CN115121126A - Structure for regulating and controlling interfacial polymerization nanofiltration membrane by rare earth recovery hydrogel layer and preparation method of structure - Google Patents
Structure for regulating and controlling interfacial polymerization nanofiltration membrane by rare earth recovery hydrogel layer and preparation method of structure Download PDFInfo
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Abstract
The invention discloses a structure of an in-situ hydrogel layer regulation interface polymerization nanofiltration membrane for rare earth enrichment and recovery and a preparation method thereof. The nanofiltration membrane for regulating and controlling interfacial polymerization by the in-situ hydrogel layer comprises a supporting basement membrane and a separation surface layer, wherein a functionalized ionic liquid is used as a reactive monomer, a cross-linking agent and a photoinitiator are combined, a free radical in-situ polymerization reaction is initiated by one-step ultraviolet light to form a hydrogel layer (Gel), and then a polyamine and a polybasic acyl chloride are used as interfacial polymerization monomers to form a hydrogel-polyamide (Gel-PA) separation surface layer on the surface of the porous supporting basement membrane through the interfacial polymerization reaction. The invention utilizes the hydrophilicity of hydrogel and a three-dimensional network to regulate and control the interfacial polymerization process, optimizes the microstructure of a polyamide separation layer and obtains a nanofiltration membrane with higher pore connectivity and larger free volume. The prepared membrane greatly improves the water flux while ensuring high mono/multivalent salt retention rate, has good long-term operation stability, and has wide application prospect in monovalent or multivalent ion nanofiltration, especially in the field of rare earth enrichment and separation in the metallurgical industry.
Description
Technical Field
The invention relates to the field of nanofiltration membranes, in particular to a structure for regulating and controlling an interface polymerization nanofiltration membrane by a rare earth recovery hydrogel layer and a preparation method thereof.
Background
With the development of economy, the content and the types of toxic and harmful substances in the sewage are continuously increased, and serious influence is generated on the ecological environment. In the process of mining the ionic rare earth ore, a large amount of ore leaching wastewater is generated, wherein the ore leaching wastewater contains low-concentration rare earth ions and heavy metal ions, and the direct discharge causes serious pollution to the environment and resource waste. Compared with the conventional wastewater treatment method, the membrane technology attracts wide attention due to the advantages of simplicity, high energy efficiency, small occupied area, easy operation and the like. The nanofiltration is used as a membrane separation technology with the operating pressure between ultrafiltration and reverse osmosis, the molecular weight cut-off is usually 200-1000 Da, and the method has natural advantages in the process of enriching and recovering rare earth ions.
Most of the traditional nanofiltration membranes are prepared by directly using piperazine or m-phenylenediamine as a water-phase monomer and using oil-phase acyl chloride through interfacial polymerization, but the high diffusion coefficient and the rapid polymerization of a water-soluble monomer can reduce the permeability of the nanofiltration membrane. Therefore, how to regulate and control the interfacial polymerization process and develop a nanofiltration membrane material with excellent separation performance is an urgent problem to be solved in the field of nanofiltration membranes and is also the key for further development of the nanofiltration membranes.
At present, the transition layer has been widely applied to optimize the structure of the porous substrate and control the interfacial polymerization reaction to prepare a novel composite nanofiltration membrane. In Chinese patent CN110585931A, a metal skeleton compound (HKUST-1) transition layer grows in situ on the surface of a polyimide porous base membrane containing a large amount of amino groups, and a thin and compact separation layer is prepared on the transition layer by an interfacial polymerization method, so that a composite nanofiltration membrane with excellent separation performance and good solvent resistance is obtained, but the research on rare earth ion recovery is not carried out. The Chinese patent CN111420566A discloses a polyamide solvent-resistant nanofiltration membrane containing fluorinated organic nanoparticles, wherein the interface polymerization process is regulated and controlled by utilizing the low surface energy characteristic of the fluorinated organic nanoparticles, and the prepared membrane has high separation selectivity on organic dyes and is simple and convenient in preparation method, but the interception of mono/multivalent salts cannot be realized. The zwitter-ion hydrogel material is a kind of charge neutral polyelectrolyte, and the three-dimensional network and the hydrophilicity of the zwitter-ion hydrogel material provide a thought for preparing a high-performance nanofiltration membrane. However, no patent report of using zwitterionic hydrogel as a transition layer to regulate and control the interfacial polymerization process and enhance the stability of the nanofiltration membrane is found.
