CN109603563B - Preparation method of zinc coordination organic nanoparticle hybrid polyamide membrane - Google Patents

Preparation method of zinc coordination organic nanoparticle hybrid polyamide membrane Download PDF

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CN109603563B
CN109603563B CN201910026131.XA CN201910026131A CN109603563B CN 109603563 B CN109603563 B CN 109603563B CN 201910026131 A CN201910026131 A CN 201910026131A CN 109603563 B CN109603563 B CN 109603563B
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CN109603563A (en
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计艳丽
顾冰心
安全福
高从堦
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Zhejiang University of Technology ZJUT
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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
    • 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
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
    • 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
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/46—Impregnation

Abstract

The invention discloses a preparation method of a zinc coordination organic nanoparticle hybrid polyamide membrane, which comprises the steps of preparing an aqueous mixed solution by using polyamine as a monomer molecule, zinc nitrate hexahydrate as a metal ion compound and dopamine as a bionic adhesive, dip-coating the aqueous mixed solution on the surface of a porous support membrane, carrying out dipping treatment on the aqueous solution containing 2-methylimidazole to form zinc coordination organic nanoparticles in situ, and finally preparing the zinc coordination organic nanoparticle hybrid polyamide membrane through polyacylchloride monomer interface crosslinking. By utilizing the unique nano microstructure of the zinc coordination organic particles, a nano channel beneficial to water permeation and selective interception of organic molecules is formed in the polyamide membrane, and high water permeability and stable separation selectivity can be obtained. The preparation method is simple and easy to implement, the particles are formed in situ in the film preparation process, the particles are uniformly and stably distributed in the film, the preparation cost is low, and the method has a good industrial application prospect.

Description

Preparation method of zinc coordination organic nanoparticle hybrid polyamide membrane
Technical Field
The invention belongs to the field of membrane separation, and particularly relates to a preparation method of a zinc coordination organic nanoparticle hybrid polyamide membrane.
Background
Membrane separation techniques typically include microfiltration, ultrafiltration, nanofiltration, reverse osmosis, forward osmosis, membrane bioreactors and the like. Membrane separation is a novel, energy-saving and environment-friendly technology, and plays an increasingly important role in the fields of seawater desalination, drinking water purification, wastewater treatment, industrial substance separation, resource recovery and the like. The membrane material is the core of the development of membrane separation technology and is the key for determining the separation performance. Since the first polyamide membrane was prepared by Cadotte et al in 1972 using interfacial polymerization, commercial nanofiltration, reverse osmosis and forward osmosis membranes were based on polyamide composite membranes (US Patent 5,693,227; j.membr. sci.,2013,446,164-. With the expansion of the market demand of the separation membrane, the variety of the polyamide separation membrane is continuously increased, researchers at home and abroad synthesize different types of organic phase/water phase monomer molecules, and the obtained novel polyamide membrane has better chlorine resistance, oxidation resistance and pollution resistance. Although China has made important research results in the fields of preparation and application of membrane materials and special separation membranes, the international advanced level has a certain gap, and the requirements of complex practical application systems cannot be completely met.
In recent years, with the rapid development of nanotechnology, the introduction of some functional inorganic nanomaterials into polyamide membranes to improve the separation performance of the membranes has developed into an important research direction. The inorganic nano hybrid polyamide membrane is prepared by introducing a NaA type zeolite molecular sieve into a polyamide membrane by Hoek professor of Hoek in Ho.A. of university of California and Yanyushan professor of Heabin.A. for the first time, and the water flux of the membrane is improved by nearly one time on the basis of not influencing the rejection rate of inorganic salts (J.Membr.Sci.2007, 294, 1-7). There have been many reports of inorganic nanomaterials as modifiers, such as zeolite molecular sieves, SiO2、TiO2CNT, GO, MOF and the like are introduced into the polyamide membrane, so that the water permeation flux and the pollution resistance of the polyamide membrane are improved. (CN 1401417A; CN 102989330A; ACS appl. Mater. interfaces 2016, 86693-15200; J.Am. chem. Soc.,2013,135, 15201-15208). However, the synthesis and modification methods of inorganic nanoparticles are complex, and the problems of self-dispersibility of the nano material and compatibility between the nano material and a polyamide-based film limit the large-scale and repeated and stable preparation of the nano material. How to prepare a functional nano material with controllable chemical composition, controllable structure, good dispersibility and strong stability by a simple and convenient method suitable for industrialized interfacial polymerization film forming is an important problem to be solved urgently for constructing a high-performance polyamide film.
