CN115282783B - Reverse osmosis membrane and preparation method and application thereof - Google Patents

Reverse osmosis membrane and preparation method and application thereof Download PDF

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Publication number
CN115282783B
CN115282783B CN202211227992.2A CN202211227992A CN115282783B CN 115282783 B CN115282783 B CN 115282783B CN 202211227992 A CN202211227992 A CN 202211227992A CN 115282783 B CN115282783 B CN 115282783B
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water
separation layer
reverse osmosis
membrane
osmosis membrane
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CN115282783A (en
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陈可可
陈涛
张宇
刘文超
谭惠芬
潘巧明
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Hangzhou Water Treatment Technology Development Center Co Ltd
Bluestar Hangzhou Membrane Industry Co Ltd
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Hangzhou Water Treatment Technology Development Center Co Ltd
Bluestar Hangzhou Membrane Industry Co Ltd
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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
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • 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
    • 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
    • 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
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Nanotechnology (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention relates to a reverse osmosis membrane and a preparation method and application thereof. The preparation method of the reverse osmosis membrane comprises the following steps of providing a support membrane; sequentially placing a water phase solution and an oil phase solution on a first surface of a support membrane, and then carrying out heat treatment to form a separation layer, wherein the water phase solution comprises polyamine, phosphate, a first metal salt and a water-based polymer, a molecular chain of the water-based polymer comprises hydroxyl and a phosphate group, and the oil phase solution comprises polyacyl chloride; placing an alkaline aqueous solution on the surface of the separation layer far away from the support membrane, and carrying out decomposition reaction on the aqueous polymer, wherein the separation layer contains phosphate radicals to obtain a prefabricated membrane; and forming an anti-pollution layer on the surface of the separation layer far away from the support membrane to obtain the reverse osmosis membrane. The preparation method can ensure that the water-based polymer is uniformly and stably dispersed in the separation layer, and simultaneously, the anti-pollution layer is prevented from falling off, so that the prepared reverse osmosis membrane has excellent anti-pollution performance and water flux.

Description

Reverse osmosis membrane and preparation method and application thereof
Technical Field
The invention relates to the technical field of water treatment, in particular to a reverse osmosis membrane and a preparation method and application thereof.
Background
The reverse osmosis membrane is a core component of the reverse osmosis technology, and can effectively remove dissolved salts, colloids, microorganisms and organic matters in water.
In order to prevent the membrane pores of the reverse osmosis membrane from being blocked due to pollution of organic matters, mineral oil and the like in the using process, a hydrophilic anti-pollution layer is usually formed on the surface of the reverse osmosis membrane, but the traditional anti-pollution layer is easy to fall off, and the water flux of the reverse osmosis membrane is greatly reduced, so that the membrane performance is influenced. Therefore, in order to reduce the influence of the anti-pollution layer on the performance of the reverse osmosis membrane, polyvinyl alcohol is conventionally added into an aqueous phase solution for preparing a separation layer, but due to the viscosity characteristic of the polyvinyl alcohol and the instant completion of an interfacial reaction, a polyvinyl alcohol aqueous polymer cannot diffuse into the separation layer in time, and the water flux of the reverse osmosis membrane cannot be improved.
Disclosure of Invention
In view of the above, there is a need to provide a reverse osmosis membrane, a method for preparing the same, and applications thereof; the preparation method can uniformly and stably disperse the water-based polymer in the separation layer, and can prevent the anti-pollution layer from falling off, so that the prepared reverse osmosis membrane has excellent anti-pollution performance and high water flux.
The invention provides a preparation method of a reverse osmosis membrane, which comprises the following steps:
providing a support film;
sequentially placing a water phase solution and an oil phase solution on the first surface of the support membrane, and then carrying out heat treatment to form a separation layer, wherein the water phase solution comprises polyamine, phosphate, a first metal salt and a water-based polymer, the molecular chain of the water-based polymer comprises hydroxyl and phosphate groups, and the oil phase solution comprises polyacyl chloride;
placing an alkaline aqueous solution on the surface of the separation layer away from the support membrane, and performing decomposition reaction on the aqueous polymer, wherein the separation layer contains phosphate radical to obtain a prefabricated membrane; and
and forming an anti-pollution layer on the surface of the separation layer far away from the support membrane to obtain the reverse osmosis membrane.
