CN114931865A - Polyamide ceramic composite nanofiltration membrane, preparation method and application thereof - Google Patents
Polyamide ceramic composite nanofiltration membrane, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a polyamide ceramic composite nanofiltration membrane, which is formed by sequentially compounding a ceramic membrane, an organic polymer intermediate layer and a selective separation layer, wherein the organic polymer intermediate layer is prepared from sodium alginate and chitosan. According to the invention, the organic polymer intermediate layer is introduced between the inorganic ceramic membrane and the separation layer, so that the surface defects and large aperture of the inorganic ceramic membrane can be improved, the composite membrane is ensured to have high interception performance, stability and anti-solvent performance while maintaining excellent permeation flux, and the intercepted molecular weight can be reduced.
Description
Technical Field
The invention belongs to the technical field of ceramic membranes, and particularly relates to a polyamide ceramic composite nanofiltration membrane, a preparation method and application thereof.
Background
In the traditional antibiotic production process, a large amount of antibiotic-containing stock solution produced by fermentation needs to be subjected to solvent extraction, and then is subjected to a series of operation processes such as water washing, acidity adjustment, reverse phase extraction, filtration, concentration and the like to finally obtain a finished product. However, in this production process, the organic solvent, acid, and alkali solution are repeatedly used, and therefore, the consumption amount is large, the process flow is lengthy, and the yield of antibiotics is low. The organic solvent is recovered by distillation method, and has high energy consumption, and is the main energy consumption section in the antibiotic production process. The use of a large amount of organic solvents may cause a series of problems of low antibiotic yield, increased antibiotic production process load, large amount of antibiotic-containing waste generated in the washing process, increased waste treatment amount and treatment difficulty, increased acid and alkali consumption, increased solvent loss and the like. Therefore, the development and design of novel antibiotic extraction technology to solve the disadvantages of the traditional production process is still a difficult challenge.
In recent years, the membrane technology is widely applied to the pharmaceutical industry due to the advantages of no phase change, low energy consumption, high efficiency, easy aggregation and the like. The nanofiltration membrane is a pressure-driven permeable membrane with separation performance between reverse osmosis and ultrafiltration, the molecular weight cutoff is usually 200-1000Da, and the nanofiltration membrane is generally used for removing organic matters and pigments in surface water, partially removing dissolved salts and extracting and concentrating useful substances in food and medicine production. The nanofiltration technology is adopted to treat the organic solvent extract to achieve the aim of concentrating the antibiotics. Meanwhile, the method has the advantages of reducing energy consumption and consumption of organic solvents, greatly improving the yield of antibiotics, simplifying the process flow and the like.
The ceramic film is mainly made of TiO with different specifications 2 、Al 2 O 3 、SiO 2 、ZrO 2 Inorganic materials are used as a supporting layer, and then a separation layer is formed by methods such as surface coating, surface graft polymerization, interfacial polymerization and the like, so that the membrane material has the advantages of high temperature resistance, high pressure resistance, solvent resistance, good permeability and stability, and excellent performance, and can be used for preparing a solvent-resistant system. Interfacial polymerization process and the use thereofThe method has the advantages of simple operation, rapid reaction, continuity and the like, can be widely applied to the technical field of membranes, and has the reaction principle that two monomers with high reaction activity are subjected to polycondensation reaction at two immiscible phase interfaces to form a thin dense layer on the surface of a ceramic membrane. However, the nanofiltration membrane has a trade-off effect of 'trade off', and the non-uniform pore size distribution on the surface of the inorganic ceramic membrane has large defects, so that a low-viscosity aqueous phase monomer quickly permeates from the surface of a support body to the inside of the support body, thereby causing the defects of a separation layer and influencing the separation performance of the nanofiltration membrane; meanwhile, the surface of the ceramic membrane is lack of charged functional groups, so that the Donnan effect is weakened, and the selective performance of the nanofiltration membrane is reduced.