Inspired by mussel bionic chemistry, Messersmith et al, 2007 reported surface modification of various organic and inorganic materials with dopamine-binding materials. Recent studies have found that under certain induction conditions, dopamine and its self-polymers can assemble in aqueous solution to form melanoid nanoparticles, which can be incorporated into polymer films to improve the structural stability, separability, and anti-contamination properties of the films (J.Membr.Sci.2014,457, 73-81; J.Membr.Sci.2015,476, 10-19). The zinc nano material has good hydrophilicity, pollution resistance and antibacterial performance (CN 201420432075.2; CN 201710359570.3). By combining the above analysis, if the nano particles can be formed in situ in the interfacial polymerization film-forming process, and the nano particles contain dopamine and zinc nano components, the unique nano microstructure, strong hydrophilicity and good anti-pollution stability of zinc organic particles can be simultaneously utilized to form nano channels which are beneficial to water permeation and selective permeation of organic molecules in a polyamide film, so that high water permeability and stable separation selectivity can be obtained, and the obtained film can better meet the requirements of practical application.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a zinc coordination organic nanoparticle hybrid polyamide membrane.
The preparation method of the zinc coordination organic nanoparticle hybrid polyamide membrane comprises the following steps:
1) preparing a water-phase mixed solution by using polyamine as a monomer molecule, zinc nitrate hexahydrate as a metal ion compound and dopamine as a bionic adhesive, dip-coating the water-phase mixed solution on the surface of a porous support membrane, and carrying out dipping treatment on the porous support membrane by using a 2-methylimidazole water solution to form a zinc-containing coordination organic nanoparticle nascent state membrane on the surface of the porous support membrane in situ;
2) dissolving a polybasic acyl chloride monomer in an organic solvent to prepare an organic phase solution, dip-coating the organic phase solution on the surface of the nascent-state membrane loaded with the zinc coordination organic nano particles to perform interface crosslinking reaction, performing thermocuring treatment, and finally washing by deionized water to obtain a zinc coordination organic nano particle hybrid polyamide membrane;
the polyamine monomer molecule in the step 1) is piperazine, N-aminoethyl piperazine, ethylenediamine, m-phenylenediamine, p-phenylenediamine or 1,3, 5-triaminobenzene; the polybasic acyl chloride monomer in the step 2) is phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesoyl chloride or biphenyl tetracarboxyl chloride; the mass percentage concentration of polyamine monomer molecules in the water-phase mixed solution in the step 1) is 0.2-2%; the mass percentage concentration of zinc nitrate hexahydrate in the water-phase mixed solution in the step 1) is 0.1-1%; the mass percentage concentration of the dopamine in the water-phase mixed solution in the step 1) is 0.05-0.5%; the porous support membrane in the step 1) is a flat ultrafiltration membrane made of polysulfone, polyethersulfone, polyacrylonitrile or polyvinylidene fluoride; the dip-coating condition of the water-phase mixed solution in the step 1) is dip-coating for 10-60 minutes at 15-25 ℃; the mass percentage concentration of the 2-methylimidazole water solution in the step 1) is 0.5-5%; the 2-methylimidazole aqueous solution dipping treatment condition in the step 1) is that dipping is carried out for 10-100 minutes at 15-25 ℃; the mass percentage concentration of the molecules of the polybasic acyl chloride monomer in the organic phase solution in the step 2) is 0.1-1%; the solvent of the organic phase solution in the step 2) is n-hexane, cyclohexane or heptane; the condition for carrying out the interfacial crosslinking reaction by dip coating the organic phase solution in the step 2) is that the reaction is carried out for 2-10 minutes at 15-25 ℃; the thermosetting treatment condition in the step 2) is curing for 10-40 minutes at 45-65 ℃.
