CN113368709A - Polyaniline-modified alumina ceramic membrane and electro-adsorption defluorination method thereof - Google Patents
Polyaniline-modified alumina ceramic membrane and electro-adsorption defluorination method thereof Download PDFInfo
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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
- B01D71/025—Aluminium oxide
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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
- 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
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the 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
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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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 polyaniline-modified alumina ceramic membrane and an electro-adsorption defluorination method thereof, wherein polyaniline is used for modifying the ceramic membrane to prepare the polyaniline-modified alumina ceramic membrane, then an electro-adsorption technology is combined, a negative electrode material is inserted into a central hole of the polyaniline-modified alumina ceramic membrane, the negative electrode material is titanium, and then a voltage of 0.2-1.0V is applied between a positive electrode and a negative electrode to form an electro-adsorption defluorination component for treating a water body. The invention increases the adsorption capacity, can still keep higher adsorption rate after repeated cycle regeneration, has no secondary pollution to ecology and is more environment-friendly.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of water treatment, and particularly relates to a polyaniline modified alumina ceramic membrane and an electro-adsorption defluorination method thereof.
[ background of the invention ]
The ceramic membrane mainly contains aluminum oxide, has the outstanding characteristics of high mechanical strength, high flux, high thermal stability and chemical stability, acid and alkali corrosion resistance, stable operation under extreme pollution conditions and the like, and is widely applied to organic wastewater which is difficult to treat. The most common municipal applications are microfiltration and ultrafiltration membranes, which can effectively retain pollutants such as particulate matters, colloids, microorganisms, macromolecular organic matters and the like in water. Although ceramic membranes have certain advantages in the aspects of removing certain pollutants and controlling membrane pollution compared with organic membranes, the effect of removing soluble ions in surface water by using a single ceramic membrane is very limited, particularly in the treatment of high-fluorine water, and the particle size of fluorine ions is far smaller than the pore size of the ceramic membrane, so that reasonable modification of the ceramic membrane is urgently needed to improve the removal efficiency of the ceramic membrane on the fluorine ions.
Although fluorine is one of the trace elements necessary for the human body, excessive intake of fluoride, however, causes dental fluorosis and fluorosis. The fluorine content of drinking water is not more than 1.5mg/L according to the drinking water health standard of the world health organization. In China, the corresponding standard is 1mg/L, and defluorination of drinking water is a problem which is generally concerned by the water supply industry and is also a difficult problem faced by a plurality of rural distributed water purification projects. According to the report of the annual book of Chinese hygiene and family planning statistics, the distribution range of the high fluorine water is spread over 29 provinces, cities and regions in China. Wherein, the northern areas of Anhui province (northern Huai province, dormitory, mussel port and other areas) are influenced by geological factors such as diversion of yellow river, and the monitoring result of the drinking water source area shows that the concentration of fluorine ions is more than 1.5mg/L for a long time, and the fluorine content of some water source areas is more than 3 mg/L. Therefore, the method is of great significance for removing the fluoride ions in the drinking water.
Therefore, it is necessary to provide a new polyaniline-modified alumina ceramic membrane and an electro-adsorption defluorination method thereof to solve the above problems.
[ summary of the invention ]
The invention mainly aims to provide a polyaniline-modified alumina ceramic membrane, which greatly improves the removal efficiency of fluoride ions, has no secondary pollution to ecology and is more environment-friendly.
