CN112516814A - Preparation method of high-desalting solvent-resistant polyamide composite nanofiltration membrane - Google Patents
Preparation method of high-desalting solvent-resistant polyamide composite nanofiltration membrane Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/12—Composite membranes; Ultra-thin membranes
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- B01D67/0002—Organic membrane manufacture
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/06—Flat membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
Abstract
The invention discloses a preparation method of a high-desalting solvent-resistant polyamide composite nanofiltration membrane, which comprises the following steps: a specific diamine cross-linking agent solution is selected by a chemical cross-linking method to be cross-linked with a traditional polyimide ultrafiltration membrane for modification to form a membrane, and then the membrane is compounded with a piperazine monomer raw material and an acyl chloride monomer raw material by an interfacial polymerization method to obtain the polyamide composite nanofiltration membrane. The high-desalting solvent-resistant polyamide composite nanofiltration membrane prepared by the invention not only maintains high rejection performance to divalent salt, but also greatly improves rejection performance to monovalent salt, has strong tolerance to some organic solvents such as methanol, ethanol, normal hexane and the like, can solve the problems of low desalting rate of monovalent salt and desalting of an organic solvent system of the nanofiltration membrane in the prior art, has low cost and has important application prospect.
Description
Technical Field
The invention relates to a preparation method of an organic polymer separation membrane, in particular to a preparation method of a high-desalting solvent-resistant polyamide composite nanofiltration membrane with excellent performance.
Background
The nanofiltration membrane is a separation membrane with the pore diameter specification being consistent, the rated pore diameter is generally 1-2nm, and the nanofiltration membrane is a functional semipermeable membrane which allows solvent molecules, certain low molecular weight solutes or low valence ions to permeate. The nanofiltration membrane is named because the size of the trapped substance is about nanometer size, and can effectively trap bivalent and high-valence ions and organic molecules with relative molecular mass higher than 200. Nanofiltration membrane separation is carried out at normal temperature, has no phase change, no chemical reaction, no damage to biological activity and low cost, and is widely used for removing organic matters and chromaticity of surface water, removing hardness of underground water, partially removing soluble salt, concentrating fruit juice, separating useful substances in medicines and the like.
Nanofiltration membranes are mainly classified into asymmetric nanofiltration membranes and composite nanofiltration membranes, and the composite nanofiltration membranes have higher water permeability, higher desalination rate and smaller flow attenuation coefficient than asymmetric membranes produced by a phase inversion method, so that the composite nanofiltration membranes are widely researched. At present, the main research directions of the composite nanofiltration membrane are improvement of pollution resistance, improvement of acid-base resistance and solvent resistance and the like, and the main application directions are softening of water quality, separation of medicine components, filtration of an organic solvent and the like. However, in the fields of petrochemical industry and the like, high-salinity wastewater is usually generated, wherein the wastewater contains a small amount of organic solvent and a large amount of monovalent and divalent salts, so that the treatment and the recovery of the wastewater become very difficult, and multiple steps and multiple processes are often required to be cooperated, so that the treatment is complicated and the cost is high. Therefore, a solvent-resistant nanofiltration membrane separation technique with a high salt rejection rate is focused.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to overcome the defects of the prior art and provide a preparation method of a high-desalination solvent-resistant polyamide composite nanofiltration membrane with reasonable process design and high separation efficiency.
