CN111186881B - Chitosan modified nano TiO2Preparation method of photocatalytic ultrafiltration membrane - Google Patents
Chitosan modified nano TiO2Preparation method of photocatalytic ultrafiltration membrane Download PDFInfo
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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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
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/34—Polyvinylidene fluoride
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- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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Abstract
The invention relates to chitosan modified nano TiO2A preparation method of a photocatalytic ultrafiltration membrane belongs to the technical field of membrane separation and water treatment. Aiming at the traditional nano TiO2Easy to agglomerate and compound on a separation membrane and is easy to continuously run off, and an improved TiO is developed2A preparation method of a photocatalytic ultrafiltration membrane. The method uses amino silane coupling agent as a bridge to prepare nano TiO2The surface of the cross-linked chitosan grafted with loose surface can effectively open the nano TiO2The particles are aggregated to be highly dispersed on the separation membrane, and the particle size of the particles is expanded by 3 to 5 times compared with that of the particles which are not modified, so that the nano TiO in the operation of the photocatalytic membrane is effectively prevented2Loss of the catalyst. The modified photocatalytic ultrafiltration membrane prepared by the method can maintain the long-time efficient and stable operation of the separation membrane in the wastewater treatment process, has a water flux attenuation coefficient far lower than that of an unmodified separation membrane after 10 hours of operation, and has a wide application prospect.
Description
Technical Field
The invention relates to chitosan modified nano TiO2A preparation method of a photocatalytic ultrafiltration membrane belongs to the technical field of membrane separation and water treatment.
Background
In the field of membrane preparation and application, a membrane separation technology with a single function is difficult to meet the increasingly improved technical requirements of social industrial production and environmental pollution prevention and treatment. Particularly in the field of water treatment application, although the membrane separation technology is always applied to water pollution prevention and treatment projects under different water quality conditions and different requirements as a quick, efficient and practical technology, the wider application and deep popularization of the membrane separation technology are severely restricted due to the single function of the membrane separation technology. Therefore, the development, application and popularization of the multifunctional novel membrane separation technology are the leading directions of the membrane industry development which are not negligible.
As a new pollution treatment technology, photocatalytic degradation of organic pollutants is receiving more and more attention. The organic pollutant decomposing agent is applied to degrading environmental organic pollutants and has the capability of completely converting most of the organic pollutants into water, carbon dioxide and the like, namely completely mineralizing. The photocatalyst has the advantages of relatively low cost, stable chemical property, no toxicity and environmental friendliness. The photocatalytic technology and the membrane separation technology are coupled, so that the technical defect of a single treatment process can be effectively overcome, and the photocatalytic technology and the membrane separation technology become hot spots for researches of scholars at home and abroad in recent years. TiO22Semiconductor photocatalysts were the first discovered photocatalyst capable of reacting with H under UV irradiation2O、O2Or OH-The action generates reactive oxygen species including hydroxyl radicals which can completely degrade almost all organics to H2O、CO2And the like, and is low in price, safe and nontoxic, and is also the most commonly used photocatalyst. Adding TiO into the mixture2The photocatalysis load separation membrane can give full play to the separation characteristic of the membrane and the degradation effect of the photocatalyst, and can quickly and effectively separate and mineralize organic matters in the wastewater, thereby improving the separation performance and the pollution resistance of the separation membrane.
Nano-grade TiO prepared by traditional sol-gel method2Although having higher photocatalytic performance, the particle size of the composite nano TiO nano composite photocatalytic membrane is smaller than the aperture of most wastewater treatment separation membranes2Can continuously run off to influence the stable operation of the photocatalytic film. And due to the nanoscale TiO2The surface energy of the catalyst is relatively high, particles are easy to agglomerate and cannot be uniformly dispersed in the separation membrane, and the photocatalytic performance of the catalyst in the separation membrane is limited.
