CN114272680B - Composite chromatographic filter membrane material based on nano-fiber and polymer microsphere and preparation method thereof - Google Patents
Composite chromatographic filter membrane material based on nano-fiber and polymer microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention provides a composite chromatographic filter membrane material based on nano fibers and polymer microspheres and a preparation method thereof. Mixing PVA-co-PE nano fibers and sulfonated polymer microspheres according to a preset mass ratio to prepare a suspension; then the suspension is made into a fiber membrane material, and the sulfonated polymer microspheres are distributed on the fiber surface and among fiber pores of the fiber membrane material to form a multi-level filtration pore structure so as to synchronously improve the flux, the rejection rate, the filtration stability and the cation adsorption performance of the fiber membrane material. According to the invention, the nano-fibers and the sulfonated polymer microspheres with higher content are compounded to prepare the membrane material, so that the optimization of the membrane material structure is realized, and the permeation flux is improved; meanwhile, the sulfonated polymer microspheres have excellent cation adsorption, swelling property and good toughness, the strength of the membrane material is improved, and the membrane material can be applied to filtration and chromatography under high pressure, so that the filtration-chromatography efficiency and the filtration-chromatography stability are improved.
Description
Technical Field
The invention relates to the technical field of preparation of filter materials, in particular to a composite chromatographic filter membrane material based on nano fibers and polymer microspheres and a preparation method thereof.
Background
Along with the development of social economy, the higher requirements on the filtering and separating effects and the functionality of the filtering and separating membrane material are provided by industries such as environmental management and medicines, and the excellent multifunctional filtering membrane material structure has important significance on high-efficiency and low-consumption water treatment. Good filtration and separation membrane materials should generally have 1) high flux to reduce filtration resistance and improve filtration efficiency; 2) The retention rate is high, so that the adsorption and retention of harmful substances in the water body are improved; 3) High filtration stability, long service life of the membrane material and high flux and interception rate. 4) Specific adsorption performance, and ensures the selective separation of target substances in high-end application fields such as medicine. However, the permeation flux of the membrane material generally has a positive correlation with the pore size and the porosity, and the rejection rate has an inverse correlation with the pore size and the porosity, so that the permeation flux and the rejection rate (particularly the rejection rate of small-particle-size particles) are generally difficult to be combined; the membrane material with a simple filtering function is difficult to meet various separation requirements.
With the gradual maturity of the nanofiber material preparation technology, the nanofiber-based membrane material is also gradually used for preparing a filter membrane material due to the characteristics of high specific surface area, high strength, convenience for large-scale preparation and the like.
For example, the chinese patent application CN106730150A discloses a gradient aperture filter membrane and a preparation method and an application thereof, which realizes the filtration of infusion apparatus particles through the design of gradient aperture. For example, chinese utility model CN207056133U discloses a gradient filtration composite nonwoven fabric material, which is composed of a spunlace nonwoven fabric layer, a spunbond nonwoven fabric layer and an ultra-fine meltblown nonwoven fabric layer. The spunlace nonwoven fabric layer is fluffy and soft, the porosity is high, the strength of the spunbonded nonwoven fabric layer is good, the porosity of the meltblown nonwoven fabric layer is minimum, the filtering efficiency is high, the porosity of the three layers of fibers is arranged in a gradient decreasing trend, the spunlace nonwoven fabric layer has excellent filtering performance, the frequency of replacing the filtering material can be reduced, and the cost is reduced. The gradient design can improve the filtration performance to a certain degree, but the multi-layer design can result in the increase of the thickness, and the permeation flux can be influenced.
