CN113019160B - Titanium dioxide modified film and preparation method thereof - Google Patents
Titanium dioxide modified film and preparation method thereof Download PDFInfo
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- CN113019160B CN113019160B CN202110323576.1A CN202110323576A CN113019160B CN 113019160 B CN113019160 B CN 113019160B CN 202110323576 A CN202110323576 A CN 202110323576A CN 113019160 B CN113019160 B CN 113019160B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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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
- B01D71/024—Oxides
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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
- B01D71/12—Cellulose derivatives
- B01D71/14—Esters of organic acids
- B01D71/18—Mixed esters, e.g. cellulose acetate-butyrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention discloses a titanium dioxide modified film and a preparation method thereof, and relates to the technical field of nano materials. The preparation method of the titanium dioxide modified film comprises the following steps: (1) Dissolving nano titanium dioxide, catechol-containing compound and amino-containing compound in tris solution to obtain a mixed dispersion liquid; (2) Soaking the initial membrane material in the mixed dispersion liquid obtained in the step (1) to obtain a membrane material with a titanium dioxide seed layer on the surface; (3) And (3) immersing the membrane material with the titanium dioxide seed layer on the surface, which is obtained in the step (2), into a mixed solution of tetrabutyl titanate and urea, and taking out after reaction to obtain the titanium dioxide modified membrane. The preparation method provided by the application is simple in process, greatly improves the stability of the membrane material for the separation of the oil-containing emulsion, can recover the flux through water washing after long-time separation, and is excellent in recycling performance.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a titanium dioxide modified film and a preparation method thereof.
Background
The oily wastewater is a pollutant widely generated in the development and utilization activities of petroleum substances, and comprises wastewater containing grease and various oils, and in addition, various impurities such as cleaning agents, emulsifying agents and the like can be mixed. The oily waste water features high COD and BOD, certain smell and colour, easy combustion and oxidation decomposition, and generally lower density than water. The oily wastewater discharged after being not treated to reach the standard is easy to deteriorate the water quality, influence the aquaculture, harm the human health, pollute the atmosphere and influence the crop production. In addition, various aliphatic hydrocarbon, aromatic hydrocarbon, alkyne and other compounds contained in the oily wastewater still have certain economic value, and the process of losing the compounds to the environment is also a process of wasting resources.
On one hand, the discharge of oily wastewater from industries such as steel, petrifaction and food becomes the most common pollution source in the global scope; on the other hand, a large number of leakage accidents associated with the exploitation of fossil fuels such as oil and natural gas threaten the safety of ocean and land fresh water resources and ecology. Facing such enormous challenges, researchers have been working on developing new technologies and materials for the treatment of oily wastewater. Gravity, centrifugation, ultrasonic separation, air flotation, electric field, coagulation, biological treatment and the like are all used. However, the application range of these methods has been limited by the disadvantages of low separation efficiency, easy generation of secondary contaminants, and small applicable particle range.
In recent years, with the application and development of membrane technology, separation of emulsions, oil solutions and even organic substances has been achieved by using techniques such as size exclusion and reverse osmosis, and the application of the separation treatment of oil-containing wastewater is expanding. However, the application of membrane technology is limited by the strict requirements on the composition of the oily wastewater, especially the problems of fouling and high cost of the membrane. The porous polymer inorganic materials commonly used at present can absorb oil from wastewater. However, these materials have low selective absorption of oil, reducing selectivity and efficiency of separation. Furthermore, the recovery of these materials and oils is difficult to carry out, and the materials used are generally burnt or buried, which causes pollution of the soil and atmosphere, causing secondary pollution to the environment. At present, the development of a novel membrane material which has strong separation capacity, high selectivity, controllable and reversible membrane pollution and easy recycling is urgently needed to meet the ever-increasing demand on the treatment of oily wastewater.
Disclosure of Invention
Based on the above, the present invention aims to overcome the defects of the prior art and provide a titanium dioxide modified film and a preparation method thereof.