In order to obtain a composite membrane with high permeability and high selectivity, researchers introduce an intermediate transition layer between an inorganic ceramic membrane and a separation layer to improve the surface appearance and properties of the inorganic ceramic membrane, and further obtain the ultrathin, compact and defect-free separation layer. The intermediate transition layer mainly comprises organic materials (dopamine, tannic acid, etc.) and inorganic materials (TiO) 2 COFs, MOFs, etc.), organic-inorganic materials (PDA-COFs, PDA @ SiO) 2 Etc.), however, the bonding force between the inorganic intermediate layer and the ceramic membrane is weak, so that the stripping phenomenon is easy to occur, and the performance of the composite membrane is influenced; the organic-inorganic intermediate layer is easy to have the phenomena of uneven distribution, easy agglomeration, easy leaching and the like of inorganic materials, and influences the selection performance of the membrane.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a polyamide ceramic composite nanofiltration membrane, wherein an organic polymer intermediate layer is introduced between an inorganic ceramic membrane and a separation layer so as to improve the surface defects and large pore diameters of the inorganic ceramic membrane and provide more reactive sites and a uniform reaction platform for subsequent interfacial polymerization.
In order to achieve the above object, the present invention adopts the following technical solutions:
the composite nanofiltration membrane is formed by sequentially compounding a ceramic membrane, an organic polymer intermediate layer and a selective separation layer, wherein the organic polymer intermediate layer comprises a sodium alginate layer and a chitosan layer which are sequentially laminated.
Preferably, the aforementioned selective separation layer is a polyamide separation layer.
A preparation method of a polyamide ceramic composite nanofiltration membrane comprises the following specific preparation steps:
s1, providing a ceramic membrane;
s2, sequentially applying a solution containing sodium alginate and a solution containing chitosan on the ceramic membrane by a layer-by-layer self-assembly method to form an organic polymer intermediate layer;
s3, preparing a selective separation layer on the surface of the organic polymer intermediate layer by an interfacial polymerization method.
Preferably, in step S1, the ceramic membrane is one of an alumina ceramic tube ultrafiltration membrane, a zirconia ceramic tube ultrafiltration membrane, a titania ceramic tube ultrafiltration membrane, or a silicon carbide ceramic tube ultrafiltration membrane; before the ceramic membrane is used, hydroxyl activation treatment is needed, the ceramic membrane is soaked in water, water enters membrane holes, and then the water on the surface is removed.
Preferably, the foregoing step S2 is specifically as follows:
(1) immersing a ceramic membrane into a solution containing sodium alginate, oscillating at constant temperature, cleaning and drying to obtain a ceramic base membrane containing a sodium alginate layer;
(2) immersing the ceramic base membrane containing the sodium alginate layer into a solution containing chitosan, oscillating at constant temperature, cleaning and drying to obtain a ceramic membrane containing the sodium alginate layer and the chitosan layer;
(2) and (3) repeating the steps (1) and (2) for multiple times to finish the application of the organic polymer intermediate layer on the ceramic membrane.
Preferably, the concentration of the sodium alginate in the solution containing the sodium alginate is 2-8 g/L, the solution further comprises 1-5 mL/100mL of glycerin and 0.2-0.7 mol/L of sodium chloride, and the pH value is 6.5; the chitosan-containing solution contains 1-2 g/L of chitosan, 1-5 mL/100mL of glycerol, 0.5-1.5 mL/100mL of acetic acid and 0.2-0.7 mol/L of sodium chloride, and the pH value is 2.0; the oscillation time in the step (1) is 10-90 min, and the oscillation time in the step (2) is 30-90 min.
Preferably, the foregoing step S3 is specifically as follows:
(1) fixing the ceramic membrane applied with the organic polymer intermediate layer on a dead-end filtering device, pouring the aqueous phase solution, and drying;
(2) carrying out interfacial polymerization reaction on the dried ceramic membrane and the organic phase monomer solution;
(3) and taking out the reacted ceramic membrane for heat treatment to obtain the polyamide ceramic composite nanofiltration membrane containing the sodium alginate/chitosan intermediate layer.
