CN111346523A - Multifunctional bio-based composite microporous membrane and preparation method thereof - Google Patents
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Abstract
The invention discloses a multifunctional bio-based composite microporous membrane and a preparation method thereof, belonging to the field of water treatment and purification. The multifunctional bio-based composite microporous membrane mainly comprises a separation layer and a support layer, wherein the separation layer is mainly prepared by mixing a nano material and an additive and has a three-dimensional structure capable of intercepting dye micromolecules; the support layer comprises a stereo composite polylactic acid microporous membrane and noble metal nano particles with catalytic performance loaded in the stereo composite polylactic acid microporous membrane, so that the aromatic compounds in a sewage system are rapidly degraded. Compared with the microporous membrane in the prior art, the multifunctional bio-based composite microporous membrane can treat dye molecules and aromatic compounds in sewage more stably and efficiently under the synergistic action of the separation layer and the supporting layer, and meanwhile, the multifunctional bio-based composite microporous membrane is simple in preparation process, convenient to operate and has very important scientific and application prospects.
Description
Technical Field
The invention belongs to the field of water treatment and purification, and particularly relates to a multifunctional bio-based composite microporous membrane with separation and catalytic performances and a preparation method thereof.
Background
Water pollution and water resource shortages are becoming major challenges for the sustainable development of the world economy and society. A large amount of waste water polluted by various dyes is discharged in the textile dyeing process, and the dye waste water seriously pollutes the ecological environment. Moreover, many dyes are toxic in nature and have potential carcinogenic and genotoxic effects. However, the treatment of dyes has proven to be rather difficult to handle, since most commercial dyes have complex aromatic structures and are difficult to degrade and decolorize. Therefore, the removal of dye molecules from printing and dyeing wastewater is of crucial environmental importance.
In most cases, nanofiltration membranes are capable of separating dye molecules (200-. However, due to the aggregation of the dye molecules and the simultaneous concentration polarization, the nanofiltration membrane faces severe contamination, resulting in a significant drop in permeate flux. In contrast, micro/ultrafiltration membranes have high throughput, low operating pressures and anti-fouling properties. However, the micro/ultrafiltration membrane cannot intercept dye molecules because the pore diameter is larger than that of the dye molecules. At present, the main method is to co-deposit pyrocatechol and polyethyleneimine (WZ Qiu, et al. journal of Materials Chemistry A,2015,3: 14438-. The dye wastewater is treated by adding nano titanium dioxide with photocatalytic performance into a membrane body (RA Damodar, et al. journal of Hazardous Materials,2009,172: 1321-. But the binding between the inorganic photocatalytic nanoparticles and the polymer film is poor. Therefore, there is a need to produce polymer films that efficiently process dye molecules. And traditional petrochemical polymer materials such as polyvinylidene fluoride, polysulfone, polyethersulfone and polytetrafluoroethylene are difficult to degrade and easily cause white pollution.
Recently, many nanomaterials such as graphene, graphene oxide, graphite phase carbon nitride and COF are gradually applied to the field of water treatment and purification. Because the nano materials have unique sheet structures, the nano materials can be assembled into a three-dimensional membrane structure with nano channels, and have the advantages of flexible structure, excellent separation performance, excellent thermal stability, nano-scale fluid and the like in the field of water treatment. The membrane separation layer is assembled by nano materials, and has good interception effect on small molecules.
Meanwhile, the strongly toxic aromatic compounds with smaller sizes in the sewage, such as p-nitrophenol, bring huge pollution to water resources and are also a difficult problem in the aspect of water treatment. Many noble metal nanoparticles such as gold, silver and palladium have good catalytic reduction properties for aromatic compounds.
Therefore, for the above reasons, it is necessary to develop a bio-based multifunctional water filtration composite membrane capable of simultaneously removing small dye molecules and aromatic compounds from water.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a multifunctional bio-based composite microporous membrane and a preparation method thereof.