In order to realize the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a titanium dioxide modified film comprises the following steps:
(1) Dissolving nano titanium dioxide, catechol-containing compound and amino-containing compound in tris solution to obtain a mixed dispersion liquid;
(2) Soaking the initial membrane material in the mixed dispersion liquid obtained in the step (1) to obtain a membrane material with a titanium dioxide seed layer on the surface;
(3) And (3) immersing the membrane material with the titanium dioxide seed layer on the surface, which is obtained in the step (2), into a mixed solution of tetrabutyl titanate and urea, and taking out the membrane material after reaction to obtain the titanium dioxide modified membrane.
According to the method, catechol containing catechol compounds and amino containing amino compounds are crosslinked and complexed, so that the nano titanium dioxide is fixed on the surface of the film to form a titanium dioxide seed layer. Nano-titania may this help in the subsequent synthesis of a denser titania layer on the membrane surface.
Preferably, dissolving nano titanium dioxide, dopamine hydrochloride and aminopropyltriethoxysilane in a tris solution, and performing ultrasonic dispersion for 1-30 minutes to obtain a mixed dispersion liquid. The ultrasonic dispersion is carried out for a certain time to ensure that the nano titanium dioxide is dispersed more uniformly because the nano titanium dioxide is insoluble in water.
Preferably, in the tris solution of step (1), the tris volume concentration is 1-5mg/mL, and the pH of the tris solution is 8-9; in the mixed dispersion liquid in the step (1), the volume concentration of the catechol-containing compound is 1-5mg/mL, the volume concentration of the amino-containing compound is 1-5mg/mL, and the volume concentration of the nano titanium dioxide is 1-5mg/mL. If the concentrations of the catechol-containing compound and the amino-containing compound are too high, the crosslinking polymerization reaction may be too fast, the structures may be stacked, the rate may be slow if the concentrations are small, and the thickness of the crosslinked layer may not be satisfactory.
Further preferably, in the mixed dispersion liquid in the step (1), the volume concentration of the catechol-containing compound is 2mg/mL, and the volume concentration of the amino-containing compound is 2mg/mL.
Preferably, in the mixed dispersion liquid in the step (1), the catechol-containing compound is dopamine hydrochloride, and the amino-containing compound is aminopropyltriethoxysilane.
Dopamine belongs to a common biological component, is harmless to the environment and inspired by the strong viscosity of mussels, and the functional group of the dopamine is catechol (catechol) which can be used as a coating material with excellent performance through research. However, free dopamine is unstable and easily oxidized, and contains a component containing both catechol and primary amine in its molecular structure, and the primary amine is highly basic, and catechol is easily oxidized by oxygen in a basic environment, so free dopamine is more unstable than catechol, and therefore, hydrochloride thereof is often used.
Aminopropyltriethoxysilane, commonly known as silane coupling agents, is reacted with organic and inorganic substances primarily through its amino and ethoxy groups to cause them to be connected in series. Because the amino group can react with dopamine and the ethoxy group can react with titanium dioxide, the titanium dioxide can be chemically fixed on the surface of the membrane, and the stability of the membrane is enhanced.
Preferably, in the step (2), the initial film material is at least one of a polyvinylidene fluoride film, a polytetrafluoroethylene film, a polypropylene film and a mixed cellulose ester film; the pore size of the initial membrane material is less than 1 μm. The size of oil drops in the emulsion is more than 0.1-1 mu m, so that the repellency of the oil drops can be effectively enhanced by forming a more compact titanium dioxide layer on the surface of the membrane.
Preferably, in the step (2), the soaking time is 18-36 hours, and the membrane material with the titanium dioxide seed layer on the surface is obtained after the soaking and the washing and the drying; wherein, the water washing adopts deionized water to wash.