Patent CN104014196A discloses a high adsorption nanofiber composite filter material and a preparation method thereof, which comprises carrying out composite spinning on nano active particles and a polymer, then coating the nano active particles and the polymer to form a membrane, and utilizing the high adsorption of the active particles to improve the filtration performance of the fiber membrane material. Patent CN107137979A discloses a micron fiber three-dimensional skeleton/polymer nanofiber composite filter material and a preparation method thereof, which is characterized in that polymer nanofibers and a cross-linking agent are dispersed in a solvent to form a suspension, then a micron fiber non-woven fabric skeleton is soaked in the suspension, freeze-dried to form a solidified block, and then the solvent is removed, so as to obtain a non-woven material with polymer nanofiber aerogel distributed in gradient among micron fiber skeletons. The fiber-based membrane material has good flexibility, high efficiency and low resistance air filtration performance, but the flux of water treatment is difficult to ensure. Patent CN104689724A discloses an organic-inorganic composite nanofiber membrane filter material and a preparation method thereof, wherein nanofiber and a small amount of inorganic micron active particles are mixed to prepare a suspension, and then the suspension is coated to form a membrane, and the three-dimensional structure of the membrane is regulated and controlled through the difference between the size and the shape of the nanofiber and the micron-sized particles, so that the pressure resistance is reduced, and the adsorption rate is improved by utilizing the adsorbability of the active particles. Although the material can regulate and control the structure of the fiber membrane material to a certain extent, the size structure difference of the inorganic micron active particles and the nano fibers is large, and subsequent experiments show that the pore structure of the membrane material prepared by the method still cannot reach the optimal structure, and the entrapment rate and the entrapment stability for water treatment are poor.
Therefore, the pore structure of the filter material in the technical scheme is still not optimized, the water permeation flux still needs to be further improved, the adsorption principle is mainly physical adsorption, and the adsorption strength and selectivity are poor.
In view of the above, there is a need to design an improved composite chromatographic filter membrane material based on nanofibers and polymeric microspheres and a preparation method thereof to solve the above problems.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a composite chromatographic filter membrane material based on nano fibers and polymer microspheres and a preparation method thereof. The nano-fiber and the sulfonated polymer microsphere with higher content are compounded to prepare the membrane material, so that the optimization of the membrane material structure is realized, and the permeation flux is improved; meanwhile, the sulfonated polymer microspheres have excellent cation adsorption, swellability and good toughness, the strength of the membrane material is improved, and the membrane material can be applied to filtration and chromatography under high pressure, so that the filtration-chromatography efficiency and the filtration-chromatography stability are improved.
In order to realize the aim, the invention provides a preparation method of a composite chromatography filter membrane material based on nano-fibers and polymer microspheres, which comprises the following steps:
s1, mixing PVA-co-PE nano fibers and sulfonated polymer microspheres according to a preset mass ratio to prepare a suspension; wherein the particle size and the mass of the sulfonated polymer microsphere are respectively more than or equal to the diameter and the mass of the PVA-co-PE nanofiber;
s2, preparing the suspension into a fiber membrane material with the thickness of 1-100 mu m, and distributing the sulfonated polymer microspheres on the fiber surface and among fiber pores of the fiber membrane material to form a multi-level filtration pore structure so as to synchronously improve the flux, rejection rate, filtration stability and cation adsorption performance of the fiber membrane material.
As a further improvement of the invention, in the step S1, the preset mass ratio of the nano-fibers to the sulfonated polymer microspheres is 1 (1-4); the solvent of the suspension is a mixed solvent of ethanol and water.
As a further improvement of the invention, in step S1, the diameter of the nano-fiber is 50-1000nm, and the particle size of the sulfonated polymer microsphere is 100-1200nm.
As a further improvement of the invention, the diameter of the nano fiber is 100-700nm, and the particle size of the sulfonated polymer microsphere is 100-800nm.
As a further improvement of the invention, the diameter of the nano-fiber is 100-300nm, and the particle size of the sulfonated polymer microsphere is 100-600nm; the preset mass ratio of the nanofiber to the sulfonated polymer microsphere is 1.
As a further improvement of the present invention, in step S2, the sulfonated polymer microspheres are sulfonated polystyrene microspheres.
As a further improvement of the invention, in step S2, the fiber membrane material is prepared by spraying or suction filtration; the gram weight of the fiber membrane material is 3-20 g/m 2 。
As a further improvement of the invention, in step S1, the nano-fiber is obtained by carrying out melt blending spinning and solvent phase separation on PVA-co-PE and cellulose acetate butyrate.
As a further improvement of the invention, the filter membrane material further comprises a support layer for supporting the fiber membrane material, wherein the support layer is one of viscose non-woven fabric, cotton fiber non-woven fabric, polyester fiber non-woven fabric, polyamide fiber non-woven fabric, polyethylene fiber non-woven fabric, polypropylene fiber non-woven fabric, polyurethane fiber non-woven fabric and polyacrylonitrile fiber non-woven fabric; the gram weight of the supporting layer is 30-150 g/m 2 The aperture is 5-20 μm, and the fiber diameter is larger than 1 μm.
