CN113101816B - Preparation method and application of self-antibacterial silver nanoparticle and cellulose nanocrystal composite filter membrane - Google Patents
Preparation method and application of self-antibacterial silver nanoparticle and cellulose nanocrystal composite filter membrane Download PDFInfo
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- CN113101816B CN113101816B CN202110280552.2A CN202110280552A CN113101816B CN 113101816 B CN113101816 B CN 113101816B CN 202110280552 A CN202110280552 A CN 202110280552A CN 113101816 B CN113101816 B CN 113101816B
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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
- B01D71/08—Polysaccharides
- B01D71/10—Cellulose; Modified cellulose
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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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
- B01D71/02—Inorganic material
- B01D71/022—Metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to a preparation method of a self-antibacterial silver nanoparticle/cellulose nanocrystal composite filter membrane, which comprises the steps of uniformly mixing a silver nitrate solution and a cellulose nanocrystal water dispersion liquid, carrying out hydrothermal reaction on the obtained mixed solution at 80-150 ℃ and 47 kPa-475 k Pa to obtain a silver nanoparticle-loaded cellulose nanocrystal water dispersion liquid, and directly forming a membrane by using the obtained silver nanoparticle-loaded cellulose nanocrystal water dispersion liquid through vacuum-assisted filtration to obtain the self-antibacterial silver nanoparticle/cellulose nanocrystal composite filter membrane. According to the invention, no additive is needed, and the silver nanoparticles are synthesized in situ on the surface of the cellulose nanocrystals by a hydrothermal reduction method, so that the dispersion performance of the silver nanoparticles on the surface of the cellulose nanocrystals is effectively improved, and the obtained filter membrane has antibacterial performance and does not influence the wettability of the material.
Description
Technical Field
The invention relates to a preparation method of a self-antibacterial silver nanoparticle/cellulose nanocrystal composite filter membrane and an oil-water separation application thereof, belonging to the fields of chemistry, chemical engineering and high polymer functional materials.
Background
In the current society, the pollution of oily wastewater is still an invisible problem, and the treatment of the oily wastewater is very critical. The oil drops are classified into emulsifiable oil (the grain diameter of the oil drops is more than 100 mu m), dispersed oil (the grain diameter of the oil drops is 10 mu m-100 mu m) and emulsified oil (the grain diameter of the oil drops is less than 10 mu m) according to the existing form of the oil drops in the oily wastewater and the difference of the sizes of the oil drops. The traditional oil-water separation methods such as centrifugal separation, coarse graining method, flotation method and the like can only separate floating oil and dispersed oil, but emulsified oil is difficult to separate due to small oil drop size and stable state. The common methods for separating the emulsified oil, such as sedimentation separation, air flotation, adsorption, advanced oxidation, chemical flocculation and the like, have the problems of incapability of recycling water, secondary pollution to the environment, low economic benefit and the like, and the separation membrane can avoid the problems. Common separation membranes include polymeric and ceramic membranes. The preparation of the polymer film usually needs a phase transformation process, so that harmful substances are inevitably used, and the preparation process is complex; the ceramic membrane has large mass due to large density and high preparation cost.
The cellulose nanocrystal has the characteristics of high length-diameter ratio, high elastic modulus, high thermal stability, high specific surface area and the like, has good biocompatibility and is degradable and environment-friendly, and can be widely applied to the fields of sewage treatment, papermaking, foods, new energy batteries, buildings and the like. Because the cellulose nanocrystals are polysaccharides composed of glucose units, the cellulose nanocrystals are very easy to be corroded by bacteria in air, particularly in aqueous dispersion, on one hand, the structural integrity of the cellulose nanocrystals is damaged, and on the other hand, the fine growth on the surfaces of the nanocrystals is easy to block water passage channels after film formation, so that the water flux is reduced, and the separation efficiency is reduced. Therefore, it is necessary to provide cellulose nanocrystals with antibacterial properties.
