CN114028956A - Reverse osmosis membrane and preparation method and application thereof - Google Patents
Reverse osmosis membrane and preparation method and application thereof Download PDFInfo
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- CN114028956A CN114028956A CN202111366859.0A CN202111366859A CN114028956A CN 114028956 A CN114028956 A CN 114028956A CN 202111366859 A CN202111366859 A CN 202111366859A CN 114028956 A CN114028956 A CN 114028956A
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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
- B01D71/66—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
- 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
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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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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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
- B01D71/26—Polyalkenes
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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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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- 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
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 the water phase solution and the oil phase solution on the surface of the support membrane, and performing heat treatment to form a compact layer to obtain the reverse osmosis membrane; the water-phase solution comprises water-soluble salt, a first additive and a first monomer, the oil-phase solution comprises a second additive and a second monomer, the first additive and the second additive are the same, and the mass fraction of the first additive in the water-phase solution is x1The second additive is dissolved in the oil phaseMass fraction in the liquid is x2，x2Greater than x1. The preparation method can increase the water flux of the reverse osmosis membrane, and simultaneously keep the high rejection rate of the reverse osmosis membrane, so that the reverse osmosis membrane can be better applied to the field of water treatment.
Description
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
In the preparation process of the traditional reverse osmosis membrane, an ester plasticizer is usually added into an oil phase solution to improve the water flux of the reverse osmosis membrane. However, the plasticizing effect of the ester plasticizer is too strong, so that the distance between molecular chains of the compact layer is easily increased too much, the compact layer is too loose, and the rejection rate of the reverse osmosis membrane is reduced. Therefore, it is difficult for the conventional reverse osmosis membrane to combine high water flux and rejection rate at the same time.
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 increase the water flux of the reverse osmosis membrane, and simultaneously keep the high rejection rate of the reverse osmosis membrane, so that the reverse osmosis membrane can be better applied to the field of water treatment.
The invention provides a preparation method of a reverse osmosis membrane, which comprises the following steps:
providing a support film; and
sequentially placing the water phase solution and the oil phase solution on the same surface of the support membrane, and then performing heat treatment to form a compact layer to obtain the reverse osmosis membrane; the water-phase solution comprises a water-soluble salt, a first additive and a first monomer, the oil-phase solution comprises a second additive and a second monomer, the first additive and the second additive are the same, and the mass fraction of the first additive in the water-phase solution is x1The mass fraction of the second additive in the oil phase solution is x2X is said2Greater than said x1。
In one embodiment, the water soluble salt comprises at least one of magnesium chloride, magnesium sulfate, potassium chloride, potassium fluoride, sodium chloride, ammonium chloride, or sodium fluoride.
In one embodiment, the water-soluble salt is present in the aqueous solution in a mass fraction of 3% to 8%.
In one embodiment, the mass fraction of the first additive in the aqueous phase solution is between 0.1% and 0.4%.
In one embodiment, the mass fraction of the second additive in the oil phase solution is 0.5% to 1.5%.
In one embodiment, the first additive and the second additive have a formula as shown in formula (I) or formula (II),
in the formula (I), n is 1-4; said L1Selected from a first alkylene group having a carbon chain length of 1 to 5; the R is1Selected from a first hydrocarbyl group having a carbon chain length of 1 to 5;
in the formula (II), R is2Selected from a second hydrocarbyl group having a carbon chain length of 1 to 5, said R3Selected from a third hydrocarbyl group having a carbon chain length of 1 to 5.
In an embodiment, the first and second additives include at least one of ethylene glycol butyl ether, ethylene glycol methyl ether, isopropyl alcohol, or diethylene glycol methyl ether.
In one embodiment, the first monomer comprises a polyamine, the second monomer comprises an aromatic polyacyl chloride, and the aqueous solution further comprises an acid scavenger.
A reverse osmosis membrane prepared by the preparation method of the reverse osmosis membrane.
An application of the reverse osmosis membrane in a water treatment device.
