CN112090282A - High-selectivity polyamide nanofiltration membrane and preparation method thereof - Google Patents
High-selectivity polyamide nanofiltration membrane and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high-selectivity polyamide nanofiltration membrane and a preparation method thereof, wherein the high-selectivity polyamide nanofiltration membrane consists of a porous support base membrane and a polyamide separation layer; the polyamide separation layer is prepared by polymerizing a polybasic acyl chloride organic solution and an aqueous solution of 1, 4-diazepan or a mixture thereof on the surface interface of a porous supporting basement membrane; the high-selectivity polyamide nanofiltration membrane has excellent primary and divalent salt selectivity and water flux, and is expected to have wide application prospect in the fields of wastewater salt separation and recycling, seawater desalination and drinking water purification.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a high-selectivity polyamide nanofiltration membrane and a preparation method thereof.
Background
In the membrane separation process, the difference of selective permeability of each component of the separation membrane is utilized, so that the separation and purification of solutes and solvents in the components are realized. Nanofiltration membranes are a functional semipermeable membrane that allows the permeation of solvent molecules or certain low molecular weight solutes or low valent ions. At present, in practical application, the nanofiltration membrane separation technology faces many challenges, wherein the development of a nanofiltration membrane with high water flux and high selectivity is a hotspot and difficulty in the separation membrane and water treatment fields.
The interfacial polymerization method is a method commonly adopted for preparing commercial nanofiltration membranes at present, and the polyamide nanofiltration membranes prepared by the interfacial polymerization method have the advantages of high water flux and good interception performance, and are widely used in the field of water treatment. However, the prior commercial polyamide nanofiltration membrane still has the problems of low selectivity of the primary and the divalent salts and insufficient water flux.
In recent years, domestic and foreign technology researchers have conducted a series of effective research works in the aspects of improving the selectivity and water flux of the nanofiltration membrane based on the interfacial polymerization reaction, and the research mainly comprises the research of an interfacial polymerization reaction process regulation and control method, the construction of a mixed matrix separation layer with an ion selective channel, the regulation and control of polyamide surface structure efficiency and the design of novel polymeric monomer molecules. Wherein, the development or selection of novel polymeric monomer is the fundamental requirement for improving the water flux of the polyamide nanofiltration membrane and the selectivity of the mono-salt and the divalent salt.
Chinese patent CN108452689A discloses a high-selectivity full-alicyclic polyamide nanofiltration membrane and a preparation method thereof, wherein at least one alicyclic acyl chloride solution and at least one alicyclic amine solution are alternately and uniformly coated on a porous support membrane by adopting a standing method or a spin coating method for interfacial polymerization to form at least one layer of full-alicyclic polyamide nanofiltration membrane.
1, 4-diazepan or homopiperazine (CAS number: 505-66-8), a seven-membered nitrogen-containing heterocycle, is a common water-soluble pharmaceutical intermediate. From the chemical structure, the homopiperazine has two secondary amines with high reaction activity, and can meet the membrane preparation requirement of interfacial polymerization; from the perspective of molecular space structure, compared with the traditional piperazine molecule, the cyclic alkyl chain of the 1, 4-diazepan or homopiperazine molecule is extended, and the space structure forms a twisted chair-type structure. The stacking density of polyamide polymer chains formed by interfacial polymerization can be reduced due to the increase of the distance between two reaction sites and the change of the spatial configuration, so that a nanofiltration membrane separation layer with improved aperture and pore and higher flux can be obtained. In view of the above, the present invention provides a high selectivity polyamide nanofiltration membrane and a preparation method thereof.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a high-selectivity polyamide nanofiltration membrane and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme.
The invention relates to a high-selectivity polyamide nanofiltration membrane, which is characterized in that: it is formed by compounding a porous supporting base membrane and a polyamide separation layer; the polyamide separating layer is formed by polymerizing polyacyl chloride solution and 1, 4-diazepane or water solution of the mixture thereof on the surface of a porous supporting base membrane.