The zinc coordination organic nanoparticle hybrid polyamide membrane can be used in the field of separation of charged organic molecules with different molecular weights.
The invention relates to a method for testing the separation performance of a zinc coordination organic nanoparticle hybrid polyamide membrane, which comprises the following steps: the membrane is placed in a conventional flat pressure driven membrane testing device in the field, the membrane is pre-pressed for 1h under the operation pressure of 0.5MPa before testing, and then under the testing conditions of 25 ℃ and 0.2MPa, the water permeation flux (J) and the retention rate (R) of organic molecules of the membrane are measured, and the calculation formula is as follows: j ═ V/(A.t); r is 1-Cp/Cf(ii) a Wherein, the volume of the V-feed liquid permeating the membrane and the effective area of the A-membrane are 22.4cm2T-run time, CpConcentration of permeate, Cf-feed liquid concentration; and measuring the total organic carbon content in the solution to obtain the concentration of the organic matter solution.
The separating layer of the zinc coordination organic nanoparticle hybrid polyamide membrane consists of zinc coordination organic nanoparticles and polyamide macromolecules, the zinc coordination organic particles are generated in situ in the membrane preparation process, the unique nano microstructure, strong hydrophilicity and good adhesion stability of the zinc coordination organic nanoparticle hybrid polyamide membrane can form nano beneficial to water permeation and selective interception of organic molecules in the polyamide separating layerA channel. By regulating the particle size and content of the zinc coordination organic nanoparticles in the polyamide membrane, the water permeation flux of the obtained membrane is generally higher than 80L.m-2.h-1.bar-1The retention rate of the organic dye molecules with negative charges is higher than 95%, and the retention rate of the organic dye molecules with positive charges is generally lower than 30%. In addition, the zinc coordination organic nano-particles contain a large number of reactive groups and dopamine components, and strong covalent bonds and non-covalent bonds can be formed between the particles and the polyamide separation layer and between the particles and the porous support membrane, so that the membrane has high permeation selectivity and good stability; in addition, the nano particles are formed in situ in the membrane preparation process, can be uniformly introduced into the polyamide membrane in a large amount, and the membrane preparation method is simple and convenient, is easy to regulate and control, and has good industrial large-scale preparation and application prospects.
Detailed Description
The preparation method of the zinc coordination organic nanoparticle hybrid polyamide membrane comprises the following steps:
1) preparing a water-phase mixed solution by using polyamine as a monomer molecule, zinc nitrate hexahydrate as a metal ion compound and dopamine as a bionic adhesive, dip-coating the water-phase mixed solution on the surface of a porous support membrane, and carrying out dipping treatment on the porous support membrane by using a 2-methylimidazole water solution to form a zinc-containing coordination organic nanoparticle nascent state membrane on the surface of the porous support membrane in situ;
2) dissolving a polybasic acyl chloride monomer in an organic solvent to prepare an organic phase solution, dip-coating the organic phase solution on the surface of the nascent-state membrane loaded with the zinc coordination organic nano particles to perform interface crosslinking reaction, performing thermocuring treatment, and finally washing by deionized water to obtain a zinc coordination organic nano particle hybrid polyamide membrane;
the polyamine monomer molecule in the step 1) is piperazine, N-aminoethyl piperazine, ethylenediamine, m-phenylenediamine, p-phenylenediamine or 1,3, 5-triaminobenzene; the polybasic acyl chloride monomer in the step 2) is phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesoyl chloride or biphenyl tetracarboxyl chloride; the mass percentage concentration of polyamine monomer molecules in the water-phase mixed solution in the step 1) is 0.2-2%; the mass percentage concentration of zinc nitrate hexahydrate in the water-phase mixed solution in the step 1) is 0.1-1%; the mass percentage concentration of the dopamine in the water-phase mixed solution in the step 1) is 0.05-0.5%; the porous support membrane in the step 1) is a flat ultrafiltration membrane made of polysulfone, polyethersulfone, polyacrylonitrile or polyvinylidene fluoride; the dip-coating condition of the water-phase mixed solution in the step 1) is dip-coating for 10-60 minutes at 15-25 ℃; the mass percentage concentration of the 2-methylimidazole water solution in the step 1) is 0.5-5%; the 2-methylimidazole aqueous solution dipping treatment condition in the step 1) is that dipping is carried out for 10-100 minutes at 15-25 ℃; the mass percentage concentration of the molecules of the polybasic acyl chloride monomer in the organic phase solution in the step 2) is 0.1-1%; the solvent of the organic phase solution in the step 2) is n-hexane, cyclohexane or heptane; the condition for carrying out the interfacial crosslinking reaction by dip coating the organic phase solution in the step 2) is that the reaction is carried out for 2-10 minutes at 15-25 ℃; the thermosetting treatment condition in the step 2) is curing for 10-40 minutes at 45-65 ℃.
