CN116603402B - An asymmetric anti-opal structured microfiltration membrane and its preparation method - Google Patents
An asymmetric anti-opal structured microfiltration membrane and its preparation methodInfo
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- CN116603402B CN116603402B CN202310733536.3A CN202310733536A CN116603402B CN 116603402 B CN116603402 B CN 116603402B CN 202310733536 A CN202310733536 A CN 202310733536A CN 116603402 B CN116603402 B CN 116603402B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
- B01D67/00793—Dispersing a component, e.g. as particles or powder, in another component
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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Abstract
本发明属于新型分离膜材料技术领域，具体公开了一种不对称类反蛋白石结构微滤膜及其制备方法，通过牺牲SiO2微球模板制备类反蛋白石结构微滤膜，进一步通过有机溶剂处理类反蛋白石结构膜单侧膜表面，形成单侧无序结构即制备得到不对称类反蛋白石结构微滤膜；这样制备的微滤膜既具有孔径分布均一、高截留性的有序层结构，又具有高孔隙率、高渗透性的无序层，避免类反蛋白石结构牺牲膜渗透性，在固液分离领域具有良好的应用前景。
This invention belongs to the field of novel separation membrane materials technology, specifically disclosing an asymmetric inverse opal-like microfiltration membrane and its preparation method. The inverse opal-like microfiltration membrane is prepared by sacrificing SiO2 microsphere templates. Further, the surface of one side of the inverse opal-like membrane is treated with an organic solvent to form a unilateral disordered structure, thus obtaining the asymmetric inverse opal-like microfiltration membrane. The microfiltration membrane prepared in this way possesses both an ordered layer structure with uniform pore size distribution and high retention capacity, and a disordered layer with high porosity and high permeability, avoiding the permeability issues of sacrificial membranes in inverse opal structures. It has good application prospects in the field of solid-liquid separation.
Description
Technical Field
The invention relates to the technical field of novel separation membrane materials, in particular to an asymmetric inverse opal structure microfiltration membrane and a preparation method thereof.
Background
The problem of sewage treatment is the current research focus. The membrane separation technology has the advantages of environmental friendliness, low energy consumption, high separation precision, simplicity and convenience in operation and the like and is paid attention to. The microfiltration membrane has good solid-liquid separation performance and is widely applied to the fields of food technology (Gan, howell et al 2001), biological medicine (VAN REIS AND Zydney 2007), industrial production (Leivisk ä, R ä m et al 2009) and the like. However, microfiltration membranes still present many challenges in terms of structure, performance and fabrication.
The separation performance of the microfiltration membrane depends on the characteristics of pore size distribution, porosity, pore structure and the like. Microfiltration membranes with uniformly distributed pore structures can allow the passage of particles of a specific size while achieving high efficiency retention of the target substance and maintaining good permeability. Brans et al (2006) prepared a filter membrane with a controllable pore structure shape and a regular distribution, and shows good permeability, retention and anti-pollution properties. Therefore, the preparation of microfiltration membranes with highly ordered structures has great potential in improving the performance of separation membranes, and has attracted attention from various nationists.
In recent years, various porous film production methods have been developed, such as a template method (Pietsch, gindy et al 2009, xu, sun et al 2015), a phase conversion method (Luo, young et al 2003, yin, goldovsky et al 2013), a respiratory method (Bai, du et al 2013), and the like. Inverse Opal (IO) is a typical photonic crystal exhibiting a highly ordered, three-dimensionally connected microporous structure and is widely used in the fields of medicine (Xia, shang et al 2020, wang, sun et al 2022) and photocatalysis (Bakos, karajz et al 2020, chen, wang et al 2021). There are studies on preparing a microfiltration membrane (He, fan et al 2023) with an IO-like structure by a template method, firstly, regularly arranging polymer colloid microspheres into crystals, and obtaining the microfiltration membrane with the IO-like structure by sacrificing a colloid microsphere template, wherein the microfiltration membrane has a controllable microstructure and uniform pores, thereby being beneficial to high-precision separation of the membrane. However, the membrane prepared by the method has uniform overall pore diameter, and in order to ensure higher interception performance, the pore diameter is generally smaller, certain permeability is inevitably sacrificed, and the membrane is often unsuitable for being used as a microfiltration membrane for water treatment (Yu, luo et al 2018).