In the preparation method of the reverse osmosis membrane, when the water phase solution and the oil phase solution are contacted to form a water-oil interface, the first additive in the water phase solution and the second additive in the oil phase solution can exchange among the water phase solution, the water-oil interface and the oil phase solution to form a diffusion channel; the formation of the diffusion channel can improve the interface area of a water-oil interface on one hand; on the other hand, part of soluble metal salt and water in the water phase solution can enter the oil phase solution through the diffusion channel, and the water-soluble salt is insoluble in the solvent of the oil phase solution, so that the water-soluble salt is gathered in the water of the oil phase solution, the concentration of the water-soluble salt in the oil phase solution is higher than that of the water-soluble salt in the water phase solution, and meanwhile, the concentration of the second additive in the oil phase solution is higher than that of the first additive in the water phase solution, so that osmotic pressure exists on two sides of the polymer membrane for the initial interfacial polymerization, the osmotic pressure promotes the water to diffuse into the oil phase solution from the water phase solution, the polymer membrane keeps a swelling state all the time, and the water-oil interface keeps a very large interface area.
Because interfacial polymerization is carried out in the water-oil interface, the increase of the interfacial area of the water-oil interface can improve the surface area of a compact layer in the reverse osmosis membrane, thereby expanding a water flow passage and improving the water flux of the reverse osmosis membrane. Therefore, the reverse osmosis membrane prepared by the preparation method of the reverse osmosis membrane has high water flux and rejection rate.
Drawings
FIG. 1 is a schematic diagram of a reverse osmosis membrane manufacturing process provided by the present invention;
FIG. 2 is a schematic diagram of a reverse osmosis membrane according to one embodiment of the present invention;
FIG. 3 is an electron microscope image of the surface of a reverse osmosis membrane provided in example 1.
In the figure: a. an aqueous phase solution; b. a water-oil interface; c. an oil phase solution; 10. a support film; 20. a dense layer; 30. a base layer.
Detailed Description
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:
s1, providing a support film; and
and S2, sequentially placing the water phase solution and the oil phase solution on the surface of the support membrane, and performing heat treatment to form a compact layer to obtain the reverse osmosis membrane.
In step S1, the support membrane is selected from a polysulfone membrane, a polypropylene membrane or a polyacrylonitrile membrane, wherein the polysulfone membrane is cheap and easily available, the membrane is simple to prepare, the mechanical strength is good, the compression resistance and the sealing performance are good, the chemical properties are stable, the support membrane is nontoxic and can resist biological degradation, and therefore, the support membrane is preferably selected from the polysulfone membrane.
In step S2, the aqueous solution includes a water-soluble salt, a first additive and a first monomerThe oil phase solution comprises a second additive and a second monomer, the first additive and the second additive are the same, and the mass fraction of the first additive in the water phase solution is x1The mass fraction of the second additive in the oil phase solution is x2，x2Greater than x1。
Since the aqueous phase solution including the first additive and the oil phase solution including the second additive are homogeneous and stable dispersion systems, the first additive and the second additive of the present invention can be dissolved in both water and a solvent of the oil phase solution. Specifically, the solubility of the first additive and the second additive in water is greater than or equal to 0.1g/100g of water, and the solubility of the first additive and the second additive in the solvent of the oil phase solution is greater than or equal to 0.5g/100g of the solvent of the oil phase solution. In one embodiment, the solvent of the oil phase solution comprises at least one of isoparaffin solvent, n-hexane or cyclohexane, and specifically, the isoparaffin solvent comprises at least one of isododecane or isotetradecane.
In one embodiment, the first additive and the second additive have a formula as shown in formula (I) or formula (II),
in the formula (I), n is 1-4; l is1Selected from a first alkylene group having a carbon chain length of 1 to 5; r1Selected from a first hydrocarbyl group having a carbon chain length of 1 to 5; in the formula (II), R2Selected from a second hydrocarbyl group having a carbon chain length of 1 to 5, R3Selected from a third hydrocarbyl group having a carbon chain length of 1 to 5.
