CN112808021B - Method for preparing reverse osmosis membrane by adopting novel water phase system - Google Patents
Method for preparing reverse osmosis membrane by adopting novel water phase system Download PDFInfo
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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
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
Abstract
The invention relates to a method for preparing a reverse osmosis membrane by adopting a novel water phase system, wherein the reverse osmosis membrane is prepared by adopting interfacial polymerization, and a water phase solution participating in the interfacial polymerization is prepared according to the following method: and (2) forming a compound system by the anionic surfactant and the cationic surfactant according to a proportion, adding the compound system into the aqueous phase solution containing the polyamine monomer together, and stirring, mixing and/or ultrasonically dispersing to obtain the aqueous phase solution for the interfacial polymerization reaction. On one hand, the invention utilizes the synergistic solubilization of the anion and cation surfactant compound system to improve the solubility and dispersion uniformity of the polyamine in the water phase. On the other hand, due to the unique existence state of the anionic and cationic surfactant complexing system in the water phase, the water phase can generate a nano structure, the purpose of adjusting the structure of the functional separation layer can be achieved by adjusting the respective concentration of the anionic and cationic surfactant in the water phase solution and the dosage ratio of the anionic and cationic surfactant in the water phase solution, and the reverse osmosis membrane can obtain high rejection rate and water flux.
Description
Technical Field
The invention relates to the technical field of sea water desalination or sewage treatment, in particular to a method for preparing a reverse osmosis membrane by adopting a novel water phase system.
Background
One of the most serious problems facing the 21 st century is the growing water pollution and the shortage of global fresh water resources. Seawater desalination and sewage recycling based on reverse osmosis technology are effective ways for increasing fresh water resources. The reverse osmosis membrane is an artificial semipermeable membrane with certain characteristics and is made by simulating a biological semipermeable membrane, and is a core component of a reverse osmosis technology. Currently, polyamide reverse osmosis composite membranes are the most advanced, efficient and widely used reverse osmosis membrane type. The polyamide reverse osmosis composite membrane generally comprises a non-woven fabric substrate, a polysulfone support layer and a polyamide compact functional separation layer. Wherein, the key layer for realizing material screening is a polyamide compact functional separation layer. The polyamide compact functional separation layer is generally prepared by interfacial polymerization reaction of polyamine monomer (dissolved in water phase) and polyacyl chloride monomer (dissolved in oil phase) through a water-oil interface, and the performance of the polyamide compact functional separation layer mainly depends on the dissolution degree and the dispersion uniformity of the polyamine monomer in the water phase. Although the performance of the reverse osmosis composite membrane is greatly improved after more than 30 years of development, the research and development of the reverse osmosis composite membrane with high flux and high rejection is still one of the main research and development directions in the field.
Disclosure of Invention
Technical problem to be solved
In view of the above disadvantages and shortcomings of the prior art, the present invention provides a method for preparing a reverse osmosis membrane by using a novel aqueous phase system, wherein the composition of the aqueous phase solution is adjusted to adjust the dissolution degree and dispersion uniformity of polyamine monomers in the aqueous phase solution, so as to form a compact functional separation layer with a controllable structure, thereby achieving the purpose of improving the water flux and rejection rate of the reverse osmosis membrane.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
in a first aspect, the present invention provides a method for preparing a reverse osmosis membrane using a novel aqueous system, wherein a polyamide functional separation layer of the reverse osmosis membrane is prepared by interfacial polymerization, and an aqueous solution participating in the interfacial polymerization is prepared as follows: and (2) forming a compound system by the anionic surfactant and the cationic surfactant according to a proportion, adding the compound system into the aqueous phase solution containing the polyamine monomer together, and stirring, mixing and/or ultrasonically dispersing to obtain the aqueous phase solution for the interfacial polymerization reaction.
Wherein the agitation mixing and/or sonication comprises: only stirring and mixing, only ultrasonic treatment, firstly stirring and then ultrasonic treatment, or firstly ultrasonic and then stirring; preferably, only mixing with stirring is performed.
According to a preferred embodiment of the present invention, an acid scavenger (acid scavenger) is further added to the aqueous solution. The acid scavenger is a weak base.