A composite chromatography filter membrane material based on nanofibers and polymer microspheres is prepared by any one of the preparation methods.
The invention has the beneficial effects that:
1. according to the preparation method of the composite chromatographic filtration membrane material based on the nano-fibers and the polymer microspheres, provided by the invention, the nano-fibers with different diameter ranges and the high-content sulfonated polymer microspheres are subjected to composite spraying to prepare the filtration membrane with excellent performance, and the combination of the nano-fibers and the sulfonated microspheres in the structure regulates the aperture of the membrane; the smooth transmission of liquid media such as water and the like is guaranteed, so that the synergistic improvement of the filtering efficiency and the water flux is realized, and the high-efficiency and low-consumption filtering is realized; thirdly, the water-soluble organic acid has certain adsorption effect on protein (lysozyme) in the water body; can be used for filtration and chromatography under high pressure, thereby improving filtration-chromatography efficiency and filtration-chromatography stability.
2. According to the invention, the micro-nano structure of the composite filter membrane material is regulated and controlled by adding the sulfonated polymer microspheres with higher content to form a multi-layer network structure with mutually staggered and penetrated point lines, so that the composite filter membrane material can filter nano-scale particlesThe efficiency can reach more than 99 percent, and the water flux can be kept to 5500L/m 2 More than h; the sulfonated polymer microspheres have excellent cation adsorbability, so that the adsorption capacity to lysozyme is improved by more than 10 times, and the filtration efficiency equivalent to that of a microfiltration membrane and the water flux equivalent to that of an ultrafiltration membrane are realized. In addition, the sulfonated polymer microspheres have good toughness and compressibility, so that the filter membrane material can meet high strength, and water filtration treatment can be performed under high pressure difference; and the sulfonated polymer microspheres can adjust the micro-nano porous structure of the composite filtering membrane after being extruded, so that the filtering stability and the filtering efficiency are obviously improved.
3. The nanofiber and sulfonated microsphere composite membrane material disclosed by the invention is large in specific surface area and excellent in medium transmission performance, is beneficial to later-stage functionalization, and realizes efficient preparation of a multifunctional microfiltration flat membrane. The composite membrane of the nano-fiber and the sulfonated microsphere is used as a filter layer, and is compounded with non-woven materials such as spunlace non-woven fabrics, needle-punched non-woven fabrics, spun-bonded non-woven fabrics, melt-blown non-woven fabrics, heat-seal non-woven fabrics, stitch-bonded non-woven fabrics, pulp air-laid non-woven fabrics or wet non-woven fabrics and the like as a support layer, so that the composite membrane is firm and durable; in addition, the interaction and mutual protection between the sulfonated microspheres and the fibers of the nanofiber and sulfonated microsphere composite membrane material are beneficial to improving the strength of a coating and ensuring the service life of the whole membrane material.
Drawings
FIG. 1 is an infrared spectrum of a composite filtration membrane composed of nanofibers and sulfonated microspheres with different diameters.
FIG. 2 shows the saturated adsorption capacities of comparative example 1 and examples 2, 7 and 9 for lysozyme.
FIG. 3 is a graph showing the change of the adsorption capacity of examples 2, 7 and 9 for lysozyme with time.
Fig. 4 is an SEM image of the nanofiber composite sulfonated microsphere filtration membrane prepared in example 2.
FIG. 5 is a graph showing pore size distributions of the filtration membranes of examples 1 to 5 and comparative example 1.
FIG. 6 is a graph showing the change of water flux with time of the filtration membranes of examples 1 to 5 and comparative example 1.
FIG. 7 is a graph showing the distribution of the pore sizes of the filtration membranes of examples 6 to 8 and comparative example 2.
FIG. 8 is a graph showing the change of water flux with time of the filtration membranes of examples 6 to 8 and comparative example 2.
FIG. 9 is a graph showing the pore size distribution of the filtration membranes of examples 9 to 11 and comparative example 3.
