CN112657343A - Polyamide hollow fiber composite separation membrane and preparation method thereof - Google Patents
Polyamide hollow fiber composite separation membrane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polyamide hollow fiber composite separation membrane and a preparation method thereof. The method comprises the following steps: a) preparing a high polymer hollow fiber porous support membrane containing amine monomers by a thermally induced phase separation method: mixing a high polymer, a diluent and an amine monomer to be used as a membrane casting solution, preparing a hollow fiber membrane by an extruder, cooling, solidifying and forming a membrane, and extracting the diluent in the membrane by using an extracting agent to obtain a high polymer hollow fiber porous support membrane containing the amine monomer; b) immersing the porous support membrane of the high polymer hollow fiber obtained in the step a) into an oil phase acyl chloride monomer solution, taking out and drying to obtain the polyamide hollow fiber composite separation membrane with a polyamide layer. According to the invention, the amine monomer is mixed in the membrane casting solution and uniformly dispersed on the surface of the prepared support layer, so that a thinner and more uniform polyamide layer can be prepared, the binding force between the polyamide separation layer and the support layer can be effectively improved, and the stability of the hollow fiber composite membrane structure is improved.
Description
Technical Field
The invention relates to a polyamide hollow fiber composite separation membrane and a preparation technology thereof, in particular to a method for preparing the polyamide hollow fiber composite separation membrane by a thermal induced phase separation method and an interface polymerization method integrated process and the polyamide hollow fiber composite separation membrane prepared by the method.
Background
The membrane technology has the functions of separation, concentration, purification and the like, is widely applied to the fields of food, medicine, biology, environmental protection, chemical industry, water treatment and the like, and becomes one of the most important means in the separation science at present. Among them, nanofiltration and reverse osmosis have been receiving more and more attention due to their high desalting ability. Nanofiltration and reverse osmosis are both pressure-driven membranes, and compared with the traditional thermal desalination technology, the method has the advantages of no phase change in the separation process, high separation efficiency, small occupied area, simplicity in operation and the like. At present, most of commercial nanofiltration and reverse osmosis membranes are roll-type composite membranes which are composed of a non-woven fabric enhancement layer, a high-molecular porous support layer and a polyamide separation layer, and the problems of poor pollution resistance, difficult cleaning, high requirement on the quality of inlet water and the like generally exist in the application process. Compared with the prior art, the hollow fiber nanofiltration/reverse osmosis membrane combines the characteristics of nanofiltration/reverse osmosis membranes and hollow fiber membranes, is in a self-supporting structure, has the advantages of high packing density, strong pollution resistance, high recovery rate, easiness in cleaning, low replacement cost and the like, and is one of the hot spots of the nanofiltration/reverse osmosis membrane research in recent years.
Commercial nanofiltration/reverse osmosis membrane products are typically made by phase inversion or interfacial polymerization processes. Patent (CN103097007B) reports a method for preparing a cellulose acetate hollow fiber reverse osmosis membrane by a phase inversion method, but the method produces a reverse osmosis membrane separation layer too thick, about 0.1 to 7 μm, resulting in low flux. The interface polymerization method can realize the preparation of the ultrathin separation layer, and is characterized in that the surface of the porous support layer is firstly immersed into an aqueous phase solution containing an amine monomer and then immersed into an oil phase solution containing an acid chloride monomer, and the polyamide separation layer is formed by polymerization at an aqueous-oil phase interface. However, the method is not suitable for continuous production of the hollow fiber composite separation membrane, because the concentration of the amine monomer in the water phase is low, the viscosity of the water phase solution is low, and the amine monomers such as PIP and the like coated on the surface of the hollow fiber membrane in the continuous production process are often uneven, so that the thickness of the finally prepared hollow fiber composite separation membrane separation layer is uneven, and the performance difference is large.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a polyamide hollow fiber composite separation membrane. The method adopts an integrated process of a Thermally Induced Phase Separation (TIPS) method and an Interfacial Polymerization (IP) method, adds an amine monomer into a casting solution for preparing a high polymer supporting layer, and uniformly distributes the amine monomer in the hollow fiber supporting layer by adding the amine monomer into the casting solution of the supporting layer in advance, thereby avoiding the problem of nonuniform distribution of an aqueous solution of the amine monomer on the surface of the hollow fiber supporting layer due to low viscosity.