Disclosure of Invention
In order to solve the technical problems, the invention provides the micro-filtration membrane with the asymmetric inverse opal-like structure and the preparation method thereof, and the prepared micro-filtration membrane not only has the IO-like structure characteristics, such as uniform pore size distribution, and is beneficial to accurate separation, but also has the advantages of large porosity and good permeability of the three-dimensional through hole structure.
In order to achieve the above purpose, the invention is implemented according to the following technical scheme:
The first object of the invention is to provide a method for preparing an asymmetric inverse opal-like structure microfiltration membrane, which comprises the following steps:
S1, dispersing SiO 2 microspheres with an organic solvent to obtain a SiO 2 microsphere dispersion, adding 8-wt-15 wt% of polymer into the SiO 2 microsphere dispersion, and uniformly mixing to obtain a casting solution;
s2, fixing a glass plate with an upward polymer/SiO 2 microsphere composite film in a mold, and treating the upper surface 15S-180S of the polymer/SiO 2 microsphere composite film with an organic solvent to obtain an asymmetric polymer/SiO 2 microsphere composite film;
S3, immersing the asymmetric polymer/SiO 2 microsphere composite membrane into hydrofluoric acid solution to remove SiO 2 microspheres, and obtaining the asymmetric inverse opal structure microfiltration membrane.
Further, the organic solvent in the steps S1 and S2 is one of N, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.
Further, the particle size of the SiO 2 microsphere in the step S1 is between 180 nm and 800 and nm.
Further, the polymer in the step S1 is one of polyvinylidene fluoride, polyethersulfone and polysulfone.
Further, the concentration of hydrofluoric acid in the step S3 is 2 wt% -10 wt%, and the hydrofluoric acid treatment time is 2 h-10 h.
The second object of the invention is to provide an asymmetric inverse opal-like structure micro-filtration membrane prepared by the method, wherein the lower layer of the asymmetric inverse opal-like structure micro-filtration membrane is an ordered layer with an inverse opal-like structure, and the upper layer is a disordered layer with a three-dimensional through hole structure.
Compared with the prior art, the preparation method has the advantages of simple preparation process, short preparation period and low energy consumption, the reverse opal-like structure micro-filtration membrane is prepared by sacrificing the SiO 2 microsphere template, the surface of the single-side membrane of the opal-like structure membrane is further treated by an organic solvent, and the asymmetric reverse opal-like structure micro-filtration membrane is prepared by forming a single-side disordered structure, so that the prepared micro-filtration membrane has an ordered layer structure with uniform pore size distribution and high retention, has a disordered layer with high porosity and high permeability, avoids the sacrifice of membrane permeability of the opal-like structure, and has good application prospect in the field of solid-liquid separation.
Drawings
FIG. 1 shows a cross-sectional profile of an N, N-dimethylformamide treated film surface 30 s obtained in example I.
FIG. 2 shows a cross-sectional profile of an N, N-dimethylformamide treated film surface 60 s obtained in example two.
FIG. 3 is a film cross-sectional profile of N, N-dimethylformamide treated film surface 90 s obtained in example three.
FIG. 4 shows a cross-sectional profile of an N, N-dimethylformamide treated film surface 150 s obtained in example four.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. The specific embodiments described herein are for purposes of illustration only and are not intended to limit the invention.
Example 1
(1) Dispersing 20 wt% of SiO 2 microspheres with the diameter of 494 nm by using N, N-dimethylformamide to obtain a SiO 2 microsphere dispersion liquid, adding 10 wt% polyvinylidene fluoride into the SiO 2 microsphere dispersion liquid to obtain a casting solution, pouring the casting solution on the upper surface of a glass plate, and curing in a constant-temperature oven at 80 ℃ until an organic solvent volatilizes to obtain a polymer/SiO 2 microsphere composite film;
(2) Fixing a glass plate with an upward polymer/SiO 2 microsphere composite film in a mould, and treating the upper surface 30 s of the polymer/SiO 2 microsphere composite film with N, N-dimethylformamide to prepare an asymmetric polymer/SiO 2 microsphere composite film;
(3) Immersing the asymmetric polymer/SiO 2 microsphere composite membrane in 4 wt% hydrofluoric acid solution to soak 4h to remove SiO 2 microspheres, and obtaining the asymmetric inverse opal structure microfiltration membrane.
From fig. 1, it can be seen that the section of the micro-filtration membrane presents an obvious asymmetric structure, the lower layer of the micro-filtration membrane with the asymmetric inverse opal-like structure is an ordered layer with the inverse opal-like structure, and the upper layer is a disordered layer with a three-dimensional through hole structure.