In a first aspect, the invention provides a multifunctional bio-based composite microporous membrane, which mainly comprises a separation layer and a support layer, wherein the separation layer is mainly prepared by mixing a nano material and an additive, and the support layer comprises a stereo composite polylactic acid microporous membrane and noble metal nanoparticles loaded in the stereo composite polylactic acid microporous membrane.
The multifunctional bio-based composite microporous membrane utilizes a unique stacked structure of nano materials to form a three-dimensional separation layer for intercepting small dye molecules, wherein the molecular weight of the small dye molecules is generally in the range of 450-; meanwhile, precious metal nanoparticles with catalytic performance are loaded on the stereo composite polylactic acid microporous membrane in the supporting layer, so that the aromatic compounds (such as p-nitrophenol and the like) in the sewage system are rapidly degraded. Under the synergistic effect of the separation layer and the support layer, the functional bio-based composite microporous membrane can more stably and efficiently treat dye molecules and aromatic compounds in sewage compared with the microporous membrane in the prior art, and meanwhile, the preparation process is simple, the operation is convenient, and the functional bio-based composite microporous membrane has very important scientific and application prospects.
As a preferred embodiment of the multifunctional bio-based composite microporous membrane of the present invention, the nanomaterial is one of graphene, graphene oxide, graphite-phase carbon nitride, MOF (metal organic framework material), COF (covalent organic framework material). The graphene, the graphene oxide, the graphite-phase carbon nitride, the MOF and the COF have unique sheet structures, can be assembled into a three-dimensional membrane structure with a nano-channel, and have the advantages of flexible structure, excellent separation performance, excellent thermal stability, nano-scale fluid and the like in the field of water treatment.
As a preferred embodiment of the multifunctional bio-based composite microporous membrane of the present invention, the additive is one of dopamine, a positively charged ionic material, branched polyethyleneimine, a carbon nanotube, and bacterial cellulose.
As a preferred embodiment of the multifunctional bio-based composite microporous membrane of the present invention, the mass ratio of the nanomaterial to the additive is nanomaterial: (1-5) an additive: (10-50).
As a preferred embodiment of the multifunctional bio-based composite microporous membrane, the stereocomplex polylactic acid microporous membrane is mainly prepared by carrying out in-situ polymerization reaction on D-type polylactic acid and L-type polylactic acid, wherein the mass ratio of the D-type polylactic acid to the L-type polylactic acid is (0.1-50): 50-99.9), and the loading amount of the noble metal nanoparticles in the stereocomplex polylactic acid microporous membrane is 20-80%.
As a preferred embodiment of the multifunctional bio-based composite microporous membrane of the present invention, the noble metal nanoparticles are at least one of gold, silver, copper, platinum and palladium.
In a second aspect, the invention further provides a preparation method of the multifunctional bio-based composite microporous membrane, which comprises the following steps:
(1) dissolving D-type polylactic acid and L-type polylactic acid in an organic solvent under the protection of protective gas to obtain a film-forming precursor solution, then adding an active solution into the film-forming precursor solution to carry out in-situ polymerization reaction, stopping the protection of the protective gas after the reaction is finished, and defoaming to prepare a polylactic acid nascent membrane, curing the polylactic acid nascent membrane, soaking the polylactic acid nascent membrane in water, and drying to obtain a stereo composite polylactic acid microporous membrane;
(2) loading noble metal nanoparticles on the stereo composite polylactic acid microporous membrane prepared in the step (1) to obtain a polylactic acid microporous membrane (namely a supporting layer) loaded with the noble metal nanoparticles;
(3) and (3) loading the uniform mixed solution of the nano material and the additive on the polylactic acid microporous membrane loaded with the noble metal nano particles prepared in the step (2), and drying to obtain the multifunctional bio-based composite microporous membrane.
The stereo composite polylactic acid microporous membrane prepared by the preparation method is a stereo composite structure and forms a plurality of microporous structures with different scales, and noble metal nano particles can enter the micropores after being loaded on the stereo composite polylactic acid microporous membrane, so that the noble metal nano particles can be well loaded in the stereo composite polylactic acid microporous membrane; meanwhile, the nano material and the additive form a separation layer with a multi-layer structure on the supporting layer, and the separation layer and the supporting layer have strong bonding force.
