CN115125403A - Structure and preparation method of acid-resistant composite nanofiltration membrane for rare earth recovery - Google Patents
Structure and preparation method of acid-resistant composite nanofiltration membrane for rare earth recovery Download PDFInfo
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Abstract
A structure and a preparation method of an acid-resistant composite nanofiltration membrane for rare earth recovery. Due to the lack of precise membrane structure regulation and control, preparation of nanofiltration membranes with excellent acid resistance and separation performance remains a great challenge in the metallurgical industry. Covalent Organic Frameworks (COFs) are an effective approach for preparing high-flux nanofiltration membranes due to their abundant mass transfer pores and highly ordered structures. An acid-resistant COF layer and a polyamide layer are sequentially prepared on an ultrafiltration base film by an in-situ interfacial polymerization method, and the prepared composite film has a sub-nanometer pore size and excellent rare earth ion separation performance. After soaking for more than 3 months under the strong acid condition (pH is 1), the membrane still maintains higher retention rate and flux to trivalent rare earth ions. The membrane has excellent separation performance and acid resistance, and has wide application prospect in the metallurgical industry, particularly in the separation and acid recovery of rare earth metal ions.
Description
Technical Field
The invention belongs to the technical field of nanofiltration membrane materials, and particularly designs a structure and a preparation method of an acid-resistant nanofiltration membrane material for rare earth recovery.
Background
Many processes in wastewater treatment and resource recovery are under acidic conditions, such as wastewater treatment in the metal industry, removal of nitrogen-containing compounds from acidic wastewater in the metallurgical industry, recovery of acids, and the like. When the low-concentration rare and precious metals in the acidic waste liquid are recovered, the traditional process usually adopts a method of acid-base neutralization, precipitation filtration and roasting dissolution, a large amount of acid and base are consumed, salt-containing waste water is generated, the process is long, and the energy consumption is high. Therefore, it is necessary to develop a low-energy-consumption, short-flow, green and environment-friendly separation technology for recovering low-concentration rare and noble metals in the acidic waste liquid, reduce the cost and simultaneously improve the recovery rate of the rare and noble metals and the dilute acid.
Nanofiltration (NF) is a pressure driven membrane based separation process for removing 100 to 1000Da solutes and has been widely used in wastewater treatment and the like. The conventional Polyamide (PA) NF membrane containing amido bond is easy to be H under high acidic condition + Because the separation performance is drastically reduced by nucleophilic attack hydrolysis, it is necessary to develop an acid-stable nanofiltration membrane for separation in an acidic environment.
Covalent Organic Frameworks (COFs) are two-dimensional organic crystalline polymers with ordered, uniform pores, predesignable structures and backbone diversity, with enormous separation application potential. At present, almost no reports about acid-resistant COF nanofiltration membranes exist, and the development of high-flux COF acid-resistant nanofiltration membranes is urgently needed. The research reports the synthesis and characterization of a novel acid-resistant composite nanofiltration membrane, and the cross stacking structure enables the composite membrane to show remarkable rare earth ion screening performance and acid resistance. The preparation process, the micropore structure, the rare earth ion separation performance and the acid resistance of the composite acid-resistant nanofiltration membrane are systematically researched, and the composite acid-resistant nanofiltration membrane has huge application prospects in the nanofiltration process under the acidic condition.
The acid-resistant nanofiltration composite membrane material prepared by the Chinese patent CN110479100A is applied to a strong acid material solution with the pH value within the range of 1-7 and outside the pH value range, but the research on the recovery of rare earth ions is not carried out. The oil phase reactant of the acid-resistant nanofiltration membrane disclosed in chinese patent CN102120149A is 1,3, 6-naphthalene trisulfonyl chloride, and forms a polysulfonamide structure with polyamine through interfacial polymerization reaction, which improves the separation layer, but the rejection rate of the prepared acid-resistant nanofiltration membrane for inorganic salt ions needs to be further improved. The acid-resistant nanofiltration membrane prepared by the Chinese patent CN112717712A comprises a support membrane and an active separation layer loaded on the support membrane, and the acid-resistant nanofiltration membrane has better inorganic salt ion separation capacity and structural stability under an acidic condition, but the preparation method is more complex. Therefore, the development of the interfacial polymerization acid-resistant nanofiltration membrane with stability and excellent rare earth separation effect under acidic conditions is of great significance.