FIG. 10 is a graph showing the water flux of the filtration membranes of examples 9 to 11 and comparative example 3 with time.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail with reference to specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the solution of the present invention are shown in the specific embodiments, and other details not closely related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation method of a composite chromatography filter membrane material based on nano-fibers and polymer microspheres, which comprises the following steps:
s1, mixing PVA-co-PE nano fibers and sulfonated polymer microspheres according to a preset mass ratio to prepare a suspension; wherein the particle size and the mass of the sulfonated polymer microsphere are respectively more than or equal to the diameter and the mass of the PVA-co-PE nano fiber; preferably, the preset mass ratio of the nanofibers to the sulfonated polymer microspheres is 1 (1-4), more preferably 1 (1.5-3), more preferably 1. The solvent of the suspension is a mixed solvent of ethanol and water, preferably ethanol and water in a volume ratio of 1. The composite membrane is prepared by selecting the PVA-co-PE nano-fiber and the sulfonated polymer microsphere, on one hand, the PVA-co-PE nano-fiber and the sulfonated polymer microsphere both have hydrophilic groups and have good compatibility, so that the distribution uniformity of the filtering membrane is convenient to improve, and on the other hand, when the composite membrane is used for water treatment, the composite membrane can improve the water permeability and the adsorption performance on hydrophilic impurities or harmful substances (such as inorganic salt, lysozyme and the like) in water. The sulfonated polymer microspheres have excellent cation adsorption, swellability and good toughness, the strength of the membrane material is improved, and the membrane material can be applied to filtration and chromatography under high pressure, so that the filtration-chromatography efficiency and the filtration-chromatography stability are improved.
The experimental result shows that the mass ratio of the nano-fiber and the sulfonated polymer microsphere has obvious influence on the filtering performance, the micro-nano structure of the composite filtering membrane material is regulated and controlled by adding the sulfonated polymer microsphere with higher content, and a multi-layer network structure with mutually staggered and penetrated point lines is formed, so that the filtering efficiency of the composite filtering membrane material on nano-scale particles can reach more than 99%, and the water flux can be kept at 5500L/m 2 More than h, the adsorption capacity to lysozyme is improved by more than 10 times, and the filtration efficiency equivalent to that of a microfiltration membrane and the water flux equivalent to that of an ultrafiltration membrane are realized. In addition, the sulfonated polymer microspheres have good toughness and compressibility, so that the filter membrane material can meet the requirement of high strength, and thus, water filtration treatment can be performed under higher pressure difference; moreover, the sulfonated polymer microspheres can adjust the micro-nano porous structure of the composite filtering membrane after being extruded, so that the filtering stability and the filtering efficiency are obviously improved.
The sulfonated polymer microspheres are preferably sulfonated polystyrene microspheres. The polystyrene microsphere is simple and easy to obtain, and has good flexibility, but the invention is not limited by the polystyrene microsphere, and other polymer microspheres with similar properties to the polystyrene microsphere are also suitable for the invention.
The nano-fiber is obtained by carrying out melt blending spinning and solvent phase separation on PVA-co-PE and cellulose acetate butyrate. Specifically, the PVA-co-PE nanofibers obtained in the step S1 are respectively dispersed in a mixed solvent with the mass ratio of 1.
Preferably, the solid content is any one of 1.0%, 1.2%, 1.5%, 1.8%, 2.2%, 2.5%, 3.0%, 3.3%, 3.5%, and 4.0%.
S2, preparing the suspension into a fiber membrane material with the thickness of 1-100 microns, and distributing the sulfonated polymer microspheres on the fiber surface and among fiber pores of the fiber membrane material to form a multi-level filtration pore structure so as to synchronously improve the flux, the rejection rate, the filtration stability and the cation adsorption performance of the fiber membrane material. In step S2, the fiber membrane material is prepared by spraying or suction filtration; the gram weight of the fiber membrane material is 3 to 20g/m 2 . Preferably, the spray coating gram weight is 5g/m 2 、7g/m 2 、10g/m 2 、15g/m 2 、18g/m 2 Is one of the above.
When the sulfonated microspheres are singly filmed, the space between the microspheres is very small, the flux of liquid is small, the surfaces of a plurality of microspheres are covered by other microspheres, and the functional groups exposed outside are limited; and the nanofiber is added for film forming, the nanofiber and the microsphere are mutually supported, the distance between the nanofiber and the distance between the microsphere and the microsphere can be increased, particularly, when the diameter of the microsphere is larger than or equal to the diameter of the fiber, the thickness of the whole film can be increased, the pore channel inside the film can be elongated, and the number of the pore channels can also be increased, so that under the condition that the effective pore diameter is the same, a single pore of the composite film is larger, the number of pores is more, and the flux is correspondingly increased.