Preferably, in the step (1), the aqueous phase solution is a mixed solution of an aqueous phase monomer and an alkali liquor, the mass concentration of the aqueous phase monomer is 0.2 to 8wt%, the aqueous phase monomer is an organic matter containing a plurality of amino groups, and is selected from one or more of piperazine, m-phenylenediamine, ethylenediamine, diethylenetriamine and dopamine, and the alkali liquor is a NaOH solution, and the mass concentration of the alkali liquor is 0.1 to 0.7 wt%;
in the step (2), the organic phase monomer solution is a mixed solution of an organic phase monomer and an organic solvent, the mass concentration of the organic phase monomer solution is 0.1-0.3 wt%, the organic phase monomer is an organic matter containing a polybasic acyl chloride group and is selected from one or more of trimesoyl chloride, phthaloyl chloride or pyromellitic tetracarbonyl, and the organic solvent is one of normal hexane, cyclohexane or normal heptane; the interfacial polymerization reaction time is 10-300 s;
in the step (3), the heat treatment temperature is 20-120 ℃, and the heat treatment time is 20-40 min.
The application of the polyamide ceramic composite nanofiltration membrane in purifying and concentrating antibiotics in an organic solvent.
The application of the organic polymer intermediate layer containing sodium alginate/chitosan in improving the stability of the polyamide ceramic composite nanofiltration membrane.
The invention has the advantages that:
1. according to the invention, the sodium alginate/chitosan organic intermediate layer is constructed on the inner surface of the ceramic matrix membrane by a layer-by-layer self-assembly method, so that the large aperture and the roughness of the surface of the ceramic matrix membrane are effectively adjusted, the aperture distribution of the surface of the ceramic matrix membrane is more uniform, the formation of a uniform and continuous polyamide separation layer in an interface polymerization process is facilitated, the separation performance of the composite membrane is obviously improved, and the molecular weight cut-off can be reduced;
2. sodium alginate (mainly with negative charges) and chitosan (mainly with positive charges) can be deposited in sequence in a layer-by-layer self-assembly mode, and substances in a solution are successfully adsorbed on the surface of the ceramic ultrafiltration membrane by utilizing the interaction of anions and cations to form a stable organic polymer intermediate layer;
3. the solution containing sodium alginate is a mixed solution prepared from sodium alginate, glycerol and sodium chloride, wherein the glycerol can increase the flexibility of chitosan and sodium alginate, so that the problem of insufficient mechanical properties of the sodium alginate and chitosan due to hardness and brittleness of a formed film can be solved, the sodium chloride can increase the charge density between polyelectrolyte solutions, and further a polyelectrolyte layer can be more compact, and the sieving capability is enhanced;
4. part of amino groups on the unreacted chitosan molecules can continuously react with the unreacted acyl chloride groups, so that the binding force of the polyamide separation layer and the ceramic base membrane is enhanced, and the composite membrane has high interception performance, stability and solvent resistance while maintaining excellent permeation flux;
5. before coating sodium alginate solution, at first adopt bubble in the deionized water, be in order to let the deionized water at first inside occupy-place that forms of ceramic base film, inside subsequent sodium alginate did not enter the base film, avoided the jam in diaphragm orifice.
Drawings
FIG. 1 shows the separation performance of the polyamide ceramic composite nanofiltration membrane on different antibiotic methanol solutions;
fig. 2 is a long-time running stability test of the polyamide ceramic composite nanofiltration membrane: (a) comparative example, (b) example 1;
FIG. 3 shows the membrane morphology change after long-time running stability test of the polyamide ceramic composite nanofiltration membrane: (a) comparative example, (b) example 1;
figure 4 is the molecular weight cut-off of the polyamide ceramic composite nanofiltration membrane;
FIG. 5 is a graph of the morphology of a ceramic flake film without and with glycerol added;
FIG. 6 (1) shows a ceramic film (a), an organic polymer intermediate layer (b), and a polyamide ceramic composite filmXPS plots for filters (c); (2 organic Polymer interlayer (CM- (SA/CS) 1 ) High resolution N1s spectra; (3) polyamide ceramic composite nanofiltration membrane (CM- (SA/CS) 1 -PA) high resolution N1s spectrum;
fig. 7 shows Zeta potential test results of the ceramic membrane (a), the organic polymer intermediate layer (b), and the polyamide ceramic composite nanofiltration membrane (c).