Disclosure of Invention
The invention aims to provide a preparation method of an acid-resistant composite nanofiltration membrane material, which aims to solve the problems of low flux, poor acid resistance and the like of the conventional nanofiltration membrane. The prepared acid-resistant composite nanofiltration membrane material has wide prospect in the separation application of an acidic aqueous solution system. The preparation method of the acid-resistant composite nanofiltration membrane material for rare earth recovery comprises the steps of firstly carrying out in-situ interfacial polymerization on a ultrafiltration base membrane to obtain a COF (chip on film) and then carrying out interfacial polymerization on an acid-resistant amide layer on the COF to obtain the acid-resistant composite nanofiltration membrane, wherein the reaction formula of the COF is as follows:
R a 、R b 、R c 、R d 、R e a group selected from-H, -C n H (2n+1) (n is a positive integer), -NH 2 Either one or a combination of both; r f 、R g 、R h A group selected from-H, -C n H (2n+1) (n is a positive integer), -OH or a combination of at least two thereof.
The technical scheme adopted by the invention is carried out according to the following steps:
(1) immersing an ultrafiltration base membrane into deionized water, vacuumizing for 2-6 hours, and removing microporous bubbles of the base membrane;
(2) fixing an ultrafiltration basal membrane in a closed container, pouring a monomer A solution containing a catalyst on the surface of the ultrafiltration basal membrane, keeping for 10 seconds to 5 minutes, and removing the excessive monomer A solution;
(3) pouring the monomer B solution on the surface of the membrane, and keeping for 10 seconds to 5 minutes;
(4) keeping the obtained AB/ultrafiltration basal membrane composite membrane for 3-10 minutes at ambient temperature;
(5) soaking the composite membrane in a surfactant solution for 3-20 minutes;
(6) pouring the high molecular polymer C solution on the surface of the membrane, keeping for 3-20 minutes, and removing the redundant solution;
(7) after the membrane is dried, spraying the monomer D solution on the surface of the membrane, and reacting for 0.5-20 minutes;
(8) and drying the obtained membrane in a constant-temperature oven, and storing the membrane in deionized water to obtain the acid-resistant composite membrane.
The ultrafiltration support base membrane in the step (1) is an organic ultrafiltration membrane and an inorganic ultrafiltration membrane, and is further preferably selected from the group consisting of but not limited to a sulfone ultrafiltration membrane, a polyethersulfone ultrafiltration membrane, a cellulose acetate ultrafiltration membrane, a polyvinylidene fluoride ultrafiltration membrane, a polyethylene ultrafiltration membrane, a polypropylene ultrafiltration membrane and an aromatic polyamide ultrafiltration membrane; further preferably, the inorganic ultrafiltration membrane comprises a ceramic ultrafiltration membrane and an inorganic metal ultrafiltration membrane. The ultrafiltration membrane is used as a base membrane, so that the selection strength and the acid resistance of the acid-resistant composite nanofiltration membrane material can be ensured.
The catalyst in the step (2) includes but is not limited to carboxylic acid, carboxylic ester, acid anhydride, acyl halide, amide;
further preferably, the catalyst in the step (2) is in a concentration of 0.05-0.4g L -1 ；
Further preferably, the diamine monomer A in the step (2) is selected from one or more of m-phenylenediamine, p-phenylenediamine, 4-diaminodiphenyl ether, 2,3,5, 6-tetramethyl-1, 4-phenylenediamine, 2,4, 6-trimethyl-1, 3-phenylenediamine and 4, 5-dimethyl-o-phenylenediamine;
more preferably, the concentration of the diamine monomer A in the step (2) is 0-30 g L -1 ；
Further preferably, the monomer A solvent in the step (2) is one or a mixture of water, ethanol, propanol and acetone;
more preferably, the solvent addition amount of the monomer A in the step (2) is 2 to 10 times of that of the diamine monomer.