The invention realizes the purpose through the following technical scheme: a polyaniline-modified alumina ceramic membrane is prepared by the following steps:
s1) preparation of alumina support: selecting a tubular structure made of an alumina material as a raw material, soaking the raw material in 5-10% dilute hydrochloric acid for 12-24 hours, then ultrasonically cleaning the raw material with deionized water for 20-60 minutes, then drying the raw material in a blast drying oven at 105-120 ℃ for 6-10 hours, finally roasting the dried raw material in a muffle furnace at 200-300 ℃ for 0.5-2 hours, and then sealing and storing the roasted product to obtain an alumina support body; after the aluminum oxide support is soaked in hydrochloric acid and roasted, oil stains and impurities on the surface of the aluminum oxide support can be removed;
s2) preparing coating liquid: uniformly dispersing Ag alumina powder into Bg deionized water, adding 0.8-1.0 g of acrylic resin serving as a dispersing agent into the deionized water to obtain a dispersion liquid, and then performing ball milling on the dispersion liquid for 20-40 min to obtain a uniformly dispersed alumina dispersion liquid; dissolving 2-5 g of polyvinyl alcohol and polyvinylpyrrolidone into deionized water according to the ratio of 2: 1-4: 1 to prepare 30-40 g of binder, mixing the binder into the alumina dispersion, continuing ball milling for 50-60 min, and then performing vacuum defoaming for 15-30 min to obtain a uniform coating liquid; wherein A is 5-20, and B is 70-A;
s3) preparation of alumina ceramic membranes: fixing the alumina support prepared in the step S1) on a ceramic membrane fixture, then dipping and coating the coating liquid prepared in the step S2) on the inner wall surface of the alumina support, wherein the total dipping time is 10-40S, after the redundant coating liquid is dried, vertically placing the alumina support in a constant-temperature constant-humidity drying oven for drying for 15-20 h, controlling the temperature at 40-60 ℃ so as to prevent the ceramic membrane from cracking in the drying process, heating the dried alumina support to 500-600 ℃ at the heating rate of 1.5-2.0 ℃/min, keeping the temperature for 1h, then heating to 1000-1500 ℃ at the temperature of 5-6 ℃/min, keeping the temperature for 2-3 h, and finally naturally cooling along with the furnace to obtain the alumina ceramic membrane;
s4) preparation of polyaniline layer: adding 0.01-0.015 mol of tetradecyl trimethyl ammonium bromide, 0.01-0.015 mol of hexadecyl trimethyl ammonium bromide and 1g/L of polyvinylpyrrolidone into 0.05-0.1 mol of aniline base solution to prepare a deposition solution, adjusting the pH value of the deposition solution to 4, stirring at room temperature for 20-30 min, and then performing ultrasonic dispersion for 20-30 min; using a stainless steel plate as a cathode and the alumina ceramic membrane prepared in the step S3) as an anode, wherein the current density is 1-2 mA/cm2And depositing for 1-5 min at the temperature of 30-40 ℃, forming a polyaniline organic layer on the surface of the alumina ceramic membrane, fully cleaning with distilled water, and then drying in vacuum to prepare the polyaniline-modified alumina ceramic membrane.
Further, in the step S1), the length of the tubular structure made of alumina is 160mm, the outer diameter is 12.9mm, and the inner diameter is 8.4 mm. The size of the alumina support is scaled according to the ceramic membrane module commonly used in the industry, and the ceramic membrane with the proportional size has the best hydraulic condition and the largest membrane flux.
The invention also aims to provide an electro-adsorption defluorination method which comprises the steps of taking the polyaniline-modified alumina ceramic membrane as a positive electrode, taking a titanium plate or a titanium strip as a negative electrode, applying a voltage of 0.2-1.0V between the positive electrode and the negative electrode to form an electro-adsorption defluorination component, and performing adsorption defluorination on a water body to be treated.
Furthermore, the titanium plate or the titanium strip is parallel to the central axis of the polyaniline-modified alumina ceramic membrane and is positioned in the inner hole of the polyaniline-modified alumina ceramic membrane.
Compared with the prior art, the polyaniline modified alumina ceramic membrane and the electro-adsorption defluorination method thereof have the beneficial effects that: the ceramic membrane is modified by polyaniline modification, so that the removal efficiency of the ceramic membrane component on fluorine ions is improved, and the treated effluent can reach the national drinking water standard; the process has the advantages that a certain electric field is applied to the polyaniline-modified ceramic membrane component, so that the membrane flux can be remarkably improved, the process is convenient to operate and stable to operate, and the secondary pollution of the ceramic membrane is effectively avoided; fluorine ions are selectively filtered through the action of electric adsorption, and organic pollutants and fluorine ions in a water body can be removed in a synergistic manner by a separation technology coupled with a ceramic membrane; the service life is long.