Detailed Description
The invention is described in detail below with reference to the figures and the embodiments.
Example 1
A preparation method of a polyamide ceramic composite nanofiltration membrane comprises the following specific preparation steps:
1. preparation of ceramic membrane containing sodium alginate/chitosan intermediate layer
(1) After a ceramic membrane is subjected to hydroxyl activation operation (a ceramic base membrane is soaked in deionized water for 2 hours and then is taken out and put in a vacuum drying oven for drying for 3 hours, then is taken out and cooled for standby application), then the outer surface of a ceramic membrane tube is wrapped by a preservative film, the two sides of the ceramic membrane tube are coated with AB glue and solidified, and then the ceramic membrane tube is soaked in the deionized water for 10 minutes, so that membrane holes in the inner surface of the ceramic membrane are filled with the deionized water, and the ceramic membrane is taken out and the redundant moisture on the surface of the ceramic membrane is dried;
(2) immersing the ceramic membrane treated in the step (1) into a 2g/L solution containing sodium alginate (wherein the solution also contains 3ml/100ml of glycerol and 0.5mol/L of sodium chloride) (pH is 6.5), oscillating for 30min in a gas bath constant temperature oscillation box (25 ℃, 100rpm), taking out, washing for 2-3 times by using an electrolyte solution, and then placing in the air for drying to obtain a ceramic base membrane containing a sodium alginate layer;
(3) and (2) placing the ceramic base membrane containing the sodium alginate layer in 1g/L solution containing chitosan (wherein the solution also contains 3ml/100ml of glycerol, 0.5mol/L of sodium chloride and 1ml/100ml of acetic acid) (pH is 2.0), oscillating in a gas-bath constant-temperature oscillation box (25 ℃, 100rpm) for 30min, taking out, washing for 2-3 times by using electrolyte solution, and then placing in the air for drying to obtain the ceramic membrane containing the sodium alginate/chitosan intermediate layer.
2. Preparation of polyamide ceramic composite nanofiltration membrane
(1) Fixing a ceramic membrane containing a sodium alginate/chitosan intermediate layer on a dead-end filtering device, firstly pouring a 4 wt% aqueous phase piperazine monomer and a 0.2 wt% NaOH solution into the device, standing for 120s, pouring out the aqueous phase solution, taking out the ceramic membrane, drying in the air for 30min, and naturally drying the water on the inner surface of the ceramic membrane;
(2) fixing the dried membrane in a dead-end filtering device again, pouring an organic phase monomer trimesoyl chloride solution with the mass concentration of 0.2 wt% into the device, carrying out interfacial polymerization reaction for 120s, and taking out the ceramic membrane;
(3) and (3) placing the ceramic membrane in an oven at the temperature of 120 ℃ for heat treatment for 40min to obtain the polyamide ceramic composite membrane containing the sodium alginate/chitosan middle layer.
Example 2
The procedure of this example was the same as in example 1, except that the concentration of the sodium alginate-containing solution was 8g/L, the concentration of the chitosan-containing solution was 2g/L, and the shaking time of the sodium alginate-containing solution and the chitosan-containing solution in the gas bath constant temperature shaking chamber was 90 min.
Example 3
The preparation steps of this example are the same as those of example 1, except that the mass concentration of the aqueous piperazine monomer solution is 8wt%, and the interfacial polymerization reaction time is 300s, the heat treatment temperature is 60 ℃, and the heat treatment time is 30min when the polyamide ceramic composite nanofiltration membrane is prepared.
Example 4
The preparation steps of this example are the same as those of example 1, except that the heat treatment temperature is 20 ℃, the heat treatment time is 20min, and the interfacial polymerization reaction time is 10s when the polyamide ceramic composite nanofiltration membrane is prepared.
Comparative example 1
Compared with the example 1, the surface of the ceramic membrane does not use a layer-by-layer self-assembly mode to prepare the intermediate layer containing chitosan and sodium alginate, but directly carries out interfacial polymerization on the surface of the ceramic membrane.