In one embodiment, the aqueous polymer is selected from ammonium polyvinyl alcohol phosphates;
and/or the mass fraction of the water-based polymer in the aqueous phase solution is 0.2-1.5%.
In one embodiment, the phosphate is selected from at least one of sodium hexametaphosphate, sodium tripolyphosphate, or sodium dimeric phosphate; the first metal salt is selected from at least one of magnesium chloride, calcium chloride or magnesium sulfate.
In one embodiment, the mass fraction of the phosphate in the aqueous solution is between 1.0% and 3.5%, and the mass fraction of the first metal salt in the aqueous solution is between 0.2% and 1.5%.
In one embodiment, the pH of the basic aqueous solution is from 12.5 to 13.5.
In one embodiment, the step of performing the decomposition reaction is performed at a temperature of 15 ℃ to 35 ℃ for a time of 15s to 45s.
In one embodiment, before the step of forming the anti-contamination layer on the surface of the separation layer away from the support membrane, the method further comprises the step of cleaning the prefabricated membrane.
In one embodiment, the step of forming an anti-contamination layer on the surface of the separation layer away from the support membrane comprises:
sequentially forming a second metal salt aqueous solution and a high polymer aqueous solution on the surface of the separation layer away from the support membrane; or forming a mixed aqueous solution of a second metal salt and a high polymer on the surface of the separation layer away from the support membrane;
and then carrying out heat treatment, wherein the second metal salt and the high polymer are subjected to flocculation reaction to form an anti-pollution layer, so as to obtain the reverse osmosis membrane.
A reverse osmosis membrane prepared by the preparation method of the reverse osmosis membrane comprises a support membrane, a separation layer and an anti-pollution layer which are arranged in a stacking mode.
An application of the reverse osmosis membrane in a water treatment device.
In the preparation method of the reverse osmosis membrane provided by the invention, the phosphate and the first metal salt can generate a water-soluble complex compound to form a water-soluble three-dimensional network; meanwhile, the molecular chain of the water-based polymer comprises hydroxyl and phosphate groups, so that the water-based polymer has the excellent water-solubility property of salt and the long molecular chain characteristic of a high molecular compound; therefore, the water-solubility property of the water-soluble polymer enables the water-soluble polymer to be doped in a water-soluble three-dimensional network, and the long molecular chain characteristic of the water-soluble polymer can enable the water-soluble polymer and the water-soluble three-dimensional network to be rapidly diffused into a water-oil interface together; therefore, on one hand, the water-soluble three-dimensional network can participate in the process of interfacial polymerization reaction and be used as a soft template of interfacial polymerization, thereby ensuring the ordered crosslinking of the separation layer and reducing the occurrence of defects; on the other hand, the aqueous polymer can be stably doped in a separation layer generated by an interface reaction and is not easy to fall off.
Because the aqueous polymer can be stably doped in the separation layer, in the step of decomposition reaction, the alkaline aqueous solution can enable ammonium phosphate groups in the aqueous polymer to generate decomposition reaction to form phosphate groups, so that a large number of hydroxyl groups and phosphate groups are uniformly distributed in the separation layer, the hydrophilicity of the separation layer is greatly improved, and the prefabricated membrane has certain pollution resistance and high water flux; meanwhile, the anti-pollution layer is further formed on the surface of the separation layer and is obtained by flocculation reaction of high polymer and metal salt, so that the anti-pollution layer is of a loose structure and cannot reduce the water flux of the separation layer.
Therefore, in the reverse osmosis membrane prepared by the invention, the phosphate radical in the separation layer and the anti-pollution layer are cooperated, so that the reverse osmosis membrane has excellent water flux, anti-pollution performance and salt rejection rate.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the accompanying examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The reverse osmosis membrane provided by the invention and the preparation method and application thereof will be further explained below.