Examples of the present invention are given below, but the present invention is not limited by the examples:
example 1:
dissolving 0.2g of piperazine, 0.1g of zinc nitrate hexahydrate and 0.05g of dopamine in 100g of deionized water to prepare a water-phase mixed solution, dipping the water-phase mixed solution on the surface of a polysulfone ultrafiltration membrane for 60 minutes at 15 ℃, further dipping the surface of the polysulfone ultrafiltration membrane for 100 minutes by using a 2-methylimidazole water solution with the mass percentage concentration of 0.5% at 15 ℃ to obtain a zinc-containing coordination organic nanoparticle nascent state membrane, then dipping the zinc-containing coordination organic nanoparticle nascent state membrane into a trimesoyl chloride n-hexane solution with the mass percentage concentration of 0.1%, carrying out interface crosslinking reaction for 10 minutes at 15 ℃, finally curing for 40 minutes at 45 ℃, and washing by using deionized water to obtain the zinc-containing coordination organic nanoparticle hybrid polyamide membrane.
The zinc-containing coordination organic nano particle hybrid polyamide film is at 25 ℃, and under the pressure of 0.2MPa, for 1g.L-1The separation result of the Congo red and basic blue organic dye solution is as follows: the water flux is 87.5L.m-2.h-1.bar-1The rejection rate for congo red was 97.5%, and the rejection rate for basic blue was 25.3%.
Example 2:
dissolving 2g of piperazine, 1g of zinc nitrate hexahydrate and 0.5g of dopamine in 100g of deionized water to prepare a water-phase mixed solution, dip-coating the water-phase mixed solution on the surface of a polysulfone ultrafiltration membrane for 10 minutes at 25 ℃, further performing immersion treatment for 10 minutes at 25 ℃ by using a 2-methylimidazole water solution with the mass percentage concentration of 5% to obtain a zinc-containing coordination organic nanoparticle nascent state membrane, then dipping the zinc-containing coordination organic nanoparticle nascent state membrane into a trimesoyl chloride n-hexane solution with the mass percentage concentration of 1%, performing interface crosslinking reaction for 2 minutes at 25 ℃, finally curing for 10 minutes at 65 ℃, and washing by using deionized water to obtain the zinc-containing coordination organic nanoparticle hybrid polyamide membrane.
The zinc-containing coordination organic nano particle hybrid polyamide film is at 25 ℃, and under the pressure of 0.2MPa, for 1g.L-1The separation result of the Congo red and basic blue organic dye solution is as follows: the water flux is 98.5L.m-2.h-1.bar-1The rejection rate for congo red is 98.2%, and the rejection rate for basic blue is 27.5%.