The application needs to provide a nanofiltration membrane with in-situ hydrogel layer regulated interfacial polymerization, and the interface polymerization process is regulated by utilizing the hydrogel layer, so that the obtained membrane has higher pore connectivity and larger free volume, and has larger water flux and high mono/multivalent salt rejection rate for rare earth recovery.
Disclosure of Invention
The invention aims to provide a structure of an in-situ hydrogel layer regulation and control interface polymerization nanofiltration membrane and a preparation method thereof, which can obtain the nanofiltration membrane with higher water flux and rejection rate for rare earth enrichment and recovery.
In order to achieve the purpose, the invention adopts the following technical scheme:
an in-situ hydrogel layer regulation interface polymerization nanofiltration membrane for rare earth enrichment and recovery comprises a supporting bottom membrane and a separation surface layer, wherein the separation surface layer is a hydrogel-polyamide layer, and the hydrogel is formed by using functionalized ionic liquids A and B as reactive monomers, combining a cross-linking agent N, N' -Methylene Bisacrylamide (MBA) and a photoinitiator and initiating a free radical in-situ polymerization reaction through one-step ultraviolet light.
The reactive monomers a and B have the following structures:
wherein R is 1 Is selected from R a 、R b Any one of the groups or a combination of at least two of the groups; r is 2 Is selected from R c 、R d Any one of the groups or a combination of at least two of the groups; r 3 Is selected from R c 、R e Any one of the groups or a combination of at least two of the groups; x - Represents Cl — ,Br — One or more of; y is + Represents Li + ,Na + ,K + One or more of (a).
Preferably, the molar ratio of M (MBA) to n (reactive monomer A + reactive monomer B) in the aqueous solution, i.e., m: n is 1 (10-40).
Polyamides are formed from the interfacial polymerization reaction product of a polyamine and a polybasic acid chloride.
The second purpose of the application is to provide a preparation method of the nanofiltration membrane for rare earth enrichment and recovery in-situ hydrogel layer regulation and control interfacial polymerization, which comprises the following steps:
(1) vacuum degassing a supporting base film in deionized water, and then soaking the supporting base film in 0.01M photoinitiator C solution;
(2) pouring a gel precursor solution containing reactive monomers A and B and a cross-linking agent N, N' -Methylene Bisacrylamide (MBA) onto the support basement membrane obtained in the step (1), irradiating under an ultraviolet lamp to perform radical in-situ polymerization reaction, and then washing with an aqueous solution to obtain a hydrogel membrane;
(3) and (3) immersing the hydrogel film obtained in the step (2) into a polyamine aqueous solution for 5-30 min, drying at 15-40 ℃, pouring a polyacyl chloride/n-hexane solution onto the film for reaction, and drying in vacuum at 40-70 ℃ after the reaction to obtain the high-performance nanofiltration membrane with in-situ hydrogel layer regulation and control interfacial polymerization.
The Photoinitiator C in the step (1) is any one or the combination of at least two selected from 2-hydroxy-2-methyl-1-phenyl-1-acetone (Photonititor 1173), 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl acetone (Irgacure 2959) and 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide (Photonititor TPO);
preferably, the vacuum degassing time in the step (1) is 5-15 hours, and the soaking time in the photoinitiator C solution is 1-6 hours.
The reactive monomer A in the step (2) is selected from 1-allyl-3-methylimidazole bromine salt ([ MPIm ] [ Br ]), 1-vinyl-3-ethylimidazole bromine salt ([ VEIm ] [ Br ]), and 1-vinyl-3-ethylimidazole chlorine salt ([ VEIm ] [ Cl ]); the reactive monomer B is selected from 3-sulfopropyl methacrylate potassium Salt (SMP) and 2-propylene-1-sulfonic acid sodium salt (AAS);
preferably, the total molar concentration of the reactive monomer A and the reactive monomer B in the gel precursor solution in the step (2) is 0-0.3M, and the molar ratio of the reactive monomer B to the reactive monomer A is 1: (9-1);
preferably, the irradiation time in the step (2) is 0-50 min, and the distance between the ultraviolet lamp and the membrane is 20-150 mm.
