CN113244779B - 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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- CN113244779B CN113244779B CN202110672998.XA CN202110672998A CN113244779B CN 113244779 B CN113244779 B CN 113244779B CN 202110672998 A CN202110672998 A CN 202110672998A CN 113244779 B CN113244779 B CN 113244779B
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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
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
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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
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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- 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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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, and forming a polyamide layer on the surface of the support membrane, wherein the polyamide layer comprises acyl halide groups; and providing a mixed solution, wherein the mixed solution comprises polyamine, a polar small molecular solvent and a hydrophilic polymer, the mixed solution is placed on the surface, away from the support membrane, of the polyamide layer and is subjected to heat treatment, so that acyl halide groups in the polyamide layer react with the polyamine in the mixed solution, the polyamide layer becomes a dense layer, and the reverse osmosis membrane is obtained, wherein the mass fraction of the polar small molecular solvent in the mixed solution is greater than or equal to 50%, the mass fraction of the hydrophilic polymer in the mixed solution is less than or equal to 1%, and the structure of the dense layer also comprises the hydrophilic polymer. The reverse osmosis membrane prepared by the preparation method of the reverse osmosis membrane has high desalination rate and water flux, and can be better applied to a water treatment device.
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 some water treatment apparatuses requiring desalination, such as a seawater desalination apparatus, in order to increase the desalination rate of a reverse osmosis membrane, multiple coating is generally performed on the surface of a dense layer when the reverse osmosis membrane is prepared.
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 reverse osmosis membrane obtained by the preparation method has high desalination rate and water flux, so that the reverse osmosis membrane can be better applied to water treatment devices such as seawater desalination devices and the like.
The preparation method of the reverse osmosis membrane provided by the invention comprises the following steps:
providing a support film and forming a polyamide layer on the surface of the support film, wherein the polyamide layer comprises acyl halide groups; and
providing a mixed solution, wherein the mixed solution comprises polyamine, a polar small molecule solvent and a hydrophilic polymer, placing the mixed solution on the surface of the polyamide layer away from the support membrane and carrying out heat treatment to enable acyl halide groups in the polyamide layer to react with the polyamine in the mixed solution, so that the polyamide layer becomes a compact layer, and obtaining the reverse osmosis membrane,
wherein the mass fraction of the polar small molecule solvent in the mixed solution is greater than or equal to 50%, the mass fraction of the hydrophilic polymer in the mixed solution is less than or equal to 1%, and the structure of the dense layer further comprises the hydrophilic polymer.
In one embodiment, the mass fraction of the polar small molecule solvent in the mixed solution is 50% to 85%.
In one embodiment, the mass fraction of the hydrophilic polymer in the mixed solution is 0.1% to 0.9%.
In one embodiment, the mass fraction of the polyamine in the mixed solution is 0.5% to 1.5%.
In one embodiment, the polar small molecule solvent comprises at least one of ethanol, chloroform, acetone, N-dimethylformamide, or N, N-dimethylacetamide.
In one embodiment, the hydrophilic polymer includes a nonionic hydrophilic group in a molecular chain thereof.
In one embodiment, the hydrophilic polymer comprises at least one of polyvinyl alcohol, polyethylene glycol, nonionic polyacrylamide, nonionic polyvinylpyrrolidone, or chitosan.
In one embodiment, the acid halide group comprises at least one of an acid fluoride group, an acid chloride group, an acid bromide group, or an acid iodide group;
and/or the polyamine comprises at least one of m-phenylenediamine, piperazine or polyethyleneimine.
In one embodiment, the material of the support membrane comprises at least one of polysulfone, polypropylene, or polyacrylonitrile;
and/or the reverse osmosis membrane further comprises a non-woven fabric layer, and the non-woven fabric layer is arranged on the surface, far away from the compact layer, of the support membrane in a laminated mode.
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, the mixed solution is placed on the surface of the polyamide layer and is subjected to heat treatment, the polar small molecular solvent in the mixed solution can swell the polyamide layer, so that the distance between polyamide molecular chains in the polyamide layer is increased, unreacted acyl halide groups are released and are subjected to secondary reaction with polyamine in the mixed solution, the polyamide layer is more compact and becomes a compact layer, and the desalination rate of the reverse osmosis membrane is improved.