According to a preferred embodiment of the invention, the method further comprises: coating the prepared water phase solution on a bottom membrane material of a permeable membrane, standing for a period of time, removing (e.g. pouring) the water phase solution flowing on the bottom membrane material of the permeable membrane, coating an oil phase solution dissolved with a polybasic acyl chloride monomer on the bottom membrane material of the permeable membrane, and performing heat treatment to obtain a polyamide compact functional separation layer on the bottom membrane material of the permeable membrane; alternatively, the first and second electrodes may be,
soaking a permeable membrane bottom membrane material in a water phase solution, standing for a period of time, taking out the permeable membrane bottom membrane material, coating an oil phase solution in which a polybasic acyl chloride monomer is dissolved on the permeable membrane bottom membrane material or soaking the permeable membrane bottom membrane material in the oil phase solution in which the polybasic acyl chloride monomer is dissolved for a period of time, taking out, and carrying out heat treatment to obtain the polyamide compact functional separation layer on the permeable membrane bottom membrane material.
It should be noted that the present invention is not limited to the above-mentioned coating method, and any method can be used to uniformly transfer (e.g., spray coating, dipping, soaking, etc.) the aqueous phase solution and the oil phase solution onto the permeable membrane base material.
According to the preferred embodiment of the invention, the bottom membrane material of the permeable membrane comprises a non-woven fabric substrate and a supporting layer, wherein the supporting layer is superposed on the surface of the non-woven fabric substrate; and the water phase solution and the oil phase solution are coated on the supporting layer, or the supporting layer of the permeable membrane bottom membrane material is sequentially and respectively soaked in the water phase solution and the oil phase solution in an upward mode. Wherein, the supporting layer is made of one of polysulfone, polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene and polyacrylonitrile.
According to the preferred embodiment of the invention, the anionic surfactant is one or a mixture of several of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium laurate, sodium camphor sulfonate and sodium citrate; the mass percentage concentration of the water phase solution is 0.1-5%.
According to the preferred embodiment of the invention, the cationic surfactant is one or a mixture of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride and benzyl triethyl ammonium chloride; the mass percentage concentration of the water phase solution is 0.1-5%.
According to the preferred embodiment of the invention, the polyamine monomer is one or a mixture of more of m-phenylenediamine, p-phenylenediamine, piperazine, o-phenylenediamine, diaminotoluene and 2, 5-dimethylpiperazine, and the mass percentage of the polyamine monomer in the aqueous phase is 0.1-3%.
According to a preferred embodiment of the present invention, the acid scavenger (acid scavenger) in the aqueous solution is an organic base, and the mass percentage of the organic base in water is 0.1-1.5%. The organic base is preferably triethylamine or diisopropylethylamine, more preferably diisopropylethylamine, which makes the aqueous solution more stable. Triethylamine has a certain probability of acylation with acyl and removal of an ethyl group. Diisopropylethylamine is more stable.
According to a preferred embodiment of the present invention, in the oil phase solution, the poly-acyl chloride monomer is one or a mixture of several of trimesoyl chloride, terephthaloyl chloride, phthaloyl chloride and isophthaloyl chloride; and the mass percentage of the oil phase solution is 0.1-2.0%. Preferably, the polybasic acid chloride monomer is trimesoyl chloride (TMC). More preferably, the mass percentage of trimesoyl chloride (TMC) in the oil phase solution is 0.1-1.5%.
According to a preferred embodiment of the present invention, in the oil phase solution dissolved with the polybasic acid chloride monomer, the oil phase solvent is one or a mixture of Isopar L (1 isoparaffin solvent), n-hexane, cyclohexane, toluene and benzene.
According to the preferred embodiment of the present invention, the heat treatment condition is a temperature of 100 ℃ to 130 ℃; the preferred temperature is 110 ℃ to 130 ℃.