The high-selectivity polyamide nanofiltration membrane comprises: the polybasic acyl chloride is at least one of phthaloyl chloride, paraphthaloyl chloride, isophthaloyl chloride, trimesoyl chloride, 5-isocyanate-isophthaloyl chloride or 5-oxoformyl chloride-isophthaloyl chloride; the content of the polybasic acyl chloride in the organic solvent is 0.01% (w/v) to 5.0% (w/v); the organic solvent used for preparing the polyacyl chloride solution is one or more of aliphatic hydrocarbon, alicyclic hydrocarbon and aromatic hydrocarbon containing 6 to 14 carbon atoms, and also comprises isoalkane (IsoPar) series solvent;
the 1, 4-diazepan mixture is prepared by mixing 1, 4-diazepan with at least one of piperazine, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminopiperazine, 1, 4-bis (3-aminopropyl) piperazine, N-aminoethyl piperazine, 4-aminomethyl piperazine, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3, 5-diaminobenzoic acid, polyethyleneimine, dopamine, triethylamine, camphorsulfonic acid, sodium hydroxide, hydrochloric acid, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate and phosphoric acid; the content of 1, 4-diazepane in the water phase is 0.01% (w/v) to 10.0% (w/v), and the content of other monomers or auxiliary agents in the water phase is 0 to 10.0% (w/v);
the porous supporting base membrane is a porous flat membrane, a porous tubular membrane or a hollow fiber membrane which is made of polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyester fibers, polyvinyl alcohol fibers, polyetherimide, sulfonated polyether ether ketone, cellulose acetate or alloy materials thereof; the preferred range of membrane pore size is 0.001 microns to 1.0 microns.
The preparation method of the high-selectivity polyamide nanofiltration membrane is characterized by comprising the following steps of:
firstly, cleaning a porous supporting base film to ensure that no sundries remain on the surface of the porous supporting base film;
secondly, coating the surface of the porous supporting base membrane cleaned in the first step with 1, 4-diazepane or a mixture water solution thereof for 1s to 30 min;
removing aqueous phase solution and liquid drops remained on the surface of the porous support base membrane treated in the second step by air blowing, airing, erasing, solvent displacement and the like;
fourthly, coating the surface of the porous support base membrane treated in the third step with polyacyl chloride solution, and carrying out interfacial polymerization reaction to form a polyamide separation layer, wherein the polymerization reaction time is 1 s-30 min;
fifthly, after draining or purging the residual organic solution, placing the porous support base membrane subjected to the interfacial polymerization reaction in the fourth step in a closed environment for post-treatment, wherein the temperature of the closed environment is 5-90 ℃, and the post-treatment time is 1 s-30 min, so as to obtain the high-selectivity polyamide nanofiltration membrane;
and sixthly, washing the post-treated high-selectivity polyamide nanofiltration membrane in the fifth step by using deionized water, and storing the high-selectivity polyamide nanofiltration membrane in the deionized water or carrying out conventional protection treatment on the high-selectivity polyamide nanofiltration membrane.
In the preparation method of the high-selectivity polyamide nanofiltration membrane, the polybasic acyl chloride is at least one of phthaloyl chloride, terephthaloyl chloride, isophthaloyl chloride, trimesoyl chloride, 5-isocyanate-isophthaloyl chloride or 5-oxoformyl chloride-isophthaloyl chloride; the content of the polybasic acyl chloride in the organic solvent is 0.01% (w/v) to 5.0% (w/v); the organic solvent used for preparing the polyacyl chloride solution is one or more of aliphatic hydrocarbon, alicyclic hydrocarbon and aromatic hydrocarbon containing 6 to 14 carbon atoms, and also comprises isoalkane (IsoPar) series solvent; the temperature of the coating of the polyacyl chloride organic solution during the interfacial polymerization reaction is-20 ℃ to 50 ℃.
In the preparation method of the high-selectivity polyamide nanofiltration membrane, the 1, 4-diazepan mixture is prepared by mixing 1, 4-diazepan with at least one of piperazine, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminopiperazine, 1, 4-bis (3-aminopropyl) piperazine, N-aminoethyl piperazine, 4-aminomethyl piperazine, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3, 5-diaminobenzoic acid, polyethyleneimine, dopamine, triethylamine, camphorsulfonic acid, sodium hydroxide, hydrochloric acid, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate and phosphoric acid; the content of 1, 4-diazepane in the water phase is 0.01% (w/v) to 10.0% (w/v), the content of other monomers or auxiliary agents in the water phase is 0 to 10.0% (w/v), and the temperature of the water phase solution is 0 ℃ to 35 ℃.
The preparation method of the high-selectivity polyamide nanofiltration membrane comprises the following steps: the porous supporting base membrane is a porous flat membrane, a porous tubular membrane or a hollow fiber membrane which is made of polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyester fibers, polyvinyl alcohol fibers, polyetherimide, sulfonated polyether ether ketone, cellulose acetate or alloy materials thereof; the preferred range of membrane pore size is 0.001 microns to 1.0 microns.