Therefore, the reverse osmosis membrane prepared by the preparation method has high salt rejection rate and water flux at the same time.
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:
s10, providing a supporting film, and forming a polyamide layer on the surface of the supporting film, wherein the polyamide layer comprises acyl halide groups; and
s20, providing a mixed solution, wherein the mixed solution comprises polyamine, a polar small molecule solvent and a hydrophilic polymer, placing the mixed solution on the surface of the polyamide layer away from the support membrane and carrying out heat treatment to enable acyl halide groups in the polyamide layer to react with the polyamine in the mixed solution, enabling the polyamide layer to become a compact layer, and obtaining the reverse osmosis membrane,
wherein, the mass fraction of the polar micromolecule solvent in the mixed solution is more than or equal to 50 percent, the mass fraction of the hydrophilic polymer in the mixed solution is less than or equal to 1 percent, and the structure of the compact layer also comprises the hydrophilic polymer.
In one embodiment, step S10 includes, without limiting the technique for forming the polyamide layer in the present invention:
s101, providing a water phase solution and an oil phase solution, wherein the water phase solution comprises a first monomer, and the oil phase solution comprises a second monomer; and
s102, providing a support membrane, sequentially placing the water phase solution and the oil phase solution on the surface of the support membrane, performing heat treatment, performing a cross-linking reaction on the first monomer and the second monomer, and forming a polyamide layer on the surface of the support membrane, wherein the polyamide layer comprises an acyl halide group.
In step S101, the first monomer includes at least one of an aromatic polyamine or an aliphatic polyamine, and further preferably includes at least one of m-phenylenediamine, piperazine, or polyethyleneimine; in one embodiment, the mass fraction of the first monomer in the aqueous solution is between 1% and 4%.
Specifically, the second monomer comprises at least one of aromatic polybasic acyl fluoride, aromatic polybasic acyl chloride, aromatic polybasic acyl bromide, aromatic polybasic acyl iodide, aliphatic polybasic acyl fluoride, aliphatic polybasic acyl chloride, aliphatic polybasic acyl bromide or aliphatic polybasic acyl iodide, and further preferably comprises at least one of trimesoyl chloride and adipoyl chloride, and in one embodiment, the mass fraction of the second monomer in the oil phase solution is 0.1% -0.35%.
In order to absorb the by-product generated by the cross-linking reaction of the first monomer and the second monomer, in an embodiment, the aqueous solution further comprises an acid scavenger, and the acid scavenger preferably comprises at least one of triethylamine or sodium hydroxide.
In the step S102, 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 in the surface layer of the support membrane, then removing the redundant aqueous phase solution and drying the surface of the support membrane by blowing, and at the moment, the holes in 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 removing the redundant oil phase solution.
It should be noted that when the aqueous phase solution and the oil phase solution contact each other, a water-oil interface is formed, the first monomer and the second monomer undergo a cross-linking reaction at the water-oil interface to form a polyamide layer, and the polyamide layer includes unreacted acyl halide groups due to the self-limiting nature of the cross-linking reaction.
Specifically, the acid halide group includes at least one of an acid fluoride group, an acid chloride group, an acid bromide group, or an acid iodide group, and since the stability of the acid chloride group is relatively high, in one embodiment, the acid halide group further preferably includes the acid chloride group.
In one embodiment, the temperature of the heat treatment in step S102 is 50 ℃ to 100 ℃ for 2min to 10 min.
In one embodiment, the material of the support membrane comprises at least one of polysulfone, polypropylene or polyacrylonitrile, wherein polysulfone is cheap and easily available, the membrane is simple to prepare, the mechanical strength is good, the compression resistance is good, the chemical properties are stable, no toxicity is generated, and biodegradation can be prevented, so the material of the support membrane is preferably polysulfone.
In order to increase the strength of the reverse osmosis membrane, in one embodiment, the reverse osmosis membrane further comprises a non-woven fabric layer, and the non-woven fabric layer is laminated on the surface of the support membrane far from the dense layer.