In the step (1), the dissolving temperature of the D-type polylactic acid and the L-type polylactic acid in the organic solvent is 80-110 ℃, and the dissolving time is 3-24 hours.
As a preferred embodiment of the preparation method, in the step (1), the time of the in-situ polymerization reaction is 2-48 h.
In a preferred embodiment of the preparation method of the present invention, in the step (1), the curing temperature is 0 to 60 ℃.
As a preferred embodiment of the preparation method, in the step (1), the soaking in water is carried out at the temperature of 10-60 ℃ for more than 12 hours.
As a preferable embodiment of the production method of the present invention, the organic solvent is at least one of N-methylpyrrolidone, N-dimethylacetamide, dimethylsulfoxide, dimethylformamide, and triethyl phosphate.
In a preferred embodiment of the preparation method of the present invention, the total mass concentration of the D-type polylactic acid and the L-type polylactic acid in the film-forming precursor solution is 12% to 25%.
As a preferred embodiment of the preparation process of the present invention, the active solution consists essentially of azobisisobutyronitrile, N-vinylpyrrolidone and vinyltriethoxysilane.
In a preferred embodiment of the production method of the present invention, the polylactic acid primary membrane is at least one of a flat membrane, a homogeneous membrane, and an asymmetric membrane.
As a preferred embodiment of the preparation method of the invention, the step (2) and the step (3) are carried out by vacuum filtration.
Compared with the prior art, the invention has the following advantages: the separating layer of the multifunctional bio-based composite microporous membrane forms a three-dimensional structure capable of intercepting dye micromolecules by utilizing a unique stacked structure of nano materials; the support layer takes a biodegradable stereo composite polylactic acid microporous membrane as a matrix and is loaded with noble metal nano particles with catalytic performance, so that aromatic compounds in a sewage system can be rapidly degraded; compared with the microporous membrane in the prior art, the multifunctional bio-based composite microporous membrane can treat dye molecules and aromatic compounds in sewage more stably and efficiently under the synergistic action of the separation layer and the supporting layer, and meanwhile, the multifunctional bio-based composite microporous membrane is simple in preparation process, convenient to operate and has very important scientific and application prospects.
Drawings
FIG. 1 is a surface microtopography of the multifunctional bio-based composite microporous membrane obtained in example 2;
FIG. 2 is a cross-sectional micro-topography photograph and an elemental distribution chart of the multifunctional bio-based composite microporous membrane obtained in example 2;
FIG. 3 is a graph of the effect of the multifunctional bio-based composite microporous membrane obtained in example 3 on Congo red retention;
FIG. 4 shows the effect of the multifunctional bio-based composite microporous membrane obtained in example 3 on the retention of paranitrophenol.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention is further illustrated by the following examples. It is apparent that the following examples are only a part of the embodiments of the present invention, and not all of them. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention.