In step S1, the diameter of the nanofiber is 50-1000nm, and the particle size of the sulfonated polymer microsphere is 100-1200nm. For example: the diameter of the nanofiber is in the order of 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm and 800nm. The nano-sized sulfonated microspheres have several grades: a 50nm level, a 100nm level, a 200nm level, a 300nm level, a 400nm level, a 500nm level, a 600nm level, a 700nm level, an 800nm level, a 1000nm level, and a 1200nm level.
Furthermore, the particle size of the microspheres used for the filter layer can be larger than or equal to the pore size of the nanofiber membrane.
Preferably, the pore size structure of the PVA-co-PE nano fiber is in the order of 100nm, and the diameter of the nano microsphere is in the order of 100 nm.
Preferably, the pore size structure of the PVA-co-PE nano fiber is in the order of 100nm, and the diameter of the nano microsphere is in the order of 300 nm.
Preferably, the pore size structure of the PVA-co-PE nano fiber is in the order of 100nm, and the diameter of the nano microsphere is in the order of 600 nm.
Preferably, the pore size structure of the PVA-co-PE nano fiber is in the order of 300nm, and the diameter of the nano microsphere is in the order of 300 nm.
Preferably, the pore size structure of the PVA-co-PE nano fiber is in the order of 300nm, and the diameter of the nano microsphere is in the order of 500 nm.
Preferably, the pore size structure of the PVA-co-PE nano fiber is in the order of 300nm, and the diameter of the nano microsphere is in the order of 700 nm.
Preferably, the pore size structure of the PVA-co-PE nano fiber is 700nm grade, and the diameter of the nano microsphere is 600nm grade.
Preferably, the pore size structure of the PVA-co-PE nano fiber is 700nm grade, and the diameter of the nano microsphere is 1000nm grade.
Preferably, the pore size structure of the PVA-co-PE nano fiber is 700nm grade, and the diameter of the nano microsphere is 1500nm grade.
Preferably, the diameters of the nanofibers in step S1 are on the order of 100nm and 300nm, respectively.
In particular, the filter membrane material further comprises a support layer, preferably a nonwoven material, for supporting the fibrous membrane material; the non-woven material is one of spunlace non-woven fabrics, needle-punched non-woven fabrics, spun-bonded non-woven fabrics, melt-blown non-woven fabrics, heat-seal non-woven fabrics, stitch-bonded non-woven fabrics, pulp air-laid non-woven fabrics or wet non-woven fabrics. Specifically, the supporting layer is one of viscose non-woven fabric, cotton non-woven fabric, polyester non-woven fabric, polyamide non-woven fabric, polyethylene non-woven fabric, polypropylene non-woven fabric, polyurethane non-woven fabric and polyacrylonitrile non-woven fabric; the gram weight of the supporting layer is 30-150 g/m 2 The aperture is 5-20 μm, and the fiber diameter is larger than 1 μm.
Preferably, the nonwoven material is a polyethylene spunbonded fabric. Preferably, the nonwoven material is a PET spunbonded. Preferably, the nonwoven material is a viscose needle-punched nonwoven. Preferably, the nonwoven material is a PP meltblown nonwoven. Preferably, the nonwoven material is a PP spunbond nonwoven. Preferably, the nonwoven material is a PBT spunbond nonwoven.
Examples 1 to 3
A preparation method of a composite chromatography filter membrane material based on nanofibers and polymer microspheres comprises the following steps:
a melt spinning phase separation method is adopted to blend PVA-co-PE and Cellulose Acetate Butyrate (CAB) to spin 100nm PVA-co-PE nano fibers, and 12g of 100nm PVA-co-PE nano fibers are taken. Weighing 100nm sulfonated polystyrene microsphere solutions with different masses according to the table 1, dissolving the solutions in 1L mixed solution of water and ethanol with the proportion of 1. The gram weight is 50g/m 2 Uniformly coating 6g/m on PP spunbonded fabric 2 The 100nm PVA-co-PE nano-fiber is dried at room temperature to obtain the filter layer with the thickness of 6g/m 2 The composite membrane filter material of the nano-fiber and the sulfonated microsphere. FIG. 1 shows that the composite membrane filter material prepared in each example contains both PVA-co-PE and sulfonated polystyrene microsphere structures. As can be seen from FIG. 4, the PVA-co-PE nanofibers and the sulfonated polystyrene microspheres are mutually crossed, penetrated and supported, and are uniformly distributed, so that the pore structure of the fiber membrane is enriched.