The present invention is directed to the aboveDisclosure of the invention technical problem an improved TiO has been developed2A preparation method of a photocatalytic ultrafiltration membrane. The method uses amino silane coupling agent as a bridge to prepare nano TiO2Grafting loose crosslinked chitosan on the surface to obtain modified nano TiO2The particles can be effectively dispersed, the particle size of the particles is expanded by 3 to 5 times compared with that of the particles without modification, and the nano TiO in the operation of the photocatalytic film can be effectively prevented2Loss of the catalyst. At the same time, inorganic particle TiO2And the modified chitosan can improve the hydrophilicity of the ultrafiltration membrane and further improve the anti-pollution performance of the membrane. The preparation method has the advantages of rich raw materials, environmental protection, low price, simple preparation process, easy operation, high wastewater treatment efficiency of the obtained photocatalytic ultrafiltration membrane and wide application prospect.
Disclosure of Invention
The invention aims to provide chitosan modified nano TiO2The preparation method of the photocatalytic ultrafiltration membrane comprises the following preparation steps:
(1) the nano TiO prepared by the traditional preparation method2Dispersing in deionized water, ultrasonic dispersing for 1-3h, adding aminosilane coupling agent, reflux reacting at 30-50 deg.C for 2-4h to make TiO2Grafting a large amount of amino on the surface, and centrifugally separating the reaction solution to obtain a product for later use;
(2) dispersing the product obtained in the step (1) in a methanol solution, ultrasonically dispersing for 1-3h, placing the dispersion system in a water bath at 30-50 ℃, adding glutaraldehyde, dropwise adding a small amount of acetic acid, and carrying out reflux reaction for 1-4 h; adding chitosan solution dissolved in dilute nitric acid, and continuously performing reflux reaction for 2-8h to ensure that the chitosan is fully crosslinked in the TiO2After the reaction is finished, the chitosan modified nano TiO is obtained by centrifugal separation2；
(3) Dissolving a proper amount of membrane material by using a solvent, and adding the modified nano TiO obtained in the step (2)2Stirring to obtain a casting solution, standing for defoaming, coating the casting solution on a glass plate, scraping to form a film, and soaking the film into a deionized water coagulating bath at the temperature of 0-50 ℃ to form the film to obtain the chitosan modified nano TiO modified by the chitosan2And (3) a photocatalytic ultrafiltration membrane.
In the present invention, an aminosilane is usedUsing the coupling agent as inorganic nano TiO2And bridges of natural organic chitosan molecules. The amino group can react with glutaraldehyde in Schiff base under mild reaction conditions. Therefore, the amino group in the silane coupling agent and a large amount of amino groups carried on the surface of the chitosan provide conditions for cross-linking grafting.
Further, the aminosilane coupling agent is selected from one or more of aminopropyltrimethoxysilane, aminopropyltriethoxysilane and phenylaminomethyltriethoxysilane.
Further, the membrane material is selected from polyvinylidene fluoride, polytetrafluoroethylene, polysulfone, polyethersulfone, polyacrylonitrile and polyetherimide.
Further, the solvent is selected from N, N dimethylformamide, N dimethylacetamide and dimethyl sulfoxide.
Further, the modified TiO2The addition amount of (B) is 1-10wt% of the membrane material.
Further, the nano TiO2The mass ratio of the amino silane coupling agent to the glutaraldehyde to the chitosan is 1:0.01-0.1:0.01-0.2: 0.05-0.5; preferably 1:0.05-0.08:0.05-0.1: 0.2-0.3. Cross-linked chitosan in TiO2Density of graft crosslinks on the surface to the resulting TiO2The influence of physical properties of (A) is large. Too dense of grafting will reduce TiO2Exposure to organic substances, thereby reducing their photocatalytic activity. The product obtained by the mass ratio can ensure that the chitosan is in TiO2The surface forms a loose cross-linked structure.