The monomer B in the step (3) is selected from one or more of trimesic aldehyde, 2,4, 6-triacyl trimesic phenol, 2-hydroxy-1, 3, 5-benzene tricarbaldehyde, 1, 3-dihydroxy-2, 4, 6-trioxybenzene and 2,4, 6-trimethylbenzene-1, 3, 5-trimethylaldehyde;
further preferably, the concentration of the monomer B in the step (3) is 0-1 g L -1 ；
Further preferably, the monomer B solvent in step (3) includes but is not limited to N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) and Dimethylsulfoxide (DMSO).
The film in the step (4) is an acid-stable COF layer.
The anionic surfactant in the step (5) includes, but is not limited to, sulfonate, sulfate ester salt, carboxylate, and phosphate ester salt.
The high molecular polymer C in the step (6) includes but is not limited to polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl amide, polyquaternium;
more preferably, the concentration of the solution of the high molecular polymer C in the step (6) is 0-15 g L -1 ；
Further preferably, the polymer solvents in step (6) include, but are not limited to, water, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), and Dimethylsulfoxide (DMSO).
In the step (7), the monomer D is an acyl chloride-containing monomer R-M ═ O-Cl, and R is selected from R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Any one of the groups or a combination of at least two of the groups; m is a non-metal element selected from C, S, P, etc.;
further preferably, the monomer D in the step (7) is selected from one or more of benzoyl chloride, benzenesulfonyl chloride, 2-naphthalenesulfonyl chloride, isophthaloyl chloride, 1, 3-benzenedisulfonyl chloride, terephthaloyl chloride, p-methylbenzoyl chloride and 2,4, 6-trimethylbenzoyl chloride;
further preferably, the concentration of the monomer D solution in the step (7) is 0-1.5 g L -1 ；
Further preferably, the monomer solvent in step (7) includes, but is not limited to, water, alcohols, and diethyl ether.
The constant temperature drying range in the step (8) is 25-120 ℃;
further preferably, the film in the step (8) is dried in a constant temperature oven for 3-6 minutes;
further preferably, the temperature of the deionized water stored in the membrane in the step (8) is 0-5 ℃.
An acid-resistant COF membrane and a polyamide membrane are sequentially prepared on an ultrafiltration base membrane by adopting an interfacial polymerization method. Due to the fact that the cross stacking structure between the COF layer and the polysulfonamide layer regulates and controls the membrane aperture, the acid-resistant composite nanofiltration membrane shows high rare earth rejection rate. Soaking the composite membrane in strong acid condition (pH 1) for more than 3 months to RE 3+ Still maintaining a retention rate of 92.7%, 43.3L (m) 2 h bar) -1 Shows good acid stability.
A staggered stacking structure is constructed between polyamide layers, so that a new idea is brought to the design of a novel acid-resistant material, and the material has great potential in the aspect of acid wastewater treatment. The invention enriches the research and development and production ideas of acid-resistant nanofiltration membrane products, and the prepared acid-resistant composite nanofiltration membrane material has wide market prospect.
Drawings
FIG. 1 shows the surface contact angle of the acid-resistant nanofiltration membrane, which is sequentially provided with a base membrane, a COF membrane and an acid-resistant composite membrane from left to right;
FIG. 2 shows an acid resistant nanofiltration membraneAt 1mol L -1 Scanning electron micrographs before and after 3 months of soaking in HCl solution;
figure 3 is the result of the long-term stability of the permeability of the acid-resistant nanofiltration membrane.