(III) advantageous effects
The invention has the technical effects that: by an interfacial polymerization method, in the reaction process, on one hand, the solubility and dispersion uniformity of the polyamine in the water phase are improved by utilizing the synergistic solubilization of a compound system of the anionic and cationic surfactants, the variety range of the polyamine which can be used is expanded, the consumption of the polyamine monomer in the water phase solution is reduced, and the uniform polyamide functional separation layer and the reverse osmosis membrane with stable membrane performance are obtained; on the other hand, due to the unique existence state of the complex system of the anionic and cationic surfactants in the water phase, the water phase can generate a nano structure (micelle, vesicle and the like), the structure of the functional separation layer can be adjusted by adjusting the respective concentration of the anionic and cationic surfactants in the water phase solution and the dosage ratio of the anionic and cationic surfactants, and the reverse osmosis membrane can obtain high rejection rate and water flux. Repeated experiments prove that the method has simple operation process, easily controlled technical parameters, better reproducibility and low preparation cost, and can greatly improve the performance of the reverse osmosis composite membrane, thereby having ideal commercial application prospect.
In the invention, the permeable membrane basement membrane material can be any basement membrane provided by manufacturers, and the performance difference of the basement membrane and the type of the basement membrane have no direct influence on the result of the invention, so that commercially purchased polysulfone basement membrane (or polyether sulfone, polyvinylidene fluoride or polytetrafluoroethylene basement membrane) or self-made basement membrane can be selected. In the preparation method, the raw materials of the components are easy to obtain, and the raw materials used in the aqueous phase solution are very easy to dissolve in water, so that the preparation process is very simple, and for production enterprises, any production link and process of the existing production line are not required to be changed completely in the production process. Therefore, the preparation method has universal adaptability and is beneficial to commercial popularization and application.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail below with reference to specific embodiments.
The embodiment of the invention provides a method for preparing a reverse osmosis membrane by adopting a novel water phase system, wherein a polyamide functional separation layer of the reverse osmosis membrane is prepared by adopting interfacial polymerization, and a water phase solution participating in the interfacial polymerization is prepared according to the following method: and (2) forming a compound system by the anionic surfactant and the cationic surfactant according to a proportion, adding the compound system into the aqueous phase solution containing the polyamine monomer together, and stirring, mixing and/or ultrasonically dispersing to obtain the aqueous phase solution for the interfacial polymerization reaction.
When preparing a reverse osmosis membrane of a novel water phase system, the following steps can be designed according to the idea of the invention:
step 1: preparing an aqueous phase solution:
and (2) forming a compound system by the anionic surfactant and the cationic surfactant according to a proportion, adding the compound system into the aqueous solution containing the polyamine monomer and the acid absorbent together, and stirring, mixing and/or ultrasonically dispersing to obtain the aqueous solution for the interfacial polymerization reaction.
Step 2: polymerizing to obtain polyamide functional separation layer
Coating the prepared water phase solution on a bottom membrane material of a permeable membrane, standing for a period of time, removing (such as pouring) the water phase solution flowing on the bottom membrane material of the permeable membrane, coating an oil phase solution dissolved with a polybasic acyl chloride monomer on the bottom membrane material of the permeable membrane, and performing heat treatment (the heat treatment promotes the polymerization reaction of the polybasic acyl chloride monomer and the polybasic acyl chloride monomer to generate polyamide) to obtain a polyamide compact functional separation layer on the bottom membrane material of the permeable membrane; alternatively, the first and second electrodes may be,
soaking a permeable membrane bottom membrane material in a water phase solution, standing for a period of time, taking out the permeable membrane bottom membrane material, coating an oil phase solution in which a polybasic acyl chloride monomer is dissolved on the permeable membrane bottom membrane material, or soaking the permeable membrane bottom membrane material in the oil phase solution in which the polybasic acyl chloride monomer is dissolved for a period of time, taking out, carrying out heat treatment (promoting the polyreaction of the polyamine monomer and the polybasic acyl chloride monomer to generate polyamide), and then obtaining a polyamide compact functional separation layer on the permeable membrane bottom membrane material.
Wherein, the membrane material of the bottom of the permeable membrane can be purchased or self-made in the market. The permeable membrane base membrane material comprises a non-woven fabric base material and a supporting layer, wherein the supporting layer is superposed on the surface of the non-woven fabric base material; and the water phase solution and the oil phase solution are coated on the supporting layer, or the supporting layer of the permeable membrane bottom membrane material is sequentially and respectively soaked in the water phase solution and the oil phase solution in an upward mode. Wherein, the supporting layer is made of one of polysulfone, polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene and polyacrylonitrile.
