CN109876681B - High-flux mixed matrix nanofiltration membrane and preparation method thereof - Google Patents
High-flux mixed matrix nanofiltration membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-flux mixed matrix nanofiltration membrane and a preparation method thereof, wherein a polysulfone ultrafiltration membrane support membrane and a zinc nitrate hexahydrate aqueous solution are immersed for a period of time and then dried; soaking the obtained film and the water-phase monomer for a period of time, and then airing to form a water-phase liquid layer; wherein the water phase monomer is piperazine; contacting the obtained film with an organic phase solution containing an active monomer for a period of time, and drying in an oven; wherein the organic phase active monomer is trimesoyl chloride; the membrane was soaked in a methanol solution containing 2-methylimidazole ligands for a period of time and then excess ligands were washed away with methanol solvent. The ZIF-8 nano particles can be dispersed at the bottom, middle and surface of a nanofiltration membrane layer by an in-situ growth method, so that the surface area of a separation layer can be increased, and the water flux is improved.
Description
Technical Field
The invention relates to the technical field of nanofiltration membranes, in particular to a high-flux mixed matrix nanofiltration membrane and a preparation method thereof.
Background
The nano particles added in the nano-filtration functional layer to modify the nano-filtration functional layer have many advantages, the added nano particles have the characteristic of simple operation, and the nano-particles are a more durable, cleaner and safer product as a nano technology in a molecular scale functional system, and become a very important means in the conventional modified nano-filtration membrane. The modification of composite films by particle filling has attracted more and more researchers' attention, and inorganic nanoparticles have also evolved from the first general particle method to nanoparticles that are less detrimental to the performance of composite films, such as: nano TiO 22Nano SiO2NaX, nano Al2O3Nano Ag, ZIF-8 and other nano particles. The Yaghi group originally developed and prepared the ZIF-8 material in the 21 st century, and the ZIF-8 zeolite imidazole framework material is prepared by respectively dissolving zinc nitrate hexahydrate and 2-methylimidazole in N, N-dimethylformamide and synthesizing by a solvothermal method. It has low density, high specific surface area, designable structure function, adjustable pore canal size, etcIs characterized in that the method is applied to various fields such as membrane separation, gas adsorption, catalysis, drug release and the like. However, the conventional particle filling method has the problem of interface compatibility between inorganic and organic materials, and the in-situ growth method is used for leading Zn to be compatible2+ can complex with water phase monomer, thus overcome the interface compatibility problem of inorganic and organic materials; meanwhile, the surface area of the mixed matrix membrane is increased, the problem of low water flux of the nanofiltration membrane in the prior art is solved, and the sewage treatment capacity of the nanofiltration membrane is improved.
Disclosure of Invention
The invention solves the technical problems that the interface polymerization mode has the defects of non-uniform film forming and surface defects, so that ZIF-8 nano particles can be dispersed at the bottom, the middle and the surface of a nanofiltration membrane layer by an in-situ growth method, and the surface area of a separation layer can be increased; at the same time due to Zn2+Can be complexed with aqueous monomers, thereby overcoming the problem of interfacial compatibility between inorganic and organic materials.
Therefore, the technical scheme adopted by the invention is as follows:
a preparation method of a high-flux mixed matrix nanofiltration membrane comprises the following steps:
(1) soaking a polysulfone ultrafiltration membrane support membrane and zinc nitrate hexahydrate aqueous solution for a period of time and then airing;
(2) soaking the film obtained in the step (1) and an aqueous phase monomer for a period of time, and then airing to form an aqueous phase liquid layer; wherein the water phase monomer is piperazine;
(3) contacting the film obtained in the step (2) with an organic phase solution containing an active monomer for a period of time, and drying in an oven; wherein the organic phase active monomer is trimesoyl chloride;
(4) soaking the membrane obtained in the step (3) in a methanol solution containing 2-methylimidazole ligand for a period of time, and washing away excessive ligand by using a methanol solvent.
Preferably, the mass fraction of the zinc nitrate hexahydrate aqueous solution in the step (1) is 0.01-10 wt%; the soaking time is 1-15 min.
Preferably, the mass fraction of the aqueous phase monomer in step (2) is 0.001-0.5 wt%; the soaking time is 1-10 min.
Preferably, the mass fraction of the organic phase reactive monomer in step (3) is 0.001-0.5 wt%; the soaking time is 1-5 min.
Preferably, the oven temperature in the step (3) is 30-80 ℃, and the drying time is 5-30 min.
Preferably, the mass fraction of the 2-methylimidazole ligand in the step (4) is 0.1-2 wt%, and the soaking time is 1-24 h.
The method can obtain a high-flux mixed matrix nanofiltration membrane.
The invention has the following effects:
(1) ZIF-8 nano-particles can be dispersed at the bottom, middle and surface of a nanofiltration membrane layer by an in-situ growth method, so that the surface area of a separation layer can be increased, and the water flux is improved.
