CN114349134A - Electric control adsorption film, preparation method, electropolymerization device and self-cleaning method - Google Patents
Electric control adsorption film, preparation method, electropolymerization device and self-cleaning method Download PDFInfo
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- CN114349134A CN114349134A CN202210061444.0A CN202210061444A CN114349134A CN 114349134 A CN114349134 A CN 114349134A CN 202210061444 A CN202210061444 A CN 202210061444A CN 114349134 A CN114349134 A CN 114349134A
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Abstract
The invention provides an electric control adsorption film, a preparation method, an electropolymerization device and a self-cleaning method, wherein the preparation method comprises the following steps: (1) mixing a surfactant, water and a conductive material, dispersing to obtain a conductive material dispersion liquid, and then loading the conductive material dispersion liquid on a bottom film to obtain a conductive film; (2) mixing a surfactant, water, an additive and an electropolymerization monomer to obtain an electropolymerization electrolyte; (3) mixing the conductive film obtained in the step (1) and the electropolymerization electrolyte obtained in the step (2), and performing electropolymerization to obtain a conductive film with an adsorption function layer; (4) and (4) sequentially soaking and cleaning the conductive film obtained in the step (3) to obtain the electric control adsorption film. The electric control adsorption film provided by the invention has the functions of electric adsorption, electric desorption and electric cleaning, avoids adding medicaments in the sewage treatment process, and can realize the synchronous removal of macromolecular pollutants and micromolecular organic matters.
Description
Technical Field
The invention belongs to the field of membrane technical treatment, relates to an electric control adsorption membrane, and particularly relates to an electric control adsorption membrane, a preparation method, an electropolymerization device and a self-cleaning method.
Background
Various organic substances, such as natural organic substances (NOM), medicines and personal care products (PPCPs) and trace agricultural chemicals, exist in drinking water sources, and cannot be completely removed in the drinking water treatment process. In addition, during the disinfection process of drinking water, residual NOM in the water reacts with the disinfectant, and disinfection byproducts such as halogenated methane and the like are easily generated. Therefore, trace organic matters remained in the effluent of the water plant and disinfection byproducts generated in the disinfection process can be detected in the tap water. It is worth noting that hydrophobic or semi-hydrophobic small molecule organic substances such as Persistent Organic Substances (POPs) and trihalomethanes have high toxicity and have high threat to human health. At the end of a pipe network, in order to further remove particulate matters and turbidity, a deep purification process using a membrane as a core, particularly nanofiltration as a core is often adopted, hydrophobic or semi-hydrophobic small molecule organic matters such as persistent organic matters (POPs) and trihalomethanes are electrically neutral, and even if the deep purification process using nanofiltration as the core is adopted, the electrically neutral small molecule organic pollutants cannot be completely removed.
The adsorption function and the membrane separation function of the material are combined to prepare the membrane material with adsorption and separation performances, so that the efficient removal of small molecular pollutants can be realized at lower operating pressure. CN 110451692A discloses a water purification treatment method based on adsorption and solid-liquid separation, which comprises the following steps: the method comprises the following steps that firstly, aiming at organic pollutants in water, the huge specific surface area of powdered activated carbon is utilized, middle and low molecular weight organic matters in the water are adsorbed through physical adsorption, chemical adsorption or exchange adsorption, and part of macromolecular organic matters can be removed through a coagulation part at the front end or the chemical structure of the macromolecular organic matters is changed through pre-oxidation; secondly, the organic pollutants in the water are transferred from a dissolved state to a suspended state of the activated carbon through adsorption, and the water purification process is realized through physical separation of a microfiltration membrane after the organic matters with phase transfer adhere to the activated carbon; thirdly, removing turbidity substances, calcium, iron and high-stability organic complexes thereof in the processes of coagulation, pre-oxidation and activated carbon adsorption to reduce the influence of the turbidity substances, the calcium, the iron and the high-stability organic complexes on the membrane flux; and fourthly, utilizing activated carbon as an adsorbent for the preoxidant influencing the chemical structure of the membrane so as to improve the service time and the membrane flux of the microfiltration membrane. It is worth noting that desorption and reactivation processes are often very cumbersome and expensive, and regeneration of the adsorption functional membrane is a major problem at present.
Conductive polymers and monomers thereof are generally doped with different additives during the polymerization process to adjust the conductivity and morphology of the polymers. The macromolecular surfactant can be blocked in a macromolecular framework and is not easy to lose, the hydrophilicity and the hydrophobicity of the polymer can be converted through the oxidation reduction of the conductive polymer, and the conversion of the hydrophilicity and the hydrophobicity can just realize the switching of the affinity of the low-polarity micromolecular organic matter.
CN 110550698A discloses a membrane method water treatment process based on micro flow field-micro electric field coupling, which comprises the following steps: water to be treated enters a membrane method water treatment device for filtration and separation, wherein the water to be treated flows through membrane holes of the membrane method water treatment device, and pollutants in the water to be treated are degraded and filtered under a micro electric field and a micro flow field at the membrane holes; wherein the membrane method water treatment facilities includes: the reaction tank is internally provided with a membrane component, the aperture of a membrane hole on the membrane of the membrane component is 0.1-10 mu m, a conductive micro-nano material is deposited at the membrane hole to form a micro-electric field under an external electric field, and water to be treated continuously and directionally flows through the membrane hole to form a micro-flow field; the step of filtering and separating the water to be treated in the membrane method water treatment device comprises the following steps: the water to be treated is filtered and separated in the reaction tank, and pollutants in the water to be treated are subjected to chemical reaction and physical action in a micro-electric field and are filtered and cleaned in the micro-electric field. Although the above patent adopts the conductive technology to remove pollutants in water, the conductive micro-nano material is only deposited on the membrane component, and an integral membrane is not formed, so that the structure is complex, the preparation process is complex, and the large-scale wide application is difficult.
Therefore, if the conductive polymer can be introduced onto the ultrafiltration/microfiltration membrane, the conductive polymer can remove macromolecular organic matters and adsorb small-molecular organic matters in water at the same time, desorption and regeneration of weak-polarity organic matters are realized on the surface of the same membrane through free switching of electric field charge signals after adsorption saturation, and in addition, the free switching of hydrophilicity and hydrophobicity can greatly reduce the adhesion of the macromolecular organic matters to the surface of the membrane in the desorption process, so that the membrane can be effectively cleaned on line, and the stability and effectiveness of treatment are improved.