Preferably, in the mixed solution of tetrabutyl titanate and urea in the step (3), the volume concentration of tetrabutyl titanate is 7-9mg/mL, and the volume concentration of urea is 8-10mg/mL. Preferably, in the step (3), the reaction temperature is 60-100 ℃, and the reaction time is 12-24 hours; and taking out after the reaction, washing by using deionized water, and airing to obtain the titanium dioxide modified membrane. Through a great deal of experimental research, the inventor of the application finds that the hydrolysis duration can be controlled by controlling the reaction time, and the growth thickness and growth form of titanium dioxide on the seed layer can be influenced. The reaction time is 12-24 hours, and the titanium dioxide modified film is best.
In the mixed solution in the step (3), tetrabutyl titanate is a precursor for synthesizing titanium dioxide, and urea is added as an initiator for hydrolysis, so that hydrolysis of tetrabutyl titanate can be continuously initiated under a mild temperature condition, and a compact structure of titanium dioxide can be grown on a titanium dioxide seed layer on the surface of a film.
In addition, the application provides a titanium dioxide modified film prepared by the preparation method.
Further, the application provides the application of the titanium dioxide modified membrane in the field of oily wastewater treatment.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a titanium dioxide modified membrane and a preparation method thereof, and the preparation method of the titanium dioxide modified membrane assembles nano titanium dioxide on the surface of a membrane material with a surface structure needing to be strengthened through surface crosslinking to form a titanium dioxide seed layer, continuously grows a titanium dioxide microsphere stack structure on the seed layer on the surface of the membrane material through a mild hydrothermal reaction, and quickly obtains the titanium dioxide modified membrane material through an organic-inorganic hybrid modification method.
The method has simple process, greatly improves the stability of the membrane material for separating the oil-containing emulsion, can recover the flux by washing after long-time separation, and has excellent recycling performance.
Drawings
FIG. 1 is a scanning electron micrograph of a starting film material; wherein the big picture is 5000 times of magnified images, and the small picture at the lower right corner is 50000 times of magnified images;
FIG. 2 is a scanning electron micrograph of the titanium dioxide-modified film obtained in example 1, in which the large image is a 5000-fold enlarged image and the small image at the lower right corner is a 50000-fold enlarged image;
FIG. 3 is a schematic diagram of flux and COD removal rate of the initial membrane material and the titanium dioxide modified membrane obtained in example 1;
fig. 4 is a schematic diagram of the COD removal rate of the initial membrane material and the titania-modified membrane obtained in example 1 in five cycles.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
Example 1
In an embodiment of the present application, the method for preparing a titanium dioxide modified film includes the following steps:
(1) Dissolving nano titanium dioxide, dopamine hydrochloride and aminopropyltriethoxysilane in a tris solution, and performing ultrasonic dispersion for 5 minutes to obtain a mixed dispersion liquid; wherein the volume concentration of the tris is 1.2mg/mL, and the pH value of the tris solution is 8.5; in the mixed dispersion liquid, the volume concentrations of dopamine hydrochloride, aminopropyl triethoxysilane and nano titanium dioxide are respectively 2mg/mL;
(2) Placing an initial membrane material (a polytetrafluoroethylene membrane with the aperture of 0.1 mu m) into the mixed dispersion liquid obtained in the step (1) to soak for 24 hours to obtain a membrane material with a titanium dioxide seed layer on the surface;
(3) And (3) immersing the membrane material with the titanium dioxide seed layer on the surface, which is obtained in the step (2), into a mixed solution of tetrabutyl titanate and urea, wherein the volume concentration of tetrabutyl titanate is 8.1mg/mL, the volume concentration of urea is 9mg/mL, taking out after reaction, the reaction temperature is 80 ℃, and the reaction time is 18 hours, so as to obtain the titanium dioxide modified membrane.