The preparation method of the reverse osmosis membrane provided by the invention comprises the following steps:
s10, providing a support film;
s20, sequentially placing a water phase solution and an oil phase solution on the first surface of the support membrane, and then carrying out heat treatment to form a separation layer, wherein the water phase solution comprises polyamine, phosphate, first metal salt and a water-based polymer, a molecular chain of the water-based polymer comprises hydroxyl and a phosphate group, and the oil phase solution comprises polyacyl chloride;
s30, placing an alkaline aqueous solution on the surface of the separation layer, which is far away from the support membrane, and carrying out decomposition reaction on the aqueous polymer, wherein the separation layer contains phosphate radicals, so as to obtain a prefabricated membrane; and
and S40, forming an anti-pollution layer on the surface of the separation layer far away from the support membrane to obtain the reverse osmosis membrane.
In step S10, the material of the support membrane may include at least one of polysulfone, polypropylene, or polyacrylonitrile, wherein polysulfone is cheap and easily available, the membrane is simple to manufacture, the mechanical strength is good, the compression resistance is good, the chemical properties are stable, and the support membrane is non-toxic and can resist biological degradation, so the material of the support membrane is preferably polysulfone.
The support film has a first surface and a second surface which are opposite to each other, and in order to increase the strength of the support film, in one embodiment, the second surface of the support film is laminated with a non-woven fabric layer.
In step S20, a water-soluble three-dimensional network is formed because the phosphate and the first metal salt can generate a water-soluble complex; meanwhile, the molecular chain of the water-based polymer comprises hydroxyl and phosphate groups, so that the water-based polymer has the excellent water-solubility property of salt and the long molecular chain characteristic of a high molecular compound; therefore, the water-solubility property of the water-soluble polymer enables the water-soluble polymer to be doped in a water-soluble three-dimensional network, and the long molecular chain characteristic of the water-soluble polymer can enable the water-soluble polymer and the water-soluble three-dimensional network to be rapidly diffused into a water-oil interface together; on one hand, the water-soluble three-dimensional network can participate in the process of interfacial polymerization reaction and serve as a soft template of interfacial polymerization to adjust the density of the generated separation layer; on the other hand, the aqueous polymer can be stably doped in a separation layer generated by an interface reaction and is not easy to fall off.
In one embodiment, the phosphate is at least one selected from sodium hexametaphosphate, sodium tripolyphosphate and sodium dipolyphosphate, and the sodium hexametaphosphate preferably is sodium hexametaphosphate, and because the structure formula of the sodium hexametaphosphate has more charged groups, a water-soluble complex can be formed better, and a water-soluble three-dimensional network can be formed better.
It should be noted that the water-soluble complex formed by the phosphate and the first metal salt is removed by dissolving in water during washing and use, and therefore, in order to better improve the compactness of the separation layer and the water flux, in one embodiment, the mass fraction of the phosphate in the aqueous phase solution is 1.0% to 3.5%, including but not limited to 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4% or 3.5%, and preferably 1.8% to 3.5%.
In one embodiment, the first metal salt is selected from at least one of magnesium chloride, calcium chloride, or magnesium sulfate.
In order to better improve the compactness of the separation layer and the water flux, in one embodiment, the mass fraction of the first metal salt in the aqueous phase solution is 0.2% to 1.5%, including but not limited to 0.2%, 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4% or 1.5%, preferably 0.2% to 0.8%.
For better generation of the water-soluble complex and formation of a water-soluble three-dimensional network, the mass ratio of the phosphate to the first metal salt in the aqueous solution is 4.
In one embodiment, the aqueous polymer is selected from ammonium polyvinyl alcohol phosphates; in one embodiment, the mass fraction of the aqueous polymer in the aqueous solution is between 0.2% and 1.5%, including but not limited to 0.2%, 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, or 1.5%, preferably between 0.2% and 0.8%, combined with economics and membrane functionality.