Disclosure of Invention
The invention aims to provide an electric control adsorption film, a preparation method, an electropolymerization device and a self-cleaning method. The electric control adsorption film has the functions of electric adsorption, electric desorption and electric cleaning, avoids additional medicament in the sewage treatment process, and can realize the synchronous removal of macromolecular pollutants and micromolecular organic matters.
The weak-polarity trace organic pollutant comprises any one or the combination of at least two of 1-naphthol, 1-naphthylamine, bisphenol A, bisphenol S or 2, 4-dichlorophenol.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing an electrically controlled adsorption film, comprising the steps of:
(1) mixing a surfactant, water and a conductive material, dispersing to obtain a conductive material dispersion liquid, and then loading the conductive material dispersion liquid on a bottom film in a vacuum-assisted physical deposition manner to obtain a conductive film;
(2) mixing a surfactant, water, an additive and an electropolymerization monomer to obtain an electropolymerization electrolyte;
(3) mixing the conductive film obtained in the step (1) and the electropolymerization electrolyte obtained in the step (2), and performing electropolymerization to obtain a conductive film with an adsorption function layer;
(4) sequentially soaking and cleaning the conductive film obtained in the step (3) to obtain the electric control adsorption film;
the step (1) and the step (2) are not in sequence.
The electric control adsorption film obtained by the preparation method of the invention shows greatly different hydrophilicity and hydrophobicity after applying short-range oxidation/reduction potential, and realizes the switching of affinity to trace organic matters. In addition, the electric control adsorption film has the functions of electric adsorption, electric desorption and electric cleaning, avoids additional medicament and can realize the synchronous removal of macromolecular pollutants and micromolecular organic matters.
Preferably, the surfactant of step (1) comprises any one of or a combination of at least two of sodium docusate, potassium perfluorooctanesulfonate, tetraethylene perfluorooctanesulfonate or dodecylbenzene sulfonic acid, typical but non-limiting combinations include a combination of sodium docusate and potassium perfluorooctanesulfonate, a combination of potassium perfluorooctanesulfonate and tetraethylene perfluorooctanesulfonate, a combination of tetraethylene perfluorooctanesulfonate and dodecylbenzene sulfonic acid, a combination of sodium docusate, potassium perfluorooctanesulfonate and tetraethylene perfluorooctanesulfonate, a combination of potassium perfluorooctanesulfonate, tetraethylene perfluorooctanesulfonate and dodecylbenzene sulfonic acid, or a combination of sodium docusate, potassium perfluorooctanesulfonate, tetraethylene perfluorooctanesulfonate and dodecylbenzene sulfonic acid.
Preferably, the concentration of the surfactant in the conductive material dispersion of step (1) is 0.5-2g/L, such as 0.5g/L, 0.8g/L, 1.0g/L, 1.2g/L, 1.4g/L, 1.6g/L, 1.8g/L, or 2g/L, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
The concentration of the surfactant in the conductive material dispersion liquid is 0.5-2g/L, and the uniformity of the conductive film is influenced if the concentration is too low.
Preferably, the conductive material in step (1) includes any one or a combination of at least two of carbon nanotube, graphene, carbon powder, carbon nanosphere or metal-organic framework, and typical but non-limiting combinations include a combination of carbon nanotube, graphene and carbon powder, a combination of graphene, carbon powder, carbon nanosphere and metal-organic framework, a combination of nanotube, graphene, carbon powder and carbon nanosphere, or a combination of carbon nanotube, graphene, carbon powder, carbon nanosphere and metal-organic framework.
Preferably, the concentration of the conductive material in the conductive material dispersion of step (1) is 10-1000mg/L, such as 10mg/L, 100mg/L, 200mg/L, 300mg/L, 400mg/L, 500mg/L, 600mg/L, 700mg/L, 800mg/L, 900mg/L or 1000mg/L, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
The concentration of the conductive material in the conductive material dispersion liquid is 10-1000mg/L, and if the concentration is too high, the dispersibility of the conductive material is influenced, and if the concentration is too low, the loading capacity of the conductive layer is influenced.
Preferably, the dispersing of step (1) comprises ultrasonic dispersing.
Preferably, the power of the ultrasonic dispersion is 100-950W, such as 100W, 200W, 300W, 400W, 500W, 600W, 700W, 800W, 900W or 950W, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the time of ultrasonic dispersion is 0.5 to 10 hours, for example, 0.5 hour, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the mode of operation of the ultrasonic dispersion comprises intermittent operation.
Preferably, the intermittent operation includes: the operation is carried out alternately for 1 to 10s and then for 1 to 10s, and the operation or the stop time can be, for example, 1s, 2s, 3s, 4s, 5s, 6s, 7s, 8s, 9s or 10s, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the deposition time of the vacuum assisted physical deposition in step (1) is 5-30min, such as 5min, 10min, 15min, 20min, 25min or 30min, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the vacuum assisted physical deposition is at a vacuum level of 0.5 to 0.9bar, such as 0.5bar, 0.6bar, 0.7bar, 0.8bar or 0.9bar, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the material of the bottom membrane in step (1) includes any one of polyvinylidene fluoride, polytetrafluoroethylene, polypropylene or mixed fiber membrane.
Preferably, the membrane type of the bottom membrane of step (1) comprises a flat sheet membrane or a hollow fiber membrane.
Preferably, the average pore diameter of the base film in step (1) is 30 to 1000nm, and may be, for example, 30nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or 1000nm, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
The average pore diameter of the bottom membrane can affect the performance of the electric control adsorption membrane, the conductive layer can be unstable when the average pore diameter is too large, and the membrane resistance can be increased when the average pore diameter is too small.
Preferably, the loading amount of the conductor material on the conductive film in the step (1) is 0.05-5g/m2For example, it may be 0.05g/m2、0.1g/m2、0.5g/m2、1g/m2、2g/m2、3g/m2、4g/m2Or 5g/m2But not limited to the recited values, other values not recited within the numerical range are equally applicable.
The conductive capacity of the electric control adsorption film is influenced by too low load of the conductor material on the conductive film, and the electric polymerization process is difficult to carry out by too low load.
Preferably, the water of step (1) comprises ultrapure water and/or deionized water.
In the preparation method provided by the invention, the solvent adopted in the mixing process of the step (1) and the step (2) is ultrapure water and/or deionized water, and tap water contains many impurities such as calcium and magnesium ions, which can affect the preparation of the electric control adsorption film and further affect the adsorption and desorption effects of the electric control adsorption film.