The polyamine in the step (3) is one or more of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, piperazine and 1,3, 5-triaminobenzene; the polybasic acyl chloride is one or more of trimesoyl chloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride and pyromellitic chloride;
preferably, the reaction time in the step (3) is 0.5-5 min.
The interfacial polymerization process is regulated and controlled by adjusting the total molar concentration of the reactive monomer A and the reactive monomer B in the aqueous solution, the molar ratio of the reactive monomer B to the reactive monomer A and the irradiation time of an ultraviolet lamp, the microstructure of a polyamide separation layer and the separation performance of the nanofiltration membrane are optimized, and the permeability of the nanofiltration membrane is firstly increased and then reduced along with the total molar concentration of the reactive monomer A and the reactive monomer B in the aqueous solution, the molar ratio of the reactive monomer B to the reactive monomer A and the increase of the irradiation time of the ultraviolet lamp.
The third purpose of the application is to provide the second purpose of the in-situ hydrogel layer regulation and control interface polymerization nanofiltration membrane for rare earth enrichment and recovery, wherein the nanofiltration membrane is used in the fields of water softening, resource recovery, rare earth enrichment and separation, seawater desalination, concentration, wastewater decoloration and the like.
Compared with the prior art, the method has the following beneficial effects:
the in-situ hydrogel layer regulation interface polymerization nanofiltration membrane for rare earth enrichment and recovery has high rejection rate of mono-multivalent salt and high water permeability; the in-situ hydrogel layer provided by the application has hydrophilic groups and a three-dimensional network structure, and can retain and continuously release an amine solution so as to regulate and control the transmission of polyamine to a water/n-hexane interface, thereby obtaining a thinner, more hydrophilic and porous hydrogel-polyamide nanofiltration membrane.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
However, it should be noted that the detailed description is only an embodiment and explanation of the spirit of the present invention, and should not be construed as a limitation of the scope of the present invention.
The reagents and instruments used in the examples are commercially available and the detection methods are conventional methods well known in the art.
Example 1
An in-situ hydrogel layer regulation interface polymerization nanofiltration membrane for rare earth enrichment and recovery is prepared by the following method:
(1) carrying out vacuum degassing on a polyether sulfone supporting base film in deionized water for 10 hours, and then soaking the polyether sulfone supporting base film in a 0.01M 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl acetone (Irgacure 2959) solution for 3 hours;
(2) a gel precursor solution containing 1-vinyl-3-ethylimidazole chloride ([ VEIm ] [ Cl ]), 3-sulfopropylmethacrylate potassium Salt (SMP) and N, N' -Methylenebisacrylamide (MBA) was prepared with deionized water, where M (MBA) N (SMP + [ VEIm ] [ Cl ]) was 1:20, the molar concentration of SMP + [ VEIm ] [ Cl ] was 0.01M, and the molar ratio of SMP to [ VEIm ] [ Cl ] was 1: 8. and (2) pouring the gel precursor solution onto the polyether sulfone support base membrane obtained in the step (1), and irradiating for 5min under an ultraviolet lamp to perform free radical in-situ polymerization reaction, wherein the distance between the ultraviolet lamp and the membrane is 40 mm. Then washing with aqueous solution to obtain a hydrogel film;
(3) and (3) immersing the hydrogel membrane obtained in the step (2) into m-phenylenediamine aqueous solution for 20min, drying at 30 ℃, pouring phthaloyl chloride/n-hexane solution on the membrane for reaction for 3min, and drying in vacuum at 50 ℃ after the reaction to obtain the in-situ hydrogel layer regulation and control interface polymerization high-performance nanofiltration membrane.