The design principle of the preparation method of the invention is as follows: when the aqueous phase solution is prepared, a compound system of the anionic and cationic surfactants is added into the aqueous phase solution to solubilize the polyamine monomer together. The strong electrostatic action exists between the anionic surfactant and the cationic surfactant, so that the anionic surfactant and the cationic surfactant have high surface activity which is incomparable with a single surfactant, namely, the complex systems of the anionic surfactant and the cationic surfactant have good synergistic effect on the performance of reducing the surface tension of an aqueous solution.
The invention utilizes the aqueous phase solution with the anionic and cationic surfactant complex system as the aqueous phase of the interfacial polymerization reaction for the first time, not only can play a role in enhancing the dissolution of polyamine monomers, but also can enable the aqueous phase to have a nano structure (micelle, vesicle and the like) due to the existence of the complex system, so the structure of the functional separation layer can be adjusted by adjusting the respective concentration of the anionic and cationic surfactants in the aqueous phase solution and the dosage proportion of the anionic and cationic surfactants (obtaining nano micelles or vesicles with different sizes and quantities and the like), thereby being beneficial to forming the compact functional separation layer with a controllable structure, and improving the water flux of the reverse osmosis composite membrane while obtaining high rejection rate.
In order to better understand the above technical solutions, exemplary embodiments of the present invention will be described in more detail below with reference to specific embodiments. The bottom membrane material of the permeable membrane used in the following examples is a polysulfone bottom membrane, which is a self-made bottom membrane, and the performance of the bottom membrane is consistent with that of a commercially available bottom membrane product. The film production date was less than 30 days to the experimental date, during which time it was stored in 2% aqueous sodium bisulfite. Before the interfacial reaction is carried out to prepare the composite membrane, the polysulfone base membrane is soaked in pure water 24 hours in advance. The oil solvent in the oil phase solution of each of the following examples was Isopar L.
Example 1
A mixed aqueous solution containing 0.5 mass% of sodium lauryl sulfate and 0.5 mass% of dodecyltrimethylammonium chloride (anionic surfactant: cationic surfactant ═ 1:1) was prepared, and 1 mass% of MPD (m-phenylenediamine) and 0.2 mass% of triethylamine were added and mixed uniformly. Then preparing trimesoyl chloride (TMC) oil phase solution with the mass fraction of 0.2 percent. Firstly coating the polysulfone basement membrane with the aqueous phase solution, pouring off the redundant solution after 60s, drying in the shade, coating the oil phase solution on the dried membrane in the shade, pouring off the redundant oil phase solution after 30s, and carrying out heat treatment for 2min in a 130 ℃ oven.
Example 2
Preparing a mixed aqueous solution (anionic surfactant: cationic surfactant ═ 1:1) containing 0.5% by mass of sodium benzenesulfonate and 0.5% by mass of dodecyltrimethylammonium chloride, adding 1% by mass of MPD and 0.2% by mass of triethylamine, and uniformly mixing. Then preparing trimesoyl chloride (TMC) oil phase solution with the mass fraction of 0.2 percent. Firstly coating the polysulfone basement membrane with the aqueous phase solution, pouring off the redundant solution after 60s, drying in the shade, coating the oil phase solution on the dried membrane in the shade, pouring off the redundant oil phase solution after 30s, and carrying out heat treatment for 2min in a 120 ℃ oven.
Example 3
Preparing a mixed aqueous solution (anionic surfactant: cationic surfactant ═ 1:1) containing 0.5 mass percent of sodium dodecyl sulfate and 0.5 mass percent of dodecyl trimethyl ammonium chloride, adding 1 mass percent of MPD and 0.2 mass percent of triethylamine, and uniformly mixing. Then preparing trimesoyl chloride (TMC) oil phase solution with the mass fraction of 0.2 percent. Firstly coating the polysulfone basement membrane with the aqueous phase solution, pouring off the redundant solution after 60s, drying in the shade, coating the oil phase solution on the dried membrane in the shade, pouring off the redundant oil phase solution after 30s, and carrying out heat treatment for 2min in a 130 ℃ oven.