Preferably, the surfactant of step (2) comprises any one of or a combination of at least two of sodium docusate, potassium perfluorooctanesulfonate, tetraethylene perfluorooctanesulfonate or dodecylbenzene sulfonic acid, typical but non-limiting combinations include a combination of sodium docusate and potassium perfluorooctanesulfonate, a combination of potassium perfluorooctanesulfonate and tetraethylene perfluorooctanesulfonate, a combination of tetraethylene perfluorooctanesulfonate and dodecylbenzene sulfonic acid, a combination of sodium docusate, potassium perfluorooctanesulfonate and tetraethylene perfluorooctanesulfonate, a combination of potassium perfluorooctanesulfonate, tetraethylene perfluorooctanesulfonate and dodecylbenzene sulfonic acid, or a combination of sodium docusate, potassium perfluorooctanesulfonate, tetraethylene perfluorooctanesulfonate and dodecylbenzene sulfonic acid.
Preferably, the concentration of the surfactant in the electropolymerization electrolyte solution in step (2) is 0.01-1mol/L, and may be, for example, 0.01mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1mol/L, but is not limited to the recited values, and other values not recited in the numerical ranges are also applicable.
Preferably, the electropolymerized monomer of step (2) comprises any one of pyrrole, aniline or thiophene or a combination of at least two thereof, and typical but non-limiting combinations include a combination of pyrrole and aniline, a combination of aniline and thiophene, a combination of pyrrole and thiophene or a combination of pyrrole, aniline and thiophene.
Preferably, the concentration of electropolymerized monomer in the electropolymerization electrolyte solution in step (2) is 0.1-1mol/L, and may be, for example, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1mol/L, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
The concentration of the electropolymerization monomer in the electropolymerization electrolyte can influence the adsorption capacity of the electric control adsorption film, and the adsorption capacity of the electric control adsorption film can be reduced when the concentration is too low.
Preferably, the additive of step (2) comprises any one of lithium chloride, dipyrrole or polyethylene glycol or a combination of at least two thereof, and typical but non-limiting combinations include a combination of lithium chloride and dipyrrole, a combination of dipyrrole and polyethylene glycol, a combination of lithium chloride and polyethylene glycol, or a combination of lithium chloride, dipyrrole and polyethylene glycol.
Preferably, the concentration of the additive in the electropolymerization electrolyte solution in step (2) is 0.03-3mg/mL, and may be, for example, 0.03mg/mL, 0.1mg/mL, 1mg/mL, 1.5mg/mL, 2mg/mL, 2.5mg/mL or 3mg/mL, but is not limited to the recited values, and other values not recited in the numerical ranges are also applicable.
Preferably, the water of step (2) comprises ultrapure water and/or deionized water.
Preferably, the electropolymerization of step (3) has a current density of 0.1-10mA/cm2For example, it may be 0.1mA/cm2、1mA/cm2、2mA/cm2、3mA/cm2、4mA/cm2、5mA/cm2、6mA/cm2、7mA/cm2、8mA/cm2、9mA/cm2Or 10mA/cm2But not limited to the recited values, other values not recited within the numerical range are equally applicable.
Preferably, the electropolymerization in step (3) is carried out for a period of 5 to 8000min, for example 5min, 100min, 1000min, 2000min, 3000min, 4000min, 5000min, 6000min, 7000min or 8000min, but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
The purpose of the electropolymerization is to obtain a conductive film with an adsorption function layer, the current density and time of electropolymerization can directly influence the load capacity of the adsorption function layer and further influence the adsorption capacity of the electric control adsorption film, and the adsorption capacity of the electric control adsorption film can be reduced due to the excessively low current density and electropolymerization time.
Preferably, the soaking liquid in the soaking in the step (4) comprises ultrapure water and/or deionized water.
Preferably, the soaking time in step (4) is 12-24h, such as 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
As a preferred technical solution of the present invention, a method for preparing an electrically controlled adsorption film provided by the first aspect of the present invention includes the following steps:
(1) mixing surfactant, ultrapure water and conductive material, and applying power of 100-950WUltrasonically dispersing for 0.5-10h to obtain a conductive material dispersion liquid, and then depositing for 5-30min in a vacuum assisted physical deposition mode under the vacuum degree of 0.5-0.9barPa to load on a base film with the average pore diameter of 30-1000nm to obtain a conductive film; the concentration of the surfactant in the conductive material dispersion liquid is 0.5-2g/L, and the concentration of the conductive material is 10-1000 mg/L; the loading amount of the conductor material on the conductive film is 0.05-5g/m2；
(2) Mixing a surfactant, ultrapure water, an additive and an electropolymerization monomer to obtain electropolymerization electrolyte; the concentration of a surfactant in the electropolymerization electrolyte is 0.01-1mol/L, the concentration of an electropolymerization monomer is 0.1-1mol/L, and the concentration of an additive is 0.03-3 mg/mL;
(3) mixing the conductive film obtained in the step (1) and the electropolymerization electrolyte obtained in the step (2), and performing electropolymerization to obtain a conductive film with an adsorption function layer; the electropolymerization current density is 0.1-10mA/cm2The time is 5-8000 min;
(4) sequentially soaking and cleaning the conductive film obtained in the step (3) to obtain the electric control adsorption film; the soaking liquid in the soaking process comprises ultrapure water, and the soaking time is 12-24 h;
the step (1) and the step (2) are not in sequence.
In a second aspect, the present invention provides an electropolymerization apparatus used in the production method provided in the first aspect, the electropolymerization apparatus being used for the electropolymerization in the step (3);
the electropolymerization device comprises an electrolytic tank and a three-electrode system arranged inside the electrolytic tank;
the three-electrode system comprises a working electrode, a reference electrode and a counter electrode;
the reference electrode comprises an Ag/AgCl reference electrode;
the electropolymerization device includes a flat plate type electropolymerization device and a hollow fiber type electropolymerization device.
The electropolymerization device provided by the invention is divided into a flat plate type electropolymerization device and a hollow fiber type electropolymerization device according to different adopted basement membranes.
Preferably, the flat plate type electropolymerization device comprises a working electrode and a counter electrode which are arranged in parallel to the bottom of the electrolytic tank.
Preferably, the working electrode includes a flat conductive film, an O-ring, and a conductive ring.
Preferably, the conductive ring is in close contact with a conductive layer of a flat conductive film.
Preferably, the O-ring is used for fixing the flat conductive film.
Preferably, the counter electrode comprises a flat titanium ruthenium mesh and a titanium ruthenium rod.
Preferably, the titanium ruthenium bar is arranged on the flat titanium ruthenium net in parallel with the side wall of the electrolytic bath.