The preparation method of the polyamide hollow fiber composite separation membrane comprises the following steps:
a) preparing a high polymer hollow fiber porous support membrane containing amine monomers by a thermally induced phase separation method: mixing a high polymer, a diluent and an amine monomer to be used as a membrane casting solution, preparing a hollow fiber membrane by an extruder, cooling, solidifying and forming a membrane, and extracting the diluent in the membrane by using an extracting agent to obtain a high polymer hollow fiber porous support membrane containing the amine monomer;
b) preparation of the polyamide layer: immersing the porous support membrane of the high polymer hollow fiber obtained in the step a) into an oil phase acyl chloride monomer solution, taking out and drying to obtain the polyamide hollow fiber composite separation membrane with a polyamide layer.
The invention also provides the polyamide hollow fiber composite separation membrane obtained by the preparation method.
The invention adopts the TIPS method and the IP method integrated process to prepare the polyamide hollow fiber composite separation membrane, firstly the TIPS method is used to prepare the amine monomer-containing high polymer hollow fiber porous support layer, then the support layer is immersed into the oil phase solution containing the acyl chloride monomer, and the acyl chloride monomer and the amine monomer on the surface of the high polymer porous support layer are subjected to polymerization reaction to generate the polyamide separation layer. Therefore, compared with the prior art, the invention has the following advantages:
1. the amine monomer is added into the porous supporting layer membrane casting solution in advance, so that the amine monomer can be uniformly dispersed in the supporting layer, the prepared polyamide layer has more uniform thickness due to good dispersibility, the performance difference of a composite membrane in continuous production can be effectively reduced, the membrane separation performance is improved, the separation precision is high, and in addition, the effective regulation and control of the thickness of the polyamide separation layer can be realized by changing the concentration of the amine monomer in the membrane casting solution;
2. amine monomers are mixed with the porous supporting layer casting solution, then the hollow fiber supporting layer is prepared by a TIPS method, and then the hollow fiber supporting layer reacts with acyl chloride monomers to form a film, so that the binding force between the supporting layer and a polyamide layer generated by reaction can be enhanced, and the strength and the operation stability of the film are improved;
3. the porous support layer is prepared by a TIPS method, has high strength and high flux and is not easy to break.
Drawings
Fig. 1 is an SEM photograph of a cross section of the polyamide hollow fiber composite nanofiltration membrane prepared in example 1 near the outer surface.
Fig. 2 is an SEM photograph of the outer surface of the polyamide hollow fiber composite nanofiltration membrane prepared in example 1.
Detailed Description
In a preferred embodiment, the preparation method of the polyamide hollow fiber composite separation membrane of the present invention is performed as follows:
in step a), preferably, 20-40% by mass of high polymer, 50-80% by mass of diluent and 0.2-5.0% by mass of amine monomer are mixed as casting solution, wherein the sum of the amounts of high polymer, diluent and amine monomer is 100%. The casting solution is preferably uniformly mixed by an extruder at 170-230 ℃ and extruded to a spinneret to form a hollow fiber membrane. The hollow fiber membrane is preferably put into a cooling water bath with the temperature of 0-50 ℃ after passing through an air section, and is solidified into a membrane.
In step b), the porous support membrane of the high polymer hollow fiber obtained in step a) is preferably immersed in an oil phase acid chloride monomer solution with a concentration of 0.001 wt% to 3 wt%, preferably for 1 to 300 s. And then, preferably drying at 30-120 ℃ for 1-60min, and rinsing with deionized water to obtain the polyamide hollow fiber composite separation membrane with the polyamide layer.
Preferably, the high polymer is one or more of polyvinylidene fluoride, cellulose acetate, polysulfone, polypropylene, polyvinyl chloride, ethylene-chlorotrifluoroethylene copolymer and polyether sulfone, and preferably polyvinylidene fluoride. Preferably, the mass fraction of the high polymer in step a) is 25% to 35%.