Example 4
Preparing a mixed aqueous solution containing 0.5 mass percent of sodium dodecyl sulfate and 0.5 mass percent of hexadecyl trimethyl ammonium chloride (anionic surfactant: cationic surfactant ═ 1:1), adding 1 mass percent of MPD and 0.2 mass percent of diisopropylethylamine, and uniformly mixing. Then preparing trimesoyl chloride (TMC) oil phase solution with the mass fraction of 0.2 percent. Firstly coating the polysulfone basement membrane with the aqueous phase solution, pouring off the redundant solution after 60s, drying in the shade, coating the oil phase solution on the dried membrane in the shade, pouring off the redundant oil phase solution after 30s, and carrying out heat treatment for 2min in a 130 ℃ oven.
Example 5
Preparing a mixed aqueous solution containing 0.5 mass percent of sodium laurate and 0.5 mass percent of dodecyl trimethyl ammonium chloride (anionic surfactant: cationic surfactant ═ 1:1), adding 1 mass percent of MPD and 0.2 mass percent of triethylamine, and uniformly mixing. Then preparing trimesoyl chloride (TMC) oil phase solution with the mass fraction of 0.2 percent. Firstly coating the polysulfone basement membrane with the aqueous phase solution, pouring off the redundant solution after 60s, drying in the shade, coating the oil phase solution on the dried membrane in the shade, pouring off the redundant oil phase solution after 30s, and carrying out heat treatment for 2min in a 130 ℃ oven.
Example 6
A mixed aqueous solution containing 1.0 mass% of sodium dodecyl sulfate and 1.0 mass% of dodecyltrimethylammonium chloride (anionic surfactant: cationic surfactant ═ 1:1) was prepared, and then 1 mass% of MPD and 0.2 mass% of triethylamine were added and mixed uniformly. Then preparing trimesoyl chloride (TMC) oil phase solution with the mass fraction of 0.2 percent. Firstly coating the polysulfone basement membrane with the aqueous phase solution, pouring off the redundant solution after 60s, drying in the shade, coating the oil phase solution on the dried membrane in the shade, pouring off the redundant oil phase solution after 30s, and carrying out heat treatment for 2min in a 130 ℃ oven.
Example 7
Preparing a mixed aqueous solution containing 1.0 mass percent of sodium benzenesulfonate and 1.0 mass percent of dodecyl dimethyl benzyl ammonium chloride (anionic surfactant: cationic surfactant ═ 1:1), adding 1 mass percent of MPD and 0.2 mass percent of diisopropylethylamine, and uniformly mixing. Then preparing trimesoyl chloride (TMC) oil phase solution with the mass fraction of 0.2 percent. Firstly coating the polysulfone basement membrane with the aqueous phase solution, pouring off the redundant solution after 60s, drying in the shade, coating the oil phase solution on the dried membrane in the shade, pouring off the redundant oil phase solution after 30s, and carrying out heat treatment for 2min in a 130 ℃ oven.
Example 8
Preparing a mixed aqueous solution containing 1.5 mass percent of sodium dodecyl sulfate and 0.5 mass percent of dodecyl trimethyl ammonium chloride (anionic surfactant: cationic surfactant: 3:1), adding 1 mass percent of MPD and 0.2 mass percent of diisopropylethylamine, and uniformly mixing. Then preparing trimesoyl chloride (TMC) oil phase solution with the mass fraction of 0.2 percent. Firstly coating the polysulfone basement membrane with the aqueous phase solution, pouring off the redundant solution after 60s, drying in the shade, coating the oil phase solution on the dried membrane in the shade, pouring off the redundant oil phase solution after 30s, and carrying out heat treatment for 2min in a 120 ℃ oven.
Example 9
Preparing a mixed aqueous solution containing 1.5 mass percent of sodium laurate and 1.5 mass percent of dodecyl trimethyl ammonium chloride (anionic surfactant: cationic surfactant ═ 1:1), adding 1 mass percent of MPD and 0.2 mass percent of diisopropylethylamine, and uniformly mixing. Then preparing trimesoyl chloride (TMC) oil phase solution with the mass fraction of 0.2 percent. Firstly coating the polysulfone basement membrane with the aqueous phase solution, pouring off the redundant solution after 60s, drying in the shade, coating the oil phase solution on the dried membrane in the shade, pouring off the redundant oil phase solution after 30s, and carrying out heat treatment for 2min in a 130 ℃ oven.