The separation performance of the microfiltration membrane is tested by adopting a dead-end filtration mode, the pure water flux is 1452L/m 2 h under the pressure of 0.1 MPa, the feed liquid is SiO 2 microsphere (the size distribution is 180-494 nm) water suspension, and the retention rate of the SiO 2 microsphere is 100%.
Example 2
(1) Dispersing 20 wt% of SiO 2 microspheres with the diameter of 494 nm by using N, N-dimethylformamide to obtain a SiO 2 microsphere dispersion liquid, adding 10 wt% polyvinylidene fluoride into the SiO 2 microsphere dispersion liquid to obtain a casting solution, pouring the casting solution on the upper surface of a glass plate, and curing in a constant-temperature oven at 80 ℃ until an organic solvent volatilizes to obtain a polymer/SiO 2 microsphere composite film;
(2) Fixing a glass plate with an upward polymer/SiO 2 microsphere composite film in a mould, and treating the upper surface 60 s of the polymer/SiO 2 microsphere composite film with N, N-dimethylformamide to prepare an asymmetric polymer/SiO 2 microsphere composite film;
(3) Immersing the asymmetric polymer/SiO 2 microsphere composite membrane in 4 wt% hydrofluoric acid solution to soak 4h to remove SiO 2 microspheres, and obtaining the asymmetric inverse opal structure microfiltration membrane. The surface time of the N, N-dimethylformamide treatment film was changed to 60 s. As can be seen from FIG. 2, the disordered layer structure of the microfiltration membrane of FIG. 1 is thicker and the ordered layer structure is thinner.
Example 3
(1) Dispersing 20 wt% of SiO 2 microspheres with the diameter of 494 nm by using N, N-dimethylformamide to obtain a SiO 2 microsphere dispersion liquid, adding 10 wt% polyvinylidene fluoride into the SiO 2 microsphere dispersion liquid to obtain a casting solution, pouring the casting solution on the upper surface of a glass plate, and curing in a constant-temperature oven at 80 ℃ until an organic solvent volatilizes to obtain a polymer/SiO 2 microsphere composite film;
(2) Fixing a glass plate with an upward polymer/SiO 2 microsphere composite film in a mould, and treating the upper surface 90 s of the polymer/SiO 2 microsphere composite film with N, N-dimethylformamide to prepare an asymmetric polymer/SiO 2 microsphere composite film;
(3) Immersing the asymmetric polymer/SiO 2 microsphere composite membrane in 4 wt% hydrofluoric acid solution to soak 4h to remove SiO 2 microspheres, and obtaining the asymmetric inverse opal structure microfiltration membrane. The surface time of the N, N-dimethylformamide treatment film was changed to 90 s. As can be seen from FIG. 3, the disordered layer structure of the microfiltration membrane of FIG. 1 is thicker and the ordered layer structure is thinner.
Example 4
(1) Dispersing 20 wt% of SiO 2 microspheres with the diameter of 494 nm by using N, N-dimethylformamide to obtain a SiO 2 microsphere dispersion liquid, adding 10 wt% polyvinylidene fluoride into the SiO 2 microsphere dispersion liquid to obtain a casting solution, pouring the casting solution on the upper surface of a glass plate, and curing in a constant-temperature oven at 80 ℃ until an organic solvent volatilizes to obtain a polymer/SiO 2 microsphere composite film;
(2) Fixing a glass plate with an upward polymer/SiO 2 microsphere composite film in a mould, and treating the upper surface 150 s of the polymer/SiO 2 microsphere composite film with N, N-dimethylformamide to prepare an asymmetric polymer/SiO 2 microsphere composite film;
(3) Immersing the asymmetric polymer/SiO 2 microsphere composite membrane in 4 wt% hydrofluoric acid solution to soak 4h to remove SiO 2 microspheres, and obtaining the asymmetric inverse opal structure microfiltration membrane. The surface time of the N, N-dimethylformamide treatment film was changed to 150 s. As can be seen from FIG. 4, the disordered layer structure of the microfiltration membrane of FIG. 1 is thicker and the ordered layer structure is thinner.