(1) Fixing a ceramic membrane on a dead-end filtering device, firstly pouring a 4 wt% aqueous phase piperazine monomer and 0.2 wt% NaOH solution into the device, standing for 120s, pouring out the aqueous phase solution, taking out the ceramic membrane, drying in the air for 30min, and naturally drying the water on the surface of the ceramic membrane; (2) fixing the dried membrane in a dead-end filtering device again, pouring an organic phase monomer trimesoyl chloride solution with the mass concentration of 0.2 wt% into the device, carrying out interfacial polymerization reaction for 120s, and taking out the ceramic membrane; (3) and (3) placing the ceramic membrane in an oven at 120 ℃ for heat treatment for 40min to obtain the polyamide ceramic composite membrane.
Comparative example 2
The difference from example 1 is that: glycerol was not added to the sodium alginate-containing solution and the chitosan-containing solution, and the remaining parameters and procedures were the same. Firstly, performing experimental operation on a chitosan and sodium alginate solution without glycerol on a flat ceramic base film, then performing interfacial polymerization reaction, and standing for 3 hours under natural conditions to observe the surface morphology of the solution; secondly, changing the flat ceramic membrane into a tubular ceramic membrane, performing intermediate layer preparation on chitosan without glycerol and a chitosan solution, performing interfacial polymerization reaction, and performing performance test on the prepared composite nanofiltration membrane, wherein the morphology of the flaky ceramic membrane prepared without glycerol and with glycerol is shown in fig. 5.
Comparative example 3
The difference from example 1 is that: sodium chloride was not added to the sodium alginate-containing solution and the chitosan-containing solution, and the remaining parameters and steps were the same.
Comparative example 4
The difference from example 1 is that: only the solution containing chitosan was applied and not the solution containing sodium alginate, with the same parameters and procedure.
Comparative example 5
The difference from example 1 is that: before the solution containing sodium alginate, the ceramic membrane is not subjected to water immersion treatment, and the other parameters and steps are the same.
Test method
And (3) testing conditions: the feeding liquid is 10mg/mL alcohol solution containing antibiotics, the flow rate of the feeding liquid is 30L/h, the prepressing is carried out for 0.5h at the room temperature and the pressure of 0.6MPa, and the test is carried out at the pressure of 0.4 MPa. The antibiotic comprises any one or more of erythromycin, ampicillin, neomycin, tetracycline and aureomycin, the concentration of the raw material solution is 10mg/mL, and the solvent comprises high-carbon branched-chain alcohol such as methanol, ethanol, butanol, octanol, isopropanol, etc.
(1) The permeability of the alcohol permeation flux (J) reaction membrane is calculated according to the following formula:
wherein V is the volume (L) of the collected permeate alcohol, and A is the effective area (m) of the membrane 2 ) And t is the time (h) required to collect a volume V of alcohol permeate.
(2) The rejection (R) of the membrane reflects the separability of the membrane and is calculated as follows:
wherein, C p And C f The concentrations of solute components in the feed solution and permeate, respectively.
(3) Characterization of molecular weight cut-off
The molecular weight cut-off (MWCO) of the membrane was determined by a number of neutral organic solutes including PEG200, PEG400, PEG600, PEG1000 and PEG1500, the MWCO test procedure being similar to the performance test procedure. Different solutes (each at a concentration of 1000ppm) were mixed into deionized water and then pressed across the membrane surface at 0.2 Mpa. The solution before and after filtration was tested by gel permeation chromatography (GPC 1515, Waters, USA).