The invention has the beneficial effects that: the high-selectivity polyamide nanofiltration membrane is a moderately loose polyamide separation layer obtained by carrying out interfacial polymerization reaction on an aqueous phase solution consisting of 1, 4-diazepane or a mixture of the 1, 4-diazepane and other polyamines or assistants and an organic solution of polybasic acyl chloride on the surface of a supporting base membrane, and has excellent selectivity of mono-and divalent salts and water flux. The high-selectivity polyamide nanofiltration membrane disclosed by the invention has the characteristic of simple preparation process, is convenient to realize in continuous industrial production, and is expected to have wide application prospects in the aspects of wastewater salt separation and resource utilization, seawater desalination and drinking water purification.
Detailed description of the preferred embodiments
The invention relates to a high-selectivity polyamide nanofiltration membrane, which is characterized in that: it is formed by compounding a porous supporting base membrane and a polyamide separation layer; the polyamide separating layer is formed by polymerizing polyacyl chloride solution and 1, 4-diazepane or water solution of the mixture thereof on the surface of a porous supporting base membrane. The polybasic acyl chloride is at least one of phthaloyl chloride, paraphthaloyl chloride, isophthaloyl chloride, trimesoyl chloride, 5-isocyanate-isophthaloyl chloride or 5-oxoformyl chloride-isophthaloyl chloride; the content of the polybasic acyl chloride in the organic solvent is 0.01% (w/v) to 5.0% (w/v); the organic solvent used for preparing the polyacyl chloride solution is one or more of aliphatic hydrocarbon, alicyclic hydrocarbon and aromatic hydrocarbon containing 6 to 14 carbon atoms, and also includes isoalkane (IsoPar) series solvent. The 1, 4-diazepane mixture is prepared by mixing 1, 4-diazepane with at least one of piperazine, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminopiperazine, 1, 4-bis (3-aminopropyl) piperazine, N-aminoethyl piperazine, 4-aminomethyl piperazine, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3, 5-diaminobenzoic acid, polyethyleneimine, dopamine, triethylamine, camphorsulfonic acid, sodium hydroxide, hydrochloric acid, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate and phosphoric acid; the content of 1, 4-diazepane in the water phase is 0.01% (w/v) to 10.0% (w/v), and the content of other monomers or auxiliary agents in the water phase is 0 to 10.0% (w/v); the porous supporting base membrane is a porous flat membrane, a porous tubular membrane or a hollow fiber membrane which is made of polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyester fibers, polyvinyl alcohol fibers, polyetherimide, sulfonated polyether ether ketone, cellulose acetate or alloy materials thereof; the preferred range of membrane pore size is 0.001 microns to 1.0 microns.
The preparation method of the high-selectivity polyamide nanofiltration membrane is characterized by comprising the following steps of: firstly, cleaning a porous supporting base film to ensure that no sundries remain on the surface of the porous supporting base film; secondly, coating the surface of the porous supporting base membrane cleaned in the first step with 1, 4-diazepane or a mixture water solution thereof for 1s to 30 min; removing aqueous phase solution and liquid drops remained on the surface of the porous support base membrane treated in the second step by air blowing, airing, erasing, solvent displacement and the like; fourthly, coating the surface of the porous support base membrane treated in the third step with polyacyl chloride solution, and carrying out interfacial polymerization reaction to form a polyamide separation layer, wherein the polymerization reaction time is 1 s-30 min; fifthly, after draining or purging the residual organic solution, placing the porous support base membrane subjected to the interfacial polymerization reaction in the fourth step in a closed environment for post-treatment, wherein the temperature of the closed environment is 5-90 ℃, and the post-treatment time is 1 s-30 min, so as to obtain the high-selectivity polyamide nanofiltration membrane; and sixthly, washing the post-treated high-selectivity polyamide nanofiltration membrane in the fifth step by using deionized water, and storing the high-selectivity polyamide nanofiltration membrane in the deionized water or performing conventional protection treatment on the high-selectivity polyamide nanofiltration membrane.