Detailed Description
1. Immersing the ultrafiltration basement membrane into deionized water, vacuumizing for 4h, and fixing the ultrafiltration basement membrane in a closed container. 0.15mol L of acetic acid catalyst is added -1 P-phenylenediamine solution 5g L -1 Pouring onto the surface of ultrafiltration basement membrane, maintaining for 20s, and removing excessive m-phenylenediamine; mixing 2,4, 6-tri-benzoyl-phloroglucinol 0.13g L -1 Pouring on the surface of the membrane, keeping for 20s, and removing the excess solution; the resulting film was dried in an oven at 50 ℃ for 4min and stored in deionized water at 4 ℃ prior to testing. La 3+ The retention rate was 26.3% and the flux was 97.7L (m) 2 h bar) -1 。
2. Immersing the ultrafiltration basement membrane into deionized water, vacuumizing for 4h, and fixing the ultrafiltration basement membrane in a closed container. 0.15mol L of acetic acid containing catalyst -1 P-phenylenediamine solution 28g L -1 Pouring on the surface of the ultrafiltration basement membrane, keeping for 40s, and removing excessive p-phenylenediamine solution; mixing 2,4, 6-tri-benzoyl-phloroglucinol 0.7g L -1 Pouring on the surface of the membrane, keeping for 40s, and removing the redundant solution; the resulting film was dried in an oven at 60 ℃ for 5min and stored in deionized water at 5 ℃ prior to testing. Y is 3+ The rejection rate was 29.6%, and the flux was 91.2L (m) 2 h bar) -1 。
3. Immersing the ultrafiltration basement membrane into deionized water, vacuumizing for 4h, and fixing the ultrafiltration basement membrane in a closed container. 0.1mol L of acetic acid containing catalyst -1 16g L of 2,4, 6-trimethyl-1, 3-phenylenediamine solution -1 Pouring onto the surface of ultrafiltration membrane, maintaining for 30s, and removing excessive 2,4, 6-trimethyl-1, 3-phenylenediamine solution; 0.4g L portions of trimesic aldehyde solution -1 Pouring on the membrane surface, keeping for 30s, and removing the excess solution. The obtained COF film was kept at ambient temperature for 5 minutes; soaking the COF film in a sodium dodecyl sulfate solution for 5 minutes; polyetherimide 2g L -1 Pouring the solution on the surface of the membrane, keeping for 30s, and removing the redundant solution; after the film is dried at ambient conditions,1,3 benzene disulfonyl chloride 0.1g L -1 The solution was sprayed onto the membrane surface and reacted for 1 minute. The resulting film was dried in an oven at 70 ℃ for 5min and stored in deionized water at 4 ℃ prior to testing. Film Gd 3+ The rejection was 90.9%, and the flux was 85.9L (m) 2 h bar) -1 。
4. Immersing the ultrafiltration basement membrane into deionized water, vacuumizing for 4h, and fixing the ultrafiltration basement membrane in a closed container. 0.2mol L of acetic acid catalyst is added -1 16g L of 2,4, 6-trimethyl-1, 3-phenylenediamine solution -1 Pouring onto the surface of ultrafiltration membrane, maintaining for 40s, and removing excessive 2,4, 6-trimethyl-1, 3-phenylenediamine solution; 0.4g L portions of trimesic aldehyde solution -1 Pouring on the surface of the membrane, keeping for 40s, and removing the redundant solution; the obtained COF film was kept at ambient temperature for 5 minutes; keeping the COF film in a 1-butane sodium sulfonate solution for 5 minutes; mixing polyvinyl amide 10g L -1 Pouring the solution on the surface of the membrane, keeping for 40s, and removing the redundant solution; after the membrane was dried at ambient conditions, benzenesulfonyl chloride 0.5g L was added -1 The solution was sprayed onto the membrane surface and reacted for 1 minute. The resulting film was dried in an oven at 40 ℃ for 3min and stored in deionized water at 4 ℃ prior to testing. Film Yb 3+ The rejection was 90.7% and the flux was 87% L (m) 2 h bar) -1 。