In one embodiment, n is 1, 2, 3 or 4, L1Is selected from-CH2-、-CH(CH3)-、-(CH2)2-、-(CH2)3-、-(CH2)4-or- (CH)2)5-；R1Is selected from-CH3、-CH2CH3、-CH(CH3)2or-CH2CH2CH3。
In one embodiment, R2Is selected from-CH3、-CH2CH3、-CH(CH3)2or-CH2CH2CH3；R3Is selected from-CH3、-CH2CH3、-CH(CH3)2or-CH2CH2CH3。
In an embodiment, the first and second additives include at least one of ethylene glycol butyl ether, ethylene glycol methyl ether, isopropyl alcohol, or diethylene glycol methyl ether.
As shown in fig. 1, which is a schematic diagram of a preparation method of a reverse osmosis membrane provided by the present invention, when an aqueous phase solution and an oil phase solution contact to form a water-oil interface, a first additive in the aqueous phase solution and a second additive in the oil phase solution can exchange between the aqueous phase solution, the water-oil interface, and the oil phase solution to form a diffusion channel.
The formation of the diffusion channel can improve the interface area of a water-oil interface on one hand; on the other hand, part of the soluble metal salt and water in the aqueous phase solution can enter the oil phase solution through the diffusion channel, and the water-soluble salt is insoluble in the solvent of the oil phase solution, so that the water-soluble salt is gathered in the water of the oil phase solution, the concentration of the water-soluble salt in the oil phase solution is higher than that of the water-soluble salt in the aqueous phase solution, and meanwhile, the concentration of the second additive in the oil phase solution is higher than that of the first additive in the aqueous phase solution. Therefore, osmotic pressure exists on two sides of the polymer membrane generated by interfacial polymerization, and water is promoted to diffuse from the aqueous phase solution into the oil phase solution along the arrow direction by the osmotic pressure, so that the polymer membrane is always kept in a swelling state, and the water-oil interface is kept in a large interface area.
In order to better form the diffusion channel while maintaining the polymer layer in a more continuous swollen state, in one embodiment, the first additive has a mass fraction of 0.1% to 0.4% in the aqueous phase solution and the second additive has a mass fraction of 0.5% to 1.5% in the oil phase solution.
In one embodiment, the water-soluble salt comprises at least one of magnesium chloride, magnesium sulfate, potassium chloride, ammonium chloride, potassium fluoride, sodium chloride, or sodium fluoride, and is preferably a water-soluble metal salt in order to allow the osmotic pressure across the polymer layer to better maintain the polymer film in an expanded state.
In order to keep the polymer layer in a swelling state more continuously and simultaneously to make the water-soluble salt more completely dissolved in the aqueous phase solution, the formation of the oil phase solution is facilitated, and the mass fraction of the salt in the aqueous phase solution is 3-8%.
Because the interfacial polymerization reaction is carried out in the water-oil interface, the increase of the interfacial area of the water-oil interface finally improves the surface area of a compact layer in the reverse osmosis membrane, expands a water flow channel and improves the water flux of the reverse osmosis membrane, and meanwhile, the improvement of the contact area can enable the first monomer to be more fully contacted with the second monomer, so that the polymerization reaction is more complete, and the reverse osmosis membrane keeps high rejection rate.
In one embodiment, the interfacial polymerization reaction is to crosslink polyamine and aromatic polybasic acyl chloride to generate a polyamide molecular chain, wherein the first monomer comprises polyamine and the second monomer comprises aromatic polybasic acyl chloride. Wherein the polyamine comprises at least one of aromatic polyamine, aliphatic polyamine or alicyclic polyamine, in one embodiment, the polyamine comprises at least one of m-phenylenediamine, piperazine or polyethyleneimine, and the mass percent of the polyamine is 1-4% based on the total weight of the aqueous phase solution; the aromatic polybasic acyl chloride comprises at least one of trimesoyl chloride and adipoyl chloride, and the mass percentage of the aromatic polybasic acyl chloride is 0.1-0.35 percent based on the total weight of the oil phase solution.