Comparative example 1
Compared with the embodiment 1, the difference of the preparation method of the composite chromatography filter membrane material based on the nano-fibers and the polymer microspheres is that sulfonated polystyrene microspheres are not added, and the rest is substantially the same as the embodiment 1, and the description is omitted.
The composite membrane filter material was tested for water flux at 0.2MPa, filtration efficiency for pigment particles having a mean diameter of 100nm, and adsorption capacity for lysozyme, as shown in table 1.
TABLE 1 mass ratio of nanofibers to sulfonated microspheres and performance test results of examples 1-3 and comparative example 1
As can be seen from Table 1, when sulfonated polystyrene microspheres with a quality higher than that of the sulfonated polystyrene microspheres are added into the 100nm nanofibers, the filtration efficiency of the filtration membrane on 100nm particles can be as high as 99.9%, and the filtration performance on small-particle-size particles is good, and the filtration efficiency can reach the ultrafiltration membrane level. The water flux under 0.2MPa is slightly reduced, wherein when the mass ratio of the nano-fiber to the sulfonated microsphere is 1. The structural distribution of the fiber membrane is optimized under the proportion. Along with the increase of the mass of the sulfonated microspheres, the lysozyme adsorption capacity is gradually increased, which shows that the sulfonated microspheres have good adsorbability on lysozyme and play a main adsorption role. The support effect of the nanofibers on the sulfonated microspheres can also increase the exposed area of the microspheres and prolong the time of liquid contacting the microspheres, thereby synergistically improving the adsorption efficiency. In addition, the support effect of the nano-fiber can enable the microspheres to be integrated, and the repeated utilization rate of the microspheres is greatly improved.
As can be seen from FIG. 5, after the sulfonated microspheres are added, the pore diameter of the fiber membrane is reduced, and the pore diameter is smaller as the addition amount of the sulfonated microspheres is larger; it can be seen from the combination of table 1 that the pore size of example 2, although reduced to that typical of comparative example 1, does not significantly reduce the water flux compared to comparative example 1, thereby allowing a significant increase in filtration efficiency while still maintaining a higher water usage. As can be seen from the graph in FIG. 6, the water flux of the fiber membrane without sulfonated microspheres is significantly reduced along with the increase of the filtration time, and is reduced by about 40% after 30min, which indicates that the filtration stability is not good, and the fiber membrane is blocked after being used for a certain time. And after 30min, the filtration stability is reduced by about 25%, which shows that the addition of the sulfonated microspheres is helpful for improving the filtration stability, and in the use process, the fiber membrane is not easy to be blocked or damaged because the sulfonated microspheres have good toughness and can deform under the action of water pressure, so that the pore structure is dynamically regulated and controlled to prevent the blockage. The filtration stability is gradually improved with the increase of the diameter of the sulfonated microsphere, and when the diameter of the sulfonated microsphere is 600nm, the filtration stability is optimal because the extrusion deformation regulation and control capability is better after the diameter of the sulfonated microsphere is increased.
When the diameter of the sulfonated microsphere is increased, the pore diameter is also increased, which shows that the content and the diameter of the sulfonated microsphere have influence on the performance of the membrane filter material.
Examples 4 to 6
Compared with the embodiment 2, the difference of the preparation method of the composite chromatography filtration membrane material based on the nanofibers and the polymer microspheres is that the diameters of the nanofibers and the sulfonated microspheres are shown in table 2, and the rest are substantially the same as those of the embodiment 2, so that the details are not repeated.
Table 2 mass ratios of nanofibers and sulfonated microspheres and performance test results of examples 4 to 11 and comparative examples 1 to 3
As can be seen from examples 1, 4-5 and comparative example 1 in Table 2, the diameter of the nanofiber is unchanged, the water flux is gradually increased while the filtration efficiency is gradually reduced when the diameter of the sulfonated microsphere is increased, and the pore size is increased when the diameter of the sulfonated microsphere is increased, as can be seen from FIG. 5. When the diameter of the sulfonated microsphere is 300nm, the adsorption capacity to lysozyme is the largest.