Disclosure of Invention
The invention aims to provide a preparation method and application of a self-antibacterial silver nanoparticle/cellulose nanocrystal composite filter membrane.
The scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a self-antibacterial silver nanoparticle/cellulose nanocrystal composite filter membrane comprises the following steps:
(1) uniformly mixing a silver nitrate solution and a cellulose nanocrystal water dispersion liquid;
(2) carrying out hydrothermal reaction on the obtained mixed solution at the temperature of 80-150 ℃ and the pressure of 47 kPa-475 kPa to obtain cellulose nano-crystal water dispersion liquid loaded by silver nano-particles;
(3) and directly forming a film by using the obtained silver nanoparticle loaded cellulose nanocrystal water dispersion through vacuum-assisted filtration to obtain the self-antibacterial silver nanoparticle/cellulose nanocrystal composite filter membrane.
Preferably, the concentration of the cellulose nanocrystals in the mixed solution obtained in the step (1) is 0.05 wt% -1.0 wt%, and the concentration of the silver nitrate is 1 mmol/L-250 mmol/L.
Preferably, the content of the cellulose nanocrystals in the cellulose nanocrystal water dispersion liquid adopted in the step (1) is 0.01 wt% -1 wt%, and the volume ratio of the silver nitrate solution to the cellulose nanocrystal water dispersion liquid is 1: 4-8: 1.
Preferably, the hydrothermal reaction time in the step (2) is 12-36 h.
Preferably, the mass content of the silver nanoparticles in the composite filter membrane obtained in the step (3) is 0.01 wt% -2 wt%.
Preferably, the vacuum-assisted filtration membrane formation in the step (3) adopts a common filter membrane as a substrate, and the average pore diameter of the common filter membrane is 0.22 μm.
The invention also aims to provide a self-antibacterial silver nanoparticle/cellulose nanocrystal composite filter membrane which is prepared by the preparation method, wherein the particle size of the silver nanoparticles in the filter membrane is 3.5-9.5 nm.
The invention also aims to provide the application of the antibacterial silver nanoparticle/cellulose nanocrystal composite filter membrane obtained by the preparation method in oil-water emulsion separation, wherein the size of oil drops in the separated oil-water emulsion is 100 nm-20 mu m.
According to the invention, no additive is needed, and the silver nanoparticles are synthesized in situ on the surface of the cellulose nanocrystals by a hydrothermal reduction method, so that the dispersion performance of the silver nanoparticles on the surface of the cellulose nanocrystals is effectively solved, and the obtained filter membrane has antibacterial performance and does not influence the wettability of the material. The cellulose nanocrystal can be used as a dispersing agent and a stabilizing agent of silver nanoparticles, and the obtained silver nanoparticles have small size and good dispersibility. The composite cellulose nanocrystal water dispersion is directly filtered under reduced pressure to form a film, and the preparation process is simple, quick and convenient. In addition, the average pore diameter, the thickness and the water flux of the membrane can be effectively regulated and controlled by regulating the using amount of the composite cellulose nanocrystals in unit area, the antibacterial performance can be controlled by regulating the loading amount of silver nanoparticles on the cellulose nanocrystals in unit area, and the emulsion separation efficiency is not influenced by the introduction of the silver nanoparticles, so that the controllable separation of oil drops with different size grades is realized. Meanwhile, the composite filter membrane can be stored for a long time and can keep the cleanness of the composite membrane to a certain extent in the oil-water emulsion separation process.