Preferably, the diluent is a high polymer high-temperature solvent or a mixture of the high polymer high-temperature solvent and a high polymer non-solvent, the mass fraction of the high-temperature solvent in the mixture is 40% -100%, and the mass fraction of the non-solvent is 0% -60%. The high-temperature polymer solvent is a solvent which can form a uniform solution with the high polymer in the temperature range of 170-230 ℃ and the phase separation of the uniform solution is carried out in the temperature range of 0-50 ℃. The non-solvent for the high polymer means a solvent which does not form a uniform solution with the high polymer in any temperature range.
Preferably, the high polymer high temperature solvent is one or more of benzophenone, diphenyl carbonate, methyl benzoate, ethyl benzoate, triacetin, diethylene glycol ethyl ether acetate, methyl salicylate, diethylene glycol ethyl ether, triethyl citrate, 1, 2-propylene carbonate, acetophenone, cyclohexanone, gamma-butyrolactone, methyl isoamyl ketone, caprolactam or phthalate; the polymer non-solvent is one or a mixture of more of 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-hexadecanol, 1-octadecanol, 1-eicosanol, 1-tetracosanol, 1, 2-propanediol, 1, 3-propanediol, glycerol, benzyl alcohol, sorbitol, mannitol, diethylene glycol, triethylene glycol, tetraethylene glycol or 2-hydroxy-2-phenylacetophenone.
Preferably, the mass fraction of the diluent in step a) is between 55% and 75%.
Preferably, the amine monomer for preparing the polyamide is a compound containing two or more amine groups and having a boiling point higher than 170 ℃, preferably a mixture of one or more of 1, 4-cyclohexanediamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,3, 5-triaminobenzene, N-aminoethylpiperazine, glucosamine, chitosan, polyacrylamide or polyethyleneimine. Preferably, the mass fraction of the amine monomer in step a) is 1% to 4%.
The extruder may use various extruders known in the art that can be used to prepare the hollow fiber membrane, for example, a twin screw extruder. The air zone temperature is preferably 5-30 deg.C, for example 25 deg.C. The air space residence time can be chosen at will and is generally between 10 and 300 ms. The cooling bath temperature is preferably from 30 to 50 ℃ for example 30 ℃ and the residence time in the cooling bath is generally from 0.1 to 10 s.
Preferably, the extractant is one or more of water, methanol, ethanol, propanol, n-butanol or isobutanol.
Preferably, the acid chloride monomer is a compound containing two or more acid chloride groups, preferably one or more of trimesoyl chloride, terephthaloyl chloride, and biphenyltetracarboxyl chloride.
Preferably, the concentration of acid chloride monomer in the oil phase acid chloride monomer solution is from 0.01 wt% to 1 wt%. By selecting the concentration of the acyl chloride monomer, the compactness and the thickness of the separation layer can be influenced, and then the interception rate and the flux of the membrane can be regulated and controlled.
The oil phase solvent is a non-polar organic solvent, preferably cyclohexane, n-hexane, heptane, octane, naphtha or a mixture of one or more of ISOPAR series, such as n-hexane, toluene or ISOPAR series. By selecting the oil phase solvent, the diffusion rate of the amine monomer in the interfacial polymerization process can be changed, and then the regulation and control of the separation layer structure are realized.
Preferably, the temperature of the oil phase acyl chloride monomer solution in the step b) is 10-40 DEG C
Preferably, the drying temperature in the step b) is 40-100 ℃, and the drying time is 3-60 min.
By controlling the temperature of the oil-phase acyl chloride monomer solution in the step b) and the drying temperature, namely the temperature of the amine monomer and the acyl chloride monomer during reaction, the interfacial polymerization rate can be controlled, and the compactness of the prepared separation layer is further influenced.
The polyamide hollow fiber composite separation membrane of the present invention can be used as a reverse osmosis membrane or a nanofiltration membrane according to its separation performance. Preferably, the polyamide hollow fiber composite separation membrane has a retention rate of 260mg/L NaCl solution of not less than 98% under a test pressure of 0.41MPa, and is suitable for being used as a reverse osmosis membrane.
Preferably, another polyamide hollow fiber composite separation membrane of the invention is used for CaSO under the test pressure of 0.41MPa4Retention rate of>95% retention rate for NaCl<30 percent, can realize the effective separation of divalent ions and is suitable for being used as a nanofiltration membrane.
The present invention will be described in detail with reference to specific examples, but the present invention is not limited to the description of the examples.