[ description of the drawings ]
FIG. 1 is a schematic view of an embodiment of an electro-adsorption fluorine removal assembly;
FIG. 2 is an SEM image of an alumina ceramic film in an example of the present invention;
FIG. 3 is an SEM image of a polyaniline-modified ceramic film in an example of the present invention;
FIG. 4 is a graph showing fluoride effluent concentrations in a water body after treatment according to examples of the present invention and comparative example treatment methods;
FIG. 5 is a diagram showing the change of the COD removal rate of the effluent of the membrane module before and after modification in the example of the present invention;
FIG. 6 is a diagram showing the change of membrane flux of the membrane module system before and after modification in the example of the present invention.
[ detailed description ] embodiments
The first embodiment is as follows:
the embodiment is a polyaniline-modified alumina ceramic membrane, which is prepared by the following steps:
s1) preparation of alumina support: selecting a tubular structure made of an alumina material as a raw material, wherein the length of the tubular structure is 160mm, the outer diameter of the tubular structure is 12.9mm, and the inner diameter of the tubular structure is 8.4 mm; soaking the alumina support in 5% dilute hydrochloric acid for 12h, ultrasonically cleaning with deionized water for 30min, drying in a blast drying oven at 105 deg.C for 8h, calcining in a muffle furnace at 300 deg.C for 1h, and sealing for storage to obtain alumina support; after the aluminum oxide support is soaked in hydrochloric acid and roasted, oil stains and impurities on the surface of the aluminum oxide support can be removed;
s2) preparing coating liquid: uniformly dispersing 5g of alumina powder into 65g of deionized water, adding 1g of acrylic resin (PAA for short) serving as a dispersing agent to obtain a dispersion liquid, and then carrying out ball milling on the dispersion liquid for 30min to obtain a uniformly dispersed alumina dispersion liquid; then, 2g of polyvinyl alcohol (abbreviated as PVA) and polyvinyl pyrrolidone (abbreviated as PVP) were mixed in a ratio of 3: 1 into deionized water to prepare 30g of binder, mixing the binder into the alumina dispersion, continuing ball milling for 60min, and then performing vacuum defoaming for 15min to obtain uniform coating liquid;
s3) preparation of alumina ceramic membranes: fixing the alumina support prepared in the step S1) on a ceramic membrane fixture, then dipping and coating the coating liquid prepared in the step S2) on the inner wall surface of the alumina support, wherein the total dipping time is 10S, after the redundant coating liquid is dripped to be dry, vertically placing the alumina support in a constant-temperature constant-humidity drying oven for drying for 15h, controlling the temperature at 40 ℃ so as to prevent the ceramic membrane from cracking in the drying process, heating the dried alumina support to 600 ℃ at the heating rate of 1.5 ℃/min and preserving the heat for 1h, then heating to 1000 ℃ at the heating rate of 5 ℃/min and preserving the heat for 2h, and finally naturally cooling along with a furnace to obtain the alumina ceramic membrane; the SEM image of the alumina ceramic membrane prepared in the step is shown in figure 2;
s4) preparation of polyaniline layer: adding 0.01 mol of tetradecyl trimethyl ammonium bromide, 0.01 mol of hexadecyl trimethyl ammonium bromide and 1g/L of polyvinylpyrrolidone into 0.05 mol of aniline base solution to prepare a deposition solution, adjusting the pH value of the deposition solution to 4, stirring at room temperature for 20min, and performing ultrasonic dispersion for 20 min; using a stainless steel plate as a cathode and the alumina ceramic membrane prepared in the step S3) as an anode at a current density of 1mA/cm2And depositing for 1min at the temperature of 30 ℃, forming a polyaniline organic layer on the surface of the alumina ceramic membrane, fully cleaning with distilled water, and then drying in vacuum to prepare the polyaniline-modified alumina ceramic membrane. An SEM image of the polyaniline-modified alumina ceramic membrane prepared in this step is shown in fig. 3.