However, when the reverse osmosis membrane prepared in step S10 is applied, the salt rejection and the water flux are both low, and in order to increase the salt rejection and the water flux, the invention further performs step S20 after forming the polyamide layer on the surface of the support membrane, and places the mixed solution on the surface of the polyamide layer for heat treatment, during which the polar small molecule solvent in the mixed solution can swell the polyamide layer, so that the distance between polyamide molecular chains in the polyamide layer is increased, so as to release unreacted acyl halide groups and perform secondary reaction with polyamine in the mixed solution, so that the polyamide layer is more dense and becomes a dense layer, thereby increasing the salt rejection of the reverse osmosis membrane, and at the same time, because of the hydrogen bonding between the hydrophilic polymer in the mixed solution and the polyamide molecular chains, the hydrophilic polymer can permeate and wind around the polyamide molecular chains, and the support is a framework support, so that a water channel is formed in the compact layer, and the water flux of the reverse osmosis membrane is further improved.
In step S20, the mass fraction of the polar small molecule solvent in the mixed solution is 50% to 85% for better swelling of the polyamide layer. In one embodiment, the polar small molecule solvent comprises at least one of ethanol, chloroform, acetone, N-dimethylformamide, or N, N-dimethylacetamide.
In order to improve the water flux of the polyamide layer and better avoid the hydrophilic polymer from forming a film on the surface of the polyamide layer away from the support layer and hindering the polar small-molecule solvent from swelling the polyamide layer, in one embodiment, the mass fraction of the hydrophilic polymer in the mixed solution is 0.1-0.9%.
Since there is no mutual attraction or repulsion between the non-charged hydrophilic polymer and the anions or cations of the salt in the concentrated water, the non-charged hydrophilic polymer does not affect the salt rejection rate of the composite membrane for treating different types of concentrated water, and the molecular chain of the hydrophilic polymer preferably includes a non-ionic hydrophilic group, such as at least one of a hydroxyl group, an ether group, an ester group or an amide group, and in one embodiment, the hydrophilic polymer includes at least one of polyvinyl alcohol, polyethylene glycol, non-ionic polyacrylamide, non-ionic polyvinylpyrrolidone or chitosan.
In one embodiment, the polyamine includes at least one of an aromatic polyamine or an aliphatic polyamine, and more preferably includes at least one of m-phenylenediamine, piperazine, and polyethyleneimine, and the structures of the polyamine and the first monomer may be the same or different.
It should be noted that the reactivity between the acid halide group and the polyamine is extremely strong, and the acid halide group reacts with the polyamine more easily than other components in the mixed solution, such as the polar small molecule solvent and the hydrophilic polymer.
In one embodiment, the solvent of the mixed solution includes water.
In order to further increase the degree of crosslinking between the molecular chains in the dense layer, the temperature of the heat treatment of step S20 is 50 ℃ to 90 ℃ for 2min to 5 min.
The preparation method of the reverse osmosis membrane can increase the crosslinking degree of the compact layer, does not excessively increase the thickness of the compact layer, and simultaneously forms a water channel in the compact layer, so that the preparation method of the reverse osmosis membrane can improve the desalination rate of the reverse osmosis membrane and simultaneously improve the water flux of the reverse osmosis membrane.
The invention also provides a reverse osmosis membrane prepared by the preparation method of the reverse osmosis membrane, which comprises a support membrane and a compact layer laminated on the surface of the support membrane.
The reverse osmosis membrane prepared by the preparation method of the reverse osmosis membrane has high desalination rate and water flux, and the water flux can reach 67L/(m) for 32000ppm sodium chloride aqueous solution under the high-pressure environment of 5.55MPa2H), the salt rejection can reach 99.77%.
The invention also provides application of the reverse osmosis membrane in a water treatment device.
Specifically, 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 desalination rate of the reverse osmosis membrane, the thickness of the dense layer is 200nm-300 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
2.0% by weight of m-phenylenediamine and 0.2% by weight of triethylamine based on the total weight of the aqueous solution were added to 97.8% by weight of water and mixed uniformly to obtain an aqueous solution.