Example 1
This example is an example of a method for preparing a multifunctional bio-based composite microporous membrane according to the present invention. The preparation method of the multifunctional bio-based composite microporous membrane in the embodiment comprises the following steps:
(1) under the protection of nitrogen, dissolving 3g D type polylactic acid and 17g L type polylactic acid in 80g N-methyl pyrrolidone to obtain a film-forming precursor solution, wherein the dissolving temperature is 85 ℃, and the dissolving time is 5 hours; then adding 20g of active solution into the film-forming precursor solution to perform in-situ polymerization reaction, wherein the active solution consists of azobisisobutyronitrile, N-vinylpyrrolidone and vinyltriethoxysilane (mass ratio is N-diisobutyronitrile: N-vinylpyrrolidone: vinyltriethoxysilane is 1: 80: 50), and the reaction time is 24 hours; stopping protective gas protection after the reaction is finished, defoaming, preparing a polylactic acid primary membrane by adopting a flat membrane scraping system, then curing the polylactic acid primary membrane in a water bath at 25 ℃, soaking in deionized water at 25 ℃ for 20 hours, and drying to obtain a stereo composite polylactic acid microporous membrane;
(2) loading nano palladium particles prepared by a sodium borohydride reduction method on the stereo composite polylactic acid microporous membrane prepared in the step (1) through a vacuum filtration system, and drying to obtain a polylactic acid microporous membrane loaded with noble metal nanoparticles with a catalytic function, wherein the loading capacity of the noble metal nanoparticles in the stereo composite polylactic acid microporous membrane is 50%, and the particle size is 3-5 nm;
(3) ultrasonically dispersing 5mg of nano graphene oxide powder in 100mL of deionized water, then mixing with 10mg of branched polyethyleneimine, and ultrasonically treating for 10min to obtain a uniform mixed solution of graphene oxide and branched polyethyleneimine; and (3) fixing the polylactic acid microporous membrane loaded with the noble metal nanoparticles prepared in the step (2) on a filter element of a vacuum filtration device, then adding 10mL of the uniform mixed solution of the graphene oxide and the branched polyethyleneimine onto the polylactic acid microporous membrane loaded with the noble metal nanoparticles, carrying out vacuum filtration until no liquid drops, and drying to obtain the multifunctional bio-based composite microporous membrane.
Example 2
This example is an example of a method for preparing a multifunctional bio-based composite microporous membrane according to the present invention. The preparation method of the multifunctional bio-based composite microporous membrane in the embodiment comprises the following steps:
(1) under the protection of nitrogen, 6g D type polylactic acid and 14g L type polylactic acid are dissolved in 80g N-methyl pyrrolidone to obtain a film-forming precursor solution, wherein the dissolving temperature is 80 ℃, and the dissolving time is 7 hours; then adding 20g of active solution into the film-forming precursor solution to carry out in-situ polymerization reaction, wherein the active solution consists of azobisisobutyronitrile, N-vinylpyrrolidone and vinyltriethoxysilane (mass ratio is N-diisobutyronitrile: N-vinylpyrrolidone: vinyltriethoxysilane is 1: 70: 30), and the reaction time is 24 hours; stopping protective gas protection and defoaming after the reaction is finished, preparing a polylactic acid primary membrane by adopting a flat membrane knifing system, then placing the polylactic acid primary membrane in a water bath at 25 ℃ for curing, soaking in deionized water at 25 ℃ for 24 hours, and drying to obtain a stereo composite polylactic acid microporous membrane;
(2) loading the nano gold colloid prepared by a sodium citrate reduction method on the stereo composite polylactic acid microporous membrane prepared in the step (1) through a vacuum filtration system, and drying to obtain a polylactic acid microporous membrane loaded with noble metal nanoparticles with a catalytic function, wherein the loading capacity of the noble metal nanoparticles in the stereo composite polylactic acid microporous membrane is 50%, and the particle size is 18-20 nm;
(3) ultrasonically dispersing 10mg of bacterial cellulose in 15mL of formamide solution, then mixing with 5mL of 1mg/mL graphene oxide dispersion liquid (the solvent is deionized water), and ultrasonically treating for 10 minutes to obtain a uniform mixed solution of the bacterial cellulose and the graphene oxide; and (3) fixing the polylactic acid microporous membrane loaded with the noble metal nanoparticles prepared in the step (2) on a filter element of a vacuum filtration device, then adding 10mL of the uniform mixed solution of the oxygen bacterial cellulose and the graphene oxide onto the polylactic acid microporous membrane loaded with the noble metal nanoparticles, carrying out vacuum filtration until no liquid drops, and drying to obtain the multifunctional bio-based composite microporous membrane.
As can be seen from fig. 1, bacterial cellulose and graphene oxide are uniformly distributed on the surface of the multifunctional bio-based composite microporous membrane in this embodiment. As can be seen from fig. 2, in the separation layer of the multifunctional bio-based composite microporous membrane in the present embodiment, a multilayer structure in which bacterial cellulose and graphene oxide are combined exists; a stereo composite structure exists in the supporting layer, a multi-scale microporous structure is formed, and the nano gold particles are loaded.