Example 3:
dissolving 0.3g of piperazine, 0.3g of zinc nitrate hexahydrate and 0.2g of dopamine in 100g of deionized water to prepare a water-phase mixed solution, dipping the water-phase mixed solution on the surface of a polysulfone ultrafiltration membrane for 30 minutes at 25 ℃, further dipping the surface of the polysulfone ultrafiltration membrane for 30 minutes by using a 2-methylimidazole water solution with the mass percentage concentration of 0.4% at 25 ℃ to obtain a zinc-containing coordination organic nanoparticle nascent state membrane, then dipping the zinc-containing coordination organic nanoparticle nascent state membrane into a trimesoyl chloride n-hexane solution with the mass percentage concentration of 0.2%, carrying out interface crosslinking reaction for 5 minutes at 25 ℃, finally curing for 20 minutes at 60 ℃, and washing by using deionized water to obtain the zinc-containing coordination organic nanoparticle hybrid polyamide membrane.
Comparative example 1
Referring to the procedure of example 3, a polyamide film was directly prepared from piperazine and trimesoyl chloride as raw materials without in-situ formation of zinc-containing complex organic nanoparticles (see example 3 for film preparation conditions).
Comparative example 2
A zinc ion-containing polyamide film was directly prepared without treatment with an aqueous 2-methylimidazole solution (see example 3 for film formation conditions) in accordance with the procedure of example 3.
Comparative example 3
With reference to the procedure of example 3, dopamine nanoparticles were added to the polyamide film production process (the film production conditions were as in example 3), and a polyamide film containing dopamine nanoparticles was produced.
TABLE 1 comparison of separation Performance of Polyamide membranes prepared in example 3 and comparative examples 1 to 3
Figure BDA0001942559330000061
The results in table 1 show that the polyamide membranes can be obtained by 4 methods, but the retention rates and water fluxes of the organic dye molecules are greatly different due to the difference in the chemical compositions and microstructures used to prepare the polyamide membranes.
In comparative example 1, no other modified material was added, and the polyamide membrane was formed by crosslinking semi-aromatic polyamide polymer chains, and the membrane was dense and had low flux; in the comparative example 2, the treatment of 2-methylimidazole aqueous solution is not carried out, hydrophilic zinc metal ions are introduced into the polyamide membrane, the influence on the membrane structure is small, and the hydrophilicity of the membrane is improved, so that the water flux is increased; in comparative example 3, the dopamine nanoparticles are added as the modified materials, and the nano materials are directly added in the polyamide membrane, so that the dispersibility is poor, the water flux is increased, but a through effective water channel structure cannot be formed in the membrane.
In example 3, zinc-coordinated organic nanoparticles are formed in situ during the film formation process, and by using the unique nano microstructure and strong hydrophilicity thereof, a nanochannel structure beneficial to water permeation and selective separation of organic molecules can be formed in the polyamide separation layer, and meanwhile, the nanoparticles contain a large amount of reactive groups and dopamine components, and the particles can be uniformly and stably distributed in the polyamide separation layer, so that the obtained zinc-coordinated organic nanoparticle hybrid polyamide membrane has high water permeability, high separation selectivity of organic molecules, and good stability.
Example 4:
dissolving 0.2g N-aminoethyl piperazine, 0.3g of zinc nitrate hexahydrate and 0.15g of dopamine in 100g of deionized water to prepare a water-phase mixed solution, dipping the water-phase mixed solution on the surface of a polysulfone ultrafiltration membrane for 40 minutes at 25 ℃, further dipping the surface of the polysulfone ultrafiltration membrane for 30 minutes by using a 2-methylimidazole water solution with the mass percentage concentration of 0.3% at 25 ℃ to obtain a zinc-containing coordination organic nanoparticle nascent state membrane, then dipping the membrane into a trimesoyl chloride cyclohexane solution with the mass percentage concentration of 0.5%, carrying out interface crosslinking reaction for 2 minutes at 25 ℃, finally curing for 30 minutes at 50 ℃, and washing the membrane by using deionized water to obtain the zinc-containing coordination organic nanoparticle hybrid polyamide membrane.
The zinc-containing coordination organic nano particle hybrid polyamide film is at 25 ℃, and under the pressure of 0.2MPa, for 1g.L-1The separation result of the Congo red and basic blue organic dye solution is as follows: the water flux is 85.8L.m-2.h-1.bar-1The rejection rate for congo red is 96.5%, and the rejection rate for basic blue is 24.6%.