Preferably, the distance between the flat conductive film and the flat titanium ruthenium mesh is 0.3-3cm, such as 0.3cm, 0.5cm, 1cm, 1.5cm, 2cm, 2.5cm or 3cm, but not limited to the values listed, and other values not listed in the range of values are also applicable.
The flat-plate type electropolymerization device is used for the electropolymerization process of the flat-plate type bottom film, wherein a reference electrode, a flat conductive film and a flat titanium ruthenium net with a titanium ruthenium rod form a three-electrode system.
Preferably, the hollow fiber type electropolymerization device includes a working electrode and a counter electrode disposed in parallel to a side wall of the electrolytic bath.
Preferably, the working electrode includes a hollow fiber conductive film and a conductive ring.
Preferably, the counter electrode comprises a barrel-shaped titanium ruthenium mesh.
Preferably, the conductive ring is in close contact with the conductive layer of the hollow fiber conductive film.
Preferably, the distance between the hollow fiber conductive membrane and the barrel-shaped titanium ruthenium net is 0.3-8cm, for example, 0.3cm, 0.5cm, 1cm, 2cm, 3cm, 4cm, 5cm, 6cm, 7cm or 8cm, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
The hollow fiber type electropolymerization device is used for the electropolymerization process of the hollow fiber type, wherein a reference electrode, a hollow fiber conducting film and a barrel-shaped titanium ruthenium net form a three-electrode system.
In a third aspect, the invention provides an electrically-controlled adsorption film, which is prepared by the preparation method provided in the first aspect.
The electric control adsorption film is used for treating weak polar trace organic pollutants in water, such as 1-naphthol, 1-naphthylamine, bisphenol A, bisphenol S or 2, 4-dichlorophenol in water.
In a fourth aspect, the present invention provides a self-cleaning method for the electrically controlled adsorption membrane prepared by the preparation method provided in the first aspect, wherein the self-cleaning method is performed in an electrochemical filtration device;
the self-cleaning method comprises the following steps:
and placing the polluted electric control adsorption membrane in an electrochemical filtering device, and sequentially carrying out reduction and oxidation to obtain a clean electric control adsorption membrane.
The self-cleaning method can effectively recover the flux of the electric control adsorption membrane and clean dirt on the surface of the membrane.
Preferably, the electrolyte in the reduction comprises a sodium chloride solution.
Preferably, the sodium chloride concentration is 0.08-0.15mol/L, for example 0.08mol/L, 0.09mol/L, 0.1mol/L, 0.11mol/L, 0.12mol/L, 0.13mol/L, 0.14mol/L or 0.15mol/L, but not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
Preferably, the potential in the reduction is from-1 to-0.5V, and may be, for example, -1V, -0.9V, -0.8V, -0.7V, -0.6V or-0.5V, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the time in the reduction is 8-15min, for example 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15min, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the electrolyte in the oxidation comprises a sodium chloride solution.
Preferably, the sodium chloride concentration is 0.08-0.15mol/L, for example 0.08mol/L, 0.09mol/L, 0.1mol/L, 0.11mol/L, 0.12mol/L, 0.13mol/L, 0.14mol/L or 0.15mol/L, but not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
Preferably, the potential in the oxidation is 0.5-0.8V, which may be, for example, 0.5V, 0.55V, 0.6V, 0.65V, 0.7V, 0.75V or 0.8V, but is not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
Preferably, the oxidation time is 8-15min, for example 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15min, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the electrochemical filter device comprises a fixing device, a conductive device and an electrically controlled adsorption film.
Preferably, the fixing means comprise a first and a second plexiglass in two opposite ways.
Preferably, a cylindrical groove is arranged on the center of the fixing device.
Preferably, a through hole is arranged on the central point of the first organic glass.
Preferably, the conductive device comprises a titanium ruthenium rod, a titanium ruthenium net, a conductive ring and an O-shaped ring.
Preferably, the titanium ruthenium bar is arranged on the central point of the titanium ruthenium net through a through hole.
Preferably, the O-shaped ring is used for fixing the electric control adsorption film.
Preferably, the conductive ring is arranged between the electrically-controlled adsorption film and the titanium ruthenium net.
Preferably, the electrically controlled adsorption film is spaced from the ti-ru mesh by 0.5-1.5cm, such as 0.5cm, 0.6cm, 0.7cm, 0.8cm, 0.9cm, 1cm, 1.1cm, 1.2cm, 1.3cm, 1.4cm or 1.5cm, but not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the effective area of the electric control adsorption film and the titanium ruthenium net is 10-15cm2For example, it may be 10cm2、11cm2、12cm2、13cm2、14cm2Or 15cm2But not limited to the recited values, other values not recited within the numerical range are equally applicable.
The working method of the electrochemical filtering device of the invention is as follows:
the first organic glass and the second organic glass are respectively and independently provided with a cylinder groove, the first organic glass and the second organic glass are combined to form a cylinder space, and the self-cleaning method is carried out in the cylinder space.
As a preferable technical solution of the self-cleaning method according to the fourth aspect of the present invention, the self-cleaning method includes the steps of:
and placing the polluted electric control adsorption membrane in an electrochemical filtering device, and sequentially reducing and oxidizing to obtain a clean electric control adsorption membrane.
The electrolyte in the reduction is a sodium chloride solution with the concentration of 0.08-0.15mol/L, the potential in the reduction is-1 to-0.5V, and the time is 8-15 min; the electrolyte for oxidation is a sodium chloride solution with the concentration of 0.08-0.15mol/L, the potential for oxidation is 0.5-0.8V, and the time is 8-15 min.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method provided by the invention utilizes the conductivity of the conductive material, loads the conductive polymer on the membrane in an electropolymerization mode to prepare the conductive membrane which can freely switch the hydrophilicity and hydrophobicity of the surface of the membrane, has the functions of electric adsorption, electric desorption and electric cleaning, can realize the desorption and regeneration of the membrane through simple electric signals, and can clean the membrane surface on line in the desorption process;
(2) the preparation method provided by the invention introduces the conductive polymer, and the introduction of the conductive polymer can improve the conductivity and stability of the conductive layer, thereby being beneficial to the continuous and stable operation of the membrane filtration process;
(3) the invention obtains the electric control adsorption film by utilizing a simple electropolymerization method, avoids adding a medicament in the desorption process, has simple process, economy and environmental protection, and can realize the synchronous removal of macromolecular pollutants and micromolecular organic matters;
(4) the preparation method of the electric control adsorption membrane provided by the invention greatly promotes the development of drinking water advanced treatment technology and membrane technology, and is suitable for industrial popularization and application.