Compared with the prior art, the invention has the beneficial effects that:
(1) the raw materials are safe and nontoxic, the cost is low, the operation method is simple, the preparation condition is mild, and the preparation method is suitable for large-scale production;
(2) the invention uses amino silane coupling agent as bridge and uses nano TiO as material2Grafting loose crosslinked chitosan on the surface to obtain modified nano TiO2The particles can be effectively dispersed, the particle size of the particles is expanded by 3 to 5 times compared with that of the particles without modification, and the nano TiO in the operation of the photocatalytic film can be effectively prevented2Loss of the solution;
(3) the inorganic of the inventionParticle TiO2The modified chitosan can improve the hydrophilicity of the ultrafiltration membrane and further improve the anti-pollution performance of the membrane;
(4) the nano TiO obtained by the invention2The photocatalytic ultrafiltration membrane can maintain the long-time efficient and stable operation of the separation membrane in the wastewater treatment process, and the water flux attenuation coefficient after 10 hours of operation is far lower than that of an unmodified separation membrane, so that the photocatalytic ultrafiltration membrane has a wide application prospect.
Drawings
FIG. 1 shows nano TiO before and after modification with chitosan2TEM/SEM image of; a. unmodified nano TiO2(TEM); b. nano TiO modified by chitosan2(SEM)。
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Nano TiO prepared by sol-gel method2Dispersing in deionized water, performing ultrasonic dispersion for 2h, adding aminopropyltrimethoxysilane, performing reflux reaction for 3h at 40 ℃, and performing centrifugal separation on reaction liquid to obtain a product for later use;
(2) dispersing the product obtained in the step (1) in a methanol solution, ultrasonically dispersing for 2h, placing the dispersion system in a water bath at 40 ℃, adding glutaraldehyde, dropwise adding a small amount of acetic acid, and carrying out reflux reaction for 3 h; adding chitosan solution dissolved in dilute nitric acid, continuously refluxing and reacting for 3h, and after the reaction is finished, performing centrifugal separation to obtain chitosan modified nano TiO2；
(3) Dissolving a proper amount of PVDF (polyvinylidene fluoride) by using N, N-dimethylacetamide, and adding the modified nano TiO obtained in the step (2)2Stirring to obtain casting solution, standing to remove bubbles, coating the casting solution on a glass plate, scraping to form a film, and soaking in 40 deg.C deionized water coagulating bathForming a film to obtain the chitosan modified nano TiO2A photocatalytic ultrafiltration membrane; wherein the modified TiO2The addition amount of (A) is 3wt% of PVDF, and nano TiO2The mass ratio of aminopropyl trimethoxy silane to glutaraldehyde to chitosan is 1:0.06:0.08:0.2, and the obtained photocatalytic film is marked as number M-1; nano TiO before and after modification2And respectively using TEM and SEM for characterization, and referring to the attached figure 1.
As can be seen from FIG. 1, the nano TiO before modification2Is about 20-30nm of nano-crystal, and the agglomeration is very serious; nano TiO modified by chitosan2The particle size is expanded by 3-5 times, and the particles are relatively dispersed.
Examples 2 to 4
A photocatalytic film was prepared in the same manner as in example 1, except that modified TiO was used2The addition amount of (A) is in the proportion of PVDF and nano TiO2The mass ratio of aminopropyl trimethoxy silane to glutaraldehyde to chitosan is as follows:
photocatalytic film No. M-2: modified TiO2The addition amount of (A) is 1wt% of PVDF, and nano TiO is2The mass ratio of aminopropyl trimethoxy silane to glutaraldehyde to chitosan is 1:0.06:0.08: 0.2;
photocatalytic film No. M-3: modified TiO2The addition amount of (A) is 5wt% of PVDF, and nano TiO2The mass ratio of aminopropyl trimethoxy silane to glutaraldehyde to chitosan is 1:0.06:0.08: 0.2;
photocatalytic film No. M-4: modified TiO2The addition amount of (A) is 3wt% of PVDF, and nano TiO2The mass ratio of aminopropyl trimethoxy silane to glutaraldehyde to chitosan is 1:0.06:0.1: 0.3.
Comparative example
Using unmodified nano TiO2Adding the membrane material into the membrane casting solution to prepare a photocatalytic membrane, TiO2The amount of added (D) was 3wt% of PVDF, and the obtained photocatalytic film was denoted as D-1.
