the step 3), adjusting a scraper and the non-woven fabric to a proper gap in advance to enable the thickness of the scraped film coating to be 30-40 microns;
taking high-strength non-woven fabrics as a support, keeping the thickness of the non-woven fabrics at 100 micrometers, keeping a scraper still, keeping the non-woven fabrics to move relatively at a constant speed relative to the scraper, slowly pouring the homogeneous casting solution obtained after standing and defoaming in the step 2.2) into a liquid storage tank of a film scraping machine when the running speed reaches 5m/min, uniformly coating the casting solution on the non-woven fabrics, and curing the film subjected to the scraper by using a pure water tank gel bath at 20 ℃, and then using 3 pure water tanks at 35 ℃, 50 ℃ and 55 ℃ to obtain the base film.
The hydrophilic basement membrane for preparing the high-flux reverse osmosis membrane, which is prepared by the invention, adopts sulfonated polyether sulfone as a high polymer material, and two types of nano particles are added: the magnetic nano particles and the nano cellulose crystals are combined, the binding force of the additive in the base membrane is enhanced, the hydrophilic modification is carried out on the base membrane to the maximum extent, and the flux of the reverse osmosis membrane is improved on the basis of improving the flux of the base membrane.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the present invention.
The invention starts from the base membrane, improves the hydrophilicity of the base membrane and simultaneously can improve the flux of the reverse osmosis membrane. Common base film materials include polysulfone, polyethersulfone, polyvinylidene fluoride and other high molecular materials. The polyether sulfone material has excellent mechanical performance, high heat stability and high chemical stability, and is widely applied to the field of base films. However, as the polyethersulfone is a hydrophobic material, the pure polyethersulfone-based membrane generally has a low water flux, and researches show that the sulfonated polyethersulfone has a better hydrophilic property and can better improve the flux compared with the polyethersulfone, thereby further improving the flux of the reverse osmosis membrane.
The nano-cellulose crystal is used as a filler for modifying a basement membrane, the nano-cellulose crystal is extracted from natural fibers by a special method, and cellulose is one of the most abundant natural high-molecular polymers in the nature. The Nanocellulose (NCC), also called cellulose nanocrystals, is a rigid rod-like cellulose with a diameter of 1 to 100nm and a length of several tens to several hundreds of nanometers. The surface of NCC contains a large number of hydroxyl groups, making it easy to chemically modify the surface to impart different properties to the surface. The dispersibility of the nano-crystalline cellulose in a hydrophobic matrix material can be improved through surface modification, and the application range of the nano-crystalline cellulose is expanded, so that the hydrophilic property of the nano-crystalline cellulose is utilized to improve the hydrophilic performance of the base membrane, and the anti-pollution capability of the membrane is improved.
The magnetic nanoparticles have good biocompatibility with various polymers, can be better compounded with other nanoparticles, also have good dispersibility and magnetic conductivity in aqueous solution, are favorable for enhancing the polarity of organic molecules, enable organic matters to flow more smoothly, are easier to wash, prevent protein adsorption and better enhance the anti-pollution capacity of the membrane.
The invention combines the magnetic nano particles and the nano cellulose crystals to carry out hydrophilic modification on the basal membrane to the maximum extent, thereby improving the flux of the reverse osmosis membrane on the basis of improving the flux of the basal membrane.
A method for preparing a hydrophilic base membrane for a high flux reverse osmosis membrane, the method comprising the steps of:
1) preparation of sulfonated polyether sulfone
1.1) adding 240g of polyether sulfone into 1.2L of 98% concentrated sulfuric acid, and stirring and dissolving at room temperature to obtain a mixed solution A;
1.2) slowly dripping 36mL of chlorosulfonic acid into the mixed solution A, and fully reacting to obtain a mixed solution B;
1.3) putting the mixed solution B into ice water, fully stirring to obtain a precipitate, filtering the precipitate by a vacuum filtration device of 0.1Mpa, and washing the precipitate for 3 times by deionized water to obtain the sulfonated polyether sulfone.
2) Preparation of casting solution
2.1) sequentially adding pore-foaming agent with the mass percent ratio of 5-10%, nano cellulose crystal with the mass percent ratio of 1-3%, magnetic nano cobalt particles with the mass percent ratio of 1-3% and sulfonated polyether sulfone with the mass percent ratio of 18-22% into solvent with the mass percent ratio of 62-75%, and stirring at 80 ℃ to fully dissolve the mixture;
2.2) standing and defoaming the casting solution fully dissolved in the step 2.1) at the temperature of 30-40 ℃ for 6-12 hours.
3) And coating the casting solution on a high-strength non-woven fabric, and then putting the non-woven fabric in water for solvent-phase non-solvent-phase conversion to obtain the hydrophilic base film.
The component of the pore-foaming agent in the step 2.1) is one of ethylene glycol monomethyl ether, polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG-400) or a mixture thereof.