In order to absorb the hydrochloric acid generated as a byproduct in the cross-linking reaction between the polyamine and the aromatic polybasic acid chloride, the aqueous solution further comprises an acid scavenger, and in one embodiment, the acid scavenger comprises triethylamine.
In the step of sequentially placing the aqueous phase solution and the oil phase solution on the surface of the support membrane, firstly coating the aqueous phase solution on the surface of the support membrane, standing for a period of time to enable the aqueous phase solution to fill the holes on the surface layer of the support membrane, then pouring out the redundant aqueous phase solution and drying the surface of the support membrane by blowing, and at the moment, the holes on the surface layer of the support membrane are still filled with the aqueous phase solution; and finally, coating the oil phase solution on the surface of the blow-dried support membrane, standing for a period of time, and pouring off the redundant oil phase solution.
In step S2, the temperature of the heat treatment is 50-120 ℃ and the time is 1-10 min, so that the molecular chain in the compact layer is more compact.
The invention also provides a reverse osmosis membrane prepared by the preparation method, as shown in figure 2, which is a schematic structural diagram of the reverse osmosis membrane and comprises a support membrane 10 and a compact layer 20 which are sequentially stacked.
In one embodiment, the reverse osmosis membrane further comprises a base layer 30, wherein the base layer 30 is stacked on the surface of the support membrane 10 away from the dense layer 20, the base layer 30 can further improve the strength of the reverse osmosis membrane, and specifically, the base layer 30 is selected from a non-woven fabric layer.
The reverse osmosis membrane prepared by the preparation method of the reverse osmosis membrane has high water flux and rejection rate.
The invention also provides an 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 raw water to be purified enters from the dense layer of the reverse osmosis membrane in the water purification process, and the raw water permeates the reverse osmosis membrane under the action of pressure to form pure water, and the thickness of the dense layer is 40nm-100nm in one embodiment for low energy consumption and economic reasons.
Particularly, the invention also provides a seawater desalination device comprising the reverse osmosis membrane, in addition, the salt concentration in seawater is high, in order to overcome the osmotic pressure of the seawater, a high-pressure pump is required in the desalination process, and in order to further improve the rejection rate of the reverse osmosis membrane, the thickness of a dense layer is 150nm-270 nm.
Hereinafter, the reverse osmosis membrane, and the method and use of the same will be further described by the following specific examples.
Example 1
Based on the total weight of the aqueous phase solution, 3.5 wt% of magnesium chloride, 0.1 wt% of ethylene glycol butyl ether, 1.0 wt% of m-phenylenediamine, and 1.0 wt% of triethylamine were added to 94.4 wt% of water and mixed uniformly to obtain an aqueous phase solution.
0.15 wt% of trimesoyl chloride was added to 99.35 wt% of isododecane, and 0.5 wt% of ethylene glycol butyl ether was added thereto and mixed uniformly, based on the total weight of the oil phase solution, to obtain an oil phase solution.
Coating the water phase solution on the surface of the polysulfone support membrane, standing for 60 seconds, pouring out the redundant water phase solution, and drying by cold air; and coating the oil phase solution on the surface of the blow-dried support membrane, standing for 30 seconds, pouring out the redundant oil phase solution, and putting the obtained membrane into a forced air drying oven for heat treatment at 100 ℃ for 2 minutes to obtain the reverse osmosis membrane, wherein the thickness of the compact layer is 85 nm. An electron micrograph of the surface of the reverse osmosis membrane is shown in FIG. 3.
The rejection rate and the water flux of the reverse osmosis membrane in a low-pressure environment are tested, and reverse osmosis test conditions are as follows: the concentrate was a 250ppm aqueous sodium chloride solution, the test pressure was 0.5MPa, the concentrate flow was 1.0GPM, the pH of the concentrate was 7.0, the ambient temperatures were all 25 deg.C, and the results are described in Table 1.
Example 2
Based on the total weight of the aqueous phase solution, 5.5% by weight of magnesium chloride, 0.2% by weight of ethylene glycol monomethyl ether, 1.0% by weight of m-phenylenediamine, and 1.0% by weight of triethylamine were added to 92.3% by weight of water and mixed uniformly to obtain an aqueous phase solution.