In a membrane separation performance test experiment, the prepared hollow fiber reverse osmosis membranes are pre-pressed by pure water for more than half an hour under the condition of 0.41MPa, and the pure water flux is measured after the flux is stable. The membrane was then tested for desalting performance with 260mg/L NaCl solution.
The prepared hollow fiber nanofiltration membranes are all pre-pressed by pure water for more than half an hour under the condition of 0.41MPa, and the pure water flux is measured after the flux is stable. Then adding 260mg/L of CaSO4The solution and 260mg/L NaCl solution are respectively used for testing the separation performance of the membrane on different valence salts.
The pure water flux and the retention rate of the membrane are respectively calculated as shown in (1) and (2):
J＝V/A/t (1)
wherein J is the pure water flux of the membrane (L/(m)2H)), A is the effective membrane area (m)2) T is the permeate time (h), and V is the volume (L) of permeate collected during the predetermined time t hours.
R＝(Cf-Cp)/Cp×100％ (2)
Wherein R is the rejection of the membrane, CfAs the concentration of the feed solution, CpIs the permeate concentration. Wherein the concentration of the inorganic salt solution is determined by conductivityAnd (6) measuring by an instrument.
Example 1
The preparation method of the polyamide hollow fiber composite reverse osmosis membrane comprises the following steps:
1) preparing a polyvinylidene fluoride hollow fiber porous support membrane containing m-phenylenediamine by a thermally induced phase separation method: mixing polyvinylidene fluoride with the mass fraction of 20%, diphenyl carbonate with the mass fraction of 75% and m-phenylenediamine with the mass fraction of 5.0% to serve as a casting solution, uniformly mixing at 220 ℃ through a double-screw extruder, extruding the mixture to a spinning nozzle to form a hollow fiber membrane, allowing the hollow fiber membrane to pass through a room-temperature air section, then entering a cooling water bath with the temperature of 25 ℃ for 3 seconds, curing to form a membrane, extracting a diluent in the membrane with ethanol, and drying to obtain a polyvinylidene fluoride hollow fiber porous support membrane containing m-phenylenediamine;
2) preparation of the polyamide layer: immersing the polyvinylidene fluoride hollow fiber porous support membrane in the step 1) into a normal hexane solution of oil phase trimesoyl chloride with the concentration of 0.25 weight percent and the temperature of 30 ℃ for 120s, drying for 10min at the temperature of 80 ℃, and rinsing with deionized water to obtain the polyamide hollow fiber composite reverse osmosis membrane.
Example 2
A polyamide hollow fiber composite reverse osmosis membrane is prepared, wherein in the step of 1) preparing a polyvinylidene fluoride hollow fiber porous support membrane containing m-phenylenediamine by a thermally induced phase separation method in example 1, the mass fraction of polyvinylidene fluoride is increased to 40%, the mass fraction of diphenyl carbonate is reduced to 55%, and other conditions are not changed.
Example 3
A polyamide hollow fiber composite reverse osmosis membrane was prepared by increasing the trimesoyl chloride concentration to 1 wt% in the preparation step of the 2) polyamide layer of example 1, with the other conditions being unchanged.
Example 4
A polyamide hollow fiber composite reverse osmosis membrane was prepared by reducing the immersion time to 15s in the step of preparing the 2) polyamide layer of example 1, with the other conditions being unchanged.
Example 5
A polyamide hollow fiber composite reverse osmosis membrane was prepared by setting the drying temperature at 40 ℃ in the preparation step of the 2) polyamide layer in example 1, and the other conditions were not changed.
Example 6
A polyamide hollow fiber composite reverse osmosis membrane was prepared by setting the drying time in the preparation step of the 2) polyamide layer in example 1 to 60min, with the other conditions being unchanged.
Example 7
A polyamide hollow fiber composite reverse osmosis membrane is prepared, wherein the cooling water bath temperature in the step of preparing the polyvinylidene fluoride hollow fiber porous support membrane containing the m-phenylenediamine by the thermally induced phase separation method 1) in example 1 is set to be 50 ℃, and other conditions are not changed.
Example 8
A polyamide hollow fiber composite reverse osmosis membrane was prepared by replacing the oil phase solvent with n-heptane in the step of preparing the 2) polyamide layer in example 1, and the other conditions were not changed.