The present invention is not particularly limited in kind of the polyamine and the polybasic acid chloride, and in one embodiment, the polyamine is at least one selected from the group consisting of an aromatic polyamine, an aliphatic polyamine, and an alicyclic polyamine, and preferably, the polyamine is at least one selected from the group consisting of m-phenylenediamine and piperazine; in one embodiment, the polyamine is present in the aqueous solution at a mass fraction of 0.5% to 1.5%.
In one embodiment, the polyacyl chloride is selected from at least one of aromatic polyacyl chloride and aliphatic polyacyl chloride, preferably, the polyacyl chloride is selected from at least one of trimesoyl chloride or adipoyl chloride, and in one embodiment, the mass fraction of the polyacyl chloride in the oil phase solution is 0.05% to 0.30%.
The solvent of the oil phase solution is selected from isoparaffin solvents, which in one embodiment comprises at least one of isododecane or isotetradecane.
It is understood that the polyamine and the poly-acyl chloride can be crosslinked to form a polyamide molecular chain, and in step S20, the separation layer includes the polyamide molecular chain, and the phosphate reacts with the first metal salt to form the water-soluble complex and the aqueous polymer.
In order to absorb a byproduct generated by a cross-linking reaction of polyamine and polybasic acyl chloride, the aqueous phase solution further comprises an acid-binding agent, wherein in one embodiment, the acid-binding agent is selected from triethylamine, and the mass fraction of the acid-binding agent in the aqueous phase solution is 0.1-0.3%.
In one embodiment, the step of sequentially placing the aqueous phase solution and the oil phase solution on the first surface of the support membrane specifically comprises: firstly, coating a water phase solution on the first surface of a support membrane, standing for a period of time to enable the water phase solution to fill holes in the surface layer of the support membrane, then pouring out the redundant water phase solution and drying the surface of the support membrane by blowing; and finally, coating the oil phase solution on the first surface of the support membrane, standing for a period of time, and pouring off the redundant oil phase solution.
In one embodiment, in the step of heat treatment in step S20, the temperature is 50 ℃ to 100 ℃ for 2min to 10min.
In the step S30, since the aqueous polymer can be stably doped into the separation layer, in the step of decomposition reaction, the alkaline aqueous solution can decompose ammonium phosphate groups in the aqueous polymer to form phosphate groups, so that a large amount of hydroxyl groups and phosphate groups are uniformly distributed in the separation layer, and the hydrophilicity of the separation layer is greatly improved, so that the prefabricated membrane has certain contamination resistance and high water flux.
In the course of the decomposition reaction, NH is formed 3 Can be used as an acid-binding agent for interfacial polymerization, can ensure more complete polymerization of the separation layer, and ensures the salt rejection rate of the separation layer.
In order to better avoid hydrolysis of the polyamide molecular chains in the alkaline aqueous solution and at the same time to more completely decompose the phosphate groups to form phosphate groups, in one embodiment the pH of the alkaline aqueous solution is in the range of 12.5 to 13.5.
In one embodiment, the step of performing the decomposition reaction is at a temperature of 15 ℃ to 35 ℃ for a time of 15s to 45s.
In the step S40, an anti-pollution layer is further formed on the surface of the separation layer, and the anti-pollution layer is obtained by flocculation reaction of high polymer and metal salt, so that the anti-pollution layer is of a loose structure, the water flux of the separation layer cannot be reduced, in addition, the anti-pollution layer and the hydroxyl on the surface layer of the separation layer can form hydrogen bond action, the anti-pollution layer can be firmly adsorbed on the surface of the separation layer and is not easy to fall off, a water channel can be formed, and the water flux is further improved on the basis of a prefabricated membrane.
In step S40, in order to better avoid the generation of metal hydroxide due to the contact of the metal salt with the alkaline aqueous solution, in one embodiment, before step S40, a step of washing the prefabricated membrane is further included, and preferably, the prefabricated membrane is washed with water.