Wherein the polybasic acyl chloride is at least one of phthaloyl chloride, paraphthaloyl chloride, isophthaloyl chloride, trimesoyl chloride, 5-isocyanate-isophthaloyl chloride or 5-oxoformyl chloride-isophthaloyl chloride; the content of the polybasic acyl chloride in the organic solvent is 0.01% (w/v) to 5.0% (w/v); the organic solvent used for preparing the polyacyl chloride solution is one or more of aliphatic hydrocarbon, alicyclic hydrocarbon and aromatic hydrocarbon containing 6 to 14 carbon atoms, and also comprises isoalkane (IsoPar) series solvent; the temperature of the coating of the polyacyl chloride organic solution during the interfacial polymerization reaction is-20 ℃ to 50 ℃. The 1, 4-diazepane mixture is prepared by mixing 1, 4-diazepane with at least one of piperazine, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminopiperazine, 1, 4-bis (3-aminopropyl) piperazine, N-aminoethyl piperazine, 4-aminomethyl piperazine, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3, 5-diaminobenzoic acid, polyethyleneimine, dopamine, triethylamine, camphorsulfonic acid, sodium hydroxide, hydrochloric acid, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate and phosphoric acid; the content of 1, 4-diazepane in the water phase is 0.01% (w/v) to 10.0% (w/v), the content of other monomers or auxiliary agents in the water phase is 0 to 10.0% (w/v), and the temperature of the water phase solution is 0 ℃ to 35 ℃. The porous supporting base membrane is a porous flat membrane, a porous tubular membrane or a hollow fiber membrane which is made of polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyester fibers, polyvinyl alcohol fibers, polyetherimide, sulfonated polyether ether ketone, cellulose acetate or alloy materials thereof; the preferred range of membrane pore size is 0.001 microns to 1.0 microns.
In the following examples, the test of the high selectivity polyamide nanofiltration membrane of the present invention uses an operating pressure of 0.35MPa, and the raw material solutions are 1g/L NaCl aqueous solution and 1g/L Na aqueous solution2SO4An aqueous solution; the performance evaluation of the nanofiltration membrane included rejection and water flux.
The rejection characterizes the selectivity of the membrane, which is defined by the formula: r is 100 (C)f-Cp)/Cf (1)
(1) In the formula CfAs the concentration of the feed solution, CpThe concentration of the permeate was used. The concentration of the salt solution was determined by measuring the conductance by a conductivity meter and a salt concentration-conductivity scale.
The water flux characterizes the permeability of the membrane, which is defined by the formula: f ═ V/At (2)
(2) Wherein V is the volume (L) of the permeation solution of the permeation membrane, and A is the effective membrane area (m)2) And t is the running time (h).
In the following examples, the values of retention and flux are taken as the average of 3 samples.
In examples 1 to 14 and comparative example 1, a polyvinyl chloride hollow fiber ultrafiltration membrane was used as a base membrane, the inner/outer diameter of the membrane filaments was 1.0/1.7mm, the molecular weight cut-off was 10 ten thousand daltons, and a polyamide separation layer was formed on the inner surface of the membrane filaments.
Example 1
Preparing a 0.3% (w/v) 1, 4-diazepan aqueous phase solution and a 0.3% (w/v) trimesoyl chloride n-hexane solution. Introducing a water phase solution into the inner cavity of the hollow fiber membrane wire, wherein the coating time of the water phase solution is 5min, blowing air on the surface of the membrane after water phase coating to remove residual water drops, and blowing air for 5 min; slowly putting the purged hollow membrane component into an organic phase solution for reaction for 2min, wherein the temperature of the organic phase is 25 ℃, putting the hollow membrane component into an environment at 25 ℃ for post-treatment for 15min after the reaction is finished, and then storing the membrane component in deionized water to be detected.
Example 2
Preparing a 0.3% (w/v) 1, 4-diazepan aqueous phase solution and a 0.3% (w/v) trimesoyl chloride n-hexane solution. Introducing a water phase solution into the inner cavity of the hollow fiber membrane wire, wherein the coating time of the water phase solution is 5min, blowing air on the surface of the membrane after water phase coating to remove residual water drops, and blowing air for 5 min; slowly putting the purged hollow membrane component into an organic phase solution for reaction for 2min, wherein the temperature of the organic phase is 25 ℃, putting the hollow membrane component into an environment of 60 ℃ for post-treatment for 15min after the reaction is finished, and then storing the membrane component in deionized water to be detected.