Organic wastewater is taken as membrane test sewage, and passes through a photocatalytic ultrafiltration membrane, and is irradiated by ultraviolet light for 10 hours. Measuring pure water flux before and after the operation of the photocatalytic film, and calculating the attenuation coefficient of the water flux. Adopting ICP-MS to measure Ti content before and after the operation of the photocatalytic film and calculating TiO2The run-off rates, results are listed in table 1.
Table 1 TiO2 loss rate and water flux attenuation coefficient of TiO2 photocatalytic film before and after modification
| Sample (I) | TiO2The loss rate% | Water flux attenuation coefficient% |
| M-1 | 1.3 | 25.2 |
| M-2 | 1.1 | 28.7 |
| M-3 | 1.8 | 23.4 |
| M-4 | 0.9 | 29.3 |
| D-1 | 8.8 | 37.9 |
As can be seen from Table 1, the nano TiO modified by chitosan2The photocatalytic film can effectively reduce TiO2Loss of TiO increases2The anti-pollution performance of the separation membrane is improved, so that the water flux attenuation coefficient of the separation membrane is reduced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (4)
1. Chitosan modified nano TiO2The preparation method of the photocatalytic ultrafiltration membrane is characterized by comprising the following preparation steps:
(1) the nano TiO prepared by the traditional preparation method2Dispersing in deionized water, ultrasonically dispersing for 1-3h, adding an aminosilane coupling agent, carrying out reflux reaction for 2-4h at 30-50 ℃, and centrifugally separating reaction liquid to obtain a product for later use;
(2) dispersing the product obtained in the step (1) in a methanol solution, ultrasonically dispersing for 1-3h, placing the dispersion system in a water bath at the temperature of 30-50 ℃, adding glutaraldehyde, dropwise adding a small amount of acetic acid, and carrying out reflux reaction for 1-4 h; adding chitosan solution dissolved in dilute nitric acid, continuously refluxing and reacting for 2-8h, and after the reaction is finished, performing centrifugal separation to obtain chitosan modified nano TiO2(ii) a The nano TiO2The mass ratio of the amino silane coupling agent to the glutaraldehyde to the chitosan is 1:0.01-0.1:0.01-0.2: 0.05-0.5;
(3) dissolving a proper amount of membrane material by using a solvent, and adding the chitosan modified nano TiO obtained in the step (2)2Stirring to obtain casting solution, standing for defoaming, coating the casting solution on a glass plate, scraping to form a film, and soaking in deionized water coagulation bath at 0-50 ℃ to form the film to obtain the chitosan modified nano TiO2A photocatalytic ultrafiltration membrane;
the amino silane coupling agent is selected from one or more of aminopropyl trimethoxy silane, aminopropyl triethoxy silane and phenylaminomethyl triethoxy silane; the membrane material is selected from polyvinylidene fluoride, polytetrafluoroethylene, polysulfone, polyethersulfone, polyacrylonitrile and polyetherimide; through amino silane coupling agent as bridge, in nano TiO2Grafting loose crosslinked chitosan on the surface to obtain chitosan modified nano TiO2The particles can be effectively dispersed, the particle size of the particles is expanded by 3 to 5 times compared with that of the particles without modification, and the nano TiO in the operation of the photocatalytic film can be effectively prevented2Loss of the catalyst.
2. The chitosan-modified nano-TiO of claim 12The preparation method of the photocatalytic ultrafiltration membrane is characterized in that the solvent is selected from N, N dimethylformamide, N dimethylacetamide and dimethyl sulfoxide.
3. The chitosan-modified nano-TiO of claim 12The preparation method of the photocatalytic ultrafiltration membrane is characterized in that the chitosan modified nano TiO is2The addition amount of (B) is 1-10wt% of the membrane material.
4. The chitosan-modified nano-TiO of claim 12The preparation method of the photocatalytic ultrafiltration membrane is characterized in that the nano TiO is2The mass ratio of the amino silane coupling agent to the glutaraldehyde to the chitosan is 1:0.05-0.08:0.05-0.1: 0.2-0.3.
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