The embodiment also provides an electric adsorption fluorine removal method, which comprises the following steps: the method comprises the steps of taking a polyaniline-modified alumina ceramic membrane as an anode, taking a titanium plate or a titanium strip as a cathode, inserting the titanium plate or the titanium strip into the center of the polyaniline-modified alumina ceramic membrane to enable the titanium plate or the titanium strip to be parallel to the central axis of the polyaniline-modified alumina ceramic membrane, applying 0.2-1.0V voltage between the anode and the cathode to form an electro-adsorption defluorination component, and adsorbing and defluorinating a water body to be treated.
In the embodiment, the ceramic membrane and the electro-adsorption technology are combined, surface water in a certain city in the north of Anhui province is used as raw water for the experiment of the invention, and the device and the method for coupling the electro-adsorption with the ceramic membrane are used for treatment. The COD of the inlet water is 45mg/L, the BOD is 4.3mg/L, the fluorine ion concentration is 1.47mg/L, and the biodegradability is poor. The raw water is treated by the electro-adsorption defluorination method described in the embodiment, in addition, the raw water is treated by taking the modified ceramic membrane transposed original ceramic membrane in the embodiment as the anode material, as a comparative example, the inlet water has a pH of about 7.8, the voltage is adjusted to 1.0V, the original ceramic membrane and the modified ceramic membrane are respectively used as the anode material, and the operation is carried out for 24 hours, the comparison result is shown in fig. 4-6, as can be seen from fig. 4-6, the removal rate of COD of the modified ceramic membrane can reach more than 95%, the removal rate of fluoride can reach more than 80%, the membrane flux can be maintained at a high level for a long time, and the membrane pollution is reduced.
The electric field reinforced filtering technology is a filtering technology which combines an electric field and a ceramic membrane filtering technology, enables feed liquid to flow in parallel to the surface of a filter membrane, and applies a direct current electric field in a certain direction on two sides of the membrane. Under the action of electrophoresis, the charged suspended particles generate migration motion which is vertical to the membrane surface and opposite to the medium permeation direction in an electric field, and the thickness of a boundary layer on the surface of the membrane is reduced under the action of the liquid flow shear force; on the other hand, the electroosmosis effect enables the solvent in the membrane pores to be discharged to the other side of the filter membrane at an accelerated speed, so that the membrane pollution is effectively reduced, the concentration difference polarization is inhibited, and the membrane flux is improved. In the embodiment, the ceramic membrane is modified by polyaniline modification, so that the removal efficiency of the ceramic membrane component on fluorine ions is improved, and the treated effluent can reach the national drinking water standard; the process has the advantages that a certain electric field is applied to the polyaniline-modified ceramic membrane component, so that the membrane flux can be remarkably improved, the process is convenient to operate and stable to operate, and the secondary pollution of the ceramic membrane is effectively avoided; fluorine ions are selectively filtered through the action of electric adsorption, and organic pollutants and fluorine ions in a water body can be removed in a synergistic manner by a separation technology coupled with a ceramic membrane.
The polyaniline-modified alumina ceramic membrane and the electro-adsorption defluorination method thereof have the following advantages:
1) strong anti-aging capability: the conductive polyaniline modified ceramic membrane is sampled, and an external electric field is applied, so that salt ions can move directionally more regularly, water is electrolyzed on the surface of the ceramic membrane to form bubbles, scaling is reduced, the expected service life is at least more than 5 years, and the increase of the operation cost caused by replacement of core components is avoided;
2) the special ion removal effect is obvious: the ceramic membrane is micron-sized in channel width, is not easy to block compared with a reverse osmosis nano-scale channel, is strong in anti-pollution capacity, but ionic pollutants can pass through the ceramic membrane, fluorine ions can be selectively removed by the technology, chloride ions and sulfate ions can be selectively filtered, the pollution load of the ceramic membrane is reduced, the ceramic membrane is particularly suitable for pretreatment of drinking water, nutritional ions are reserved, and substances harmful to body health, such as organic matters, fluorine ions and the like are selectively removed.