0.25 wt% of trimesoyl chloride, based on the total weight of the oil phase solution, was added to 99.75 wt% of isododecane and mixed well 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 polysulfone 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 80 ℃ for 2 minutes to obtain a polyamide layer, wherein the thickness of the polyamide layer is 150 nm.
0.5% by weight of m-phenylenediamine, 70.0% by weight of ethanol, and 0.1% by weight of polyvinyl alcohol were added to 29.4% by weight of water based on the total weight of the mixed solution, and mixed uniformly to obtain a mixed solution.
And coating the mixed solution on the surface of the polyamide layer far away from the polysulfone support membrane, standing for 30 seconds, pouring out redundant liquid, putting the obtained membrane into an oven for heat treatment at 70 ℃ for 2 minutes, reacting unreacted acyl chloride groups in the polyamide layer with m-phenylenediamine in the mixed solution, and enabling the polyamide layer to become a dense layer to obtain the reverse osmosis membrane with the thickness of 148 mu m, wherein the thickness of the dense layer is 200 nm.
Testing the salt rejection rate and the water flux of the reverse osmosis membrane in a high-pressure environment, wherein the test conditions are as follows: the testing pressure is 5.55MPa, the concentrated water is 32000ppm sodium chloride aqueous solution,the concentrated water flow is 1.0GPM, the pH value of the concentrated water is 7, the ambient temperature is 25 ℃, and the effective membrane area is about 19cm2The results are described in table 1.
Example 2
2.5% by weight of m-phenylenediamine and 0.2% by weight of triethylamine based on the total weight of the aqueous solution were added to 97.3% by weight of water and mixed uniformly to obtain an aqueous solution.
0.3 wt% of trimesoyl chloride, based on the total weight of the oil phase solution, was added to 99.7 wt% of isododecane and mixed well 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 polysulfone 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 80 ℃ for 2 minutes to obtain a polyamide layer, wherein the thickness of the polyamide layer is 210 nm.
0.5% by weight of m-phenylenediamine, 60.0% by weight of acetone, and 0.1% by weight of nonionic polyacrylamide were added to 39.4% by weight of water based on the total weight of the mixed solution, and mixed uniformly to obtain a mixed solution.
And coating the mixed solution on the surface of the polyamide layer far away from the polysulfone support membrane, standing for 30 seconds, pouring out redundant liquid, putting the obtained membrane into an oven for heat treatment at 70 ℃ for 2 minutes, reacting unreacted acyl chloride groups in the polyamide layer with m-phenylenediamine in the mixed solution, and enabling the polyamide layer to become a compact layer to obtain the reverse osmosis membrane with the thickness of 158 mu m, wherein the thickness of the compact layer is 250 nm.
The reverse osmosis membrane test procedure was as in example 1 and the results are described in table 1.
Example 3
1.5% by weight of m-phenylenediamine and 0.2% by weight of triethylamine based on the total weight of the aqueous solution were added to 98.3% by weight of water and mixed uniformly to obtain an aqueous solution.
0.3 wt% of trimesoyl chloride, based on the total weight of the oil phase solution, was added to 99.7 wt% of isododecane and mixed well 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 polysulfone 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 80 ℃ for 2 minutes to obtain a polyamide layer, wherein the thickness of the polyamide layer is 188 nm.
0.5% by weight of m-phenylenediamine, 70.0% by weight of ethanol, and 0.1% by weight of cationic polyacrylamide were added to 29.4% by weight of water based on the total weight of the mixed solution, and mixed uniformly to obtain a mixed solution.
And coating the mixed solution on the surface of the polyamide layer far away from the polysulfone support membrane, standing for 30 seconds, pouring out redundant liquid, putting the obtained membrane into an oven for heat treatment at 60 ℃ for 2 minutes, reacting unreacted acyl chloride groups in the polyamide layer with m-phenylenediamine in the mixed solution, and enabling the polyamide layer to become a compact layer to obtain the reverse osmosis membrane with the thickness of 149 mu m, wherein the thickness of the compact layer is 212 nm.
The reverse osmosis membrane test procedure was as in example 1 and the results are described in table 1.
Example 4
2.5% by weight of m-phenylenediamine and 0.2% by weight of triethylamine based on the total weight of the aqueous solution were added to 97.3% by weight of water and mixed uniformly to obtain an aqueous solution.