Example 9
A polyamide hollow fiber composite reverse osmosis membrane was prepared by lowering the temperature of the oil phase solution in the step of preparing the 2) polyamide layer of example 1 to 0 ℃ without changing other conditions.
Comparative example 1
1) Preparing a polyvinylidene fluoride hollow fiber porous support membrane by a thermally induced phase separation method: mixing 20% of polyvinylidene fluoride and 80% of diphenyl carbonate as casting solution, uniformly mixing at 220 ℃ by using a double-screw extruder, extruding to a spinning nozzle to form a hollow fiber membrane, entering a cooling water bath with the temperature of 25 ℃ after passing through an air section, staying for 3s, solidifying to form a membrane, extracting a diluent in the membrane by using an extractant ethanol, and drying to obtain a polyvinylidene fluoride hollow fiber porous support membrane;
2) preparation of the polyamide layer: immersing the polyvinylidene fluoride hollow fiber porous support membrane in the step 1) into a m-phenylenediamine aqueous solution with the concentration of 5 wt% for 120s, taking out the solution, removing a surface residual solution, immersing the polyvinylidene fluoride hollow fiber porous support membrane in a n-hexane solution of trimesoyl chloride with the concentration of 0.1 wt% and the temperature of 30 ℃ for 120s, drying the solution at 80 ℃ for 10min, and rinsing the solution with deionized water to obtain the polyamide hollow fiber composite reverse osmosis membrane prepared by interfacial polymerization.
The pure water flux and NaCl rejection performance of the reverse osmosis membranes prepared in examples 1 to 9 and comparative example 1 were compared. As shown in table 1, the performance of the polyamide hollow fiber membrane can be controlled by changing the conditions in the method. Compared with the performance of the composite membrane prepared in the comparative example 1, the polyamide hollow fiber composite membrane prepared by the method has better salt rejection rate.
TABLE 1
| Pure water flux L.m-2·h-1 | Retention rate of NaCl | |
| Example 1 | 49 | 99.1％ |
| Example 2 | 38 | 98.8％ |
| Example 3 | 41 | 99.3％ |
| Example 4 | 74 | 91.9％ |
| Example 5 | 55 | 98.6％ |
| Example 6 | 43 | 99.1％ |
| Example 7 | 48 | 99.0％ |
| Example 8 | 46 | 99.2％ |
| Example 9 | 62 | 92.7％ |
| Comparative example 1 | 71 | 92.1％ |
Example 10
The preparation method of the polyamide hollow fiber composite nanofiltration membrane comprises the following steps:
1) preparing a polyvinylidene fluoride hollow fiber porous support membrane containing polyethyleneimine by a thermally induced phase separation method: mixing 30 mass percent of polyvinylidene fluoride, 65 mass percent of diphenyl carbonate and 5.0 mass percent of polyethyleneimine to form a membrane casting solution, uniformly mixing the membrane casting solution at 220 ℃ through a double-screw extruder, extruding the membrane casting solution to a spinning nozzle to form a hollow fiber membrane, allowing the hollow fiber membrane to pass through an air section, then entering a cooling water bath at 25 ℃ for 3 seconds, curing the membrane to form a membrane, extracting a diluent in the membrane with an extractant ethanol, and drying the membrane to obtain a polyvinylidene fluoride hollow fiber porous support membrane containing polyethyleneimine;
2) preparation of the polyamide layer: immersing the polyvinylidene fluoride hollow fiber porous support membrane in the step 1) into an ISOPAR solution of an oil-phase trimesoyl chloride monomer with the concentration of 0.1 weight percent and the temperature of 30 ℃ for 120s, drying for 10min at the temperature of 80 ℃, and rinsing with deionized water to obtain the polyamide hollow fiber composite nanofiltration membrane.
Example 11
The preparation method of the polyamide hollow fiber composite nanofiltration membrane comprises the steps of reducing the mass fraction of polyethyleneimine to 1% and increasing the mass fraction of diphenyl carbonate to 69% in the step of preparing the polyvinylidene fluoride hollow fiber porous support membrane containing polyethyleneimine by the thermally induced phase separation method in example 10, wherein other conditions are not changed.