Drawings
FIG. 1 is a representation of the composite cellulose nanocrystals and filters obtained in example 1, wherein (a) the cellulose nanocrystal composite filter is a physical image, (b) the cellulose nanocrystal composite filter is a scanning electron microscope image, (c) the particle size of the silver nanoparticles is a statistical image, and (d) the transmission electron microscope image of the single cellulose nanocrystals is a transmission electron microscope image;
FIG. 2 is a comparison of the cellulose nanocrystal composite filter membrane emulsion obtained in example 1 before and after separation, wherein (a) and (c) are respectively a micron-sized petroleum ether emulsion before separation and a filtrate after separation, and (b) and (d) are optical micrographs of corresponding liquid droplets;
FIG. 3 is the results of the antibacterial experiments of Escherichia coli by disc diffusion method of cellulose nanocrystal composite filter membranes with different silver nanoparticle loadings (0, 0.5 wt%, 1.0 wt%, 2.0 wt%), wherein (a) is a plot of inhibition area, and (b) is a corresponding statistical plot of inhibition zone diameter.
Detailed Description
The following examples further illustrate the present invention but should not be construed as limiting the invention. Modifications or substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Example 1
Uniformly mixing the prepared silver nitrate solution and the cellulose nanocrystal aqueous dispersion according to the mass ratio of 4:1 to ensure that the concentration of silver nitrate in the obtained mixed solution is 12mmol/L and the concentration of cellulose nanocrystals is 0.05 wt%, then adding the mixed solution into a polytetrafluoroethylene lining, putting the lining into a metal reaction kettle, carrying out hydrothermal reaction on the mixed solution at 80 ℃ and 47KPa for 24 hours to obtain a composite cellulose nanocrystal aqueous dispersion, and then adopting a common filter membrane with the average pore size of 0.22 mu m as a substrate, and carrying out reduced pressure filtration to prepare 0.82g m -2 The nano-scale composite membrane of (2). The prepared composite filter membrane shows super wettability and antibacterial property. Thermogravimetric analysis shows that the loading of the silver nanoparticles in the obtained composite film is 2 wt%.
Examples 2 to 5
The preparation method is the same as that in example 1, except that the mass ratios of the silver nitrate solution participating in the hydrothermal reaction to the cellulose nanocrystal aqueous dispersion are respectively 1:2, 1:1, 2:1 and 8:1, that is, the concentrations of silver nitrate in the obtained mixed solution are respectively 1.5mmol/L, 3mmol/L, 6mmol/L and 24mmol/L, and the concentration of the cellulose nanocrystal is 0.05 wt%. The obtained filter membranes all show super-wettability and antibacterial property. Thermogravimetric analysis shows that the loading amounts of the silver nanoparticles in the obtained composite membrane are respectively 0.2 wt%, 0.5 wt%, 1 wt% and 2 wt%.
Example 6
The preparation method was the same as in example 1 except that the hydrothermal reaction temperature was 100 ℃ and the pressure was 300 KPa. The prepared composite filter membrane shows super wettability and antibacterial property.
Example 7
The preparation method was the same as example 1 except that the hydrothermal reaction temperature was 150 ℃ and the pressure was 475 KPa. The prepared composite filter membrane shows super wettability and antibacterial property.
Comparative example 1
The same preparation method as in example 1 was used except that polyvinylidene fluoride was used instead of cellulose nanocrystals. The prepared filter membrane can not reduce silver ions, so that the filter membrane has no antibacterial property.
Comparative example 2
The same material as used in example 1 was used except that the hydrothermal method was not carried out using a reaction vessel, and silver ions were reduced by adding sodium borohydride as a reducing agent at 25 ℃. The prepared silver particles have agglomeration phenomenon, are large in size and cannot be uniformly dispersed on the surface of the cellulose nanocrystal. Furthermore, the silver particles are agglomerated to cause certain blockage of the pores of the prepared filter membrane, which results in the reduction of water flux (124 +/-10.1 L.m) -2 ·h -1 ·bar -1 )。
Comparative example 3
The same procedure as in example 1 was followed, except that the hydrothermal method was carried out at a temperature of 60 ℃. The suspension produced was unchanged as before the reaction. Silver ions in the silver nitrate are not reduced into silver nano particles, and the filter membrane obtained by vacuum auxiliary filtration has no antibacterial property.