Test results
1. Rejection performance and permeate flux testing of membranes
(1) The rejection rate and the permeation flux of the composite nanofiltration membranes prepared in examples 1 to 4 and comparative example were tested, and the results are shown in tables 1 and 2, respectively:
table 1 rejection test results for composite nanofiltration membranes
| Erythromycin rejection (%) | Ampicillin rejection (%) | Aureomycin rejection (%) | |
| Example 1 | 84.81 | / | / |
| Example 2 | / | 10.13 | / |
| Example 3 | / | / | 77.8 |
| Example 4 | 51.82 | / | / |
| Comparative example 1 | 38.55 | / | / |
| Comparative example 2 | 40.05 | / | / |
| Comparative example 3 | 60.47 | / | / |
| Comparative example 4 | 44.57 | / | / |
| Comparative example 5 | 65.29 | / | / |
Table 2 permeation flux test results of composite nanofiltration membranes
As can be seen from tables 1 and 2, the composite nanofiltration membrane of the present invention has a high rejection performance while maintaining an excellent permeation flux, because when the polyamide ceramic composite membrane is prepared, amino groups on some unreacted chitosan molecules may continue to react with unreacted acyl chloride groups, so as to enhance the binding force between the polyamide separation layer and the ceramic-based membrane, and as can be seen from fig. 6, amino groups are present in the organic polymer intermediate layer. As can be seen from Table 1, the ethanol flux of the ceramic membrane in the comparative example 5 is obviously reduced, because the ceramic membrane is not pre-wetted, and the solution containing sodium alginate enters the pores of the ceramic membrane, so that the flux of the composite nanofiltration membrane is obviously reduced.
(2) The composite nanofiltration membrane prepared in example 1 was subjected to retention performance tests of different antibiotics, the antibiotic solutions were 10mg/mL methanol solutions of erythromycin, ampicillin, neomycin, tetracycline, and aureomycin, respectively, and the test results are shown in fig. 1, where the retention rate sequence of the polyamide ceramic composite nanofiltration membrane to different antibiotics is: r erythromycin > R neomycin > R chlortetracycline > R ampicillin, and its methanol permeate is a phenomenon of increase in presentation.
2. Stability testing of membranes
The composite nanofiltration membranes prepared in example 1 and the comparative example were subjected to long-term operation stability tests for 40 hours, and the test results are shown in fig. 2 and 3. As can be seen from FIG. 2(b), the ethanol flux of the composite nanofiltration membrane in example 1 is basically 80-90 LMH/bar, the retention rate for erythromycin is kept between 45-50%, and the composite nanofiltration membrane can be kept stable for a long time. As can be seen from fig. 3, the composite nanofiltration membrane in example 1 did not change the membrane morphology significantly after long-term operation. Therefore, compared with the comparative example, the composite nanofiltration membrane prepared by the invention has excellent long-term operation stability while maintaining excellent permeation flux and interception performance.
3. Molecular weight cut-off testing of membranes
The molecular weight cut-off of the composite nanofiltration membrane in example 1 and the comparative example were measured, respectively, and the test results are shown in fig. 4. As can be seen from fig. 4, the molecular weight cutoff of the composite nanofiltration membrane in example 1 is 337Da, and the molecular weight cutoff of the composite nanofiltration membrane in the comparative example is 612Da, so that the composite nanofiltration membrane prepared by the invention has a smaller molecular weight cutoff, and the performance is significantly improved, because the large pore diameter and the roughness of the surface of the ceramic-based membrane are effectively adjusted after the sodium alginate/chitosan organic intermediate layer is added, the pore diameter distribution of the surface of the ceramic-based membrane is more uniform, which is beneficial to promoting the interfacial polymerization process to form a uniform and continuous polyamide separation layer, and significantly improving the separation performance of the composite membrane.
4. Zeta potential test
The ceramic membrane, the organic polymer intermediate layer and the polyamide ceramic composite nanofiltration membrane in example 1 are respectively subjected to Zeta potential tests, and the test results are shown in fig. 7, which shows that the Zeta potential absolute value of the polyamide ceramic composite nanofiltration membrane is greater than 40, which indicates that the polyamide ceramic composite nanofiltration membrane has higher stability.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.
Claims (10)
1. The polyamide ceramic composite nanofiltration membrane is characterized by being formed by sequentially compounding a ceramic membrane, an organic polymer intermediate layer and a selective separation layer, wherein the organic polymer intermediate layer comprises a sodium alginate layer and a chitosan layer which are sequentially stacked.
2. The nanofiltration membrane according to claim 1, wherein the selective separation layer is a polyamide separation layer.