5. Immersing the ultrafiltration basement membrane into deionized water, vacuumizing for 4h, and fixing the ultrafiltration basement membrane in a closed container. 0.15mol L of acetic acid catalyst is added -1 M-phenylenediamine solution 16g L -1 Pouring onto the surface of ultrafiltration membrane, maintaining for 20s, and removing excessive 2,3,5, 6-tetramethyl-1, 4-phenylenediamine solution; 0.4g L portions of trimesic aldehyde solution -1 Pouring on the surface of the membrane, keeping for 20s, and removing the excess solution; the obtained COF film was kept at ambient temperature for 5 minutes; soaking the mixture in a sodium dodecyl sulfate solution for 5 minutes; mixing polyacrylamide 3g L -1 Pouring the solution on the surface of the membrane, keeping for 20s, and removing the redundant solution; after the film was dried at ambient conditions, benzoyl chloride 0.15g L was added -1 The solution was sprayed onto the membrane surface and reacted for 1 minute. The resulting film was dried in an oven at 60 ℃ for 6min and stored in deionized water at 4 ℃ prior to testing. Film Y 3+ InterceptionThe rate was 92.7% and the flux was 52.2L (m) 2 h bar) -1 。
6. Immersing the ultrafiltration basement membrane into deionized water, vacuumizing for 4h, and fixing the ultrafiltration basement membrane in a closed container. 0.1mol L of acetic acid catalyst is added -1 P-phenylenediamine solution 20g L -1 Pouring onto the surface of the ultrafiltration basement membrane, keeping for 30s, and removing excessive p-phenylenediamine solution; mixing 4, 4' -m-benzenedicarboxaldehyde solution 0.5g L -1 Pouring on the surface of the membrane, keeping for 40s, and removing the excess solution; the obtained COF film was kept at ambient temperature for 5 minutes; soaking the mixture in a sodium dodecyl sulfate solution for 5 minutes; polyquaternium 5g L -1 Pouring the solution on the surface of the membrane, keeping for 40s, and removing the redundant solution; after the film was dried at ambient conditions, benzoyl chloride 0.5g L was added -1 The solution was sprayed onto the membrane surface and reacted for 1.5 minutes. The resulting film was dried in an oven at 70 ℃ for 5min and stored in deionized water at 3 ℃ before testing. Film Yb 3+ The retention rate was 92.1% and the flux was 56.3L (m) 2 h bar) -1 。
7. Immersing the ultrafiltration basement membrane into deionized water, vacuumizing for 4h, and fixing the ultrafiltration basement membrane in a closed container. 0.3mol L of acetic acid catalyst is added -1 25g L of 2,4, 6-trimethyl-1, 3-phenylenediamine solution -1 Pouring on the surface of the ultrafiltration basement membrane, keeping for 30s, and removing excessive 2,4, 6-trimethyl-1, 3-phenylenediamine solution; mixing 4, 4' -m-benzenedicarboxaldehyde solution 0.3g L -1 Pouring on the membrane surface, keeping for 30s, and removing the excess solution; the obtained COF film was kept at ambient temperature for 4 minutes; soaking the mixture in sodium dodecyl sulfate solution for 5 min; mixing polyacrylamide 6g L -1 Pouring the solution on the surface of the membrane, keeping for 30s, and removing the redundant solution; after the membrane was dried at ambient conditions, 2,4, 6-trimethylbenzoyl chloride 1g L was added -1 The solution was sprayed onto the membrane surface and reacted for 0.5 min. The resulting film was dried in an oven at 70 ℃ for 3min and stored in deionized water at 3 ℃ prior to testing. Film Gd 3+ The retention rate was 91.5% and the flux was 72.5L (m) 2 h bar) -1 。