Example 3
Preparing a 0.1% (w/v) 1, 4-diazepan aqueous phase solution and a 0.3% (w/v) trimesoyl chloride n-hexane solution. Introducing a water phase solution into the inner cavity of the hollow fiber membrane wire, wherein the coating time of the water phase solution is 5min, blowing air on the surface of the membrane after water phase coating to remove residual water drops, and blowing air for 5 min; slowly putting the purged hollow membrane component into an organic phase solution for reaction for 2min, wherein the temperature of the organic phase is 25 ℃, putting the hollow membrane component into an environment of 60 ℃ for post-treatment for 15min after the reaction is finished, and then storing the membrane component in deionized water to be detected.
Example 4
Preparing a 0.5% (w/v) aqueous phase solution of 1, 4-diazepan and a 0.3% (w/v) n-hexane solution of trimesoyl chloride. Introducing a water phase solution into the inner cavity of the hollow fiber membrane wire, wherein the coating time of the water phase solution is 5min, blowing air on the surface of the membrane after water phase coating to remove residual water drops, and blowing air for 5 min; slowly putting the purged hollow membrane component into an organic phase solution for reaction for 2min, wherein the temperature of the organic phase is 25 ℃, putting the hollow membrane component into an environment of 60 ℃ for post-treatment for 15min after the reaction is finished, and then storing the membrane component in deionized water to be detected.
Example 5
Preparing a 0.8% (w/v) aqueous phase solution of 1, 4-diazepan and a 0.3% (w/v) n-hexane solution of trimesoyl chloride. Introducing a water phase solution into the inner cavity of the hollow fiber membrane wire, wherein the coating time of the water phase solution is 5min, blowing air on the surface of the membrane after water phase coating to remove residual water drops, and blowing air for 5 min; slowly putting the purged hollow membrane component into an organic phase solution for reaction for 2min, wherein the temperature of the organic phase is 25 ℃, putting the hollow membrane component into an environment of 60 ℃ for post-treatment for 15min after the reaction is finished, and then storing the membrane component in deionized water to be detected.
Example 6
1, 4-diazepan aqueous phase solution with the concentration of 1.0 percent (w/v) and trimesoyl chloride n-hexane solution with the concentration of 0.3 percent (w/v) are prepared. Introducing a water phase solution into the inner cavity of the hollow fiber membrane wire, wherein the coating time of the water phase solution is 5min, blowing air on the surface of the membrane after water phase coating to remove residual water drops, and blowing air for 5 min; slowly putting the purged hollow membrane component into an organic phase solution for reaction for 2min, wherein the temperature of the organic phase is 25 ℃, putting the hollow membrane component into an environment of 60 ℃ for post-treatment for 15min after the reaction is finished, and then storing the membrane component in deionized water to be detected.
TABLE 1 influence of Heat treatment and high piperazine concentration on the separation Performance of nanofiltration membranes
Example 7
Preparing a 0.3% (w/v) 1, 4-diazepan aqueous phase solution and a 0.3% (w/v) trimesoyl chloride n-hexane solution. Introducing a water phase solution into the inner cavity of the hollow fiber membrane wire, wherein the coating time of the water phase solution is 5min, blowing air on the surface of the membrane after water phase coating to remove residual water drops, and blowing air for 5 min; slowly putting the purged hollow membrane component into an organic phase solution for reaction for 30s, wherein the temperature of the organic phase is 25 ℃, putting the hollow membrane component into an environment of 60 ℃ for post-treatment for 15min after the reaction is finished, and then storing the membrane component in deionized water to be detected.
Example 8
Preparing a 0.3% (w/v) 1, 4-diazepan aqueous phase solution and a 0.3% (w/v) trimesoyl chloride n-hexane solution. Introducing a water phase solution into the inner cavity of the hollow fiber membrane wire, wherein the coating time of the water phase solution is 5min, blowing air on the surface of the membrane after water phase coating to remove residual water drops, and blowing air for 5 min; slowly putting the purged hollow membrane component into an organic phase solution for reaction for 60s, wherein the temperature of the organic phase is 25 ℃, putting the hollow membrane component into an environment at 60 ℃ for post-treatment for 15min after the reaction is finished, and then storing the membrane component in deionized water to be detected.
Example 9
Preparing a 0.3% (w/v) 1, 4-diazepan aqueous phase solution and a 0.3% (w/v) trimesoyl chloride n-hexane solution. Introducing a water phase solution into the inner cavity of the hollow fiber membrane wire, wherein the coating time of the water phase solution is 5min, blowing air on the surface of the membrane after water phase coating to remove residual water drops, and blowing air for 5 min; slowly putting the purged hollow membrane component into an organic phase solution for reaction for 90s, wherein the temperature of the organic phase is 25 ℃, putting the hollow membrane component into an environment of 60 ℃ for post-treatment for 15min after the reaction is finished, and then storing the membrane component in deionized water to be detected.