In one embodiment, the step of forming the anti-contamination layer on the surface of the separation layer away from the support membrane includes:
sequentially forming a second metal salt aqueous solution and a high polymer aqueous solution on the surface of the separation layer away from the support membrane; or forming a mixed aqueous solution of a second metal salt and a high polymer on the surface of the separation layer away from the support membrane;
and then carrying out heat treatment, and carrying out flocculation reaction on the second metal salt and the high polymer to form an anti-pollution layer so as to obtain the reverse osmosis membrane.
In one embodiment, the second metal salt is selected from at least one of magnesium chloride, calcium chloride, or magnesium sulfate; the mass fraction of the second metal salt is 0.5-2%.
In one embodiment, the high polymer is selected from at least one of anionic polyacrylamide, cationic polyacrylamide or quaternary ammonium salt chitosan, and the mass fraction of the high polymer is 0.1% -0.5%.
In one embodiment, in the step of heat-treating in step S40, the temperature is 50 ℃ to 100 ℃ for 2min to 10min.
The invention also provides a reverse osmosis membrane prepared by the preparation method of the reverse osmosis membrane, which comprises a support membrane, a separation layer and an anti-pollution layer which are arranged in a stacked mode.
In the reverse osmosis membrane prepared by the invention, phosphate groups and phosphate groups in the separation layer are cooperated with the anti-pollution layer, so that the reverse osmosis membrane has excellent water flux, anti-pollution and salt rejection rate.
In one embodiment, a nonwoven fabric layer is further stacked on the surface of the support membrane remote from the separation layer.
The invention also provides application of the reverse osmosis membrane in a water treatment device.
Specifically, the invention also provides a water purifier comprising the reverse osmosis membrane, wherein in the water purifying process, raw water to be purified enters from the anti-pollution layer of the reverse osmosis membrane, and the raw water permeates the reverse osmosis membrane under the action of pressure to form pure water.
Hereinafter, the reverse osmosis membrane, the preparation method and the application thereof will be further described by the following specific examples, in which ammonium polyvinylalcohol phosphate is purchased from michelin, with a commodity number of 821233; anionic polyacrylamide was purchased from michelin under the designation P821239.
Example 1
A polysulfone base film is provided.
Adding m-phenylenediamine, magnesium chloride, sodium hexametaphosphate, ammonium polyvinyl alcohol phosphate and triethylamine into water, and uniformly mixing to obtain an aqueous phase solution, wherein the mass fraction of the ammonium polyvinyl alcohol phosphate in the aqueous phase solution is 0.5%, the mass fraction of the magnesium chloride is 0.5%, the mass fraction of the sodium hexametaphosphate is 2%, the mass fraction of the m-phenylenediamine is 1.0%, and the mass fraction of the triethylamine is 0.2%; preparing an oil phase solution of trimesoyl chloride with the mass fraction of 0.15%, wherein the solvent of the oil phase solution is an isoparaffin solvent Isopar L.
Coating the water phase solution on the first surface of the polysulfone basement membrane, standing for 60s, pouring out the redundant water phase solution, and drying the first surface by cold air; and coating the oil phase solution on the blow-dried first surface, standing for 30s, pouring out the redundant oil phase solution, and putting the membrane into a 80 ℃ forced air drying oven for heat treatment for 2min to form a separation layer.
And then coating NaOH solution with the pH value of 13 on the surface of the separation layer, which is far away from the polysulfone base membrane, for decomposition reaction at the temperature of 25 ℃ for 30s, pouring out the redundant NaOH solution, washing with water, and drying in the shade to obtain the prefabricated membrane.
Preparing a mixed solution of calcium chloride and anionic polyacrylamide, wherein the mass fraction of the calcium chloride is 1%, and the mass fraction of the anionic polyacrylamide is 0.2%, coating the mixed solution on the surface of a separation layer in a prefabricated membrane, standing for 30s, pouring out the redundant aqueous solution, and drying in an oven at 90 ℃ to obtain the reverse osmosis membrane.
Example 2
A polysulfone base film is provided.