The technical scheme is as follows: in order to realize the purpose of the invention, the invention adopts the technical scheme that:
a preparation method of a high-desalting solvent-resistant polyamide composite nanofiltration membrane comprises the following steps:
step (1): firstly, dissolving a dried diamine monomer raw material in a corresponding available solvent, and stirring for reaction to obtain a cross-linking agent solution;
step (2): dissolving a pyromellitic polyimide raw material into a polar aprotic organic solvent, uniformly stirring, coating on a supporting layer, immersing in a non-solvent coagulation bath, and standing to prepare a polyimide composite ultrafiltration membrane;
and (3): flatly placing the polyimide composite ultrafiltration membrane prepared in the step (2) on a clean and flat glass plate, tightly pressing the customized plate frame on the surface of the polyimide composite ultrafiltration membrane, and fixing the customized plate frame by using a clamp; uniformly pouring the cross-linking agent solution obtained in the step (1) on the surface of the polyimide composite ultrafiltration membrane, and standing for reaction to obtain a polyamide composite ultrafiltration membrane; then pouring off the cross-linking agent solution, removing the plate frame and the glass plate, washing the surface of the membrane with pure water, and then soaking in the pure water for later use;
and (4): respectively dissolving anhydrous piperazine and acyl chloride monomer raw materials into pure water and an organic solvent, and uniformly stirring to respectively obtain a water phase solution and an organic phase solution;
and (5): fixing the polyamide composite ultrafiltration membrane prepared in the step (3) according to the method in the step (3), pouring the aqueous phase solution of the anhydrous piperazine prepared in the step (4) on the surface of the polyamide composite ultrafiltration membrane for reaction, pouring the aqueous phase solution, and drying in the air; then pouring the organic phase solution of acyl chloride monomer raw material on the surface of the polyamide composite ultrafiltration membrane for reaction, pouring out the organic phase solution and drying; and finally, placing the polyamide composite ultrafiltration membrane in an oven for heat treatment to obtain the polyamide composite nanofiltration membrane.
As a preferable scheme, the preparation method of the high-desalting solvent-resistant polyamide composite nanofiltration membrane comprises the following steps:
step (1): firstly, dissolving a dried diamine monomer raw material in a corresponding available solvent according to the mass concentration of 5-10%, and stirring for reaction for 1-2 hours to obtain a cross-linking agent solution;
step (2): dissolving a pyromellitic polyimide raw material into a polar aprotic organic solvent according to the mass concentration of 16-22%, uniformly stirring, coating the mixture on a supporting layer by 100-150 mu m, and immersing the supporting layer in a non-solvent coagulation bath for standing for 1-24h to prepare a polyimide composite ultrafiltration membrane;
and (3): flatly placing the polyimide composite ultrafiltration membrane prepared in the step (2) on a clean and flat glass plate, tightly pressing the customized plate frame on the surface of the polyimide composite ultrafiltration membrane, and fixing the customized plate frame by using a clamp; uniformly pouring the cross-linking agent solution obtained in the step (1) on the surface of the polyimide composite ultrafiltration membrane, and standing for 10-20min for reaction to obtain a polyamide composite ultrafiltration membrane; then pouring off the cross-linking agent solution, removing the plate frame and the glass plate, washing the surface of the membrane for 5-10min by using pure water, and then soaking in the pure water for 12-24h for later use;
and (4): respectively dissolving anhydrous piperazine and acyl chloride monomer raw materials with the mass concentration of 0.1-0.3% in pure water and an organic solvent, and stirring for 1-2h to respectively obtain a uniform water phase solution and a uniform organic phase solution;
and (5): fixing the polyamide composite ultrafiltration membrane prepared in the step (3) according to the method in the step (3), pouring the water phase solution of the anhydrous piperazine prepared in the step (4) on the surface of the polyamide composite ultrafiltration membrane for reaction for 5min, pouring the water phase solution, then airing for 1min, pouring the organic phase solution of the acyl chloride monomer raw material on the surface of the polyamide composite ultrafiltration membrane for reaction for 2min, pouring the organic phase solution, airing for 1min, and finally placing the polyamide composite ultrafiltration membrane in an oven for heat treatment for 5-10min to prepare the polyamide composite nanofiltration membrane.
Preferably, in the method for preparing the high-desalting solvent-resistant polyamide composite nanofiltration membrane, the diamine monomer raw material is selected from p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2, 5-dimethyl-p-phenylenediamine and 2,4, 6-trimethyl-m-phenylenediamine.
Preferably, the solvent in the preparation method of the high-desalting solvent-resistant polyamide composite nanofiltration membrane is selected from pure water, methanol, ethanol, diethyl ether, chloroform or a mixed solvent thereof.
Preferably, the pyromellitic polyimide in the preparation method of the high desalting and solvent resistance polyamide composite nanofiltration membrane is selected from polyimides produced by polycondensation of pyromellitic dianhydride and various aromatic diamines.