TABLE 2 Effect of interfacial polymerization time on nanofiltration Membrane separation Performance
Example 10
Preparing a 0.3% (w/v) 1, 4-diazepan aqueous phase solution and a 0.3% (w/v) trimesoyl chloride n-hexane solution. Introducing a water phase solution into the inner cavity of the hollow fiber membrane wire, wherein the coating time of the water phase solution is 5min, blowing air on the surface of the membrane after water phase coating to remove residual water drops, and blowing air for 5 min; slowly putting the purged hollow membrane component into an organic phase solution for reaction for 2min, wherein the temperature of the organic phase is 0 ℃, putting the hollow membrane component into an environment of 60 ℃ for post-treatment for 15min after the reaction is finished, and then storing the membrane component in deionized water to be detected.
Example 11
Preparing a 0.3% (w/v) 1, 4-diazepan aqueous phase solution and a 0.3% (w/v) trimesoyl chloride n-hexane solution. Introducing a water phase solution into the inner cavity of the hollow fiber membrane wire, wherein the coating time of the water phase solution is 5min, blowing air on the surface of the membrane after water phase coating to remove residual water drops, and blowing air for 5 min; slowly putting the purged hollow membrane component into an organic phase solution for reaction for 2min, wherein the temperature of the organic phase is-10 ℃, putting the hollow membrane component into an environment of 60 ℃ for post-treatment for 15min after the reaction is finished, and then storing the membrane component in deionized water to be detected.
TABLE 3 influence of temperature of organic phase solution on separation performance of nanofiltration membrane
Example 12
Preparing an aqueous phase solution with the molar ratio of 1, 4-diazepane to piperazine being 1:1 and the total molar concentration being 30mmol/L and a trimesoyl chloride n-hexane solution with the concentration being 0.3% (w/v). Introducing a water phase solution into the inner cavity of the hollow fiber membrane wire, wherein the coating time of the water phase solution is 5min, blowing air on the surface of the membrane after water phase coating to remove residual water drops, and blowing air for 5 min; slowly putting the purged hollow membrane component into an organic phase solution for reaction for 2min, wherein the temperature of the organic phase is 25 ℃, putting the hollow membrane component into an environment of 60 ℃ for post-treatment for 15min after the reaction is finished, and then storing the membrane component in deionized water to be detected. Comparative example 1
Preparing an equimolar (30mmol/L) piperazine aqueous solution and a 0.3% (w/v) trimesoyl chloride n-hexane solution. Introducing a water phase solution into the inner cavity of the hollow fiber membrane wire, wherein the coating time of the water phase solution is 5min, blowing air on the surface of the membrane after water phase coating to remove residual water drops, and blowing air for 5 min; slowly putting the purged hollow membrane component into an organic phase solution for reaction for 2min, wherein the temperature of the organic phase is 25 ℃, putting the hollow membrane component into an environment of 60 ℃ for post-treatment for 15min after the reaction is finished, and then storing the membrane component in deionized water to be detected.
TABLE 4 Effect of aqueous solution composition on nanofiltration Membrane separation Performance
Example 13
Preparing a 0.3% (w/v) 1, 4-diazepan aqueous phase solution and a 0.1% (w/v) trimesoyl chloride n-hexane solution. Introducing a water phase solution into the inner cavity of the hollow fiber membrane wire, wherein the coating time of the water phase solution is 5min, blowing air on the surface of the membrane after water phase coating to remove residual water drops, and blowing air for 5 min; slowly putting the purged hollow membrane component into an organic phase solution for reaction for 2min, wherein the temperature of the organic phase is 25 ℃, putting the hollow membrane component into an environment of 60 ℃ for post-treatment for 15min after the reaction is finished, and then storing the membrane component in deionized water to be detected.
Example 14
Preparing a 0.3% (w/v) 1, 4-diazepan aqueous phase solution and a 0.5% (w/v) trimesoyl chloride n-hexane solution. Introducing a water phase solution into the inner cavity of the hollow fiber membrane wire, wherein the coating time of the water phase solution is 5min, blowing air on the surface of the membrane after water phase coating to remove residual water drops, and blowing air for 5 min; slowly putting the purged hollow membrane component into an organic phase solution for reaction for 2min, wherein the temperature of the organic phase is 25 ℃, putting the hollow membrane component into an environment of 60 ℃ for post-treatment for 15min after the reaction is finished, and then storing the membrane component in deionized water to be detected.