Example two:
the embodiment is a polyaniline-modified alumina ceramic membrane, which is prepared by the following steps:
s1) preparation of alumina support: selecting a tubular structure made of an alumina material as a raw material, wherein the length of the tubular structure is 160mm, the outer diameter of the tubular structure is 12.9mm, and the inner diameter of the tubular structure is 8.4 mm; soaking the alumina support in 8% dilute hydrochloric acid for 18h, ultrasonically cleaning with deionized water for 20min, drying in a blast drying oven at 110 deg.C for 6h, calcining in a muffle furnace at 250 deg.C for 0.5h, and sealing for storage to obtain alumina support; after the aluminum oxide support is soaked in hydrochloric acid and roasted, oil stains and impurities on the surface of the aluminum oxide support can be removed;
s2) preparing coating liquid: uniformly dispersing 12g of alumina powder into 58g of deionized water, adding 0.8g of acrylic resin (PAA for short) serving as a dispersing agent into the deionized water to obtain a dispersion liquid, and then performing ball milling on the dispersion liquid for 40min to obtain a uniformly dispersed alumina dispersion liquid; next, 4g of polyvinyl alcohol (PVA) and polyvinyl pyrrolidone (PVP) were mixed in a ratio of 4: dissolving the powder 1 into deionized water to prepare 35g of binder, mixing the binder into the alumina dispersion, continuing ball milling for 55min, and then performing vacuum defoaming for 20min to obtain uniform coating liquid;
s3) preparation of alumina ceramic membranes: fixing the alumina support body prepared in the step S1) on a ceramic membrane fixture, then dipping and coating the coating liquid prepared in the step S2) on the inner wall surface of the alumina support body, wherein the total dipping time is 25S, after the redundant coating liquid is dripped to be dry, vertically placing the alumina support body in a constant-temperature constant-humidity drying box for drying for 18h, controlling the temperature at 50 ℃ so as to prevent the ceramic membrane from cracking in the drying process, heating the dried alumina support body to 550 ℃ at the heating rate of 1.8 ℃/min, preserving the heat for 1h, then heating to 1200 ℃ at the heating rate of 5 ℃/min, continuing preserving the heat for 2.5h, and finally naturally cooling along with the furnace to obtain the alumina ceramic membrane;
s4) preparation of polyaniline layer: adding 0.012 mole of tetradecyl trimethyl ammonium bromide, 0.012 mole of hexadecyl trimethyl ammonium bromide and 1g/L of polyvinylpyrrolidone into 0.08 mole of aniline base solution to prepare a deposition solution, adjusting the pH value of the deposition solution to 4, stirring at room temperature for 25min, and performing ultrasonic dispersion for 25 min; using a stainless steel plate as a cathode and the alumina ceramic membrane prepared in the step S3) as an anode at a current density of 1.5mA/cm2And depositing for 3min at the temperature of 35 ℃, forming a polyaniline organic layer on the surface of the alumina ceramic membrane, fully cleaning with distilled water, and then drying in vacuum to prepare the polyaniline-modified alumina ceramic membrane.