In the step 2.1), the solvent is one or a mixture of N, N-Dimethylformamide (DMF) or N-methylpyrrolidone (NMP).
When the casting film liquid is coated on the high-strength non-woven fabric in the step 3), adjusting a scraper and the non-woven fabric to a proper gap in advance to enable the thickness of the scraped film coating to be 30-40 microns;
taking high-strength non-woven fabrics as a support, keeping the thickness of the non-woven fabrics at 100 micrometers, keeping a scraper still, keeping the non-woven fabrics to move relatively at a constant speed relative to the scraper, slowly pouring the homogeneous casting solution obtained after standing and defoaming in the step 2.2) into a liquid storage tank of a film scraping machine when the running speed reaches 5m/min, uniformly coating the casting solution on the non-woven fabrics, and curing the film subjected to the scraper by using a pure water tank gel bath at 20 ℃, and then using 3 pure water tanks at 35 ℃, 50 ℃ and 55 ℃ to obtain the base film.
Example 1
The invention relates to a preparation method of a hydrophilic basement membrane for preparing a high-flux reverse osmosis membrane, which comprises the following steps:
1. preparation of sulfonated polyether sulfone: adding 240g of polyether sulfone into 1.2L of 98% concentrated sulfuric acid, and stirring and dissolving at room temperature to obtain a mixed solution A; slowly dripping 36mL of chlorosulfonic acid into the mixed solution A, and fully reacting to obtain a mixed solution B; and (3) putting the mixed solution B into ice water, fully stirring to obtain a precipitate, filtering the precipitate by using a vacuum filtration device of 0.1Mpa, and washing the precipitate for 3 times by using deionized water to obtain the sulfonated polyether sulfone.
2. Accurately weighing the following raw materials of the casting solution:
sulfonated polyether sulfone: 180g
Ethylene glycol methyl ether: 80g of
Nanocellulose crystals: 20g of
Magnetic nano cobalt particles: 20g of
N, N-Dimethylformamide (DMF): 700g
3. Adding ethylene glycol monomethyl ether into DMF, stirring uniformly, slowly adding magnetic nano cobalt particles, stirring at a constant speed for uniform dispersion, slowly adding nano cellulose crystals, uniformly dispersing, slowly adding sulfonated polyether sulfone, stirring at a constant speed for half an hour, starting heating, wherein the heating temperature in the process is 80 ℃, and stirring continuously until solutes are completely dissolved to obtain a clear mixed solution, and stopping heating and stirring.
4. Defoaming the casting solution: and (3) placing the casting solution in a constant-temperature oven at 35 ℃, and standing for defoaming for 12 h.
5. Film scraping: and adjusting the scraper and the non-woven fabric to a proper gap so that the thickness of the scraped film coating is 30-40 microns. The high-strength non-woven fabric is used as a support, and the thickness of the non-woven fabric is 100 microns. Keeping the scraper still, keeping the non-woven fabric to move relative to the scraper at a constant speed, slowly pouring a homogeneous casting solution into a liquid storage tank of the film scraping machine when the running speed reaches 5m/min, so that the casting solution is uniformly coated on the non-woven fabric, carrying out gel bath on the film after passing through the scraper by a pure water tank at 20 ℃, and then carrying out solidification by 3 pure water tanks at 35 ℃, 50 ℃ and 55 ℃ to obtain the base film.
Example 2
1. The procedure for the preparation of sulfonated polyethersulfones was in accordance with example 1.
2. Accurately weighing the following raw materials of the casting solution:
sulfonated polyether sulfone: 200g
PEG-400：80g
Nanocellulose crystals: 20g of
Magnetic nano cobalt particles: 20g of
N, N-Dimethylformamide (DMF): 680g
3. The preparation of the casting solution and the film scraping process were the same as those in example 1.
Embodiment 3
1. The procedure for the preparation of sulfonated polyethersulfones was in accordance with example 1.
2. Accurately weighing the following raw materials of the casting solution:
sulfonated polyether sulfone: 220g
Polyvinylpyrrolidone (PVP): 60g of
Nanocellulose crystals: 20g of
Magnetic nano cobalt particles: 20g of
N, N-Dimethylformamide (DMF): 680g
3. The preparation of the casting solution and the film scraping process were the same as those in example 1.
Example 4
1. The procedure for the preparation of sulfonated polyethersulfones was in accordance with example 1.
2. Accurately weighing the following raw materials of the casting solution:
sulfonated polyether sulfone: 180g
Ethylene glycol methyl ether: 80g of
Nanocellulose crystals: 20g of
Magnetic nano cobalt particles: 20g of
N-methylpyrrolidone (NMP): 700g
3. The preparation of the casting solution and the film scraping process were the same as those in example 1.
Comparative example:
the other steps are the same as the embodiment 1 except that the casting solution is not added with nano-cellulose crystals and magnetic nano-cobalt particles.