8. Immersing the ultrafiltration basement membrane in deionized water, vacuumizing for 4h, and fixing the ultrafiltration basement membrane in a sealAnd closing the container. 0.25mol L of acetic acid catalyst is added -1 8g L solution of 2,4, 6-trimethyl-1, 3-phenylenediamine -1 Pouring onto the surface of ultrafiltration membrane, maintaining for 20s, and removing excessive 2,4, 6-trimethyl-1, 3-phenylenediamine solution; mixing 4, 4' -m-triphthalaldehyde solution 0.2g L -1 Pouring on the membrane surface, keeping for 20s, and removing the excess solution; the obtained COF film was kept at ambient temperature for 4 minutes; soaking the mixture in sodium dodecyl sulfate solution for 5 min; mixing polyvinyl amide 1g L -1 Pouring the solution on the surface of the membrane, keeping for 20s, and removing the redundant solution; after the film was dried at ambient conditions, terephthaloyl chloride 0.1g L -1 The solution was sprayed onto the membrane surface and reacted for 0.5 min. The resulting film was dried in an oven at 60 ℃ for 5min and stored in deionized water at 3 ℃ before testing. Film Yb 3+ The rejection was 79.7% and the flux was 88.6L (m) 2 h bar) -1 。
9. Immersing the ultrafiltration basement membrane into deionized water, vacuumizing for 4h, and fixing the ultrafiltration basement membrane in a closed container. 0.3mol L of acetic acid catalyst is added -1 P-phenylenediamine solution 25g L -1 Pouring onto the surface of the ultrafiltration basement membrane, keeping for 30s, and removing excessive p-phenylenediamine solution; adding 0.6g L solution of 2,4, 6-trimethyl acyl-phloroglucinol -1 Pouring on the membrane surface, keeping for 30s, and removing the excess solution; the obtained COF film was kept at ambient temperature for 5 minutes; soaking in sodium dodecyl sulfate for 5 min; mixing polyethyleneimine 12g L -1 Pouring the solution on the surface of the membrane, keeping for 30s, and removing the redundant solution; after the membrane was dried at ambient conditions, 1,3 benzenedisulfonyl chloride 0.75g L was added -1 The solution was sprayed onto the membrane surface and reacted for 1 minute. The resulting film was dried in an oven at 60 ℃ for 5min and stored in deionized water at 3 ℃ before testing. Film Y 3+ The retention rate was 92.8%, and the flux was 47.0L (m) 2 h bar) -1 。
10. At 0.1mol L -1 HCl and 1g L -1 YCl of 3 The acid resistance of the film was measured by soaking in the solution for a specified time. Y is 3 + The retention rate of (1) remained constant for 93 days, and the flux of example 9 slightly decreased from 47.0 to 43.3L (m) in the first 7 days 2 h bar) -1 And remained unchanged for 86 days thereafter.
Claims (11)
1. The preparation method of the acid-resistant nanofiltration composite membrane material for rare earth recovery is characterized by firstly preparing a COF (chip on film) membrane on an ultrafiltration base membrane through in-situ interfacial polymerization, and then preparing an acid-resistant polyamide layer on the COF membrane through interfacial polymerization to obtain the acid-resistant composite nanofiltration membrane.
2. The method for preparing the acid-resistant composite nanofiltration membrane material according to claim 1, wherein the reaction formula of the COF membrane is as follows:
R a 、R b 、R c 、R d 、R e a group selected from-H, -C n H (2n+1) (n is a positive integer), -NH 2 Either one or a combination of both; r f 、R g 、R h A group selected from-H, -C n H (2n+1) (n is a positive integer), -OH, or a combination of at least two thereof.