Drawings
Fig. 1 is a planar SEM image of an electrically controlled adsorption film provided in embodiment 1 of the present invention;
FIG. 2 is a schematic structural view of a flat-plate type electropolymerization apparatus provided in example 1 of the present invention;
FIG. 3 is a schematic view of the structure of a hollow fiber type electropolymerization apparatus provided in example 2 of the present invention;
FIG. 4 is a schematic structural view of an electrochemical filter device provided in application example 2 of the present invention;
fig. 5 is a diagram showing the self-cleaning effect provided by application example 2 of the present invention.
Wherein, 1 is a reference electrode, 2 is a titanium ruthenium bar, 3 is an electrolytic bath, 4 is a flat titanium ruthenium net, 5 is an O-shaped ring, 6 is a conductive ring, 7 is a flat conductive film, 8 is a barrel-shaped titanium ruthenium net, and 9 is a hollow fiber conductive film; a is a titanium ruthenium rod, B-1 is first organic glass, B-2 is second organic glass, C is a titanium ruthenium net, D is an O-shaped ring, E is a conductive ring, and F is an electric control adsorption film.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides an electronic control adsorption film and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) mixing docusate sodium, ultrapure water and carbon nano tube, performing ultrasonic dispersion for 5.5h at 500W power to obtain a conductive material dispersion liquid, and then depositing in a vacuum degree of 0.7Pa in a vacuum assisted physical deposition mannerLoading the film on a flat plate type polyvinylidene fluoride base film with the average pore diameter of 100nm for 20min to obtain a conductive film; the concentration of docusate sodium in the conductive material dispersion liquid is 1g/L, and the concentration of the conductive material is 100 mg/L; the loading amount of the conductor material on the conductive film is 1.5g/m2；
(2) Mixing docusate sodium, ultrapure water, dipyrrole and pyrrole monomer for 3h to obtain electropolymerization electrolyte; the concentration of docusate sodium in the electropolymerization electrolyte is 0.1mol/L, the concentration of pyrrole monomer is 0.1mol/L, and the concentration of dipyrrole is 0.3 mg/mL;
(3) mixing the conductive film obtained in the step (1) and the electropolymerization electrolyte obtained in the step (2), and performing electropolymerization to obtain a conductive film with an adsorption function layer; the current density of the electropolymerization is 1mA/cm2The time is 120 min;
(4) sequentially soaking and cleaning the conductive film obtained in the step (3) to obtain the electric control adsorption film; the soaking liquid in the soaking process comprises ultrapure water, and the soaking time is 18 h;
the step (1) and the step (2) are not in sequence.
The electropolymerization device adopted in the electropolymerization process in the step (3) is a flat plate type electropolymerization device shown in figure 2, and comprises an electrolytic tank 3 and a three-electrode system arranged in the electrolytic tank 3; the three-electrode system comprises a working electrode, a reference electrode 1 and a counter electrode; the reference electrode 1 comprises an Ag/AgCl reference electrode;
the flat-plate type electropolymerization device comprises a working electrode and a counter electrode which are arranged in parallel to the bottom of the electrolytic bath 1; the working electrode comprises a flat conductive film 7, an O-shaped ring 5 and a conductive ring 6; the conductive ring 6 is in close contact with the conductive layer of the flat conductive film 7; the O-shaped ring 5 is used for fixing a flat conductive film 7; the counter electrode comprises a flat titanium ruthenium net 4 and a titanium ruthenium rod 2; the titanium ruthenium bar 2 is arranged on the flat titanium ruthenium net 4 in parallel with the side wall of the electrolytic bath 1; the distance between the flat conductive film 7 and the flat titanium ruthenium net 4 is 1 cm.
The electrically controlled adsorption film obtained in this example had a contact angle of 145.7 ° after complete oxidation at 0.6V (for an Ag/AgCl reference electrode) and a contact angle of 13.1 ° after complete reduction at-0.8V (for an Ag/AgCl reference electrode), and its planar SEM image is shown in fig. 1.
Example 2
The embodiment provides an electronic control adsorption film and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) mixing potassium perfluorooctane sulfonate, ultrapure water and graphene, performing ultrasonic dispersion for 10 hours at 100W power to obtain a conductive material dispersion liquid, and then depositing for 5min in a vacuum assisted physical deposition mode under the vacuum degree of 0.5bar to load the conductive material dispersion liquid on a hollow fiber type polytetrafluoroethylene base film with the average pore diameter of 1000nm to obtain a conductive film; the concentration of potassium perfluorooctane sulfonate in the conductive material dispersion liquid is 0.5g/L, and the concentration of graphene is 10 mg/L; the loading amount of graphene on the conductive film is 0.05g/m2；
(2) Mixing potassium perfluorooctane sulfonate, ultrapure water, aniline and lithium chloride to obtain an electropolymerization electrolyte; the concentration of potassium perfluorooctane sulfonate in the electropolymerization electrolyte is 0.01mol/L, the concentration of lithium chloride is 0.1mol/L, and the concentration of aniline is 0.03 mg/mL;
(3) mixing the conductive film obtained in the step (1) and the electropolymerization electrolyte obtained in the step (2), and performing electropolymerization to obtain a conductive film with an adsorption function layer; the current density of the electropolymerization is 0.1mA/cm2The time is 800 min;
(4) sequentially soaking and cleaning the conductive film obtained in the step (3) to obtain the electric control adsorption film; the soaking liquid in the soaking process comprises ultrapure water, and the soaking time is 24 hours;
the step (1) and the step (2) are not in sequence.
The electropolymerization device adopted in the electropolymerization process in the step (3) is a hollow fiber type electropolymerization device shown in figure 3, and comprises the following components: an electrolytic cell 3 and a three-electrode system placed inside the electrolytic cell 3; the three-electrode system comprises a working electrode, a reference electrode 1 and a counter electrode; the reference electrode comprises an Ag/AgCl reference electrode.
The hollow fiber type electropolymerization device comprises a working electrode and a counter electrode which are arranged in parallel with the side wall of the electrolytic bath 3; the working electrode comprises a hollow fiber conducting film 9 and a conducting ring 6; the counter electrode comprises a barrel-shaped titanium ruthenium mesh 8; the conductive ring 6 is in close contact with the conductive layer of the hollow fiber conductive film 9; the distance between the hollow fiber conductive film 9 and the barrel-shaped titanium ruthenium net 8 is 5 cm.