TABLE 5 influence of organic phase monomer concentration on nanofiltration Membrane separation Performance
Example 15
The internal pressure hollow fiber polysulfone ultrafiltration membrane with the molecular weight cutoff of 5 ten thousand daltons is used as a base membrane to prepare the polyamide nanofiltration membrane, the internal/external diameter of the membrane filament is 0.8/1.0mm, and other membrane preparation conditions are consistent with those of the embodiment 2.
Example 16
The internal pressure hollow fiber polyethersulfone ultrafiltration membrane with the molecular weight cutoff of 5 ten thousand daltons is used as a base membrane to prepare the polyamide nanofiltration membrane, the internal/external diameter of the membrane is 0.8/1.0mm, and other membrane preparation conditions are consistent with those in the embodiment 2.
Example 17
The internal pressure hollow fiber polyvinylidene fluoride ultrafiltration membrane with the molecular weight cutoff of 10 ten thousand daltons is used as a base membrane to prepare the polyamide nanofiltration membrane, the internal/external diameter of the membrane filament is 0.8/1.0mm, and other membrane preparation conditions are consistent with those in the embodiment 2.
Example 18
Taking a polyvinyl chloride flat membrane with the molecular weight cutoff of 2.0 ten thousand daltons as a base membrane, and preparing a 0.3% (w/v) 1, 4-diazepane aqueous phase solution and a 0.3% (w/v) trimesoyl chloride n-hexane solution. Fixing a PVC membrane on a glass plate, immersing the PVC membrane in a water phase solution, coating the water phase solution for 5min, blowing the surface of the membrane with air to remove residual water drops after coating the water phase, and blowing with air for 5 min; and slowly putting the membrane after purging into an organic phase solution for reaction for 2min, wherein the temperature of the organic phase is 25 ℃, putting the membrane into an environment of 60 ℃ for post-treatment for 15min after the reaction is finished, and then storing the membrane in deionized water to be detected.
TABLE 6 nanofiltration Membrane separation Performance of different base membranes
Table 7 compares the separation performance of commercial nanofiltration membranes and nanofiltration membranes reported in the literature
As can be seen from the separation performance of the nanofiltration membranes in the above examples and comparative examples, and the commercial nanofiltration membranes in Table 7 and the nanofiltration membranes reported in the literature, the interfacial polymerization of an aqueous solution of 1, 4-diazepan or a mixture thereof with other polyamines or adjuvants and an organic solution of a polybasic acid chloride on the surface of a supporting base membrane under various process conditions can provide Na-para-ion2SO4Having a high retention rate of>95.0%), nano-filter membrane with NaCl interception rate lower than 15% and good water flux. Compared with the traditional polypiperazine amide nanofiltration membrane, the nanofiltration membrane has better selectivity of the mono-salt and the divalent salt.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications, equivalent variations and modifications of the above embodiments, including the optimization of the reaction system by the conventional interfacial polymerization regulation technology, are within the scope of the present invention.
Claims (6)
1. A high selectivity polyamide nanofiltration membrane is characterized in that: it is formed by compounding a porous supporting base membrane and a polyamide separation layer; the polyamide separating layer is formed by polymerizing polyacyl chloride solution and 1, 4-diazepane or water solution of the mixture thereof on the surface of a porous supporting base membrane.
2. The high selectivity polyamide nanofiltration membrane according to claim 1, wherein: the polybasic acyl chloride is at least one of phthaloyl chloride, paraphthaloyl chloride, isophthaloyl chloride, trimesoyl chloride, 5-isocyanate-isophthaloyl chloride or 5-oxoformyl chloride-isophthaloyl chloride; the content of the polybasic acyl chloride in the organic solvent is 0.01% (w/v) to 5.0% (w/v); the organic solvent used for preparing the polyacyl chloride solution is one or more of aliphatic hydrocarbon, alicyclic hydrocarbon and aromatic hydrocarbon containing 6 to 14 carbon atoms, and also comprises isoalkane (IsoPar) series solvent;
the 1, 4-diazepan mixture is prepared by mixing 1, 4-diazepan with at least one of piperazine, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminopiperazine, 1, 4-bis (3-aminopropyl) piperazine, N-aminoethyl piperazine, 4-aminomethyl piperazine, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3, 5-diaminobenzoic acid, polyethyleneimine, dopamine, triethylamine, camphorsulfonic acid, sodium hydroxide, hydrochloric acid, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate and phosphoric acid; the content of 1, 4-diazepane in the water phase is 0.01% (w/v) to 10.0% (w/v), and the content of other monomers or auxiliary agents in the water phase is 0 to 10.0% (w/v);
the porous supporting base membrane is a porous flat membrane, a porous tubular membrane or a hollow fiber membrane which is made of polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyester fibers, polyvinyl alcohol fibers, polyetherimide, sulfonated polyether ether ketone, cellulose acetate or alloy materials thereof; the preferred range of membrane pore size is 0.001 microns to 1.0 microns.