Example three:
the embodiment is a polyaniline-modified alumina ceramic membrane, which is prepared by the following steps:
s1) preparation of alumina support: selecting a tubular structure made of an alumina material as a raw material, wherein the length of the tubular structure is 160mm, the outer diameter of the tubular structure is 12.9mm, and the inner diameter of the tubular structure is 8.4 mm; soaking the alumina support in 10% dilute hydrochloric acid for 24h, ultrasonically cleaning with deionized water for 60min, drying in a blast drying oven at 120 deg.C for 10h, baking in a muffle furnace at 200 deg.C for 2h, and sealing for storage to obtain alumina support; after the aluminum oxide support is soaked in hydrochloric acid and roasted, oil stains and impurities on the surface of the aluminum oxide support can be removed;
s2) preparing coating liquid: uniformly dispersing 20g of alumina powder into 50g of deionized water, adding 1g of acrylic resin (PAA for short) serving as a dispersing agent to obtain a dispersion liquid, and then carrying out ball milling on the dispersion liquid for 20min to obtain a uniformly dispersed alumina dispersion liquid; then, 5g of polyvinyl alcohol (abbreviated as PVA) and polyvinyl pyrrolidone (abbreviated as PVP) were mixed in a ratio of 2:1 into deionized water to prepare 40g of binder, mixing the binder into the alumina dispersion, continuing ball milling for 50min, and then performing vacuum defoaming for 30min to obtain uniform coating liquid;
s3) preparation of alumina ceramic membranes: fixing the alumina support prepared in the step S1) on a ceramic membrane fixture, then dipping and coating the coating liquid prepared in the step S2) on the inner wall surface of the alumina support, wherein the total dipping time is 40S, after the redundant coating liquid is dripped to be dry, vertically placing the alumina support in a constant-temperature constant-humidity drying oven for drying for 20h, controlling the temperature at 60 ℃ so as to prevent the ceramic membrane from cracking in the drying process, heating the dried alumina support to 500 ℃ at the heating rate of 2.0 ℃/min, preserving the heat for 1h, then heating to 1500 ℃ at the heating rate of 6 ℃/min, continuing preserving the heat for 3h, and finally naturally cooling along with a furnace to obtain the alumina ceramic membrane;
s4) preparation of polyaniline layer: adding 0.015 mol of tetradecyl trimethyl ammonium bromide, 0.015 mol of hexadecyl trimethyl ammonium bromide and 1g/L of polyvinylpyrrolidone into 0.1 mol of aniline base solution to prepare a deposition solution, adjusting the pH value of the deposition solution to be 4, stirring at room temperature for 30min, and then performing ultrasonic dispersion for 30 min; using a stainless steel plate as a cathode, the alumina ceramic membrane prepared in the step S3) as an anode, and performing a plasma treatment at a current density of 2mA/cm2And depositing for 5min at the temperature of 40 ℃, forming a polyaniline organic layer on the surface of the alumina ceramic membrane, fully cleaning with distilled water, and then drying in vacuum to prepare the polyaniline-modified alumina ceramic membrane.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (4)
1. A polyaniline-modified alumina ceramic membrane is characterized in that: the preparation method comprises the following steps:
s1) preparation of alumina support: selecting a tubular structure made of an alumina material as a raw material, soaking the tubular structure in 5-10% dilute hydrochloric acid for 12-24 hours, ultrasonically cleaning the tubular structure with deionized water for 20-60 minutes, drying the tubular structure in a blast drying oven at 105-120 ℃ for 6-8 hours, finally roasting the tubular structure in a muffle furnace at 200-300 ℃ for 0.5-2 hours, and sealing and storing to obtain an alumina support body;
s2) preparing coating liquid: uniformly dispersing Ag aluminum oxide powder into Bg deionized water, and adding 0.8-1 g of acrylic resin to obtain a dispersion liquid; ball milling the dispersion liquid for 20-40 min to obtain an alumina dispersion liquid; dissolving 2-5 g of polyvinyl alcohol and polyvinylpyrrolidone into deionized water according to the ratio of 2: 1-4: 1 to prepare 30-40 g of binder, mixing the binder into the alumina dispersion, continuing ball milling for 50-60 min, and then performing vacuum defoaming for 15-30 min to obtain uniform coating liquid; wherein A is 5-20, and B is 70-A;
s3) preparation of alumina ceramic membranes: dipping and coating the coating liquid prepared in the step S2) on the inner wall surface of the alumina support body prepared in the step S1), wherein the total dipping time is 10-40S, after the redundant coating liquid is dripped dry, vertically placing the alumina support body in a constant-temperature constant-humidity drying box for drying for 15-20 h, controlling the temperature at 40-60 ℃, heating the dried alumina support body to 500-600 ℃ at the heating rate of 1.5-2.0 ℃/min and preserving the heat for 1h, then heating to 1000-1500 ℃ at the temperature of 5-6 ℃/min and continuing preserving the heat for 2-3 h, and finally naturally cooling along with a furnace to obtain an alumina ceramic membrane;
s4) preparation of polyaniline layer: 0.01 to 0.015 mol of tetradecyltrimethylammonium bromide and 0.05 to 0.1 mol of aniline base solutionPreparing 01-0.015 mol of hexadecyl trimethyl ammonium bromide and 1g/L of polyvinylpyrrolidone to obtain a deposition solution, adjusting the pH value of the deposition solution to be 4, stirring at room temperature for 20-30 min, and then performing ultrasonic dispersion for 20-30 min; using a stainless steel plate as a cathode and the alumina ceramic membrane prepared in the step S3) as an anode, wherein the current density is 1-2 mA/cm2And depositing for 1-5 min at the temperature of 30-40 ℃, forming a polyaniline organic layer on the surface of the alumina ceramic membrane, fully cleaning with distilled water, and then drying in vacuum to prepare the polyaniline-modified alumina ceramic membrane.