(2) At the same time due to Zn2+Can be complexed with aqueous monomers, thereby overcoming the problem of interfacial compatibility between inorganic and organic materials.
(3) The ZIF-8 nano particle modification effectively improves the water flux of the polyamide composite membrane, and the retention rate is not reduced.
Drawings
Figure 1 is a surface view of a mixed matrix nanofiltration membrane according to example 1.
Figure 2 is a cross-sectional view of the mixed matrix nanofiltration membrane of example 2.
Figure 3 is a surface view of the nanofiltration membrane in the comparative example.
In the figure, SU8010 indicates the machine model, and se (ul) indicates that the upper probe receives the secondary electronic signal.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The following examples of the invention are further illustrated:
example 1:
film making conditions: relative humidity 40% +/-2 at 25 ℃.
(1) 1.2306g of zinc nitrate hexahydrate is weighed and dissolved in 100ml of deionized water, and the polysulfone ultrafiltration membrane support membrane and the zinc nitrate hexahydrate aqueous solution are immersed for 4min and then dried.
(2) 0.2502g of piperazine is weighed and dissolved in 100ml of deionized water, and the membrane obtained in the step (1) and the aqueous phase monomer are dried after 4min to form an aqueous phase liquid layer.
(3) 0.1003g of trimesoyl chloride is weighed and dissolved in 100ml of normal hexane, and the membrane obtained in the step (2) and the organic phase solution containing the active monomer are dried for 15min in an oven at 60 ℃.
(4) 2.7111g of 2-methylimidazole is weighed and dissolved in 300ml of methanol, and the membrane obtained in the step (3) is soaked in a methanol solution containing a 2-methylimidazole ligand for 12 hours and then is tested in a methanol solvent.
The mixed matrix nanofiltration membrane obtained in example 1 was analyzed:
the film structure was observed under an electron microscope, and the results are shown in FIG. 1:
the mixed matrix nanofiltration membrane prepared by the embodiment is loaded into a membrane performance evaluation device, and the experimental conditions are as follows: 0.6M Pa, prepressing for 1h, and controlling the concentration of sodium sulfate to be 1000 ppm; the experimental results are as follows: water flux: 99.87L/m2H hold-off: 90.51 percent.
Example 2:
film making conditions: relative humidity 40% +/-2 at 25 ℃.
(1) 1.8406g of zinc nitrate hexahydrate is weighed and dissolved in 100ml of deionized water, and the polysulfone ultrafiltration membrane support membrane and the zinc nitrate hexahydrate aqueous solution are immersed for 4min and then dried.
(2) 0.2502g of piperazine is weighed and dissolved in 100ml of deionized water, and the membrane obtained in the step (1) and the aqueous phase monomer are dried after 4min to form an aqueous phase liquid layer.
(3) 0.1003g of trimesoyl chloride is weighed and dissolved in 100ml of normal hexane, and the membrane obtained in the step (2) and the organic phase solution containing the active monomer are dried for 15min in an oven at 60 ℃.
(4) 2.7111g of 2-methylimidazole is weighed and dissolved in 300ml of methanol, and the membrane obtained in the step (3) is soaked in a methanol solution containing a 2-methylimidazole ligand for 12 hours and then is tested in a methanol solvent.
The mixed matrix nanofiltration membrane obtained in example 2 was analyzed:
the mixed matrix nanofiltration membrane prepared by the embodiment is loaded into a membrane performance evaluation device, and the experimental conditions are as follows: 0.6M Pa, prepressing for 1h, and controlling the concentration of sodium sulfate to be 1000 ppm; the experimental results are as follows: water flux: 89.68L/m2H hold-off: 90.99 percent.
Example 3:
film making conditions: relative humidity 40% +/-2 at 25 ℃.
(1) 2.1501g of zinc nitrate hexahydrate is weighed and dissolved in 100ml of deionized water, and the polysulfone ultrafiltration membrane support membrane and the zinc nitrate hexahydrate aqueous solution are immersed for 4min and then dried.
(2) 0.2502g of piperazine is weighed and dissolved in 100ml of deionized water, and the membrane obtained in the step (1) and the aqueous phase monomer are dried after 4min to form an aqueous phase liquid layer.
(3) 0.1003g of trimesoyl chloride is weighed and dissolved in 100ml of normal hexane, and the membrane obtained in the step (2) and the organic phase solution containing the active monomer are dried for 15min in an oven at 60 ℃.
(4) 2.7111g of 2-methylimidazole was weighed out and dissolved in 300ml of methanol, and the membrane obtained in step (3) was tested by soaking in methanol solution containing 2-methylimidazole ligand for 12 hours.
Analysis of mixed matrix nanofiltration membranes obtained in example 3:
the mixed matrix nanofiltration membrane prepared by the embodiment is loaded into a membrane performance evaluation device, and the experimental conditions are as follows: 0.6M Pa, prepressing for 1h, and controlling the concentration of sodium sulfate to be 1000 ppm;the experimental results are as follows: water flux: 87.664L/m2H hold-off: 90.14 percent.