Example 2
An in-situ hydrogel layer regulation interface polymerization nanofiltration membrane for rare earth enrichment and recovery is prepared by the following method:
(1) vacuumizing and degassing a polyacrylonitrile supporting base membrane in deionized water for 5 hours, and then soaking the polyacrylonitrile supporting base membrane in a 0.01M solution of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl acetone (Irgacure 2959) for 1 hour;
(2) a gel precursor solution containing 1-vinyl-3-ethylimidazole chloride ([ VEIm ] [ Cl ]), 3-sulfopropylmethacrylate potassium Salt (SMP) and N, N' -Methylenebisacrylamide (MBA) was prepared with deionized water, where M (MBA) N (SMP + [ VEIm ] [ Cl ]) was 1:25, the molar concentration of SMP + [ VEIm ] [ Cl ] was 0.1M, and the molar ratio of SMP to [ VEIm ] [ Cl ] was 1: 4. and (2) pouring the gel precursor solution onto the polyether sulfone support base membrane obtained in the step (1), and irradiating for 20min under an ultraviolet lamp to perform in-situ polymerization reaction, wherein the distance between the ultraviolet lamp and the membrane is 100 mm. Then washing with aqueous solution to obtain a hydrogel film;
(3) and (3) immersing the hydrogel film obtained in the step (2) into m-phenylenediamine aqueous solution for 20min, drying at 40 ℃, pouring isophthaloyl dichloride/n-hexane solution on the film for reaction for 1min, and drying in vacuum at 40 ℃ after the reaction to obtain the high-performance nanofiltration film with in-situ hydrogel layer regulation and control interface polymerization.
Example 3
An in-situ hydrogel layer regulation interface polymerization nanofiltration membrane for rare earth enrichment and recovery is prepared by the following method:
(1) vacuumizing and degassing a polyacrylonitrile-supported base membrane in deionized water for 2 hours, and then soaking the polyacrylonitrile-supported base membrane in a 0.01M 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl acetone (Irgacure 2959) solution for 5 hours;
(2) a gel precursor solution containing 1-vinyl-3-ethylimidazole bromine ([ VEIm ] [ Br ]), 3-sulfopropyl methacrylate potassium Salt (SMP) and N, N' -Methylenebisacrylamide (MBA) was prepared with deionized water, where M (MBA) N (SMP + [ VEIm ] [ Br ]) was 1:40, the molar concentration of SMP + [ VEIm ] [ Br ] was 0.15M, and the molar ratio of SMP to [ VEIm ] [ Br ] was 1: 1.5. and (2) pouring the gel precursor solution onto the polyether sulfone support base membrane obtained in the step (1), and irradiating for 10min under an ultraviolet lamp to perform free radical in-situ polymerization reaction, wherein the distance between the ultraviolet lamp and the membrane is 100 mm. Then washing with aqueous solution to obtain a hydrogel film;
(3) and (3) immersing the hydrogel membrane obtained in the step (2) into a piperazine water solution for 5min, drying at 40 ℃, pouring a trimesoyl chloride/n-hexane solution on the membrane for reaction for 2min, and drying in vacuum at 60 ℃ after the reaction to obtain the high-performance nanofiltration membrane with in-situ hydrogel layer regulation and control interface polymerization.
Example 4
An in-situ hydrogel layer regulation interface polymerization nanofiltration membrane for rare earth enrichment and recovery is prepared by the following method:
(1) carrying out vacuum degassing on a polyether sulfone supporting base membrane in deionized water for 10 hours, and then soaking the polyether sulfone supporting base membrane in a 0.01M 2-hydroxy-2-methyl-1-phenyl-1-acetone (Photonitiator 1173) solution for 1 hour;
(2) a gel precursor solution containing 1-vinyl-3-ethylimidazole chloride ([ VEIm ] [ Cl ]), 2-propene-1-sulfonic acid sodium salt (AAS), and N, N' -Methylenebisacrylamide (MBA) was prepared with deionized water, where M (MBA) N (AAS + [ VEIm ] [ Cl ]) was 1:20, the molar concentration of AAS + [ VEIm ] [ Cl ] was 0.25M, and the molar ratio of AAS to [ VEIm ] [ Cl ] was 1: 5. and (2) pouring the gel precursor solution onto the polyether sulfone support base membrane obtained in the step (1), and irradiating for 20min under an ultraviolet lamp to perform in-situ polymerization reaction, wherein the distance between the ultraviolet lamp and the membrane is 150 mm. Then washing with aqueous solution to obtain a hydrogel film;
(3) and (3) immersing the hydrogel membrane obtained in the step (2) into a piperazine water solution for 15min, drying at 20 ℃, pouring a pyromellitic dianhydride/n-hexane solution on the membrane for reaction for 2min, and drying in vacuum at 40 ℃ after the reaction to obtain the high-performance nanofiltration membrane with in-situ hydrogel layer regulation and control interface polymerization.