Example 3
The embodiment provides an electronic control adsorption film and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) mixing perfluorooctyl sulfonic acid tetraethylene amine, ultrapure water and a metal organic frame, performing ultrasonic dispersion for 0.5h at 950W power to obtain a conductive material dispersion liquid, and then depositing for 30min in a vacuum assisted physical deposition mode under the vacuum degree of 0.9bar to load the conductive material dispersion liquid on a flat plate type mixed fiber membrane with the average pore diameter of 1000nm to obtain a conductive membrane; the concentration of the perfluorooctyl sulfonic acid tetraethylene amine in the conductive material dispersion liquid is 2g/L, and the concentration of the metal organic framework is 1000 mg/L; the loading capacity of the metal organic framework on the conductive film is 5g/m2；
(2) Mixing perfluorooctyl sulfonic acid tetraethylene amine, ultrapure water, polyethylene glycol and a thiophene monomer to obtain an electropolymerization electrolyte; the concentration of perfluorooctyl sulfonic acid tetraethylene amine in the electropolymerization electrolyte is 1mol/L, the concentration of thiophene monomer is 1mol/L, and the concentration of polyethylene glycol is 3 mg/mL;
(3) mixing the conductive film obtained in the step (1) and the electropolymerization electrolyte obtained in the step (2), and performing electropolymerization to obtain a conductive film with an adsorption function layer; the electropolymerization current density is 10mA/cm2The time is 50 min;
(4) sequentially soaking and cleaning the conductive film obtained in the step (3) to obtain the electric control adsorption film; the soaking liquid in the soaking process comprises ultrapure water, and the soaking time is 24 hours;
the step (1) and the step (2) are not in sequence.
The electropolymerization device used in the electropolymerization process in the step (3) is the same as that in the embodiment 1 except that the distance between the flat conductive film 7 and the flat titanium ruthenium mesh 4 is changed to 3 cm.
Example 4
The embodiment provides an electronic control adsorption film and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) mixing docusate sodium, ultrapure water and a carbon nano tube, performing ultrasonic dispersion for 4.5h at 650W power to obtain a conductive material dispersion liquid, and then depositing for 15min in a vacuum assisted physical deposition mode under the vacuum degree of 0.8Pa to load the conductive material dispersion liquid on a flat polyvinylidene fluoride base film with the average pore diameter of 500nm to obtain a conductive film; the concentration of docusate sodium in the conductive material dispersion liquid is 1.5g/L, and the concentration of the carbon nano tube is 500 mg/L; the loading amount of the carbon nano tube on the conductive film is 3.5g/m2；
(2) Mixing docusate sodium, ultrapure water, dipyrrole and pyrrole monomer to obtain electropolymerization electrolyte; the concentration of docusate sodium in the electropolymerization electrolyte is 0.56mol/L, the concentration of pyrrole monomer is 0.6mol/L, and the concentration of dipyrrole is 1.5 mg/mL;
(3) mixing the conductive film obtained in the step (1) and the electropolymerization electrolyte obtained in the step (2), and performing electropolymerization to obtain a conductive film with an adsorption function layer; the electropolymerization has a current density of 5.5mA/cm2The time is 300 min;
(4) sequentially soaking and cleaning the conductive film obtained in the step (3) to obtain the electric control adsorption film; the soaking liquid in the soaking process comprises ultrapure water, and the soaking time is 20 hours;
the step (1) and the step (2) are not in sequence.
The electropolymerization device adopted in the electropolymerization process in the step (3) is the same as that in the embodiment 1 except that the distance between the flat conductive film 7 and the flat titanium ruthenium mesh 4 is changed to 1.5cm
Example 5
The present embodiment provides an electrically controlled adsorption film and a method for preparing the same, which is different from embodiment 1 only in that: in this embodiment, the concentration of the conductive material in the step (1) is changed to 8mg/L, and the loading amount of the conductive material on the conductive film is 1.0g/m2。
The electropolymerization device used in the electropolymerization process in step (3) is the same as that used in example 1.
Example 6
The implementation is carriedAn electrically controlled adsorption film and a method for preparing the same are provided, which differ from example 1 only in that: in this embodiment, the concentration of the conductive material in the step (1) is changed to 1200mg/L, and the loading amount of the conductive material on the conductive film is 5.8g/m2。
The electropolymerization device used in the electropolymerization process in step (3) is the same as that used in example 1.
Example 7
The present embodiment provides an electrically controlled adsorption film and a method for preparing the same, which is different from embodiment 1 only in that: this example changed the concentration of the electropolymerized monomer described in step (2) to 0.05 mol/L.
The electropolymerization device used in the electropolymerization process in step (3) is the same as that used in example 1.
Example 8
The present embodiment provides an electrically controlled adsorption film and a method for preparing the same, which is different from embodiment 1 only in that: this example modified the concentration of electropolymerized monomer described in step (2) to 1.5 mol/L.
The electropolymerization device used in the electropolymerization process in step (3) is the same as that used in example 1.
Comparative example 1
This comparative example provides an electrically controlled adsorption film and a method for preparing the same, which differs from example 1 only in that: in the comparative example, the ultrapure water obtained in the steps (1) and (2) was replaced with deionized water.
The electropolymerization device used in the electropolymerization process in step (3) is the same as that used in example 1.
Comparative example 2
This comparative example provides an electrically controlled adsorption film and a method for preparing the same, which differs from example 1 only in that: this comparative example omits the additives described in step (2).
The electropolymerization device used in the electropolymerization process in step (3) is the same as that used in example 1.
Application example 1
The electrically controlled adsorption membranes provided in examples 1-8 and comparative examples 1-2 were used to remove low-polarity trace organic contaminants from water.
Processing the sample: 1-naphthol, 1-naphthylamine, bisphenol A, bisphenol S and 2, 4-dichlorophenol aqueous solution with the concentration of 1 mg/L;
the treatment method comprises the following steps: applying a potential of 0.6V (relative to an Ag/AgCl reference electrode) to the electric control adsorption film by using an electrochemical workstation for oxidation for 10 min; then introducing a treated sample, and controlling the water flux to be 96L/m2Filtering for 60min under the condition of/h; after filtration, 0.1mol/L sodium chloride (NaCl) solution is introduced, and the electric control adsorption membrane is subjected to reduction for 10min by applying a potential of-0.8V (relative to an Ag/AgCl reference electrode) by using an electrochemical workstation.
The operation is repeated for 3 times, and the removal rate of the self-made electric control adsorption film to different pollutants in 60min is shown in table 1.