The base membrane obtained from the 5 groups of cases is prepared into the reverse osmosis membrane by adopting the same process and formula, and the preparation process is as follows:
1. preparing an aqueous phase solution: adding 3kg of m-phenylenediamine, 0.5kg of sodium dodecyl benzene sulfonate and 4kg of N-methyl pyrrolidone into 92.5kg of water, and uniformly stirring to obtain an aqueous phase solution;
2. preparing an oil phase solution: dissolving 0.1kg of trimesoyl chloride in 100kg of ethylcyclohexane, and uniformly stirring to obtain an oil phase solution;
3. firstly, immersing a base membrane into a water phase solution for 30s, removing redundant solution on the surface by using a low-pressure air knife, then allowing a basement membrane adsorbing the water phase solution to pass through a closed space with a heat supply and air exhaust system, controlling the internal temperature of the closed space to be 26 ℃ and the relative humidity to be 60% for 1min, further volatilizing the water on the membrane surface of the basement membrane, then immersing the basement membrane into an oil phase solution for 40s, removing a part of oil phase solution on the surface by using the low-pressure air knife, then, keeping the basement membrane in a 90 ℃ oven for 5min, drying the oil phase solution to form a polyamide ultrathin separation layer, and finally obtaining the composite reverse osmosis membrane after subsequent cleaning and drying.
The 5 groups of reverse osmosis membrane membranes obtained above were tested under the following conditions: 1500ppm NaCl, pH value of 7.5-8, temperature of 25 ℃, test pressure of 145psi, and test results are as follows:
| salt rejection (%) | Flux (GFD) | |
| Comparative example | 99.65 | 32.5 |
| Example 1 | 99.58 | 39.5 |
| Example 2 | 99.54 | 41.6 |
| Example 3 | 99.46 | 36.4 |
| Example 4 | 99.53 | 38.8 |
The results show that: compared with the comparative example, when the hydrophilic base membrane prepared by the invention is applied to the preparation of the reverse osmosis membrane (examples 1-4), the flux is obviously improved, and the salt rejection rate is not obviously reduced and is within an acceptable range.
Claims (3)
1. A method for preparing a hydrophilic base membrane for a high flux reverse osmosis membrane, comprising the steps of:
1) preparation of sulfonated polyether sulfone
1.1) adding 240g of polyether sulfone into 1.2L of 98% concentrated sulfuric acid, and stirring and dissolving at room temperature to obtain a mixed solution A;
1.2) slowly dripping 36mL of chlorosulfonic acid into the mixed solution A, and fully reacting to obtain a mixed solution B;
1.3) putting the mixed solution B into ice water, fully stirring to obtain a precipitate, filtering the precipitate by a vacuum filtration device of 0.1Mpa, and washing the precipitate for 3 times by deionized water to obtain sulfonated polyether sulfone;
2) preparation of casting solution
2.1) sequentially adding pore-foaming agent with the mass percent ratio of 5-10%, nano cellulose crystal with the mass percent ratio of 1-3%, magnetic nano cobalt particles with the mass percent ratio of 1-3% and sulfonated polyether sulfone with the mass percent ratio of 18-22% into solvent with the mass percent ratio of 62-75%, and stirring at 80 ℃ to fully dissolve the mixture;
2.2) standing and defoaming the casting solution fully dissolved in the step 2.1) at the temperature of 30-40 ℃ for 6-12 hours;
3) coating the casting solution on a high-strength non-woven fabric, and then putting the non-woven fabric in water for solvent phase and non-solvent phase conversion to obtain a hydrophilic base film;
when the casting film liquid is coated on the high-strength non-woven fabric in the step 3), adjusting a scraper and the non-woven fabric to a proper gap in advance to enable the thickness of the scraped film coating to be 30-40 microns;
taking high-strength non-woven fabrics as a support, keeping the thickness of the non-woven fabrics at 100 micrometers, keeping a scraper still, keeping the non-woven fabrics to move relatively at a constant speed relative to the scraper, slowly pouring the homogeneous casting solution obtained after standing and defoaming in the step 2.2) into a liquid storage tank of a film scraping machine when the running speed reaches 5m/min, uniformly coating the casting solution on the non-woven fabrics, and curing the film subjected to the scraper by using a pure water tank gel bath at 20 ℃, and then using 3 pure water tanks at 35 ℃, 50 ℃ and 55 ℃ to obtain the base film.
2. The method for preparing a hydrophilic membrane based on a reverse osmosis membrane according to claim 1, wherein the porogen in step 2.1) is one of ethylene glycol methyl ether, polyvinylpyrrolidone, polyethylene glycol or their mixture.
3. The method for preparing a hydrophilic membrane based on a reverse osmosis membrane for high flux according to claim 1, wherein the solvent in step 2.1) is one or a mixture of N, N-dimethylformamide or N-methylpyrrolidone.
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