3. The method for preparing the acid-resistant nanofiltration membrane material according to claim 1, wherein the preparation method comprises the following steps:
(1) immersing the ultrafiltration base membrane into deionized water, vacuumizing for 2-6 hours, and removing micropore bubbles of the base membrane;
(2) fixing an ultrafiltration basal membrane in a closed container, pouring a monomer A solution containing a catalyst on the surface of the ultrafiltration basal membrane, keeping for 10 seconds to 5 minutes, and removing the excessive monomer A solution;
(3) pouring the monomer B solution on the surface of the membrane, and keeping for 10 seconds to 5 minutes;
(4) keeping the obtained AB/ultrafiltration-based membrane composite membrane at ambient temperature for 3-10 minutes;
(5) soaking the composite membrane in a surfactant solution for 3-20 minutes;
(6) pouring the high molecular polymer C solution on the surface of the membrane, keeping for 3-20 minutes, and removing the redundant solution;
(7) after the membrane is dried, adding the monomer D solution to the surface of the membrane, and reacting for 0.5-20 minutes;
(8) and drying the obtained film in a constant-temperature oven, and storing in deionized water to obtain the acid-resistant composite film.
4. The method for preparing the acid-resistant nanofiltration membrane material according to claim 2, wherein the ultrafiltration support base membrane in the step (1) is an organic ultrafiltration membrane or an inorganic ultrafiltration membrane, and further preferably, the organic ultrafiltration membrane comprises but is not limited to a polysulfone ultrafiltration membrane, a polyethersulfone ultrafiltration membrane, a cellulose acetate ultrafiltration membrane, a polyvinylidene fluoride ultrafiltration membrane, a polyethylene ultrafiltration membrane, a polypropylene ultrafiltration membrane, and an aromatic polyamide ultrafiltration membrane; further preferably, the inorganic ultrafiltration membrane comprises a ceramic ultrafiltration membrane and an inorganic metal ultrafiltration membrane.
5. The method of claim 2, wherein the catalyst of step (2) comprises but is not limited to carboxylic acid, carboxylic acid ester, acid anhydride, acid halide, acid amide;
further, the catalyst in the step (2) is 0.05-0.4g L -1 ；
Further, in the step (2), the diamine monomer A is selected from one or more of m-phenylenediamine, p-phenylenediamine, 4-diaminodiphenyl ether, 2,3,5, 6-tetramethyl-1, 4-phenylenediamine, 2,4, 6-trimethyl-1, 3-phenylenediamine and 4, 5-dimethyl-o-phenylenediamine;
further, the concentration of the diamine monomer A in the step (2) is 0-30 g L -1 ；
Further, the monomer A solvent in the step (2) is one or a mixture of water, ethanol, propanol and acetone;
further, the addition amount of the solvent of the monomer A in the step (2) is 2-10 times of that of the diamine monomer.
6. The acid-resistant nanofiltration membrane material preparation method according to claim 2, wherein the monomer B in the step (3) is selected from one or more of trimesic aldehyde, 2,4, 6-trimethyloyltrimesic phenol, 2-hydroxy-1, 3, 5-benzenetricarboxylic aldehyde, 1, 3-dihydroxy-2, 4, 6-trialdehyde benzene and 2,4, 6-trimethylbenzene-1, 3, 5-tricarboxylic aldehyde;
further, the concentration of the monomer B in the step (3) is 0-1 g L -1 ；
Further, the monomer B solvent in step (3) includes, but is not limited to, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), and Dimethylsulfoxide (DMSO).
7. The method for preparing the acid-resistant nanofiltration membrane material according to claim 2, wherein the AB/ultrafiltration-based membrane composite membrane in the step (4) is an acid-resistant COF layer.
8. The method of claim 2, wherein the anionic surfactant in step (5) comprises sulfonate, sulfate ester salt, carboxylate and phosphate ester salt.
9. The method of claim 2, wherein the high molecular polymer C of step (6) comprises but is not limited to polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl amide, polyquaternium;
further, the concentration of the solution of the high molecular polymer C in the step (6) is 0-15 g L -1 ；
Further, the polymer solvents in step (6) include, but are not limited to, water, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), and Dimethylsulfoxide (DMSO).