Comparative example 1
In the comparative example, an aqueous solution was prepared without adding a complex system of an anionic surfactant and an anionic surfactant on the basis of example 1, and a reverse osmosis membrane was prepared under the same conditions and in the same steps as in example 1. Through experimental tests, the rejection rate of the prepared reverse osmosis membrane to 500PPm sodium chloride is 98.7% at most, and the water flux is 53LMH at most.
Comparative example 2
In this comparative example, an aqueous phase solution was prepared by adding 1% by mass of dodecyltrimethylammonium chloride (cationic surfactant) to an aqueous phase based on example 1, and a reverse osmosis membrane was prepared under the same conditions and in the same manner as in example 1. Through experimental tests, the rejection rate of the prepared reverse osmosis membrane to 500PPm sodium chloride is 98.5% at most, and the water flux is 51LMH at most.
Comparative example 3
In this comparative example, a reverse osmosis membrane was prepared in the same manner as in example 1 except that 1 mass% sodium lauryl sulfate (anionic surfactant) was added to the aqueous phase alone, the mass% of MPD was 1.5%, and the other conditions and steps were the same as in example 1. Through experimental tests, the rejection rate of the prepared reverse osmosis membrane to 500PPm sodium chloride is 98.9% at most, and the water flux is 55LMH at most.
The membrane performance of the reverse osmosis membranes prepared in the above examples and comparative examples was evaluated in terms of both "sodium chloride salt rejection rate and water flux". In performance evaluation, the test pressure is 0.75MPa, the flow rate of concentrated water is 1.0GPM, the ambient temperature is 25 ℃, the pH value of the concentrated water is 6.5-7.5, and the concentrated water refers to a 500ppm sodium chloride aqueous solution.
In each example, the rejection (rejection) is defined as the difference between the concentrations of concentrate and product water divided by the concentrate concentration; the water flux is defined as the volume of water per unit time that permeates the composite separation membrane per unit area in the above test procedure and is expressed in L/m2H (LMH). Each data point above was averaged from 9 samples.
The test results were as follows:
the examples and comparative examples described above demonstrate that: the preparation method of the invention can ensure that the reverse osmosis membrane keeps high water flux while keeping high rejection rate, improves the uniformity and stability of the permeability of the reverse osmosis membrane, and has good reproducibility. In addition, in the case of using only an anionic surfactant or only a cationic surfactant, the rejection rate and water flux of the prepared reverse osmosis membrane are significantly reduced even though the amount of the anionic/cationic surfactant is equal to the total amount of the two ionic surfactants used simultaneously. From the above experimental results, in the preparation of the aqueous solution, the mass percentage concentrations of the anionic and cationic surfactants in water are preferably 0.5% -2%, and more preferably 1-1.5%; in addition, the compounding ratio (mass ratio) of the anionic surfactant and the cationic surfactant is preferably 1:1-3:1, more preferably 3:1, the highest value of the obtained water flux is the largest, and the highest retention rate is close to the maximum value.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. A method for preparing a reverse osmosis membrane by using an aqueous phase system is characterized in that a polyamide functional separation layer of the reverse osmosis membrane is prepared by adopting interfacial polymerization reaction, and an aqueous phase solution participating in the interfacial polymerization reaction is prepared according to the following method: a complex system is formed by an anionic surfactant and a cationic surfactant according to a proportion, the complex system and the anionic surfactant are added into an aqueous phase solution containing a polyamine monomer together, and the aqueous phase solution for interfacial polymerization reaction is obtained after stirring, mixing and/or ultrasonic dispersion;
wherein, the mass percentage concentration of the anionic surfactant in water is 0.5-2%, and the mass percentage concentration of the cationic surfactant in water is 1-1.5%; the compounding mass ratio of the anion surfactant to the cation surfactant is 1:1-3: 1;
the anionic surfactant is one or a mixture of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium laurate, sodium camphorsulfonate and sodium citrate;
the cationic surfactant is one or a mixture of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride and benzyl triethyl ammonium chloride.