As can be seen from examples 6-11 and comparative examples 2-3 in Table 2, when the diameters of the nanofibers are increased, the water flux is uniformly increased, and the influence rule of the sulfonated microspheres is basically consistent with that of the 100nm nanofibers. As can be seen from fig. 8 and 9, the filtration stability increased as the sulfonated microsphere diameter increased.
In conclusion, the invention realizes the optimization of the membrane material structure by compounding the nano-fiber and the sulfonated polymer microsphere with higher content into the membrane material, thereby improving the permeation flux; meanwhile, the sulfonated polymer microspheres have excellent cation adsorbability, swellability and good toughness, the strength of the membrane material is improved, the membrane material can be applied to filtration and chromatography under high pressure, and the sulfonated polymer microspheres can adjust the micro-nano porous structure of the composite filtration membrane after being extruded, so that the filtration-chromatography efficiency and the filtration-chromatography stability are improved.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (7)
1. A preparation method of a composite chromatography filter membrane material based on nanofibers and polymer microspheres is characterized by comprising the following steps:
s1, mixing PVA-co-PE nano fibers and sulfonated polymer microspheres according to a preset mass ratio to prepare a suspension; wherein the particle size and the mass of the sulfonated polymer microsphere are respectively more than or equal to the diameter and the mass of the PVA-co-PE nanofiber;
s2, preparing the suspension into a fiber membrane material with the thickness of 1-100 microns, wherein the sulfonated polymer microspheres are distributed on the fiber surface and among fiber pores of the fiber membrane material to form a multi-level filtration pore structure so as to synchronously improve the flux, rejection rate, filtration stability and cation adsorption performance of the fiber membrane material;
the diameter of the nano-fiber is 100-700nm, and the particle size of the sulfonated polymer microsphere is 100-800nm;
in step S1, the preset mass ratio of the nanofibers to the sulfonated polymer microspheres is 1: (1-4); the solvent of the suspension is a mixed solvent of ethanol and water;
the sulfonated polymer microspheres have swellability, good toughness and compressibility;
the sulfonated polymer microspheres in the composite chromatographic filtration membrane material can adjust the micro-nano porous structure of the composite filtration membrane after being extruded.
2. The preparation method of the composite chromatography filtration membrane material based on the nanofibers and the polymer microspheres as claimed in claim 1, wherein the diameter of the nanofibers is 100-300nm, and the particle size of the sulfonated polymer microspheres is 100-600nm; the preset mass ratio of the nano-fibers to the sulfonated polymer microspheres is 1:2.
3. the method for preparing a composite chromatographic filter membrane material based on nanofibers and polymer microspheres according to claim 1, wherein in step S2, the sulfonated polymer microspheres are sulfonated polystyrene microspheres.
4. The preparation method of the composite chromatography filtration membrane material based on the nanofibers and the polymer microspheres as claimed in claim 1, wherein in step S2, the fiber membrane material is prepared by spraying or suction filtration; the gram weight of the fiber membrane material is 3-20 g/m 2 。
5. The method for preparing the composite chromatographic filter membrane material based on the nano-fibers and the polymer microspheres as claimed in claim 1, wherein in step S1, the nano-fibers are obtained by melt blending spinning and solvent phase separation of PVA-co-PE and cellulose acetate butyrate.
6. The preparation method of the composite chromatography filtration membrane material based on the nanofibers and the polymer microspheres as claimed in claim 1, wherein the filtration membrane material further comprises a support layer for supporting the fiber membrane material, and the support layer is one of viscose non-woven fabric, cotton non-woven fabric, polyester non-woven fabric, polyamide non-woven fabric, polyethylene non-woven fabric, polypropylene non-woven fabric, polyurethane non-woven fabric, and polyacrylonitrile non-woven fabric; the gram weight of the supporting layer is 30-150 g/m 2 The aperture is 5-20 μm, and the fiber diameter is larger than 1 μm.
7. A composite chromatography filter membrane material based on nanofibers and polymer microspheres, which is characterized by being prepared by the preparation method of any one of claims 1 to 6.
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| CN104209023A (en) * | 2014-08-27 | 2014-12-17 | 天津大学 | Sulfonated poly(ether ether ketone)-sulfonated silicon dioxide microsphere hybrid membrane, as well as preparation and application of membrane |
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| CN104689724B (en) * | 2015-03-18 | 2018-08-10 | 武汉纺织大学 | A kind of organic and inorganic composite nanofiber membrane filtration material and preparation method thereof |
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