Example 12
The preparation method of the polyamide hollow fiber composite nanofiltration membrane is characterized in that polyethyleneimine is changed into chitosan in the step of preparing the polyvinylidene fluoride hollow fiber porous support membrane by the thermally induced phase separation method in the embodiment 10, and other conditions are not changed.
Example 13
The preparation method of the polyamide hollow fiber composite nanofiltration membrane comprises the steps of changing polyvinylidene fluoride into polysulfone in the step of preparing the hollow fiber porous support membrane containing polyethyleneimine by the thermally induced phase separation method in the step 1) in the embodiment 10, increasing the mixing temperature of an extruder to 230 ℃, and keeping other conditions unchanged.
Example 14
A polyamide hollow fiber composite nanofiltration membrane is prepared, wherein trimesoyl chloride in the step of preparing the polyamide layer 2) in the example 10 is changed into biphenyltetracarboxylic acid chloride, and other conditions are not changed.
Example 15
A polyamide hollow fiber composite nanofiltration membrane was prepared, in which the trimesoyl chloride concentration in the step of preparing the polyamide layer 2) in example 10 was reduced to 0.005 wt%, and the other conditions were not changed.
Comparative example 2
The preparation method of the polyamide hollow fiber composite nanofiltration membrane comprises the following steps:
1) preparing a polyvinylidene fluoride hollow fiber porous support membrane by a thermally induced phase separation method: mixing 20% of polyvinylidene fluoride and 80% of diphenyl carbonate as casting solution, uniformly mixing at 220 ℃ by using a double-screw extruder, extruding to a spinning nozzle to form a hollow fiber membrane, entering a cooling water bath with the temperature of 25 ℃ after passing through an air section, staying for 3s, solidifying to form a membrane, extracting a diluent in the membrane by using an extractant ethanol, and drying at 60 ℃ to obtain a polyvinylidene fluoride hollow fiber porous support membrane;
2) preparation of the polyamide layer: immersing the polyvinylidene fluoride hollow fiber porous support membrane in the step 1) into a polyethyleneimine water solution with the concentration of 3 wt% for 120s, taking out the polyvinylidene fluoride hollow fiber porous support membrane, removing a surface residual solution, immersing the polyvinylidene fluoride hollow fiber porous support membrane in an ISOPAR solution of trimesoyl chloride with the concentration of 0.1 wt% and the temperature of 30 ℃ for 120s, drying the solution at 80 ℃ for 10min, and rinsing the solution with deionized water to obtain the polyamide hollow fiber composite nanofiltration membrane prepared by interfacial polymerization.
Pure water flux to nanofiltration membranes prepared in examples 10 to 15 and comparative example 2 and pure water flux to CaSO4The retention performance was compared with that of NaCl. As shown in Table 2, the nanofiltration membrane prepared by the method of the invention has good water flux and CaSO resistance4Has better selective retention performance with NaCl.
TABLE 2
Claims (11)
1. A preparation method of a polyamide hollow fiber composite separation membrane comprises the following steps:
a) preparing a high polymer hollow fiber porous support membrane containing amine monomers by a thermally induced phase separation method: mixing a high polymer, a diluent and an amine monomer to be used as a membrane casting solution, preparing a hollow fiber membrane by an extruder, cooling, solidifying and forming a membrane, and extracting the diluent in the membrane by using an extracting agent to obtain a high polymer hollow fiber porous support membrane containing the amine monomer;
b) preparation of the polyamide layer: immersing the porous support membrane of the high polymer hollow fiber obtained in the step a) into an oil phase acyl chloride monomer solution, taking out and drying to obtain the polyamide hollow fiber composite separation membrane with a polyamide layer.