0.15 wt% of trimesoyl chloride was added to 99.35 wt% of isododecane, and 0.5 wt% of ethylene glycol monomethyl ether was added thereto, and mixed uniformly, based on the total weight of the oil phase solution, to obtain an oil phase solution.
Coating the water phase solution on the surface of the polysulfone support membrane, standing for 60 seconds, pouring out the redundant water phase solution, and drying by cold air; and coating the oil phase solution on the surface of the blow-dried support membrane, standing for 30 seconds, pouring out the redundant oil phase solution, and putting the obtained membrane into a forced air drying oven for heat treatment at 100 ℃ for 2 minutes to obtain the reverse osmosis membrane, wherein the thickness of the compact layer is 100 nm.
The procedure for testing a reverse osmosis membrane of example 2 was as in example 1 and the results are described in table 1.
Example 3
Based on the total weight of the aqueous phase solution, 3.5 wt% of sodium chloride, 0.1 wt% of ethylene glycol butyl ether, 1.0 wt% of m-phenylenediamine, and 1.0 wt% of triethylamine were added to 94.4 wt% of water and mixed uniformly to obtain an aqueous phase solution.
0.15 wt% of trimesoyl chloride was added to 99.35 wt% of isododecane, and 0.5 wt% of ethylene glycol butyl ether was added thereto and mixed uniformly, based on the total weight of the oil phase solution, to obtain an oil phase solution.
Coating the water phase solution on the surface of the polysulfone support membrane, standing for 60 seconds, pouring out the redundant water phase solution, and drying by cold air; and coating the oil phase solution on the surface of the blow-dried support membrane, standing for 30 seconds, pouring out the redundant oil phase solution, and putting the obtained membrane into a forced air drying oven for heat treatment at 100 ℃ for 2 minutes to obtain the reverse osmosis membrane, wherein the thickness of the compact layer is 82 nm.
The procedure for testing a reverse osmosis membrane of example 3 was as in example 1 and the results are described in table 1.
Example 4
3.5% by weight of magnesium chloride, 0.1% by weight of isopropyl alcohol, 1.0% by weight of m-phenylenediamine and 1.0% by weight of triethylamine were added to 94.4% by weight of water based on the total weight of the aqueous phase solution, and mixed uniformly to obtain an aqueous phase solution.
0.15 wt% of trimesoyl chloride was added to 99.35 wt% of isododecane, and 0.5 wt% of isopropyl alcohol was added thereto, and mixed uniformly, based on the total weight of the oil phase solution, to obtain an oil phase solution.
Coating the water phase solution on the surface of the polysulfone support membrane, standing for 60 seconds, pouring out the redundant water phase solution, and drying by cold air; and coating the oil phase solution on the surface of the blow-dried support membrane, standing for 30 seconds, pouring out the redundant oil phase solution, and putting the obtained membrane into a forced air drying oven for heat treatment at 100 ℃ for 2 minutes to obtain the reverse osmosis membrane, wherein the thickness of the compact layer is 91 nm.
The procedure for testing a reverse osmosis membrane of example 4 was as in example 1 and the results are described in table 1.
Example 5
Based on the total weight of the aqueous phase solution, 3.5% by weight of magnesium chloride, 0.3% by weight of butyl cellosolve, 1.0% by weight of m-phenylenediamine, and 1.0% by weight of triethylamine were added to 94.2% by weight of water and mixed uniformly to obtain an aqueous phase solution.
0.15 wt% of trimesoyl chloride was added to 99.35 wt% of isododecane, and 0.7 wt% of ethylene glycol butyl ether was added thereto and mixed uniformly, based on the total weight of the oil phase solution, to obtain an oil phase solution.
Coating the water phase solution on the surface of the polysulfone support membrane, standing for 60 seconds, pouring out the redundant water phase solution, and drying by cold air; and coating the oil phase solution on the surface of the blow-dried support membrane, standing for 30 seconds, pouring out the redundant oil phase solution, and putting the obtained membrane into a forced air drying oven for heat treatment at 100 ℃ for 2 minutes to obtain the reverse osmosis membrane, wherein the thickness of the compact layer is 98 nm.