0.3 wt% of trimesoyl chloride, based on the total weight of the oil phase solution, was added to 99.7 wt% of isododecane and mixed well 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 polysulfone 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 90 ℃ for 2 minutes to obtain a polyamide layer, wherein the thickness of the polyamide layer is 199 nm.
0.5% by weight of m-phenylenediamine, 85% by weight of acetone, and 0.9% by weight of polyvinyl alcohol were added to 13.6% by weight of water based on the total weight of the mixed solution, and mixed uniformly to obtain a mixed solution.
And coating the mixed solution on the surface of the polyamide layer, which is far away from the polysulfone support membrane, standing for 30 seconds, pouring out redundant liquid, putting the obtained membrane into an oven for heat treatment at 80 ℃ for 2 minutes, reacting unreacted acyl chloride groups in the polyamide layer with m-phenylenediamine in the mixed solution, and enabling the polyamide layer to become a dense layer to obtain the reverse osmosis membrane with the thickness of 153 mu m, wherein the thickness of the dense layer is 218 nm.
The reverse osmosis membrane test procedure was as in example 1 and the results are described in table 1.
Example 5
2.0% by weight of m-phenylenediamine and 0.2% by weight of triethylamine based on the total weight of the aqueous solution were added to 97.8% by weight of water and mixed uniformly to obtain an aqueous solution.
0.3 wt% of trimesoyl chloride, based on the total weight of the oil phase solution, was added to 99.7 wt% of isododecane and mixed well 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 polysulfone 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 90 ℃ for 2 minutes to obtain a polyamide layer, wherein the thickness of the polyamide layer is 199 nm.
1.5% by weight of m-phenylenediamine, 50% by weight of acetone, and 0.5% by weight of polyvinyl alcohol were added to 48% by weight of water based on the total weight of the mixed solution, and mixed uniformly to obtain a mixed solution.
And coating the mixed solution on the surface of the polyamide layer far away from the polysulfone support membrane, standing for 30 seconds, pouring out excessive liquid, putting the obtained membrane into an oven for heat treatment at 80 ℃ for 2 minutes, reacting unreacted acyl chloride groups in the polyamide layer with m-phenylenediamine in the mixed solution, and enabling the polyamide layer to become a dense layer to obtain the reverse osmosis membrane with the thickness of 148 mu m, wherein the thickness of the dense layer is 222 nm.
The reverse osmosis membrane test procedure was as in example 1 and the results are described in table 1.
Comparative example 1
2.0% by weight of m-phenylenediamine and 0.2% by weight of triethylamine based on the total weight of the aqueous solution were added to 97.8% by weight of water and mixed uniformly to obtain an aqueous solution.
0.25 wt% of trimesoyl chloride, based on the total weight of the oil phase solution, was added to 99.75 wt% of isododecane and mixed well 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 polysulfone 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 80 ℃ for 2 minutes to obtain a reverse osmosis membrane with the thickness of 155 mu m, wherein the thickness of the polyamide layer is 242 nm.
The reverse osmosis membrane test procedure was as in example 1 and the results are described in table 1.
Comparative example 2
2.0% by weight of m-phenylenediamine and 0.2% by weight of triethylamine based on the total weight of the aqueous solution were added to 97.8% by weight of water and mixed uniformly to obtain an aqueous solution.
0.25 wt% of trimesoyl chloride, based on the total weight of the oil phase solution, was added to 99.75 wt% of isododecane and mixed well 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 polysulfone 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 80 ℃ for 2 minutes to obtain a polyamide layer, wherein the thickness of the polyamide layer is 202 nm.
0.5% by weight of m-phenylenediamine and 0.1% by weight of polyvinyl alcohol were added to 99.4% by weight of water based on the total weight of the mixed solution, and mixed uniformly to obtain a mixed solution.
And coating the mixed solution on the surface of the polyamide layer far away from the polysulfone support membrane, standing for 30 seconds, pouring out redundant liquid, and putting the obtained membrane into an oven for heat treatment at 80 ℃ for 2 minutes to obtain the reverse osmosis membrane with the thickness of 155 mu m, wherein the thickness of the compact layer is 248 nm.