2. The polyaniline-modified alumina ceramic membrane of claim 1, wherein: the length of the tubular structure made of the alumina in the step S1) is 160mm, the outer diameter is 12.9mm, and the inner diameter is 8.4 mm.
3. An electro-adsorption fluorine removal method is characterized in that: the method comprises the steps of taking the polyaniline-modified alumina ceramic membrane as the anode in claim 1, taking a titanium plate or a titanium strip as the cathode, applying a voltage of 0.2-1.0V between the anode and the cathode to form an electro-adsorption defluorination component, and performing adsorption defluorination on a water body to be treated.
4. The method of claim 3, wherein: the titanium plate or the titanium strip is parallel to the central axis of the polyaniline-modified alumina ceramic membrane and is positioned in the inner hole of the polyaniline-modified alumina ceramic membrane.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0872278A1 (en) * | 1997-04-16 | 1998-10-21 | "VLAAMSE INSTELLING VOOR TECHNOLOGISCH ONDERZOEK", afgekort "V.I.T.O." | Electrosorption membrane |
| US20150079485A1 (en) * | 2013-09-13 | 2015-03-19 | Samsung Electronics Co., Ltd. | Composite membrane, preparation method thereof, and lithium-air battery including the composite membrane |
| CN104844244A (en) * | 2015-04-16 | 2015-08-19 | 柳州豪祥特科技有限公司 | Process for preparing tubular ceramic film by rotary method |
| US20190022597A1 (en) * | 2016-03-30 | 2019-01-24 | Ngk Insulators, Ltd. | Ceramic membrane filter and method for producing the same |
| WO2020000164A1 (en) * | 2018-06-26 | 2020-01-02 | 深圳市星源材质科技股份有限公司 | Composite lithium battery separator and preparation method therefor |
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2021
- 2021-06-17 CN CN202110672846.XA patent/CN113368709A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0872278A1 (en) * | 1997-04-16 | 1998-10-21 | "VLAAMSE INSTELLING VOOR TECHNOLOGISCH ONDERZOEK", afgekort "V.I.T.O." | Electrosorption membrane |
| US20150079485A1 (en) * | 2013-09-13 | 2015-03-19 | Samsung Electronics Co., Ltd. | Composite membrane, preparation method thereof, and lithium-air battery including the composite membrane |
| CN104844244A (en) * | 2015-04-16 | 2015-08-19 | 柳州豪祥特科技有限公司 | Process for preparing tubular ceramic film by rotary method |
| US20190022597A1 (en) * | 2016-03-30 | 2019-01-24 | Ngk Insulators, Ltd. | Ceramic membrane filter and method for producing the same |
| WO2020000164A1 (en) * | 2018-06-26 | 2020-01-02 | 深圳市星源材质科技股份有限公司 | Composite lithium battery separator and preparation method therefor |
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Application publication date: 20210910 |