Example 5
An in-situ hydrogel layer regulation interface polymerization nanofiltration membrane for rare earth enrichment and recovery is prepared by the following method:
(1) vacuumizing and degassing a polyvinylidene fluoride supporting base film in deionized water for 8 hours, and then soaking the polyvinylidene fluoride supporting base film in a 0.01M2, 4, 6-trimethylbenzoyldiphenylphosphine oxide (Photonitator TPO) solution for 1 hour;
(2) a gel precursor solution containing 1-allyl-3-methylimidazolium bromide ([ MPIm ] [ Br ]), 3-sulfopropylmethacrylate potassium Salt (SMP) and N, N' -Methylenebisacrylamide (MBA) was prepared with deionized water, where M (MBA) N (SMP + [ MPIm ] [ Br ]) was 1:10, the molar concentration of SMP + [ MPIm ] [ Br ] was 0.001M, and the molar ratio of SMP to [ MPIm ] [ Br ] was 1: 1. and (2) pouring the gel precursor solution onto the polyether sulfone support base membrane obtained in the step (1), and irradiating for 5min under an ultraviolet lamp to perform free radical in-situ polymerization reaction, wherein the distance between the ultraviolet lamp and the membrane is 30 mm. Then washing with aqueous solution to obtain a hydrogel film;
(3) and (3) immersing the hydrogel film obtained in the step (2) in a 1,3, 5-triaminobenzene aqueous solution for 30min, drying at 40 ℃, pouring a terephthaloyl chloride/n-hexane solution on the film for reaction for 0.5min, and drying in vacuum at 40 ℃ after the reaction to obtain the high-performance nanofiltration membrane with in-situ hydrogel layer regulated interface polymerization.
Comparative example 1
An in-situ hydrogel layer regulation interface polymerization nanofiltration membrane for rare earth enrichment and recovery is prepared by the following method:
(1) a polyvinylidene fluoride supporting base film is degassed in deionized water by vacuum pumping for 12 hours and then soaked in a 0.01M solution of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (Photonitiator TPO) for 1 hour;
(2) a gel precursor solution containing 1-vinyl-3-ethylimidazole chloride ([ VEIm ] [ Br ]), 3-sulfopropyl methacrylate potassium Salt (SMP) and N, N' -Methylenebisacrylamide (MBA) was prepared with deionized water, where M (MBA) N (SMP + [ VEIm ] [ Br ]) was 1:20, the molar concentration of SMP + [ VEIm ] [ Br ] was 0.05M, and the molar ratio of SMP to [ VEIm ] [ Br ] was 1: 2. and (2) pouring the gel precursor solution onto the polyether sulfone support base membrane obtained in the step (1), and irradiating for 10min under an ultraviolet lamp to perform free radical in-situ polymerization reaction, wherein the distance between the ultraviolet lamp and the membrane is 100 mm. Then washing with aqueous solution to obtain a hydrogel film;
(3) and (3) immersing the hydrogel film obtained in the step (2) into a p-phenylenediamine aqueous solution for 10min, drying at 25 ℃, pouring a trimesoyl chloride/n-hexane solution on the film for reaction for 4min, and drying in vacuum at 60 ℃ after the reaction to obtain the high-performance nanofiltration membrane with in-situ hydrogel layer regulation and control interface polymerization.