The multifunctional bio-based composite microporous membrane prepared in the embodiment is subjected to a performance test by adopting 1L of 20ppm Congo red solution and rhodamine B solution under 0.1MPa, and the result is as follows: the total retention rate of Congo red reaches 99 percent, and the average flux is 80.5L/(m)2H), the total conversion of rhodamine B is 95%, and the average flux is 100L/(m)2·h)。
Example 3
This example is an example of a method for preparing a multifunctional bio-based composite microporous membrane according to the present invention. The preparation method of the multifunctional bio-based composite microporous membrane in the embodiment comprises the following steps:
(1) under the protection of nitrogen, 4g D type polylactic acid and 13g L type polylactic acid are dissolved in 83g of dimethyl sulfoxide to obtain a film-forming precursor solution, wherein the dissolving temperature is 90 ℃, and the dissolving time is 9 hours; then adding 20g of active solution into the film-forming precursor solution to perform in-situ polymerization reaction, wherein the active solution consists of azobisisobutyronitrile, N-vinylpyrrolidone and vinyltriethoxysilane (mass ratio is N-diisobutyronitrile: N-vinylpyrrolidone: vinyltriethoxysilane is 1: 70: 30), and the reaction time is 28 h; stopping protective gas protection and defoaming after the reaction is finished, preparing a polylactic acid primary membrane by adopting a flat membrane knifing system, then placing the polylactic acid primary membrane in a water bath at 25 ℃ for curing, soaking in deionized water at 25 ℃ for 24 hours, and drying to obtain a stereo composite polylactic acid microporous membrane;
(2) loading the nano gold colloid prepared by a sodium citrate reduction method on the stereo composite polylactic acid microporous membrane prepared in the step (1) through a vacuum filtration system, and drying to obtain a polylactic acid microporous membrane loaded with noble metal nanoparticles with a catalytic function, wherein the loading capacity of the noble metal nanoparticles in the stereo composite polylactic acid microporous membrane is 50%, and the particle size is 18-20 nm;
(3) ultrasonically dispersing 1mg of graphene oxide nanosheets in 50mL of deionized water, then adding 40mg of carbon nanotubes, and ultrasonically treating for 30min to obtain a uniform mixed solution of graphene oxide and the carbon nanotubes; and (3) fixing the polylactic acid microporous membrane loaded with the noble metal nanoparticles prepared in the step (2) on a filter element of a vacuum filtration device, then adding 10mL of the uniform mixed solution of the graphene oxide and the carbon nanotubes onto the polylactic acid microporous membrane loaded with the noble metal nanoparticles, carrying out vacuum filtration until no liquid drops, and drying to obtain the multifunctional bio-based composite microporous membrane.
The multifunctional bio-based composite microporous membrane prepared in the embodiment is subjected to performance test, under 0.1MPa, 1L of 20ppm victoria blue solution and 1L of 5ppm p-nitrophenol solution are respectively adopted for testing, and the results are shown in the figure 3 and the figure 4, wherein the total retention rate of victoria blue reaches 99%, and the average flux is 95.4L/(m < m >)2H); the total conversion rate of the p-nitrophenol is 98 percent,the average flux was 105L/(m)2·h)。
As can be seen from fig. 3, the multifunctional bio-based composite microporous membrane prepared in this example has stable retention performance, which indicates that the composite microporous membrane has good ability to treat small dye molecules; as can be seen from fig. 4, the multifunctional composite microporous membrane prepared in this example has good catalytic performance on paranitrophenol, which indicates that the composite microporous membrane has good ability to treat aromatic compounds.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The multifunctional bio-based composite microporous membrane is characterized by mainly comprising a separation layer and a support layer, wherein the separation layer is mainly prepared by mixing a nano material and an additive, and the support layer comprises a stereo composite polylactic acid microporous membrane and noble metal nanoparticles loaded in the stereo composite polylactic acid microporous membrane.