TABLE 1
The above table shows that the self-made electric control adsorption film has a good effect of removing various low-polarity organic pollutants, and the electric control regeneration effect is excellent, and the adsorption capacity of the self-made electric control adsorption film on various low-polarity pollutants can be basically and completely recovered.
It can be seen from the analysis of examples 1 and 5-6 that the decrease of the loading amount of the conductive material slightly affects the adsorption performance of the electrically controlled adsorption film.
It can be seen from the analysis of examples 1 and 7-8 that the concentration of the electropolymerized monomer in the electropolymerized electrolyte solution of the present invention is too low, which may reduce the adsorption capacity of the electrically controlled adsorption film.
Analysis of example 1 and comparative example 1 shows that the deionized water has a small effect on the performance of the electrically controlled adsorption film.
Analysis of example 1 and comparative example 2 shows that the additive is the core that confers strong adsorption capacity to the less polar contaminants on the membrane.
Application example 2
The application example provides a cleaning method of the electronic control adsorption film provided in the embodiment 1, the electronic control adsorption film provided in the embodiment 1 is polluted firstly, and then self-cleaning is carried out;
the contamination procedure was as follows: sequentially carrying out pretreatment and pollution on the electric control adsorption film to obtain a polluted electric control adsorption film; the electrolyte in the pretreatment is a sodium chloride solution with the concentration of 0.1mol/L, the potential of the pretreatment is 0.6V, and the time is 10 min; the pollutant in the pollution is fulvic acid aqueous solution with the concentration of 10mg/L, the pollution mode is cross-flow filtration, the pressure of the cross-flow filtration is 1bar, and the time is 30 min.
The self-cleaning method is carried out in an electrochemical filtration device as shown in fig. 4;
the self-cleaning method comprises the following steps:
and placing the polluted electric control adsorption membrane in an electrochemical filtering device, and sequentially reducing and oxidizing to obtain a clean electric control adsorption membrane.
The electrolyte in the reduction is a sodium chloride solution with the concentration of 0.1mol/L, the potential in the reduction is-0.8V, and the time is 10 min; the electrolyte for oxidation is a sodium chloride solution with the concentration of 0.1mol/L, the potential for oxidation is 0.6V, and the time is 10 min.
The electrochemical filtering device comprises a fixing device, a conducting device and an electric control adsorption film F.
The fixing device comprises a first organic glass B-1 and a second organic glass B-2 which are opposite to each other; a cylindrical groove is formed in the center of the fixing device; and a through hole is formed in the central point of the first organic glass B-1.
The conductive device comprises a titanium ruthenium rod A, a titanium ruthenium net C, a conductive ring E and an O-shaped ring D; the titanium ruthenium bar A is arranged on the central point of the titanium ruthenium net C through a through hole; the O-shaped D ring is used for fixing the electric control adsorption film F; the conductive ring E is arranged between the electric control adsorption film F and the titanium ruthenium net C; preferably, the distance between the electric control adsorption film F and the titanium ruthenium net C is 1 cm; the effective area of the electric control adsorption film F and the titanium ruthenium net C is 11.34cm2。
The self-cleaning effect of the electrically controlled adsorption film provided by the application example is shown in fig. 5.
As can be seen from fig. 5, after 30min cross-flow filtration, the flux of the electrically controlled adsorption membrane provided in example 1 after being polluted is not significantly improved by washing with water, but after being subjected to the electrically controlled regeneration process, the flux is completely recovered, and the dirt on the surface of the membrane is completely removed. Therefore, the electrochemical filtering device provided by the invention can automatically clean the electrically-controlled adsorption membrane, effectively remove dirt on the surface of the membrane and improve the flux of the membrane.
In conclusion, the electric control adsorption film obtained by the preparation method of the invention shows greatly different hydrophilicity and hydrophobicity after applying short-range oxidation/reduction potential, and realizes the switching of affinity to trace organic matters. In addition, the electric control adsorption film has the functions of electric adsorption, electric desorption and electric cleaning, avoids additional medicament and can realize the synchronous removal of macromolecular pollutants and micromolecular organic matters.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of the electric control adsorption film is characterized by comprising the following steps:
(1) mixing a surfactant, water and a conductive material, dispersing to obtain a conductive material dispersion liquid, and then loading the conductive material dispersion liquid on a bottom film in a vacuum-assisted physical deposition manner to obtain a conductive film;
(2) mixing a surfactant, water, an additive and an electropolymerization monomer to obtain an electropolymerization electrolyte;
(3) mixing the conductive film obtained in the step (1) and the electropolymerization electrolyte obtained in the step (2), and performing electropolymerization to obtain a conductive film with an adsorption function layer;
(4) sequentially soaking and cleaning the conductive film obtained in the step (3) to obtain the electric control adsorption film;
the step (1) and the step (2) are not in sequence.
2. The method according to claim 1, wherein the surfactant in step (1) comprises any one or a combination of at least two of sodium docusate, potassium perfluorooctane sulfonate, tetraethylene amine perfluorooctyl sulfonate, or dodecylbenzene sulfonic acid;
preferably, the concentration of the surfactant in the conductive material dispersion liquid in the step (1) is 0.5-2 g/L;
preferably, the conductive material in step (1) comprises any one or a combination of at least two of carbon nanotubes, graphene, carbon powder, carbon nanospheres or metal-organic frameworks;
preferably, the concentration of the conductive material in the conductive material dispersion liquid in the step (1) is 10-1000 mg/L;
preferably, the dispersing of step (1) comprises ultrasonic dispersing;
preferably, the power of the ultrasonic dispersion is 100-950W;
preferably, the time of ultrasonic dispersion is 0.5-10 h;
preferably, the mode of operation of the ultrasonic dispersion comprises intermittent operation;
preferably, the intermittent operation includes: working for 1-10s, then stopping for 1-10s, and alternately performing;
preferably, the deposition time of the vacuum-assisted physical deposition in the step (1) is 5-30 min;
preferably, the vacuum degree of the vacuum-assisted physical deposition is 0.5-0.9 bar;
preferably, the material of the bottom membrane in the step (1) comprises any one of polyvinylidene fluoride, polytetrafluoroethylene, polypropylene or mixed fiber membrane;
preferably, the membrane type of the bottom membrane in step (1) comprises a flat sheet membrane or a hollow fiber membrane;
preferably, the average pore diameter of the base membrane in the step (1) is 30-1000 nm;
preferably, the conductive film of step (1) is made of a conductive materialThe supported amount of (A) is 0.05-5g/m2；
Preferably, the water of step (1) comprises ultrapure water and/or deionized water.