Example 5:
dissolving 1g of m-phenylenediamine, 0.5g of zinc nitrate hexahydrate and 0.2g of dopamine in 100g of deionized water to prepare a water-phase mixed solution, dip-coating the water-phase mixed solution on the surface of a polyether sulfone ultrafiltration membrane for 30 minutes at 25 ℃, further performing immersion treatment for 60 minutes at 25 ℃ by using a 2-methylimidazole water solution with the mass percentage concentration of 0.5% to obtain a zinc-containing coordination organic nanoparticle nascent state membrane, then dipping the zinc-containing coordination organic nanoparticle nascent state membrane into a trimesoyl chloride cyclohexane solution with the mass percentage concentration of 1%, performing interface crosslinking reaction for 2 minutes at 25 ℃, finally curing for 15 minutes at 50 ℃, and washing by using deionized water to obtain the zinc-containing coordination organic nanoparticle hybrid polyamide membrane.
The zinc-containing coordination organic nano particle hybrid polyamide film is at 25 ℃, and under the pressure of 0.2MPa, for 1g.L-1The separation result of the Congo red and basic blue organic dye solution is as follows: water flux of 82.5L.m-2.h-1.bar-1The rejection rate for congo red is 98.5%, and the rejection rate for basic blue is 28.5%.
Example 6:
dissolving 1g of ethylenediamine, 0.6g of zinc nitrate hexahydrate and 0.1g of dopamine in 100g of deionized water to prepare a water-phase mixed solution, dip-coating the water-phase mixed solution on the surface of a polyether sulfone ultrafiltration membrane for 30 minutes at 25 ℃, further performing immersion treatment on the surface of the polyether sulfone ultrafiltration membrane for 30 minutes at 25 ℃ by using a 2-methylimidazole water solution with the mass percentage concentration of 4% to obtain a zinc-containing coordination organic nanoparticle nascent state membrane, then immersing the zinc-containing coordination organic nanoparticle nascent state membrane into a isophthaloyl chloride n-hexane solution with the mass percentage concentration of 0.5%, performing interface crosslinking reaction for 5 minutes at 25 ℃, finally curing for 30 minutes at 50 ℃, and washing the zinc-containing coordination organic nanoparticle hybrid polyamide membrane by using deionized water.
The zinc-containing coordination organic nano particle hybrid polyamide film is at 25 ℃, and under the pressure of 0.2MPa, for 1g.L-1The separation result of the Congo red and basic blue organic dye solution is as follows: water flux of 90.7L.m-2.h-1.bar-1The rejection rate for congo red is 95.5%, and the rejection rate for basic blue is 19.6%.
Example 7:
dissolving 1.5g of 1,3, 5-triaminobenzene, 0.5g of zinc nitrate hexahydrate and 0.2g of dopamine in 100g of deionized water to prepare a water-phase mixed solution, dipping the mixed solution on the surface of a polyacrylonitrile ultrafiltration membrane for 10 minutes at 25 ℃, further dipping the mixed solution for 40 minutes at 25 ℃ by using a 2-methylimidazole water solution with the mass percentage concentration of 5% to obtain a zinc-containing coordination organic nanoparticle nascent state membrane, then dipping the membrane into a biphenyl tetracarboxyl chloride heptane solution with the mass percentage concentration of 0.2%, carrying out interface crosslinking reaction for 5 minutes at 25 ℃, finally curing for 30 minutes at 60 ℃, and washing by using deionized water to obtain the zinc-containing coordination organic nanoparticle hybrid polyamide membrane.
The zinc-containing coordination organic nano particle hybrid polyamide film is at 25 ℃, and under the pressure of 0.2MPa, for 1g.L-1The separation result of the Congo red and basic blue organic dye solution is as follows: the water flux is 106.2L.m-2.h-1.bar-1The rejection rate for congo red was 97.8%, and the rejection rate for basic blue was 26.5%.