Comparative example 4
The same procedure as in example 1 was followed, except that the hydrothermal method was carried out at a temperature of 160 ℃. The prepared suspension can be uniformly dispersed, but the cellulose nanocrystals are structurally damaged due to the overhigh reaction temperature and pressure, so that the average pore diameter of the membrane is increased (300nm), and the oil-water separation efficiency is remarkably reduced (90%).
Comparative example 5
The same procedure as in example 1 was followed, except that the hydrothermal process was carried out at a pressure of 500 KPa. The prepared suspension can be uniformly dispersed, but the cellulose nanocrystals are structurally damaged due to the overhigh reaction pressure and temperature, so that the average pore diameter of the membrane is increased (325nm), and the oil-water separation efficiency is remarkably reduced (88%).
Comparative example 6
The same preparation method as in example 1, except that silver nitrate solution was not added, and a pure cellulose nanocrystal filter membrane without silver nanoparticles was obtained.
Oil-water separation test
The composite filter membranes obtained in examples 1, 5 and 7 were used in different oil-water emulsion separation tests, and the emulsion separation results were the same as follows:
separating micron-sized petroleum ether emulsion (the mass ratio of petroleum ether to water is 1:99, the addition amount of the surfactant is 0.2 wt%), effectively demulsifying and intercepting oil drops by using the membrane, wherein the oil-water separation efficiency of the membrane is 99.9%, and the flow rate is 254 +/-19.5 L.m -2 ·h -1 ·bar -1 。
Separating micron chloroform emulsion (the mass ratio of chloroform to water is 5:95, the addition amount of surfactant is 0.1 wt%), the membrane can effectively break emulsion and retain oil drops, the oil-water separation efficiency of the membrane is 99.5%, and the flow rate is 325 +/-17.1 L.m -2 ·h -1 ·bar -1 。
The micron-sized petroleum ether emulsion is separated (the mass ratio of petroleum ether to water is 1:99, and the addition amount of the surfactant is 0.2 wt%), and the membrane can effectively break emulsion and intercept oil drops, thereby realizing oil-water separation. The membrane is recycled for 10 times, the oil-water separation efficiency of the membrane is maintained at 99.2%, and the flux is 245±16.8L·m -2 ·h -1 ·bar -1 。
Antibacterial experiments
The composite filter membranes obtained in examples 1, 4 and 5 and the original membrane without silver nanoparticles obtained in comparative example were used as samples, and an antibacterial test of escherichia coli was performed on LB medium by a disc diffusion method. As shown in fig. 3, it can be seen that, compared to the original membrane, as the loading amount of the silver nanoparticles increases, the diameter of the inhibition zone increases, and the loading amount of the silver nanoparticles of 2 wt% can reach 270%.