Example 2
In an embodiment of the present application, the method for preparing a titanium dioxide modified film includes the following steps:
(1) Dissolving nano titanium dioxide, dopamine hydrochloride and aminopropyltriethoxysilane in a tris solution, and performing ultrasonic dispersion for 1 minute to obtain a mixed dispersion liquid; wherein the volume concentration of the tris is 1mg/mL, and the pH value of the tris solution is 8; in the mixed dispersion liquid, the volume concentrations of dopamine hydrochloride, aminopropyl triethoxysilane and nano titanium dioxide are respectively 1mg/mL;
(2) Placing an initial membrane material (a mixed cellulose ester membrane with the aperture of 0.22 mu m) into the mixed dispersion liquid obtained in the step (1) to soak for 18 hours to obtain a membrane material with a titanium dioxide seed layer on the surface;
(3) And (3) immersing the membrane material with the titanium dioxide seed layer on the surface, which is obtained in the step (2), into a mixed solution of tetrabutyl titanate and urea, wherein the volume concentration of tetrabutyl titanate is 7mg/mL, the volume concentration of urea is 8mg/mL, taking out the membrane material after reaction, the reaction temperature is 60 ℃, and the reaction time is 24 hours, so as to obtain the titanium dioxide modified membrane.
Example 3
In an embodiment of the present application, the method for preparing a titanium dioxide modified film includes the following steps:
(1) Dissolving nano titanium dioxide, dopamine hydrochloride and aminopropyltriethoxysilane in a tris solution, and performing ultrasonic dispersion for 30 minutes to obtain a mixed dispersion liquid; wherein the volume concentration of the tris is 5mg/mL, and the pH value of the tris solution is 9; in the mixed dispersion liquid, the volume concentrations of dopamine hydrochloride, aminopropyl triethoxysilane and nano titanium dioxide are respectively 5mg/mL;
(2) Placing an initial membrane material (a polyvinylidene fluoride membrane with the aperture of 0.22 mu m) into the mixed dispersion liquid obtained in the step (1) to soak for 36 hours to obtain a membrane material with a titanium dioxide seed layer on the surface;
(3) And (3) immersing the membrane material with the titanium dioxide seed layer on the surface, which is obtained in the step (2), into a mixed solution of tetrabutyl titanate and urea, wherein the volume concentration of tetrabutyl titanate is 9mg/mL, the volume concentration of urea is 10mg/mL, taking out the membrane material after reaction, the reaction temperature is 100 ℃, and the reaction time is 12 hours, so as to obtain the titanium dioxide modified membrane.
Comparative example
Test example 1 scanning Electron microscope test
Scanning electron microscope detection is carried out on the initial membrane material (polytetrafluoroethylene membrane with the aperture of 0.1 μm) in example 1 and the titanium dioxide modified membrane prepared in example 1, and the results are shown in fig. 1 and fig. 2, wherein fig. 1 is the scanning electron microscope image of the initial membrane material; wherein the big picture is a 5000 times magnified picture, and the small picture at the lower right corner is a 50000 times magnified picture; FIG. 2 is a scanning electron micrograph of the titanium dioxide-modified film obtained in example 1, wherein the large image is a 5000-fold enlarged image, and the small image at the lower right corner is a 50000-fold enlarged image. Through comparison, the titanium dioxide modified membrane obtained in example 1 has a structure of titanium dioxide microsphere stacking on the surface obviously compared with the original membrane material. The results of the titanium dioxide-modified films obtained in examples 2 to 3 were similar to those of example 1 and are not repeated here.
Test example 2 Cross-flow Equipment test
The test process comprises the following steps: the titanium dioxide Modified membrane (TiO 2-Modified) and the initial membrane material (polytetrafluoroethylene membrane PTFE, pore size 0.1 μm) obtained in example 1 were subjected to a cross-flow device test under 0.1MPa using 1L of 1% strength petroleum emulsion (containing 1 ‰ surfactant) as a test solution.
And (3) test results:
the results are shown in FIGS. 3 and 4. The test procedure included in fig. 3 has five parts: the first part was a 30 minute pure water filtration, the second part was a 60 minute emulsion filtration, the third part was a 30 minute pure water filtration, the fourth part was a 30 minute water wash of the membrane, and the fifth part was a 30 minute pure water filtration, showing the change in flux during filtration, with values corresponding to the left Y-axis. In addition, the COD removal rate for 60 min emulsion filtration is shown, with the values corresponding to the right Y-axis. The test procedure included in fig. 4 consisted of five cycles of emulsion filtration, each for 60 minutes, and the membranes were washed with water for 30 minutes after the cycle was completed, with COD removal rates as shown.