10. The method for preparing the acid-resistant nanofiltration membrane material according to claim 2, wherein the monomer D in the step (7) is an acid chloride-containing monomer R-M ═ O-Cl, and R is selected from R 1 、R 2 、R 3 、R 4 、R 5 、R 6 In the groupAny one or a combination of at least two of; m is a non-metal element selected from C, S, P, etc.;
further, the monomer D in the step (7) is selected from one or more of benzoyl chloride, benzenesulfonyl chloride, 2-naphthalenesulfonyl chloride, isophthaloyl chloride, 1, 3-benzenedisulfonyl chloride, terephthaloyl chloride, p-methylbenzoyl chloride and 2,4, 6-trimethylbenzoyl chloride;
further, the concentration of the monomer D solution in the step (7) is 0-1.5 g L -1 ；
Further, the monomer solvent in step (7) includes but is not limited to water, alcohols, diethyl ether,
11. the method for preparing the acid-resistant nanofiltration membrane material according to claim 2, wherein the constant temperature drying range in the step (8) is 25-120 ℃;
further, drying the membrane in the step (8) in a constant-temperature oven for 3-6 min;
further, the temperature of deionized water stored in the membrane in the step (8) is 0-5 ℃.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107789992A (en) * | 2017-10-20 | 2018-03-13 | 天津大学 | A kind of preparation method that composite nanometer filtering film is modified by constructing pure COFs intermediate layers |
| CN108889139A (en) * | 2018-07-31 | 2018-11-27 | 南京工业大学 | A method of high-throughput covalent organic framework nanofiltration membrane is prepared based on interfacial polymerization |
| KR20190142019A (en) * | 2018-06-15 | 2019-12-26 | 경희대학교 산학협력단 | Nanofiltration Composition Membrane Having Improved Acid and Heat Resistance And Manufacturing Method Thereof |
| CN111686592A (en) * | 2019-03-11 | 2020-09-22 | 湖州欧美新材料有限公司 | Composite nanofiltration membrane and preparation method thereof |
| CN112642305A (en) * | 2021-01-12 | 2021-04-13 | 天津工业大学 | Acid-resistant composite nanofiltration membrane and preparation method thereof |
| CN112717712A (en) * | 2020-12-15 | 2021-04-30 | 中国科学院过程工程研究所 | Acid-resistant nanofiltration membrane and preparation method and application thereof |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107789992A (en) * | 2017-10-20 | 2018-03-13 | 天津大学 | A kind of preparation method that composite nanometer filtering film is modified by constructing pure COFs intermediate layers |
| KR20190142019A (en) * | 2018-06-15 | 2019-12-26 | 경희대학교 산학협력단 | Nanofiltration Composition Membrane Having Improved Acid and Heat Resistance And Manufacturing Method Thereof |
| CN108889139A (en) * | 2018-07-31 | 2018-11-27 | 南京工业大学 | A method of high-throughput covalent organic framework nanofiltration membrane is prepared based on interfacial polymerization |
| CN111686592A (en) * | 2019-03-11 | 2020-09-22 | 湖州欧美新材料有限公司 | Composite nanofiltration membrane and preparation method thereof |
| CN112717712A (en) * | 2020-12-15 | 2021-04-30 | 中国科学院过程工程研究所 | Acid-resistant nanofiltration membrane and preparation method and application thereof |
| CN112642305A (en) * | 2021-01-12 | 2021-04-13 | 天津工业大学 | Acid-resistant composite nanofiltration membrane and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 李新冬等编: "膜分离技术在离子型稀土回收及废水处理中的应用", 冶金工业出版社, pages: 76 - 100 * |
| 郭伟雄: "基于共价有机骨架材料纳滤膜的制备及其性能研究", no. 6, pages 016 - 104 * |
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