2. The multifunctional bio-based composite microporous membrane according to claim 1, wherein the nanomaterial is one of graphene, graphene oxide, graphite-phase carbon nitride, a metal-organic framework material, a covalent organic framework material; the additive is one of dopamine, positively charged ionic materials, branched polyethyleneimine, carbon nanotubes and bacterial cellulose; the mass ratio of the nano material to the additive is nano material: (1-5) an additive: (10-50).
3. The multifunctional bio-based composite microporous membrane according to claim 1, wherein the stereocomplex polylactic acid microporous membrane is mainly prepared by carrying out in-situ polymerization reaction on D-type polylactic acid and L-type polylactic acid, and the mass ratio of the D-type polylactic acid to the L-type polylactic acid is D-type polylactic acid: l-type polylactic acid (0.1-50): (50-99.9); the loading capacity of the noble metal nanoparticles in the stereo composite polylactic acid microporous membrane is 20-80%.
4. The multifunctional bio-based composite microporous membrane according to claim 1, wherein the noble metal nanoparticles are at least one of gold, silver, copper, platinum, palladium.
5. A method of making the multifunctional bio-based composite microporous membrane according to any one of claims 1 to 4, comprising the steps of:
(1) dissolving D-type polylactic acid and L-type polylactic acid in an organic solvent under the protection of protective gas to obtain a film-forming precursor solution, then adding an active solution into the film-forming precursor solution to carry out in-situ polymerization reaction, stopping the protection of the protective gas after the reaction is finished, and defoaming to prepare a polylactic acid nascent membrane, curing the polylactic acid nascent membrane, soaking the polylactic acid nascent membrane in water, and drying to obtain a stereo composite polylactic acid microporous membrane;
(2) loading noble metal nanoparticles on the stereo composite polylactic acid microporous membrane prepared in the step (1) to obtain a noble metal nanoparticle-loaded polylactic acid microporous membrane;
(3) and (3) loading the uniform mixed solution of the nano material and the additive on the polylactic acid microporous membrane loaded with the noble metal nano particles prepared in the step (2), and drying to obtain the multifunctional bio-based composite microporous membrane.
6. The preparation method according to claim 5, wherein in the step (1), the dissolving temperature of the D-type polylactic acid and the L-type polylactic acid in the organic solvent is 80-110 ℃, and the dissolving time is 3-24 h; the time of the in-situ polymerization reaction is 2-48 h; the curing temperature is 0-60 ℃; the soaking time is more than 12 hours at the temperature of 10-60 ℃ in water.
7. The production method according to claim 5, wherein the organic solvent is at least one of N-methylpyrrolidone, N-dimethylacetamide, dimethylsulfoxide, dimethylformamide, and triethyl phosphate; the total mass concentration of the D-type polylactic acid and the L-type polylactic acid in the film-forming precursor solution is 12-25%.
8. The method of claim 5, wherein the active solution consists essentially of azobisisobutyronitrile, N-vinylpyrrolidone, and vinyltriethoxysilane.
9. The production method according to claim 5, wherein the polylactic acid primary membrane is at least one of a flat membrane, a homogeneous membrane, and an asymmetric membrane.
10. The preparation method according to claim 5, wherein the step (2) and the step (3) are carried out by vacuum filtration.
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| CN112551644A (en) * | 2020-11-30 | 2021-03-26 | 东北林业大学 | Preparation method of palladium-cellulose membrane capable of synchronizing emulsion separation and dye degradation |
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| CN114660198B (en) * | 2022-03-23 | 2023-10-20 | 江南大学 | Method for detecting rhodamine B based on solid-phase microextraction film enrichment |
| CN115090132A (en) * | 2022-08-05 | 2022-09-23 | 天津工业大学 | Self-cleaning composite membrane with catalytic separation function and preparation method thereof |
| US12071446B1 (en) | 2024-02-12 | 2024-08-27 | King Faisal University | Metal organic frameworks containing face-centered cubic topology supported by carbon nanotubes |
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