Adding m-phenylenediamine, magnesium sulfate, sodium hexametaphosphate, ammonium polyvinyl alcohol phosphate and triethylamine into water, and uniformly mixing to obtain an aqueous phase solution, wherein the mass fraction of the ammonium polyvinyl alcohol phosphate in the aqueous phase solution is 1%, the mass fraction of the magnesium sulfate is 0.6%, the mass fraction of the sodium hexametaphosphate is 3%, the mass fraction of the m-phenylenediamine is 1.0%, and the mass fraction of the triethylamine is 0.2%; preparing an oil phase solution of trimesoyl chloride with the mass fraction of 0.15%, wherein the solvent of the oil phase solution is an isoalkane solvent Isopar L.
Firstly, coating the aqueous phase solution on the first surface of a polysulfone basement membrane, standing for 60s, then pouring out the redundant aqueous phase solution, and drying the first surface by cold air; and coating the oil phase solution on the blow-dried first surface, standing for 30s, pouring out the redundant oil phase solution, and putting the membrane into a 80 ℃ forced air drying oven for heat treatment for 2min to form a separation layer.
And then coating NaOH solution with the pH value of 13 on the surface of the separation layer, which is far away from the polysulfone base membrane, for decomposition reaction at the temperature of 25 ℃ for 30s, pouring out the redundant NaOH solution, washing with water, and drying in the shade to obtain the prefabricated membrane.
Preparing a mixed solution of magnesium chloride and anionic polyacrylamide, wherein the mass fraction of the magnesium chloride is 1.5%, and the mass fraction of the anionic polyacrylamide is 0.3%, coating the mixed solution on the surface of a separation layer in a prefabricated membrane, standing for 30s, pouring out excessive aqueous solution, drying in the shade, and drying in an oven at 90 ℃ to obtain the reverse osmosis membrane.
Example 3
Example 3 reference is made to example 1 except that sodium hexametaphosphate is replaced by sodium tripolyphosphate.
Example 4
Example 4 was conducted with reference to example 1, except that the mass fraction of sodium hexametaphosphate in the aqueous phase solution was 3.5%, and the mass fraction of magnesium chloride in the aqueous phase solution was 0.6%.
Example 5
Example 5 was carried out with reference to example 1, except that the mass fraction of sodium hexametaphosphate in the aqueous phase solution was 1.0%, and the mass fraction of magnesium chloride in the aqueous phase solution was 0.2%.
Example 6
Example 6 the process is carried out as in example 1, except that the mass fraction of ammonium polyvinyl alcohol phosphate in the aqueous solution is 1.0%.
Example 7
Example 7 was conducted with reference to example 1, except that the mass fraction of ammonium polyvinylalcohol phosphate in the aqueous solution was 0.2%.
Comparative example 1
Comparative example 1 reference example 1 was made except that no ammonium polyvinyl phosphate was added to the aqueous solution.
Comparative example 2
Comparative example 2 reference was made to example 1 except that ammonium polyvinyl alcohol phosphate in aqueous solution was replaced with polyvinyl alcohol.
Comparative example 3
Comparative example 3 was conducted with reference to example 1 except that magnesium chloride and sodium hexametaphosphate were not included in the aqueous solution.
Comparative example 4
Comparative example 4 was conducted with reference to example 1 except that after the separation layer was formed, the decomposition reaction was conducted without treatment with NaOH solution.
Comparative example 5
Comparative example 5 was conducted with reference to example 1 except that sodium hexametaphosphate was replaced with trisodium phosphate.
Comparative example 6
Comparative example 6 was conducted with reference to example 1, except that an anti-contamination layer was not formed on the surface of the separation layer of the prefabricated membrane.
Test example 1
The reverse osmosis membranes of examples 1 to 7 and comparative examples 1 to 6 were tested for rejection and flux, respectively, under the following test conditions: the concentrated water is 500ppm sodium chloride aqueous solution, the test pressure is 0.75MPa, the concentrated water flow is 1.0GPM, the pH value of the concentrated water is 7.0, the environmental temperature is 25 ℃, and the effective membrane area is about 19cm 2 The results are described in table 1.