The reverse osmosis membrane test procedure was as in example 1 and the results are described in table 1.
Comparative example 3
2.0% by weight of m-phenylenediamine and 0.2% by weight of triethylamine based on the total weight of the aqueous solution were added to 97.8% by weight of water and mixed uniformly to obtain an aqueous solution.
0.25 wt% of trimesoyl chloride, based on the total weight of the oil phase solution, was added to 99.75 wt% of isododecane and mixed well 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 polysulfone 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 80 ℃ for 2 minutes to obtain a polyamide layer, wherein the thickness of the polyamide layer is 198 nm.
0.5% by weight of m-phenylenediamine and 70.0% by weight of ethanol were added to 29.5% by weight of water based on the total weight of the mixed solution, and mixed uniformly to obtain a mixed solution.
And coating the mixed solution on the surface of the polyamide layer far away from the polysulfone support membrane, standing for 30 seconds, pouring out redundant liquid, and putting the obtained membrane into an oven for heat treatment at 80 ℃ for 2 minutes to obtain the reverse osmosis membrane with the thickness of 148 mu m, wherein the thickness of the dense layer is 222 nm.
The reverse osmosis membrane test procedure was as in example 1 and the results are described in table 1.
Comparative example 4
2.5% by weight of m-phenylenediamine and 0.2% by weight of triethylamine based on the total weight of the aqueous solution were added to 97.3% by weight of water and mixed uniformly to obtain an aqueous solution.
0.3 wt% of trimesoyl chloride, based on the total weight of the oil phase solution, was added to 99.7 wt% of isododecane and mixed well 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 polysulfone 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 90 ℃ for 2 minutes to obtain a polyamide layer, wherein the thickness of the polyamide layer is 202 nm.
0.5% by weight of m-phenylenediamine, 60.0% by weight of acetone, and 1.5% by weight of polyvinyl alcohol were added to 38.0% by weight of water based on the total weight of the mixed solution, and mixed uniformly to obtain a mixed solution.
And coating the mixed solution on the surface of the polyamide layer far away from the polysulfone support membrane, standing for 30 seconds, pouring out redundant liquid, and putting the obtained membrane into an oven for heat treatment at 70 ℃ for 2 minutes to obtain the reverse osmosis membrane with the thickness of 144 mu m, wherein the thickness of the dense layer is 218 nm.
The reverse osmosis membrane test procedure was as in example 1 and the results are described in table 1.
Comparative example 5
2.0% by weight of m-phenylenediamine and 0.2% by weight of triethylamine based on the total weight of the aqueous solution were added to 97.8% by weight of water and mixed uniformly to obtain an aqueous solution.
0.3 wt% of trimesoyl chloride, based on the total weight of the oil phase solution, was added to 99.7 wt% of isododecane and mixed well 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 polysulfone 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 90 ℃ for 2 minutes to obtain a polyamide layer, wherein the thickness of the polyamide layer is 198 nm.
0.5% by weight of m-phenylenediamine, 10.0% by weight of ethanol, and 0.5% by weight of polyvinyl alcohol were added to 89.0% by weight of water based on the total weight of the mixed solution, and mixed uniformly to obtain a mixed solution.
And coating the mixed solution on the surface of the polyamide layer far away from the polysulfone support membrane, standing for 30 seconds, pouring out redundant liquid, putting the obtained membrane into an oven for heat treatment at 90 ℃ for 2 minutes to obtain the reverse osmosis membrane with the thickness of 150 mu m, wherein the thickness of the dense layer is 222 nm.
The reverse osmosis membrane test procedure was as in example 1 and the results are described in table 1.
TABLE 1
| Serial number | Membrane water flux/L/(m)2·h) | Rate of salt removal/%) |
| Example 1 | 62 | 99.75 |
| Example 2 | 66 | 99.71 |
| Example 3 | 61 | 99.45 |
| Example 4 | 67 | 99.69 |
| Example 5 | 58 | 99.77 |
| Comparative example 1 | 48 | 99.60 |
| Comparative example 2 | 39 | 99.63 |
| Comparative example 3 | 42 | 99.58 |
| Comparative example 4 | 38 | 99.61 |
| Comparative example 5 | 43 | 99.65 |
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 salt rejection (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/C0) X 100%, wherein C1Is the concentration of concentrated water, C0The concentration of the permeate was used.