According to the invention, hydroxyl carried by the cellulose nanocrystals is used as a reducing agent of silver ions and a dispersing agent and a stabilizing agent of silver nanoparticles, and the reaction kettle is used for carrying out a hydrothermal method to obtain a high-pressure promoted reaction, so that the silver nanoparticles in the obtained filter membrane are uniformly dispersed in the cellulose nanocrystals, and the filter membrane shows super-wettability and antibacterial property. It is noted that the reaction temperature ranges from 80 ℃ to 150 ℃ and the pressure ranges from 47kPa to 475 kPa. The temperature and the pressure are too low, and the reduction reaction cannot be carried out; the temperature and pressure are too high, the cellulose nanocrystal structure is damaged, and the integrity and the super-wettability of the formed film cannot be ensured. The cellulose nanocrystals (example 1) obtained by the 80 ℃ hydrothermal method were structurally complete, and the silver nanoparticles obtained were small in size (average size of 6nm) and uniformly dispersed on the surface of the cellulose nanocrystals, as shown in fig. 1. The composite filter membrane obtained by vacuum-assisted filtration shows excellent wettability, the oil cut rate is as high as 99.8%, and meanwhile, the antibacterial performance is good (the diameter of a bacteriostatic zone is as high as 270%), so that the composite filter membrane is beneficial to long-term storage and use of the filter membrane, and has a wide use prospect.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (9)
1. A preparation method of a self-antibacterial silver nanoparticle/cellulose nanocrystal composite filter membrane is characterized by comprising the following steps:
(1) uniformly mixing a silver nitrate solution and a cellulose nanocrystal water dispersion liquid;
(2) carrying out hydrothermal reaction on the obtained mixed solution at the temperature of 80-150 ℃ and the pressure of 47 kPa-475 kPa to obtain cellulose nano-crystal water dispersion loaded with silver nano-particles, wherein the particle size of the silver nano-particles in the filter membrane is 3.5-9.5 nm;
(3) directly forming a film by using the obtained silver nanoparticle-loaded cellulose nanocrystal water dispersion through vacuum-assisted filtration to obtain a self-antibacterial silver nanoparticle/cellulose nanocrystal composite filter membrane;
the size of oil drops in the oil-water emulsion for separation by the composite filter membrane is 100 nm-20 mu m.
2. The preparation method according to claim 1, wherein the concentration of the cellulose nanocrystals in the mixed solution obtained in step (1) is 0.05 to 1.0 wt%, and the concentration of silver nitrate is 1 to 250 mmol/L.
3. The preparation method according to claim 1, wherein the cellulose nanocrystal content in the cellulose nanocrystal aqueous dispersion used in the step (1) is 0.01 wt% to 1 wt%, and the volume ratio of the silver nitrate solution to the cellulose nanocrystal aqueous dispersion is 1:4 to 8: 1.
4. The preparation method according to claim 1, wherein the hydrothermal reaction time in the step (2) is 12-36 h.
5. The preparation method of claim 1, wherein the mass content of the silver nanoparticles in the composite filter membrane obtained in the step (3) is 0.01 wt% to 2 wt%.
6. The method according to claim 1, wherein the vacuum-assisted filtration membrane of step (3) is formed by using a common filter membrane as a substrate, and the average pore size of the common filter membrane is 0.22 μm.
7. The self-antibacterial silver nanoparticle/cellulose nanocrystal composite filter membrane is characterized by being prepared by the preparation method of any one of claims 1-6, wherein the particle size of silver nanoparticles in the filter membrane is 3.5-9.5 nm.
8. Use of the antibacterial silver nanoparticle/cellulose nanocrystal composite filter membrane obtained by the preparation method according to any one of claims 1 to 6 for oil-water emulsion separation.
9. Use according to claim 8, characterized in that the oil droplet size in the oil-water emulsion used for separation is between 100nm and 20 μm.
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| CN103483786A (en) * | 2013-06-27 | 2014-01-01 | 浙江理工大学 | Fully-biodegradable composite membrane filled with nano silver/cellulose nanocrystal composite particles, and preparation method thereof |
| CN107983179A (en) * | 2017-11-30 | 2018-05-04 | 武汉大学 | A kind of preparation method and applications of multifunctional nano cellulose compound-split filter membrane |
| US10259725B2 (en) * | 2016-12-30 | 2019-04-16 | United Arab Emirates University | Method of synthesizing cellulose nano-crystals from date palm seeds |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103483786A (en) * | 2013-06-27 | 2014-01-01 | 浙江理工大学 | Fully-biodegradable composite membrane filled with nano silver/cellulose nanocrystal composite particles, and preparation method thereof |
| US10259725B2 (en) * | 2016-12-30 | 2019-04-16 | United Arab Emirates University | Method of synthesizing cellulose nano-crystals from date palm seeds |
| CN107983179A (en) * | 2017-11-30 | 2018-05-04 | 武汉大学 | A kind of preparation method and applications of multifunctional nano cellulose compound-split filter membrane |
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