2. The method of claim 1, comprising the steps of:
a) preparing a high polymer hollow fiber porous support membrane containing amine monomers by a thermally induced phase separation method: mixing 20-40% of high polymer by mass, 50-80% of diluent by mass and 0.2-5.0% of amine monomer by mass as membrane casting liquid, uniformly mixing at the temperature of 170-230 ℃ by an extruder, extruding the mixture to a spinning nozzle to form a hollow fiber membrane, introducing the hollow fiber membrane into a cooling water bath at the temperature of 0-50 ℃ after passing through an air section, solidifying the hollow fiber membrane to form a membrane, and extracting the diluent in the membrane by using an extractant to obtain the amine monomer-containing high polymer hollow fiber porous support membrane, wherein the sum of the usage amounts of the high polymer, the diluent and the amine monomer is 100%;
b) preparation of the polyamide layer: immersing the porous support membrane of the high polymer hollow fiber obtained in the step a) into an oil phase acyl chloride monomer solution with the concentration of 0.001-3 wt% for 1-300s, drying at 30-120 ℃ for 1-60min, and rinsing with deionized water to obtain the polyamide hollow fiber composite separation membrane with a polyamide layer.
3. The method of claim 2, wherein: the high polymer is one or a mixture of polyvinylidene fluoride, cellulose acetate, polysulfone, polypropylene, polyethylene, polyvinyl chloride, ethylene-chlorotrifluoroethylene copolymer and polyether sulfone.
4. The method according to claim 2, wherein the diluent is a high polymer high temperature solvent or a mixture of the high polymer high temperature solvent and a high polymer non-solvent, the mass fraction of the high polymer high temperature solvent in the mixture is 40% -100%, and the mass fraction of the high polymer non-solvent is 0% -60%.
5. The method according to claim 4, wherein the high polymer high temperature solvent is a mixture of one or more of benzophenone, diphenyl carbonate, methyl benzoate, ethyl benzoate, triacetin, diethylene glycol ethyl ether acetate, methyl salicylate, diethylene glycol ethyl ether, triethyl citrate, propylene 1, 2-carbonate, acetophenone, cyclohexanone, γ -butyrolactone, methyl isoamyl ketone, caprolactam, or phthalates; the polymer non-solvent is one or a mixture of more of 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-hexadecanol, 1-octadecanol, 1-eicosanol, 1-tetracosanol, 1, 2-propanediol, 1, 3-propanediol, glycerol, benzyl alcohol, sorbitol, mannitol, diethylene glycol, triethylene glycol, tetraethylene glycol or 2-hydroxy-2-phenylacetophenone.
6. The method according to claim 2, wherein the amine monomer is a compound having two or more amine groups and a boiling point higher than 170 ℃, preferably a mixture of one or more of 1, 4-cyclohexanediamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,3, 5-triaminobenzene, N-aminoethylpiperazine, glucosamine, chitosan, polyacrylamide, or polyethyleneimine.
7. The method according to claim 2, wherein the acid chloride monomer is a compound containing two or more acid chloride groups, preferably a mixture of one or more of trimesoyl chloride, terephthaloyl chloride, and biphenyltetracarboxylic acid chloride; the solvent of the oil phase acyl chloride monomer solution is a non-polar organic solvent, preferably one or a mixture of cyclohexane, n-hexane, heptane, octane, naphtha or ISOPAR series.
8. The process according to claim 2, wherein the molar ratio of acid chloride monomer to amine monomer is from 1:100 to 1:1, preferably from 1:20 to 1: 5.
9. A polyamide hollow fiber composite separation membrane prepared according to the method of any one of claims 1 to 8.
10. The polyamide hollow fiber composite separation membrane according to claim 9, which is a reverse osmosis membrane and has a retention rate of 260mg/L NaCl solution of not less than 98% at a test pressure of 0.41 MPa.
11. The polyamide hollow fiber composite separation membrane according to claim 9, characterized in that it is a nanofiltration membrane and it is resistant to CaSO at a test pressure of 0.41MPa4Retention rate of>95% retention rate for NaCl<30％。
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| CN113856472A (en) * | 2021-10-26 | 2021-12-31 | 天津工业大学 | High-flux polyamide hollow fiber nanofiltration membrane and preparation method thereof |
| CN114130218A (en) * | 2021-12-10 | 2022-03-04 | 山东招金膜天股份有限公司 | Polyamide reverse osmosis membrane and preparation method thereof |
| CN114504955A (en) * | 2022-03-10 | 2022-05-17 | 北京师范大学 | Method for preparing polymer porous membrane by low-temperature thermally-induced phase separation and product thereof |
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| CN114504955A (en) * | 2022-03-10 | 2022-05-17 | 北京师范大学 | Method for preparing polymer porous membrane by low-temperature thermally-induced phase separation and product thereof |
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