3. The production method according to claim 1 or 2, wherein the surfactant in the step (2) comprises any one or a combination of at least two of sodium docusate, potassium perfluorooctane sulfonate, tetraethylene amine perfluorooctyl sulfonate, or dodecylbenzene sulfonic acid;
preferably, the concentration of the surfactant in the electropolymerization electrolyte in the step (2) is 0.01-1 mol/L;
preferably, the electropolymerized monomer of step (2) comprises any one or a combination of at least two of pyrrole, aniline or thiophene;
preferably, the concentration of the electropolymerized monomer in the electropolymerized electrolyte solution in the step (2) is 0.1-1 mol/L;
preferably, the additive in step (2) comprises any one or a combination of at least two of lithium chloride, dipyrrole or polyethylene glycol;
preferably, the water of step (2) comprises ultrapure water and/or deionized water;
preferably, the concentration of the additive in the electropolymerization electrolyte in the step (2) is 0.03-3 mg/mL;
preferably, the electropolymerization of step (3) has a current density of 0.1-10mA/cm2；
Preferably, the time for the electropolymerization in the step (3) is 5-8000 min;
preferably, the soaking solution in the soaking in the step (4) comprises ultrapure water;
preferably, the soaking time in the step (4) is 12-24 h.
4. The production method according to any one of claims 1 to 3, characterized by comprising the steps of:
(1) mixing surfactant, ultrapure water and conductive material, ultrasonically dispersing for 0.5-10h with 100-950W power to obtain conductive material dispersion, and then physically assisting in vacuum at a vacuum degree of 0.5-0.9barDepositing for 5-30min in a deposition mode and loading the film on a bottom film with the average pore diameter of 30-1000nm to obtain a conductive film; the concentration of the surfactant in the conductive material dispersion liquid is 0.5-2g/L, and the concentration of the conductive material is 10-1000 mg/L; the loading amount of the conductor material on the conductive film is 0.05-5g/m2；
(2) Mixing a surfactant, ultrapure water, an additive and an electropolymerization monomer to obtain electropolymerization electrolyte; the concentration of a surfactant in the electropolymerization electrolyte is 0.01-1mol/L, the concentration of an electropolymerization monomer is 0.1-1mol/L, and the concentration of an additive is 0.03-3 mg/mL;
(3) mixing the conductive film obtained in the step (1) and the electropolymerization electrolyte obtained in the step (2), and performing electropolymerization to obtain a conductive film with an adsorption function layer; the electropolymerization current density is 0.1-10mA/cm2The time is 5-8000 min;
(4) sequentially soaking and cleaning the conductive film obtained in the step (3) to obtain the electric control adsorption film; the soaking liquid in the soaking process comprises ultrapure water, and the soaking time is 12-24 h;
the step (1) and the step (2) are not in sequence.
5. An electropolymerization apparatus used in the production method as claimed in any one of claims 1 to 4, characterized in that said electropolymerization apparatus is used for said electropolymerization in step (3);
the electropolymerization device comprises an electrolytic tank and a three-electrode system arranged inside the electrolytic tank;
the three-electrode system comprises a working electrode, a reference electrode and a counter electrode;
the reference electrode comprises an Ag/AgCl reference electrode;
the electropolymerization device includes a flat plate type electropolymerization device and a hollow fiber type electropolymerization device.
6. Electropolymerization device according to claim 5, characterized in that the flat plate electropolymerization device comprises a working electrode and a counter electrode arranged parallel to the bottom of the electrolytic cell;
preferably, the working electrode comprises a flat conductive film, an O-ring and a conductive ring;
preferably, the conductive ring is in close contact with a conductive layer of a flat conductive film;
preferably, the O-shaped ring is used for fixing the flat conductive film;
preferably, the counter electrode comprises a flat titanium ruthenium mesh and a titanium ruthenium rod;
preferably, the titanium ruthenium bar is arranged on the flat titanium ruthenium net in parallel with the side wall of the electrolytic bath;
preferably, the distance between the flat conductive film and the flat titanium ruthenium net is 0.3-3 cm;
preferably, the hollow fiber type electropolymerization device comprises a working electrode and a counter electrode which are arranged in parallel to the side wall of the electrolytic bath;
preferably, the working electrode comprises a hollow fiber conductive film and a conductive ring;
preferably, the counter electrode comprises a barrel-shaped titanium ruthenium mesh;
preferably, the conductive ring is in close contact with the conductive layer of the hollow fiber conductive film;
preferably, the distance between the hollow fiber conducting film and the barrel-shaped titanium ruthenium net is 0.3-8 cm.
7. An electrically controlled adsorption film, wherein the electrically controlled adsorption film is obtained by the preparation method of any one of claims 1 to 4.
8. A method of self-cleaning an electrically controllable adsorbent membrane as claimed in claim 7, wherein the self-cleaning method is carried out in an electrochemical filtration apparatus;
the self-cleaning method comprises the following steps:
and placing the polluted electric control adsorption membrane in an electrochemical filtering device, and sequentially carrying out reduction and oxidation to obtain a clean electric control adsorption membrane.
9. The self-cleaning method of claim 8, wherein the electrolyte in the reduction comprises a sodium chloride solution, the concentration of the sodium chloride being 0.08-0.15 mol/L;
preferably, the potential in the reduction is from-1 to-0.5V and the time in the reduction is from 8 to 15 min;
preferably, the electrolyte in the oxidation comprises a sodium chloride solution, and the concentration of the sodium chloride is 0.08-0.15 mol/L;
preferably, the potential in the oxidation is 0.5-0.8V and the time of the oxidation is 8-15 min.
10. A self-cleaning method according to claim 8 or 9, wherein the electrochemical filtration device comprises a fixing means, an electrically conductive means and an electrically controlled adsorption membrane;
preferably, the fixing means comprise a first and a second plexiglass in two opposite ways;
preferably, a cylindrical groove is arranged at the central position of the fixing device;
preferably, a through hole is formed in the central point of the first organic glass;
preferably, the conductive device comprises a titanium ruthenium rod, a titanium ruthenium net, a conductive ring and an O-shaped ring;
preferably, the titanium ruthenium bar is arranged on the central point of the titanium ruthenium net through a through hole;
preferably, the O-shaped ring is used for fixing the electric control adsorption film;
preferably, the conductive ring is arranged between the electric control adsorption film and the titanium ruthenium net;
preferably, the distance between the electric control adsorption film and the titanium ruthenium net is 0.5-1.5 cm;
preferably, the effective area of the electric control adsorption film and the titanium ruthenium net is 10-15cm2。
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