3. The preparation method of the high-selectivity polyamide nanofiltration membrane as claimed in claim 1, wherein the preparation method comprises the following steps:
firstly, cleaning a porous supporting base film to ensure that no sundries remain on the surface of the porous supporting base film;
secondly, coating the surface of the porous supporting base membrane cleaned in the first step with 1, 4-diazepane or a mixture water solution thereof for 1s to 30 min;
removing aqueous phase solution and liquid drops remained on the surface of the porous support base membrane treated in the second step by air blowing, airing, erasing, solvent displacement and the like;
fourthly, coating the surface of the porous support base membrane treated in the third step with polyacyl chloride solution, and carrying out interfacial polymerization reaction to form a polyamide separation layer, wherein the polymerization reaction time is 1 s-30 min;
fifthly, after draining or purging the residual organic solution, placing the porous support base membrane subjected to the interfacial polymerization reaction in the fourth step in a closed environment for post-treatment, wherein the temperature of the closed environment is 5-90 ℃, and the post-treatment time is 1 s-30 min, so as to obtain the high-selectivity polyamide nanofiltration membrane;
and sixthly, washing the post-treated high-selectivity polyamide nanofiltration membrane in the fifth step by using deionized water, and storing the high-selectivity polyamide nanofiltration membrane in the deionized water or carrying out conventional protection treatment on the high-selectivity polyamide nanofiltration membrane.
4. The method for preparing the high-selectivity polyamide nanofiltration membrane according to claim 3, wherein the poly-acyl chloride is at least one of phthaloyl chloride, terephthaloyl chloride, isophthaloyl chloride, trimesoyl chloride, 5-isocyanate-isophthaloyl chloride or 5-oxoformyl chloride-isophthaloyl chloride; the content of the polybasic acyl chloride in the organic solvent is 0.01% (w/v) to 5.0% (w/v);
the organic solvent used for preparing the polyacyl chloride solution is one or more of aliphatic hydrocarbon, alicyclic hydrocarbon and aromatic hydrocarbon containing 6 to 14 carbon atoms, and also comprises isoalkane (IsoPar) series solvent;
the temperature of the coating of the polyacyl chloride organic solution during the interfacial polymerization reaction is-20 ℃ to 50 ℃.
5. The method for preparing a high-selectivity polyamide nanofiltration membrane according to claim 3, wherein the 1, 4-diazepan mixture is 1, 4-diazepan and piperazine, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminopiperazine, 1, 4-bis (3-aminopropyl) piperazine, N-aminoethylpiperazine, 4-aminomethylpiperazine, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3, 5-diaminobenzoic acid, polyethyleneimine, dopamine, triethylamine, camphorsulfonic acid, sodium hydroxide, hydrochloric acid, sodium phosphate, disodium hydrogen phosphate, sodium hydrogen phosphate, or mixtures thereof, Mixing at least one of sodium dihydrogen phosphate and phosphoric acid; the content of 1, 4-diazepane in the water phase is 0.01% (w/v) to 10.0% (w/v), the content of other monomers or auxiliary agents in the water phase is 0 to 10.0% (w/v), and the temperature of the water phase solution is 0 ℃ to 35 ℃.
6. The preparation method of the high-selectivity polyamide nanofiltration membrane according to claim 3, wherein the preparation method comprises the following steps: the porous supporting base membrane is a porous flat membrane, a porous tubular membrane or a hollow fiber membrane which is made of polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyester fibers, polyvinyl alcohol fibers, polyetherimide, sulfonated polyether ether ketone, cellulose acetate or alloy materials thereof; the preferred range of membrane pore size is 0.001 microns to 1.0 microns.
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