TABLE 1
Figure 713619DEST_PATH_IMAGE001
In table 1, the membrane water flux (F) is calculated from the volume of water passing through the reverse osmosis membrane over a certain time, and the formula is: f = V/(a × T), where V is the volume of water passing through the reverse osmosis membrane per unit time, a is the effective membrane area, and T is the time.
The retention rate (R) is calculated by the concentration of the concentrated water and the concentration of the permeate, and the calculation formula is as follows: r = (1-C) 1 /C 0 ) X 100%, wherein C 1 Is the concentration of concentrated water, C 0 The concentration of the permeate was used.
Respectively soaking the reverse osmosis membranes of the embodiment 1 and the embodiment 2 in 70 ℃ water bath for 120h, respectively testing the rejection rate and the water flux of the reverse osmosis membranes according to the testing method, wherein after soaking, the water flux of the reverse osmosis membrane of the embodiment 1 is 89L/(m) 2 H), the rejection rate is 99.7%, and the water flux of the reverse osmosis membrane of example 2 is 87L/(m) 2 H), the retention rate is 99.6%.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples only show several embodiments of the present invention, and the description thereof is specific and detailed, but not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (5)

1. A preparation method of a reverse osmosis membrane is characterized by comprising the following steps:
providing a support film;
sequentially placing an aqueous phase solution and an oil phase solution on a first surface of the support membrane, and then carrying out heat treatment to form a separation layer, wherein the aqueous phase solution comprises polyamine, phosphate, a first metal salt and a water-based polymer, the first metal salt is selected from at least one of magnesium chloride, calcium chloride or magnesium sulfate, the phosphate and the first metal salt can generate a water-soluble complex to form a water-soluble three-dimensional network, the water-based polymer is selected from ammonium polyvinyl alcohol phosphate, the mass fraction of the phosphate is 1.0-3.5% in the aqueous phase solution, the mass fraction of the first metal salt is 0.2-1.5%, the mass fraction of the water-based polymer is 0.2-1.5%, and the oil phase solution comprises polyacyl chloride;
placing an alkaline aqueous solution with the pH value of 12.5-13.5 on the surface of the separation layer far away from the support membrane, and carrying out decomposition reaction on the aqueous polymer, wherein in the step of decomposition reaction, the temperature is 15-35 ℃, the time is 15-45 s, and the separation layer contains phosphate radicals to obtain a prefabricated membrane;
forming an anti-pollution layer on the surface of the separation layer far away from the support membrane to obtain the reverse osmosis membrane, wherein the step of forming the anti-pollution layer on the surface of the separation layer far away from the support membrane comprises the following steps:
sequentially forming a second metal salt aqueous solution and a high polymer aqueous solution on the surface of the separation layer away from the support membrane; or forming a mixed aqueous solution of a second metal salt and a high polymer on the surface of the separation layer away from the support membrane, wherein the second metal salt is selected from at least one of magnesium chloride, calcium chloride or magnesium sulfate and has a mass fraction of 0.5-2%, and the high polymer is selected from at least one of anionic polyacrylamide, cationic polyacrylamide or quaternary ammonium salt chitosan and has a mass fraction of 0.1-0.5%; and
and then carrying out heat treatment, wherein the second metal salt and the high polymer are subjected to flocculation reaction to form an anti-pollution layer, so as to obtain the reverse osmosis membrane.
2. The method of preparing a reverse osmosis membrane according to claim 1, wherein said phosphate is selected from at least one of sodium hexametaphosphate, sodium tripolyphosphate, or sodium dimeric phosphate.
3. The method of producing a reverse osmosis membrane according to claim 1 or claim 2, further comprising a step of washing the prefabricated membrane before the step of forming an anti-contamination layer on the surface of the separation layer remote from the support membrane.
4. A reverse osmosis membrane produced by the method for producing a reverse osmosis membrane according to any one of claims 1 to 3, which comprises a support membrane, a separation layer and an anti-contamination layer which are arranged in a stacked state.
5. Use of the reverse osmosis membrane of claim 4 in a water treatment plant.
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