Comparative example 2
An in-situ hydrogel layer regulation interface polymerization nanofiltration membrane for rare earth enrichment and recovery is prepared by the following method:
(1) vacuumizing and degassing a polyacrylonitrile-supported base membrane in deionized water for 6 hours, and then soaking the polyacrylonitrile-supported base membrane in a 0.01M solution of 2-hydroxy-2-methyl-1-phenyl-1-acetone (Photonitiator 1173) for 6 hours;
(2) a gel precursor solution containing 1-allyl-3-methylimidazolium bromide ([ MPIm ] [ Br ]), 3-sulfopropylmethacrylate potassium Salt (SMP) and N, N' -Methylenebisacrylamide (MBA) was prepared with deionized water, where M (MBA) N (SMP + [ MPIm ] [ Br ]) was 1:15, the molar concentration of SMP + [ MPIm ] [ Br ] was 0.3M, and the molar ratio of SMP to [ MPIm ] [ Br ] was 1: 7. and (2) pouring the gel precursor solution onto the polyether sulfone support base membrane obtained in the step (1), and irradiating for 40min under an ultraviolet lamp to perform in-situ polymerization reaction, wherein the distance between the ultraviolet lamp and the membrane is 150 mm. Then washing with aqueous solution to obtain a hydrogel film;
(3) and (3) immersing the hydrogel film obtained in the step (2) into an o-phenylenediamine aqueous solution for 25min, drying at 40 ℃, pouring a trimesoyl chloride/n-hexane solution on the film for reaction for 2min, and drying in vacuum at 50 ℃ after the reaction to obtain the high-performance nanofiltration membrane with in-situ hydrogel layer regulation and control interface polymerization.
Comparative example 3
An in-situ hydrogel layer regulation interface polymerization nanofiltration membrane for rare earth enrichment and recovery is prepared by the following method:
(1) carrying out vacuum degassing on a polyether sulfone supporting base film in deionized water for 9 hours, and then soaking the polyether sulfone supporting base film in a 0.01M 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl acetone (Irgacure 2959) solution for 1 hour;
(2) a gel precursor solution containing 1-vinyl-3-ethylimidazole chloride ([ VEIm ] [ Cl ]), 2-propene-1-sulfonic acid sodium salt (AAS), and N, N' -Methylenebisacrylamide (MBA) was prepared with deionized water, where M (MBA) N (AAS + [ VEIm ] [ Cl ]) was 1:15, the molar concentration of AAS + [ VEIm ] [ Cl ] was 0.005M, and the molar ratio of AAS to [ VEIm ] [ Cl ] was 1: 6. and (2) pouring the gel precursor solution onto the polyether sulfone support base membrane obtained in the step (1), and irradiating for 15min under an ultraviolet lamp to perform free radical in-situ polymerization reaction, wherein the distance between the ultraviolet lamp and the membrane is 30 mm. Then washing with aqueous solution to obtain a hydrogel film;
(3) and (3) immersing the hydrogel membrane obtained in the step (2) into an o-phenylenediamine aqueous solution for 10min, drying at 40 ℃, pouring a pyromellitic dianhydride/n-hexane solution on the membrane for reaction for 3min, and drying in vacuum at 55 ℃ after the reaction to obtain the high-performance nanofiltration membrane with in-situ hydrogel layer regulation and control interface polymerization.
Performance testing
And (3) testing the performance of the nanofiltration membrane: the measuring conditions are 8bar and 25 ℃, and the pair of NaCl and GdCl of the nanofiltration membrane is measured 3 、YCl 3 Retention rate and permeability to water. The test results are shown in Table 1.
Table 1 nanofiltration performance data for materials provided in examples and comparative examples
As can be seen from Table 1, the nanofiltration membranes prepared by the different examples and comparative examples and used for regulating and controlling interfacial polymerization of the in-situ hydrogel layer for NaCl and GdCl 3 、YCl 3 Has some differences in rejection and permeability to water, but the membrane substantially maintains high water permeability while ensuring high rejection.
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 (10)
1. An in-situ hydrogel layer regulation and control interface polymerization nanofiltration membrane for rare earth enrichment and recovery comprises a supporting basement membrane and a separation surface layer, and is characterized in that the supporting basement membrane is one of polyethersulfone, polyacrylonitrile or polyvinylidene fluoride ultrafiltration membranes.
2. The in-situ hydrogel layer controlled interfacial polymerization nanofiltration membrane for rare earth enrichment and recovery according to claim 1, wherein the separation surface layer is a hydrogel-polyamide layer composite membrane.