Preferably, the polar aprotic organic solvent in the preparation method of the high-desalination solvent-resistant polyamide composite nanofiltration membrane is selected from N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, the non-solvent coagulation bath in the method for preparing the high-desalting solvent-resistant polyamide composite nanofiltration membrane is pure water, methanol, ethanol or a mixed solvent thereof.
Preferably, the support layer in the preparation method of the high-desalting solvent-resistant polyamide composite nanofiltration membrane is polysulfone or polyester porous membrane.
Preferably, in the method for preparing the high-desalination solvent-resistant polyamide composite nanofiltration membrane, the acid chloride monomer is selected from trimesoyl chloride and pyromellitic chloride.
Preferably, the organic solvent in the preparation method of the high-desalting solvent-resistant polyamide composite nanofiltration membrane is selected from n-hexane and isoparaffin.
Preferably, in the preparation method of the high-desalination solvent-resistant polyamide composite nanofiltration membrane, the molar ratio of the piperazine monomer to the acyl chloride monomer in the two solutions is 1: 1.
Preferably, the heat treatment temperature in the preparation method of the high-desalting solvent-resistant polyamide composite nanofiltration membrane is 50-80 ℃.
Preferably, in the preparation method of the high-desalting solvent-resistant polyamide composite nanofiltration membrane, the polyamide composite nanofiltration membrane is a flat membrane, a hollow fiber membrane or a tubular membrane.
Process screening experiments:
1. the nature of the crosslinking agent affects the degree and rate of crosslinking and, in turn, the performance of the crosslinked film. Therefore, a plurality of diamine monomers are selected to carry out crosslinking on the membrane, and the single benzene ring diamine monomer raw material or the methyl-substituted single benzene ring diamine monomer raw material is preferably selected to be prepared into the crosslinking agent through testing the membrane performance.
Based on the cross-linking type composite nanofiltration membrane, the pure water flux and the Bovine Serum Albumin (BSA) retention rate of the membrane are considered, and the performance of the cross-linking polyamide ultrafiltration membrane is optimal and the performance of the composite nanofiltration membrane after interfacial polymerization is also optimal after screening experiments. The results of the performance tests of various crosslinked polyamide ultrafiltration membranes are as follows:
2. the type of acid chloride monomer starting material affects the formation of the polyamide layer, which in turn affects the performance of the film. Therefore, a plurality of acyl chloride monomers are selected to carry out interfacial polymerization reaction, and trimesoyl chloride and pyromellitic tetrachloryl chloride are preferably prepared into the cross-linking agent through testing the membrane performance.
On the basis, the flux of a sodium sulfate solution of the membrane and the retention rate of sodium sulfate are inspected, and after screening experiments, the performance of the polyamide nanofiltration membrane prepared by using trimesoyl chloride and pyromellitic chloride is optimal. The performance test results of the polyamide nanofiltration membrane formed by various acyl chloride monomers are as follows:
3. in order to obtain the adaptability of the composite nanofiltration membrane in various environments, such as high and low temperature environments, acid and alkali environments and the like, the invention screens the porous membrane supporting layer, preferably polysulfone membrane and polyester membrane which can resist high and low temperatures, and have acid and alkali resistance and good chemical stability.
Has the advantages that: compared with the prior art, the preparation method of the high-desalting solvent-resistant polyamide composite nanofiltration membrane provided by the invention has the following advantages:
according to the invention, a large number of tests are screened, a specific diamine is selected by a chemical crosslinking method to be crosslinked and modified with a traditional polyimide ultrafiltration membrane to form a membrane, and then the membrane is compounded by an interface polymerization method to obtain the polyamide composite nanofiltration membrane. The composite nanofiltration membrane prepared by the invention has the rejection rate of sodium chloride (NaCl) of over 99 percent at the temperature of 25 ℃ and the pressure of 0.7MPa, and has sodium sulfate (Na)2SO4) The retention rate of the catalyst is up to more than 99 percent, and the catalyst can stably run in certain organic solvent systems. Can solve the problems of multiple steps and multiple processes for treating high-salinity wastewater, complexity and higher cost in the prior art. The method has the advantages of easily obtained raw materials, simple operation, low cost and important application prospect.
Drawings
FIG. 1 is a scanning electron microscope surface view of the high desalting and solvent resistant polyamide composite nanofiltration membrane prepared by the invention.