The procedure for testing a reverse osmosis membrane of example 5 was as in example 1 and the results are described in table 1.
Example 6
Based on the total weight of the aqueous phase solution, 3.5 wt% of ammonium chloride, 0.1 wt% of ethylene glycol butyl ether, 1.0 wt% of m-phenylenediamine, and 1.0 wt% of triethylamine were added to 94.4 wt% of water and mixed uniformly to obtain an aqueous phase solution.
0.15 wt% of trimesoyl chloride was added to 99.35 wt% of isododecane, and 0.5 wt% of ethylene glycol butyl ether was added thereto and mixed uniformly, based on the total weight of the oil phase solution, to obtain an oil phase solution.
Coating the water phase solution on the surface of the polysulfone support membrane, standing for 60 seconds, pouring out the redundant water phase solution, and drying by cold air; and coating the oil phase solution on the surface of the blow-dried support membrane, standing for 30 seconds, pouring out the redundant oil phase solution, and putting the obtained membrane into a forced air drying oven for heat treatment at 100 ℃ for 2 minutes to obtain the reverse osmosis membrane, wherein the thickness of the compact layer is 87 nm.
The procedure for testing a reverse osmosis membrane of example 6 was as in example 1 and the results are described in table 1.
Comparative example 1
Comparative example 1 the procedure of example 1 was followed, except that an aqueous phase solution, specifically, 1.0% by weight of m-phenylenediamine and 1.0% by weight of triethylamine based on the total weight of the aqueous phase solution were added to 98.0% by weight of water and mixed uniformly to obtain an aqueous phase solution.
Comparative example 1 a reverse osmosis membrane was obtained with a dense layer having a thickness of 85 nm.
The procedure for testing a reverse osmosis membrane of comparative example 1 was carried out as in example 1 and the results are described in table 1.
Comparative example 2
Comparative example 2 was conducted with reference to example 1, except that the oil phase solution, specifically, 0.15 wt% of trimesoyl chloride was added to 99.85 wt% of isododecane, based on the total weight of the oil phase solution, and mixed uniformly to obtain an oil phase solution.
Comparative example 2 a reverse osmosis membrane was obtained with a dense layer having a thickness of 90 nm.
The procedure for testing a reverse osmosis membrane of comparative example 2 was performed as in example 1 and the results are described in table 1.
Comparative example 3
Comparative example 3 was conducted with reference to example 1 except that an aqueous phase solution, specifically, 3.5% by weight of magnesium chloride, 1.0% by weight of m-phenylenediamine and 1.0% by weight of triethylamine were added to 94.5% by weight of water based on the total weight of the aqueous phase solution and mixed uniformly to obtain an aqueous phase solution.
Comparative example 3 a reverse osmosis membrane was obtained with a dense layer having a thickness of 92 nm.
The procedure for testing a reverse osmosis membrane of comparative example 3 was performed as in example 1 and the results are described in table 1.
Comparative example 4
Comparative example 4 was conducted with reference to example 1 except that an aqueous phase solution, specifically, 0.1% by weight of ethylene glycol butyl ether, 1.0% by weight of m-phenylenediamine and 1.0% by weight of triethylamine were added to 97.9% by weight of water based on the total weight of the aqueous phase solution and mixed uniformly to obtain an aqueous phase solution.
Comparative example 4 a reverse osmosis membrane was obtained with a dense layer having a thickness of 87 nm.
The procedure for testing a reverse osmosis membrane of comparative example 4 was performed as in example 1 and the results are described in table 1.