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 some 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 (9)
1. A preparation method of a reverse osmosis membrane is characterized by comprising the following steps:
providing a support film and forming a polyamide layer on the surface of the support film, wherein the polyamide layer comprises acyl halide groups; and
providing a mixed solution, wherein the mixed solution comprises polyamine, a polar small molecule solvent and a hydrophilic polymer, placing the mixed solution on the surface of the polyamide layer away from the support membrane and carrying out heat treatment to enable acyl halide groups in the polyamide layer to react with the polyamine in the mixed solution, hydrogen bonding exists between the hydrophilic polymer in the mixed solution and polyamide molecular chains in the polyamide layer, the hydrophilic polymer permeates and winds the polyamide molecular chains to form a framework support, and the polyamide layer becomes a compact layer, so that the reverse osmosis membrane is obtained,
wherein the mass fraction of the polar small molecule solvent in the mixed solution is greater than or equal to 50%, the hydrophilic polymer comprises at least one of polyvinyl alcohol, polyethylene glycol, nonionic polyacrylamide, nonionic polyvinylpyrrolidone or chitosan, the mass fraction of the hydrophilic polymer in the mixed solution is less than or equal to 1%, and the structure of the dense layer further comprises the hydrophilic polymer.
2. The method for preparing a reverse osmosis membrane according to claim 1, wherein the mass fraction of the polar small molecule solvent in the mixed solution is 50% to 85%.
3. The method of manufacturing a reverse osmosis membrane according to claim 1, wherein the mass fraction of the hydrophilic polymer in the mixed solution is 0.1% to 0.9%.
4. The method of manufacturing a reverse osmosis membrane according to claim 1, wherein the mass fraction of the polyamine in the mixed solution is 0.5% to 1.5%.
5. The method of preparing a reverse osmosis membrane according to any one of claims 1-4, wherein the polar small molecule solvent comprises at least one of ethanol, chloroform, acetone, N-dimethylformamide, or N, N-dimethylacetamide.
6. A method of preparing a reverse osmosis membrane according to any one of claims 1-4 wherein the acid halide group comprises at least one of an acid fluoride group, an acid chloride group, an acid bromide group, or an acid iodide group;
and/or the polyamine comprises at least one of m-phenylenediamine, piperazine or polyethyleneimine.
7. The method of preparing a reverse osmosis membrane according to any one of claims 1-4, wherein the material of the support membrane comprises at least one of polysulfone, polypropylene, or polyacrylonitrile;
and/or the reverse osmosis membrane further comprises a non-woven fabric layer, and the non-woven fabric layer is arranged on the surface, far away from the compact layer, of the support membrane in a laminated mode.
8. A reverse osmosis membrane produced by the method of producing a reverse osmosis membrane according to any one of claims 1 to 7.
9. Use of the reverse osmosis membrane of claim 8 in a water treatment device.
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| US11855324B1 (en) | 2022-11-15 | 2023-12-26 | Rahul S. Nana | Reverse electrodialysis or pressure-retarded osmosis cell with heat pump |
| US12040517B2 (en) | 2022-11-15 | 2024-07-16 | Rahul S. Nana | Reverse electrodialysis or pressure-retarded osmosis cell and methods of use thereof |
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| CN114028956B (en) * | 2021-11-18 | 2023-05-26 | 浙江机电职业技术学院 | Reverse osmosis membrane and preparation method and application thereof |
| CN114053876B (en) * | 2021-12-02 | 2023-05-30 | 万华化学集团股份有限公司 | Preparation method of anti-pollution reverse osmosis membrane |
| US11502322B1 (en) | 2022-05-09 | 2022-11-15 | Rahul S Nana | Reverse electrodialysis cell with heat pump |
| US11502323B1 (en) | 2022-05-09 | 2022-11-15 | Rahul S Nana | Reverse electrodialysis cell and methods of use thereof |
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