3. The nanofiltration membrane according to claim 2, wherein the hydrogel layer is formed by using functionalized ionic liquids a and B as reactive monomers, combining a cross-linking agent N, N' -Methylenebisacrylamide (MBA) and a photoinitiator, and initiating a free radical in-situ polymerization reaction through one-step ultraviolet light. The reactive monomers a and B have the following structures:
wherein R is 1 Is selected from R a 、R b Any one of the groups or a combination of at least two of the groups; r 2 Is selected from R c 、R d Any one of the groups or a combination of at least two of the groups; r 3 Is selected from R c 、R e Any one of the groups or a combination of at least two of the groups; x-represents one or more of Cl-, Br-; y is + Represents Li + ,Na + ,K + One or more of (a).
4. The in-situ hydrogel layer controlled interfacial polymerization nanofiltration membrane for rare earth enrichment and recovery according to claim 3, wherein the molar ratio of M (MBA) to n (reactive monomer A + reactive monomer B) in the aqueous solution is 1 (10-40).
5. The in-situ hydrogel layer mediated interfacial polymerization nanofiltration membrane for rare earth enrichment and recovery according to claim 2, wherein the polyamide is formed from an interfacial polymerization reaction product of a polyamine and a polybasic acid chloride.
6. The preparation method of the in-situ hydrogel layer controlled interfacial polymerization nanofiltration membrane for rare earth enrichment and recovery according to claims 1 to 5, wherein the method comprises the following steps:
(1) vacuum degassing a supporting base film in deionized water, and then soaking the supporting base film in 0.01M photoinitiator C solution;
(2) pouring a gel precursor solution containing reactive monomers A and B and a cross-linking agent N, N' -Methylene Bisacrylamide (MBA) onto the support basement membrane obtained in the step (1), irradiating under an ultraviolet lamp to perform radical in-situ polymerization reaction, and then washing with an aqueous solution to obtain a hydrogel membrane;
(3) and (3) immersing the hydrogel film obtained in the step (2) into a polyamine aqueous solution for 5-30 min, drying at 15-40 ℃, pouring a polyacyl chloride/n-hexane solution onto the film for reaction, and drying in vacuum at 40-70 ℃ after the reaction to obtain the high-performance nanofiltration membrane with in-situ hydrogel layer regulation and control interfacial polymerization.
7. The preparation method according to claim 6, wherein the Photoinitiator C of step (1) is selected from any one or a combination of at least two of 2-hydroxy-2-methyl-1-phenyl-1-propanone (Photonitiator 1173), 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropanone (Irgacure 2959), and 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (Photonitiator TPO);
preferably, the vacuum degassing time in the step (1) is 5-15 hours, and the soaking time in the photoinitiator C solution is 1-6 hours.
8. The method according to claim 6, wherein the reactive monomer A of step (2) is selected from the group consisting of 1-allyl-3-methylimidazolium bromide ([ MPIm ] [ Br ]), 1-vinyl-3-ethylimidazolium bromide ([ VEIm ] [ Br ]), and 1-vinyl-3-ethylimidazolium chloride ([ VEIm ] [ Cl ]); the reactive monomer B is selected from 3-sulfopropyl methacrylate potassium Salt (SMP) and 2-propylene-1-sulfonic acid sodium salt (AAS);
preferably, the total molar concentration of the reactive monomer A and the reactive monomer B in the gel precursor solution in the step (2) is 0-0.3M, and the molar ratio of the reactive monomer B to the reactive monomer A is 1: (9-1);
preferably, the irradiation time in the step (2) is 0-50 min, and the distance between the ultraviolet lamp and the membrane is 20-150 mm.
9. The method according to any one of claims 6 to 8, wherein the polyamine in the step (3) is one or more of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, piperazine, and 1,3, 5-triaminobenzene; the polybasic acyl chloride is one or more of trimesoyl chloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride and pyromellitic chloride;
preferably, the reaction time in the step (3) is 0.5-5 min.
10. The use of the nanofiltration membrane according to claim 1, wherein the nanofiltration membrane is used in the fields of water softening, resource recovery, rare earth enrichment and separation, seawater desalination, concentration, wastewater decolorization, and the like.
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