Fig. 2 is a diagram showing the results of a filtration experiment after the high-desalting solvent-resistant polyamide composite nanofiltration membrane prepared by the invention is soaked in various solvents for one week.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not intended to limit the scope of the invention, as various equivalent modifications of the invention will occur to those skilled in the art upon reading the present disclosure and fall within the scope of the appended claims.
Example 1: a preparation method of a high-desalting solvent-resistant polyamide composite nanofiltration membrane comprises the following steps:
step (1): dissolving dry p-phenylenediamine in ethanol with the mass concentration of 10%, fully stirring for 2 hours, and standing for later use;
step (2): dissolving a pyromellitic polyimide raw material (synthesized by pyromellitic dianhydride and 4,4' -diaminodiphenyl ether) into N, N-dimethylformamide according to the mass concentration of 20%, uniformly stirring, coating the mixture on a polyester supporting layer by 120 mu m, immersing the polyester supporting layer in pure water, and standing for 24 hours to prepare a polyimide ultrafiltration membrane;
and (3): flatly placing the polyimide composite ultrafiltration membrane prepared in the step (2) on a clean and flat glass plate, tightly pressing the customized plate frame on the surface of the membrane, and fixing the customized plate frame by using a clamp. And (2) pouring the cross-linking agent solution in the step (1) on the surface of the membrane uniformly, and standing for 20min for reaction to obtain the polyamide composite ultrafiltration membrane. Then pouring off the cross-linking agent solution, removing the plate frame and the glass plate, washing the surface of the membrane for 10min by using pure water, and then soaking the membrane in the pure water for 24h for later use;
and (4): respectively dissolving anhydrous piperazine and trimesoyl chloride monomer raw materials with the mass concentration of 0.1% in pure water and isoparaffin, and stirring for 1h to respectively obtain uniform anhydrous piperazine aqueous phase solution and trimesoyl chloride monomer organic phase solution;
and (5): fixing the polyamide composite ultrafiltration membrane prepared in the step (3) according to the method in the step (3), firstly pouring the anhydrous piperazine aqueous phase solution prepared in the step (4) on the surface of the membrane for reaction for 5min, pouring the anhydrous piperazine aqueous phase solution, then airing for 1min, then pouring the trimesoyl chloride monomer organic phase solution on the surface of the membrane for reaction for 2min, pouring the trimesoyl chloride monomer organic phase solution, airing for 1min, and finally placing the membrane in an oven for heat treatment at 80 ℃ for 5min to prepare the polyamide composite nanofiltration membrane;
the cross section of the scanning electron microscope of the prepared polyamide composite nanofiltration membrane is shown in figure 1. The results of the filtration experiments after one week of soaking in various solvents are shown in figure 2.
The test results of testing the polyamide composite nanofiltration membrane are shown in table 1:
TABLE 1 Polyamide composite nanofiltration Membrane filtration experiment test results
Example 2: a preparation method of a high-desalting solvent-resistant polyamide composite nanofiltration membrane comprises the following steps:
step (1): dissolving dried m-phenylenediamine in pure water with the mass concentration of 8%, fully stirring for 2 hours, and standing for later use;
step (2): dissolving a pyromellitic polyimide raw material (synthesized by pyromellitic dianhydride and 3,3',5,5' -tetramethyl-4, 4' -diaminodiphenylmethane) into N-methylpyrrolidone according to the mass concentration of 18%, uniformly stirring, coating the mixture on a polyester supporting layer by 150 microns, immersing the polyester supporting layer in pure water containing 10% of methanol, and standing for 24 hours to prepare a polyimide ultrafiltration membrane;