Example 8:
dissolving 1g of p-phenylenediamine, 0.6g of zinc nitrate hexahydrate and 0.2g of dopamine in 100g of deionized water to prepare a water-phase mixed solution, dip-coating the water-phase mixed solution on the surface of a polysulfone ultrafiltration membrane for 60 minutes at 25 ℃, further performing immersion treatment for 30 minutes at 25 ℃ by using a 2-methylimidazole water solution with the mass percentage concentration of 2% to obtain a zinc-containing coordination organic nanoparticle nascent state membrane, then dipping the zinc-containing coordination organic nanoparticle nascent state membrane into a phthaloyl chloride n-hexane solution with the mass percentage concentration of 0.5%, performing interface cross-linking reaction for 5 minutes at 25 ℃, finally curing for 40 minutes at 50 ℃, and washing by using deionized water to obtain the zinc-containing coordination organic nanoparticle hybrid polyamide membrane.
The zinc-containing coordination organic nano particle hybrid polyamide film is at 25 ℃, and under the pressure of 0.2MPa, for 1g.L-1The separation result of the Congo red and basic blue organic dye solution is as follows: the water flux is 96.8L.m-2.h-1.bar-1The rejection rate for congo red is 94.8%, and the rejection rate for basic blue is 20.5%.

Claims (10)

1. A preparation method of a zinc coordination organic nanoparticle hybrid polyamide membrane is characterized by comprising the following steps: the method comprises the following steps:
1) preparing a water-phase mixed solution by using polyamine as a monomer molecule, zinc nitrate hexahydrate as a metal ion compound and dopamine as a bionic adhesive, dip-coating the water-phase mixed solution on the surface of a porous support membrane, and carrying out dipping treatment on the porous support membrane by using a 2-methylimidazole water solution to form a zinc-containing coordination organic nanoparticle nascent state membrane on the surface of the porous support membrane in situ;
2) dissolving a polybasic acyl chloride monomer in an organic solvent to prepare an organic phase solution, dip-coating the organic phase solution on the surface of the nascent-state membrane loaded with the zinc coordination organic nano particles to perform interface crosslinking reaction, performing thermocuring treatment, and finally washing by deionized water to obtain a zinc coordination organic nano particle hybrid polyamide membrane;
the polyamine monomer molecule in the step 1) is piperazine, N-aminoethyl piperazine, ethylenediamine, m-phenylenediamine, p-phenylenediamine or 1,3, 5-triaminobenzene; the polybasic acyl chloride monomer in the step 2) is phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesoyl chloride or biphenyl tetracarboxyl chloride.
2. The method of claim 1, wherein: the mass percentage concentration of polyamine monomer molecules in the water phase mixed solution in the step 1) is 0.2-2%.
3. The method of claim 1, wherein: the mass percentage concentration of the zinc nitrate hexahydrate in the water-phase mixed solution in the step 1) is 0.1-1%.
4. The method of claim 1, wherein: the mass percentage concentration of the dopamine in the water-phase mixed solution in the step 1) is 0.05-0.5%.
5. The method of claim 1, wherein: the porous support membrane in the step 1) is a flat ultrafiltration membrane made of polysulfone, polyethersulfone, polyacrylonitrile or polyvinylidene fluoride.
6. The method of claim 1, wherein: the dip-coating condition of the water-phase mixed solution in the step 1) is dip-coating for 10-60 minutes at 15-25 ℃.
7. The method of claim 1, wherein: the mass percentage concentration of the 2-methylimidazole water solution in the step 1) is 0.5-5%; the dipping treatment condition is dipping for 10-100 minutes at 15-25 ℃.
8. The method of claim 1, wherein: the mass percentage concentration of the molecules of the polybasic acyl chloride monomer in the organic phase solution in the step 2) is 0.1-1%.
9. The method of claim 1, wherein: the solvent of the organic phase solution in the step 2) is n-hexane, cyclohexane or heptane.
10. The method of claim 1, wherein: the condition for carrying out the interfacial crosslinking reaction by dip coating the organic phase solution in the step 2) is that the reaction is carried out for 2-10 minutes at 15-25 ℃; the thermosetting treatment condition is curing for 10-40 minutes at 45-65 ℃.
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