Example 5
(1) Dispersing 20 wt% of SiO 2 microspheres with the diameter of 180 nm by using N, N-dimethylformamide to obtain a SiO 2 microsphere dispersion liquid, adding 10 wt% polyvinylidene fluoride into the SiO 2 microsphere dispersion liquid to prepare a film casting liquid, pouring the film casting liquid on a glass plate, and curing in a constant-temperature oven at 80 ℃ until an organic solvent volatilizes to prepare a polymer/SiO 2 microsphere composite film;
(2) Fixing a glass plate with an upward polymer/SiO 2 microsphere composite film in a mould, and treating the upper surface 90 s of the polymer/SiO 2 microsphere composite film with N, N-dimethylformamide to prepare an asymmetric polymer/SiO 2 microsphere composite film;
(3) Immersing the asymmetric polymer/SiO 2 microsphere composite membrane in 4 wt% hydrofluoric acid solution to soak 4h to remove SiO 2 microspheres, and obtaining the asymmetric inverse opal structure microfiltration membrane.
Example 6
(1) Dispersing 20 wt% of SiO 2 microspheres with the diameter of 282 nm by using N, N-dimethylformamide to obtain a SiO 2 microsphere dispersion liquid, adding 10 wt% polyvinylidene fluoride into the SiO 2 microsphere dispersion liquid to prepare a film casting liquid, pouring the film casting liquid on a glass plate, and curing in a constant-temperature oven at 80 ℃ until an organic solvent volatilizes to prepare a polymer/SiO 2 microsphere composite film;
(2) Fixing a glass plate with an upward polymer/SiO 2 microsphere composite film in a mould, and treating the upper surface 90 s of the polymer/SiO 2 microsphere composite film with N, N-dimethylformamide to prepare an asymmetric polymer/SiO 2 microsphere composite film;
(3) Immersing the asymmetric polymer/SiO 2 microsphere composite membrane in 4 wt% hydrofluoric acid solution to soak 4h to remove SiO 2 microspheres, and obtaining the asymmetric inverse opal structure microfiltration membrane.
Example 7
(1) Dispersing 20 wt% of SiO 2 microspheres with the diameter of 340 nm by using N, N-dimethylformamide to obtain a SiO 2 microsphere dispersion liquid, adding 10 wt% polyvinylidene fluoride into the SiO 2 microsphere dispersion liquid to prepare a film casting liquid, pouring the film casting liquid on a glass plate, and curing in a constant-temperature oven at 80 ℃ until an organic solvent volatilizes to prepare a polymer/SiO 2 microsphere composite film;
(2) Fixing a glass plate with an upward polymer/SiO 2 microsphere composite film in a mould, and treating the upper surface 90 s of the polymer/SiO 2 microsphere composite film with N, N-dimethylformamide to prepare an asymmetric polymer/SiO 2 microsphere composite film;
(3) Immersing the asymmetric polymer/SiO 2 microsphere composite membrane in 4 wt% hydrofluoric acid solution to soak 4h to remove SiO 2 microspheres, and obtaining the asymmetric inverse opal structure microfiltration membrane.
The porosity of the asymmetric inverse opal-like structure microfiltration membrane prepared in test examples 1-7 was tested separately, and the separation performance of the asymmetric inverse opal-like structure microfiltration membrane prepared in examples 1-7 was tested separately by dead-end filtration, and pure water flux and retention rate of SiO 2 microspheres were tested at 0.1 MPa, as compared with the uniformly distributed pore structure of the inverse opal-like structure microfiltration membrane prepared by the sacrificial template method in He et al (2023) in the prior art, which also exhibited good retention performance of SiO 2 microspheres, pure water flux up to 1146L/m 2 h, and Wang et al (2010) designed an inverse colloidal crystal microfiltration membrane having uniform pore diameter, which exhibited good shunt performance, but practical porosity was only 50-60%. The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, pore size uniformity is one of the ideal microfiltration membrane characteristics, and optimizing the membrane preparation process is critical to improving the microfiltration membrane performance (e.g., porosity, water flux, etc.).
In summary, in the embodiments 1 to 4 of the present invention, the micro-filtration membrane having an asymmetric inverse opal-like structure can be prepared by treating the surface of one side of the membrane with N, N-dimethylformamide, and compared with the micro-filtration membrane having a uniform pore diameter, the present invention significantly increases the porosity of the membrane, improves the pure water flux of the micro-filtration membrane, and has good retention performance.
The technical scheme of the invention is not limited to the specific embodiment, and all technical modifications made according to the technical scheme of the invention fall within the protection scope of the invention.
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| US7282148B2 (en) * | 2003-10-30 | 2007-10-16 | International Business Machines Corporation | Porous silicon composite structure as large filtration array |
| US8840791B2 (en) * | 2011-09-01 | 2014-09-23 | Pall Corporation | Multilayer microfiltration membrane |
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