and (3): flatly placing the polyimide ultrafiltration membrane prepared in the step (2) on a clean and flat glass plate, tightly pressing the customized plate frame on the surface of the membrane, and fixing the customized plate frame by using a clamp. And (2) pouring the cross-linking agent solution in the step (1) on the surface of the membrane uniformly, and standing for 15min for reaction to obtain the polyamide composite ultrafiltration membrane. Then pouring off the cross-linking agent solution, removing the plate frame and the glass plate, washing the surface of the membrane for 10min by using pure water, and then soaking the membrane in the pure water for 24h for later use;
and (4): respectively dissolving anhydrous piperazine and pyromellitic dianhydride monomer raw materials with the mass concentration of 0.15% in pure water and isoparaffin, and stirring for 1h to respectively obtain uniform anhydrous piperazine aqueous phase solution and pyromellitic dianhydride monomer organic phase solution;
and (5): fixing the polyamide composite ultrafiltration membrane prepared in the step (3) according to the method in the step (3), pouring an anhydrous piperazine aqueous phase solution on the surface of the membrane for reaction for 5min, pouring the anhydrous piperazine aqueous phase solution, drying in the air for 1min, pouring a pyromellitic chloride monomer organic phase solution on the surface of the membrane for reaction for 2min, pouring a pyromellitic chloride raw material, drying in the air for 1min, and finally placing the membrane in an oven for heat treatment at 60 ℃ for 10min to prepare the polyamide composite nanofiltration membrane;
the test results of testing the polyamide composite nanofiltration membrane are shown in table 2:
table 2 polyamide composite nanofiltration membrane filtration experiment test results
The test results in tables 1 to 2 show that the high-desalination polyamide composite nanofiltration membrane prepared by adopting the optimized raw materials and the optimized process has excellent separation efficiency and excellent solvent resistance, can overcome the defects of the prior art, and obtains very good technical effect.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (13)
1. A preparation method of a high-desalting solvent-resistant polyamide composite nanofiltration membrane is characterized by comprising the following steps:
step (1): firstly, dissolving a dried diamine monomer raw material in a corresponding available solvent, and stirring for reaction to obtain a cross-linking agent solution;
step (2): dissolving a pyromellitic polyimide raw material into a polar aprotic organic solvent, uniformly stirring, coating on a supporting layer, immersing in a non-solvent coagulation bath, and standing to prepare a polyimide composite ultrafiltration membrane;
and (3): flatly placing the polyimide composite ultrafiltration membrane prepared in the step (2) on a clean and flat glass plate, tightly pressing the customized plate frame on the surface of the polyimide composite ultrafiltration membrane, and fixing the customized plate frame by using a clamp; uniformly pouring the cross-linking agent solution obtained in the step (1) on the surface of the polyimide composite ultrafiltration membrane, and standing for reaction to obtain a polyamide composite ultrafiltration membrane; then pouring off the cross-linking agent solution, removing the plate frame and the glass plate, washing the surface of the membrane with pure water, and then soaking in the pure water for later use;
and (4): respectively dissolving anhydrous piperazine and acyl chloride monomer raw materials into pure water and an organic solvent, and uniformly stirring to respectively obtain a water phase solution and an organic phase solution;
and (5): fixing the polyamide composite ultrafiltration membrane prepared in the step (3) according to the method in the step (3), pouring the aqueous phase solution of the anhydrous piperazine prepared in the step (4) on the surface of the polyamide composite ultrafiltration membrane for reaction, pouring the aqueous phase solution, and drying in the air; then pouring the organic phase solution of acyl chloride monomer raw material on the surface of the polyamide composite ultrafiltration membrane for reaction, pouring out the organic phase solution and drying; and finally, placing the polyamide composite ultrafiltration membrane in an oven for heat treatment to obtain the polyamide composite nanofiltration membrane.