As can be seen from fig. 3, the flux of the titanium dioxide Modified membrane (TiO 2-Modified) was more stable than the initial membrane material (PTFE) throughout the test. Although the flux is small, stability is the most important in the oil-water separation process, and if the stability is not enough, the influence of effluent quality on wastewater discharge is large. In addition, the Removal rate of COD (TiO 2-Modified-Removal) of the titanium dioxide-Modified membrane obtained in example 1 was maintained at 90% or more during the separation process for 60 minutes with respect to the emulsion, while the Removal rate of the initial membrane material (PTFE-Removal) was poor in stability, fluctuating between 80% and 100%. The results of the titanium dioxide-modified films prepared in examples 2 to 3 were similar to those of example 1 and are not repeated here.
To further explore the difference between the two, the stability of the membrane on the COD removal efficiency of the emulsion separation was verified by a cycle test method. As can be seen from fig. 4, the removal rate of the initial membrane material was very unstable and fluctuated dramatically, while the removal rate of the titania-modified membrane was substantially unchanged. The removal rate of the initial membrane material is gradually improved after each circulation begins, and presumably the surface of the initial membrane material is easily polluted by emulsion, and a large amount of oil is adsorbed on the surface and in a channel to form an oil film, so that the removal rate is improved under the action of interception, but the membrane pollution is increased inevitably, and the separation of the emulsion is not facilitated for long term and stability.
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 to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. The preparation method of the titanium dioxide modified film is characterized by comprising the following steps:
(1) Dissolving nano titanium dioxide, catechol-containing compound and amino-containing compound in tris solution to obtain a mixed dispersion liquid;
(2) Soaking the initial membrane material in the mixed dispersion liquid obtained in the step (1) to obtain a membrane material with a titanium dioxide seed layer on the surface;
(3) Immersing the membrane material with the titanium dioxide seed layer on the surface, which is obtained in the step (2), into a mixed solution of tetrabutyl titanate and urea, and taking out after reaction to obtain a titanium dioxide modified membrane; in the step (3), the reaction temperature is 60-100 ℃, and the reaction time is 12-24 hours; in the step (2), the initial film material is at least one of polyvinylidene fluoride film, polytetrafluoroethylene film, polypropylene film and mixed cellulose ester film.
2. The method according to claim 1, wherein the tris solution of step (1) has a tris volume concentration of 1 to 5mg/mL and a tris solution pH of 8 to 9; in the mixed dispersion liquid in the step (1), the volume concentration of the catechol-containing compound is 1-5mg/mL, the volume concentration of the amino-containing compound is 1-5mg/mL, and the volume concentration of the nano titanium dioxide is 1-5mg/mL.
3. The method according to claim 1, wherein the mixed dispersion liquid of step (1) has a catechol-containing compound volume concentration of 2mg/mL and an amino-containing compound volume concentration of 2mg/mL.
4. The method according to claim 1 or 2, wherein the catechol-containing compound in the mixed dispersion liquid of the step (1) is dopamine hydrochloride, and the amino-containing compound is aminopropyltriethoxysilane.
5. The method of claim 1, wherein in step (2), the pore size of the starting membrane material is less than 1 μm.
6. The method according to claim 1, wherein in the step (2), the soaking time is 18 to 36 hours.
7. The method according to claim 1, wherein in the mixed solution of tetrabutyl titanate and urea of step (3), the volume concentration of tetrabutyl titanate is 7-9mg/mL, and the volume concentration of urea is 8-10mg/mL.
8. A titanium dioxide-modified film produced by the production method according to any one of claims 1 to 7.
9. The use of the titanium dioxide modified membrane of claim 8 in the field of oily wastewater treatment.
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