3. The preparation method of the polyamide ceramic composite nanofiltration membrane according to claim 1, which comprises the following specific preparation steps:
s1, providing a ceramic membrane;
s2, sequentially applying a solution containing sodium alginate and a solution containing chitosan on the ceramic membrane by a layer-by-layer self-assembly method to form an organic polymer intermediate layer;
s3, preparing a selective separation layer on the surface of the organic polymer intermediate layer by an interfacial polymerization method.
4. The method for preparing a polyamide ceramic composite nanofiltration membrane according to claim 3, wherein in step S1, the ceramic membrane is one of an alumina ceramic tube ultrafiltration membrane, a zirconia ceramic tube ultrafiltration membrane, a titania ceramic tube ultrafiltration membrane, or a silicon carbide ceramic tube ultrafiltration membrane; before the ceramic membrane is used, hydroxyl activation treatment is needed, the ceramic membrane is soaked in water, water enters membrane holes, and then the water on the surface is removed.
5. The preparation method of the polyamide ceramic composite nanofiltration membrane according to claim 3, wherein the step S2 comprises the following steps:
(1) immersing a ceramic membrane into a solution containing sodium alginate, oscillating at constant temperature, cleaning and drying to obtain a ceramic base membrane containing a sodium alginate layer;
(2) immersing the ceramic base membrane containing the sodium alginate layer into a solution containing chitosan, oscillating at constant temperature, cleaning and drying to obtain a ceramic membrane containing the sodium alginate layer and the chitosan layer;
(2) and (3) repeating the steps (1) and (2) for multiple times to finish the application of the organic polymer intermediate layer on the ceramic membrane.
6. The preparation method of the polyamide ceramic composite nanofiltration membrane of claim 3, wherein the concentration of sodium alginate in the solution containing sodium alginate is 2-8 g/L, further comprising 1-5 mL/100mL of glycerol and 0.2-0.7 mol/L of sodium chloride, and the pH is 6.5; the chitosan-containing solution has the concentration of 1-2 g/L, and further comprises 1-5 mL/100mL of glycerol, 0.5-1.5 mL/100mL of acetic acid and 0.2-0.7 mol/L of sodium chloride, wherein the pH value is 2.0; the oscillation time in the step (1) is 10-90 min, and the oscillation time in the step (2) is 30-90 min.
7. The preparation method of the polyamide ceramic composite nanofiltration membrane according to claim 3, wherein the step S3 is specifically as follows:
(1) fixing the ceramic membrane applied with the organic polymer intermediate layer on a dead-end filtering device, pouring the aqueous phase solution, and drying;
(2) carrying out interfacial polymerization reaction on the dried ceramic membrane and the organic phase monomer solution;
(3) and taking out the reacted ceramic membrane for heat treatment to obtain the polyamide ceramic composite nanofiltration membrane containing the sodium alginate/chitosan intermediate layer.
8. The method of claim 7, wherein in the step (1), the aqueous phase solution is a mixed solution of an aqueous phase monomer and an alkali solution, the mass concentration of the mixed solution is 0.2 to 8wt%, the aqueous phase monomer is an organic substance containing a plurality of amino groups, and is one or more selected from piperazine, m-phenylenediamine, ethylenediamine, diethylenetriamine and dopamine, and the alkali solution is a NaOH solution, and the mass concentration of the alkali solution is 0.1 to 0.7 wt%;
in the step (2), the organic phase monomer solution is a mixed solution of an organic phase monomer and an organic solvent, the mass concentration of the mixed solution is 0.1-0.3 wt%, the organic phase monomer is an organic matter containing a polybasic acyl chloride group and is selected from one or more of trimesoyl chloride, phthaloyl chloride or pyromellitic tetracarboxyl chloride, and the organic solvent is one of n-hexane, cyclohexane or n-heptane; the interfacial polymerization reaction time is 10-300 s;
in the step (3), the heat treatment temperature is 20-120 ℃, and the heat treatment time is 20-40 min.
9. The use of the polyamide ceramic composite nanofiltration membrane of claim 1 in the purification and concentration of antibiotics in organic solvents.
10. The application of the organic polymer intermediate layer containing sodium alginate/chitosan in improving the stability of the polyamide ceramic composite nanofiltration membrane.
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