2. The method according to claim 1, wherein an acid scavenger is further added to the aqueous solution.
3. The method of claim 2, further comprising: coating the prepared water phase solution on a bottom membrane material of a permeable membrane, standing for a period of time, removing the water phase solution flowing on the bottom membrane material of the permeable membrane, coating an oil phase solution dissolved with a polybasic acyl chloride monomer on the bottom membrane material of the permeable membrane, and performing heat treatment to obtain a polyamide compact functional separation layer on the bottom membrane material of the permeable membrane; alternatively, the first and second electrodes may be,
soaking a permeable membrane bottom membrane material in a water phase solution, standing for a period of time, taking out the permeable membrane bottom membrane material, coating an oil phase solution in which a polybasic acyl chloride monomer is dissolved on the permeable membrane bottom membrane material or soaking the permeable membrane bottom membrane material in the oil phase solution in which the polybasic acyl chloride monomer is dissolved for a period of time, taking out, and carrying out heat treatment to obtain the polyamide compact functional separation layer on the permeable membrane bottom membrane material.
4. The method according to claim 3, wherein the bottom membrane material of the permeable membrane comprises a non-woven fabric substrate and a support layer, wherein the support layer is laminated on the surface of the non-woven fabric substrate; the water phase solution and the oil phase solution are coated on the supporting layer, or the supporting layer of the permeable membrane bottom membrane material is sequentially and respectively soaked in the water phase solution and the oil phase solution in an upward mode; wherein, the supporting layer is made of one of polysulfone, polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene and polyacrylonitrile.
5. The method according to claim 1, wherein the polyamine monomer is one or more of m-phenylenediamine, p-phenylenediamine, piperazine, o-phenylenediamine, diaminotoluene, and 2, 5-dimethylpiperazine, and the mass percentage of the polyamine monomer in the aqueous phase is 0.1-3%.
6. The method according to claim 2, wherein the acid scavenger in the aqueous solution is an organic base, and the mass percentage of the acid scavenger in water is 0.1-1.5%.
7. The method according to claim 3, wherein in the oil phase solution, the polybasic acyl chloride monomer is one or a mixture of trimesoyl chloride, terephthaloyl chloride, phthaloyl chloride and isophthaloyl chloride; and the mass percentage of the oil phase solution is 0.1-2.0%.
8. The method according to claim 7, wherein in the oil phase solution, the oil phase solvent is one or a mixture of Isopar L, n-hexane, cyclohexane, toluene and benzene;
the heat treatment condition is that the temperature is 100-130 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569308A (en) * | 2018-11-16 | 2019-04-05 | 杭州水处理技术研究开发中心有限公司 | A kind of acid absorbent system prepares the preparation method of high-flux reverse osmosis membrane |
| CN109647199A (en) * | 2018-12-20 | 2019-04-19 | 时代沃顿科技有限公司 | A kind of preparation method of reverse osmosis membrane and thus obtained reverse osmosis membrane |
| CN109999666A (en) * | 2019-04-30 | 2019-07-12 | 中国科学院生态环境研究中心 | High-throughput charged positive electricity anti-acid nanofiltration membrane, preparation method and application |
| CN109999665A (en) * | 2019-04-30 | 2019-07-12 | 中国科学院生态环境研究中心 | Lotus positive electricity anti-acid nanofiltration membrane, preparation method and application |
| CN111111475A (en) * | 2020-01-15 | 2020-05-08 | 南京工业大学 | Preparation method of graphene oxide modified triptycenyl polyamide separation membrane |
-
2021
- 2021-01-18 CN CN202110061022.9A patent/CN112808021B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569308A (en) * | 2018-11-16 | 2019-04-05 | 杭州水处理技术研究开发中心有限公司 | A kind of acid absorbent system prepares the preparation method of high-flux reverse osmosis membrane |
| CN109647199A (en) * | 2018-12-20 | 2019-04-19 | 时代沃顿科技有限公司 | A kind of preparation method of reverse osmosis membrane and thus obtained reverse osmosis membrane |
| CN109999666A (en) * | 2019-04-30 | 2019-07-12 | 中国科学院生态环境研究中心 | High-throughput charged positive electricity anti-acid nanofiltration membrane, preparation method and application |
| CN109999665A (en) * | 2019-04-30 | 2019-07-12 | 中国科学院生态环境研究中心 | Lotus positive electricity anti-acid nanofiltration membrane, preparation method and application |
| CN111111475A (en) * | 2020-01-15 | 2020-05-08 | 南京工业大学 | Preparation method of graphene oxide modified triptycenyl polyamide separation membrane |
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