Comparative example:
film making conditions: relative humidity 40% +/-2 at 25 ℃.
(1) 0.2502g of piperazine is weighed and dissolved in 100ml of deionized water, and the polysulfone ultrafiltration membrane support membrane and the water phase monomer are dried after 4min to form a water phase liquid layer.
(2) 0.1003g of trimesoyl chloride is weighed and dissolved in 100ml of n-hexane, and the membrane obtained in the step (1) and the organic phase solution containing the active monomer are dried for 15min in an oven at 60 ℃. Soaked in deionized water to be tested.
Analysis of the nanofiltration membrane obtained in comparative example 1:
the mixed matrix nanofiltration membrane prepared by the embodiment is loaded into a membrane performance evaluation device, and the experimental conditions are as follows: 0.6M Pa, prepressing for 1h, and controlling the concentration of sodium sulfate to be 1000 ppm; the experimental results are as follows: water flux: 12.29L/m2H hold-off: 90.86 percent.
Claims (7)
1. A preparation method of a high-flux mixed matrix nanofiltration membrane is characterized by comprising the following steps: the method comprises the following steps:
(1) soaking the polysulfone ultrafiltration membrane support membrane in zinc nitrate hexahydrate aqueous solution for a period of time and then airing;
(2) soaking the membrane obtained in the step (1) in an aqueous phase monomer for a period of time, and then airing to form an aqueous phase liquid layer; wherein the water phase monomer is piperazine;
(3) contacting the film obtained in the step (2) with an organic phase solution containing an active monomer for a period of time, and drying in an oven; wherein the organic phase active monomer is trimesoyl chloride;
(4) and (4) soaking the membrane obtained in the step (3) in a methanol solution containing 2-methylimidazole ligand, and washing away excessive ligand by using a methanol solvent after a period of time.
2. The method for preparing a high-flux mixed matrix nanofiltration membrane according to claim 1, wherein the method comprises the following steps: the mass fraction of the zinc nitrate hexahydrate aqueous solution in the step (1) is 0.01-10 wt%; the soaking time is 1-15 min.
3. The method for preparing a high-flux mixed matrix nanofiltration membrane according to claim 1, wherein the method comprises the following steps: the mass fraction of the water phase monomer in the step (2) is 0.001-0.5 wt%; the soaking time is 1-10 min.
4. The method for preparing a high-flux mixed matrix nanofiltration membrane according to claim 1, wherein the method comprises the following steps: the mass fraction of the organic phase active monomer in the step (3) is 0.001-0.5 wt%; the soaking time is 1-5 min.
5. The method for preparing a high-flux mixed matrix nanofiltration membrane according to claim 1, wherein the method comprises the following steps: the temperature of the oven in the step (3) is 30-80 ℃, and the drying time is 5-30 min.
6. The method for preparing a high-flux mixed matrix nanofiltration membrane according to claim 1, wherein the method comprises the following steps: the mass fraction of the 2-methylimidazole ligand in the step (4) is 0.1-2 wt%, and the soaking time is 12-24 h.
7. A high flux mixed matrix nanofiltration membrane prepared by the method of any one of claims 1 to 6.
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| CN110559889A (en) * | 2019-08-29 | 2019-12-13 | 浙江工业大学 | Hollow nano-particle composite nanofiltration membrane and preparation method and application thereof |
| CN111135733A (en) * | 2020-01-13 | 2020-05-12 | 北京赛诺膜技术有限公司 | MOFs polymer hollow fiber composite membrane and preparation method thereof |
| CN111282451A (en) * | 2020-02-24 | 2020-06-16 | 浙江工业大学 | High-flux polyamide nanofiltration membrane prepared from divalent metal ions and preparation method thereof |
| CN111939774B (en) * | 2020-08-11 | 2022-07-29 | 哈尔滨工业大学 | Method for preparing composite nanofiltration membrane by growing nano particles after etching |
| CN113318605B (en) * | 2021-07-01 | 2022-06-17 | 浙江工业大学 | MOF-based mixed matrix membrane and preparation method thereof |
| CN113694741B (en) * | 2021-09-13 | 2023-03-31 | 浙江工业大学 | Preparation method of full heat exchange membrane based on interfacial polymerization and reverse diffusion growth ZIF |
| CN113786731A (en) * | 2021-09-13 | 2021-12-14 | 浙江工业大学 | Preparation method of composite forward osmosis membrane based on ZIFs nano material modified supporting layer |
| CN114028946A (en) * | 2021-10-25 | 2022-02-11 | 浙江工业大学 | Nano composite cellulose acetate forward osmosis membrane and preparation method thereof |
| CN114849473B (en) * | 2022-04-25 | 2023-09-05 | 浙江工业大学 | Secondary polymerization synchronous self-sealing ZIF-8 modified reverse osmosis membrane and preparation method thereof |
| CN115487693A (en) * | 2022-09-30 | 2022-12-20 | 浙江工业大学 | Polyamide/polyolefin mixed matrix nanofiltration membrane and preparation method thereof |
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