2. The preparation method of the high-desalination solvent-resistant polyamide composite nanofiltration membrane according to claim 1, which is characterized by comprising the following steps:
step (1): firstly, dissolving a dried diamine monomer raw material in a corresponding available solvent according to the mass concentration of 5-10%, and stirring for reaction for 1-2 hours to obtain a cross-linking agent solution;
step (2): dissolving a pyromellitic polyimide raw material into a polar aprotic organic solvent according to the mass concentration of 16-22%, uniformly stirring, coating the mixture on a supporting layer by 100-150 mu m, and immersing the supporting layer in a non-solvent coagulation bath for standing for 1-24h to prepare a polyimide composite ultrafiltration membrane;
and (3): flatly placing the polyimide composite ultrafiltration membrane prepared in the step (2) on a clean and flat glass plate, tightly pressing the customized plate frame on the surface of the polyimide composite ultrafiltration membrane, and fixing the customized plate frame by using a clamp; uniformly pouring the cross-linking agent solution obtained in the step (1) on the surface of the polyimide composite ultrafiltration membrane, and standing for 10-20min for reaction to obtain a polyamide composite ultrafiltration membrane; then pouring off the cross-linking agent solution, removing the plate frame and the glass plate, washing the surface of the membrane for 5-10min by using pure water, and then soaking in the pure water for 12-24h for later use;
and (4): respectively dissolving anhydrous piperazine and acyl chloride monomer raw materials with the mass concentration of 0.1-0.3% in pure water and an organic solvent, and stirring for 1-2h to respectively obtain a uniform water phase solution and a uniform organic phase solution;
and (5): fixing the polyamide composite ultrafiltration membrane prepared in the step (3) according to the method in the step (3), pouring the water phase solution of the anhydrous piperazine prepared in the step (4) on the surface of the polyamide composite ultrafiltration membrane for reaction for 5min, pouring the water phase solution, then airing for 1min, pouring the organic phase solution of the acyl chloride monomer raw material on the surface of the polyamide composite ultrafiltration membrane for reaction for 2min, pouring the organic phase solution, airing for 1min, and finally placing the polyamide composite ultrafiltration membrane in an oven for heat treatment for 5-10min to prepare the polyamide composite nanofiltration membrane.
3. The method for preparing the high desalination solvent resistance polyamide composite nanofiltration membrane according to claim 1, wherein the diamine monomer raw material in the step (1) is selected from one or a mixture of p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2, 5-dimethyl-p-phenylenediamine and 2,4, 6-trimethyl-m-phenylenediamine.
4. The method for preparing the high desalination polyamide composite nanofiltration membrane according to claim 1, wherein the solvent in the step (1) is selected from pure water, methanol, ethanol, diethyl ether, chloroform or a mixed solvent thereof.
5. The method for preparing the high desalting and solvent resistance polyamide composite nanofiltration membrane according to claim 1, wherein the pyromellitic polyimide in the step (2) is selected from polyimides prepared by polycondensation of pyromellitic dianhydride and various aromatic diamines.
6. The method for preparing the high desalination solvent resistance polyamide composite nanofiltration membrane according to claim 1, wherein the polar aprotic organic solvent in the step (2) is selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
7. The method for preparing the high desalination solvent resistance polyamide composite nanofiltration membrane according to claim 1, wherein the non-solvent coagulation bath in the step (2) is pure water, methanol, ethanol or a mixed solvent thereof.
8. The method for preparing the high desalination solvent resistance polyamide composite nanofiltration membrane according to claim 1, wherein the support layer in the step (2) is polysulfone or polyester porous membrane.
9. The method for preparing the high desalination solvent resistance polyamide composite nanofiltration membrane according to claim 1, wherein the acid chloride monomer in the step (4) is selected from trimesoyl chloride and pyromellitic chloride.
10. The method for preparing the high desalting and solvent resistant polyamide composite nanofiltration membrane according to claim 1, wherein the organic solvent in the step (4) is selected from n-hexane and isoparaffin.
11. The method for preparing the high-desalination solvent-resistant polyamide composite nanofiltration membrane according to claim 1, wherein the molar ratio of the piperazine monomer to the acyl chloride monomer in the two solutions in the step (4) is 1: 1.
12. The method for preparing the high-desalination solvent-resistant polyamide composite nanofiltration membrane according to claim 1, wherein the heat treatment temperature in the step (5) is 50-80 ℃.
13. The method for preparing the high-desalination solvent-resistant polyamide composite nanofiltration membrane according to claim 1, wherein the polyamide composite nanofiltration membrane in the step (5) is a flat membrane, a hollow fiber membrane or a tubular membrane.
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Cited By (3)
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| CN113368694A (en) * | 2021-08-11 | 2021-09-10 | 湖南澳维新材料技术有限公司 | Solvent-resistant composite nanofiltration membrane and preparation method thereof |
| CN114534515A (en) * | 2022-02-22 | 2022-05-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | Novel polyamide reverse osmosis membrane and preparation method and application thereof |
| CN115920676A (en) * | 2022-12-07 | 2023-04-07 | 中复新水源科技有限公司 | Preparation method of polyimide composite nanofiltration membrane |
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