Comparative example 5
Comparative example 5 the procedure of example 1 was followed, except that the aqueous phase solution and the oil phase solution were mixed, specifically, 3.5% by weight of magnesium chloride, 0.5% by weight of butyl cellosolve, 1.0% by weight of m-phenylenediamine and 1.0% by weight of triethylamine were added to 94.0% by weight of water based on the total weight of the aqueous phase solution, and mixed uniformly to obtain an aqueous phase solution; 0.15 wt% of trimesoyl chloride was added to 99.35 wt% of isododecane, and 0.1 wt% of ethylene glycol butyl ether was added thereto and mixed uniformly, based on the total weight of the oil phase solution, to obtain an oil phase solution.
Comparative example 5 a reverse osmosis membrane was obtained with a dense layer having a thickness of 95 nm.
The procedure for testing a reverse osmosis membrane of comparative example 5 was performed as in example 1 and the results are described in table 1.
Comparative example 6
Comparative example 6 the procedure of example 1 was followed, except that the aqueous phase solution and the oil phase solution were mixed, specifically, 1.0% by weight of m-phenylenediamine and 1.0% by weight of triethylamine were added to 98.0% by weight of water based on the total weight of the aqueous phase solution, and mixed well to obtain an aqueous phase solution; 0.15 wt% of trimesoyl chloride, based on the total weight of the oil phase solution, was added to 99.85 wt% of isododecane and mixed well to obtain an oil phase solution.
Comparative example 6 a reverse osmosis membrane was obtained with a dense layer having a thickness of 92 nm.
The procedure for testing a reverse osmosis membrane of comparative example 6 was performed as in example 1 and the results are described in table 1.
TABLE 1
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 is V/(axt), 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-C1/C0) X 100%, wherein C1Is the concentration of concentrated water, C0The concentration of the permeate was used.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not 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 (10)
1. A preparation method of a reverse osmosis membrane is characterized by comprising the following steps:
providing a support film; and
sequentially placing the water phase solution and the oil phase solution on the same surface of the support membrane, and then performing heat treatment to form a compact layer to obtain the reverse osmosis membrane; the water-phase solution comprises a water-soluble salt, a first additive and a first monomer, the oil-phase solution comprises a second additive and a second monomer, the first additive and the second additive are the same, and the mass fraction of the first additive in the water-phase solution is x1The mass fraction of the second additive in the oil phase solution is x2X is said2Is greater thanSaid x1。
2. The method of preparing a reverse osmosis membrane according to claim 1 wherein the water soluble salt comprises at least one of magnesium chloride, magnesium sulfate, potassium chloride, potassium fluoride, sodium chloride, ammonium chloride or sodium fluoride.
3. The method of preparing a reverse osmosis membrane according to claim 1, wherein the water-soluble salt is present in the aqueous solution at a mass fraction of 3% to 8%.
4. The method of preparing a reverse osmosis membrane according to claim 1, wherein the first additive is present in the aqueous solution at a mass fraction of 0.1% to 0.4%.
5. The method for preparing a reverse osmosis membrane according to claim 1, wherein the mass fraction of the second additive in the oil phase solution is 0.5% to 1.5%.
6. The method of preparing a reverse osmosis membrane according to claim 1, wherein the first additive and the second additive have the formula shown in formula (I) or formula (II),
in the formula (I), n is 1-4; said L1Selected from a first alkylene group having a carbon chain length of 1 to 5; the R is1Selected from a first hydrocarbyl group having a carbon chain length of 1 to 5;
in the formula (II), R is2Selected from a second hydrocarbyl group having a carbon chain length of 1 to 5, said R3Selected from a third hydrocarbyl group having a carbon chain length of 1 to 5.
7. The method of preparing a reverse osmosis membrane according to claim 6 wherein said first additive and said second additive comprise at least one of ethylene glycol butyl ether, ethylene glycol methyl ether, isopropyl alcohol or diethylene glycol methyl ether.
8. The method of preparing a reverse osmosis membrane according to any one of claims 1-7, wherein the first monomer comprises a polyamine, the second monomer comprises an aromatic polyacyl chloride, and the aqueous solution further comprises an acid scavenger.
9. A reverse osmosis membrane produced by the method of producing a reverse osmosis membrane according to any one of claims 1 to 8.
10. Use of the reverse osmosis membrane of claim 9 in a water treatment device.
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