CN115518524A - Electric response film and preparation method and application thereof - Google Patents
Electric response film and preparation method and application thereof Download PDFInfo
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- CN115518524A CN115518524A CN202211388177.4A CN202211388177A CN115518524A CN 115518524 A CN115518524 A CN 115518524A CN 202211388177 A CN202211388177 A CN 202211388177A CN 115518524 A CN115518524 A CN 115518524A
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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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
- B01D69/10—Supported membranes; Membrane supports
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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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- 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
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/26—Electrical properties
Abstract
The invention provides an electric response membrane, which is applied to acidic wastewater treatment and comprises: the carbon nanotube layer comprises a supporting layer, a carbon nanotube layer and a conductive functional layer; wherein, the carbon nanotube layer is loaded on the support layer. And the conductive functional layer is loaded on the carbon nanotube layer, wherein the conductive functional layer is obtained by loading a conductive high-molecular polymer on the carbon nanotube layer in situ, and the conductive high-molecular polymer is obtained by performing an oxidative polymerization reaction on a monomer of the conductive polymer adsorbed on the carbon nanotube layer and an initiator. The electric response membrane provided by the invention can regulate and control the electrochemical property of the surface of the electric response membrane on line through an external voltage, further regulate and control the interception of the electric response membrane on ions, and has important significance for widening the range of membrane technology in the field of water treatment.
Description
Technical Field
The invention relates to the field of membrane separation technology and water treatment, in particular to a preparation method and application of an acid-resistant electric response membrane.
Background
The main sources of the acidic wastewater include industrial acid extraction waste liquid, acidic cleaning liquid in food industry, acidic wastewater in electroplating industry, waste acid liquid after demoulding in metal industry, fermented acidic sewage and the like. The acidity of the catalyst is strong, and if the catalyst is directly treated by an acid-base neutralization method, a large amount of resources are consumed, and meanwhile, inorganic salt byproducts are generated to cause secondary pollution, so that the treatment cost is increased.
The membrane separation technology plays an important role in the field of wastewater treatment, has the characteristics of strong selectivity, environmental protection, easy control and the like, and is already applied to the field of wastewater treatment. However, at present, most nanofiltration membranes are made of polyamide or polyester materials, and amide bonds are easily attacked by H + and broken in a strong acidic solution, so that the microstructure of the membrane is deteriorated, and finally the membrane separation performance is seriously reduced. In the traditional membrane separation process, the selective permeability of the nanofiltration membrane is difficult to regulate and control in the operation process, and the 'trade-off' effect between the membrane flux and the rejection rate still exists.
Therefore, the research and development of the membrane with strong acid resistance and on-line adjustment and control of selective permeability has important theoretical significance and application value.
Disclosure of Invention
In view of this, the embodiment of the present invention provides an electric response membrane, and a preparation method and an application thereof, wherein the electrochemical properties (such as charge property, surface charge density, and the like) of the surface of the electric response membrane can be adjusted and controlled by the action of an external electric field, so as to adjust and control the interception of ions, which is of great significance for widening the scope of the membrane technology in the field of water treatment.
According to one aspect of the present invention, there is provided an electro-responsive membrane for use in acidic wastewater treatment, the electro-responsive membrane comprising: the carbon nano tube layer is arranged on the support layer; the carbon nanotube layer is loaded on the support layer.
And the conductive functional layer is loaded on the carbon nanotube layer, wherein the conductive functional layer is obtained by loading a conductive high-molecular polymer on the carbon nanotube layer in situ, and the conductive high-molecular polymer is obtained by performing oxidative polymerization reaction on a monomer of the conductive polymer adsorbed on the carbon nanotube layer and an initiator.
According to an embodiment of the present invention, in the electric responsive film, the material of the support layer includes at least one of: polyvinylidene fluoride, polyether sulfone, phenolphthalein type non-sulfonated polyarylether sulfone, polyacrylonitrile or bisphenol A type polysulfone.
According to the embodiment of the invention, in the electric response film, the carbon nano tube layer is formed by loading the carbon nano tubes on the supporting layer in a preset mode.
The carbon nanotube includes: the carbon nano tube comprises a single-wall carbon nano tube, a double-wall carbon nano tube or a multi-wall carbon nano tube, wherein the groups carried on the surface of the carbon nano tube comprise: an amino group, a hydroxyl group, or a carboxyl group.
According to an embodiment of the present invention, in the electro-responsive film, the conductive polymer includes one of: polyaniline, polyaniline derivatives, polypyrrole derivatives, polythiophene, and polythiophene derivatives.
The initiator comprises an oxidizing agent comprising: ammonium persulfate, hydrogen peroxide, potassium dichromate, potassium iodate, ferric trichloride, ferric tetrachloride, aluminum trichloride, manganese dioxide, or benzoyl peroxide.
According to another aspect of the present invention, there is provided a method of manufacturing an electro-responsive film, including:
and loading the carbon nano tube on the supporting layer in a preset mode to form a carbon nano tube layer.
And respectively soaking the carbon nanotube layer in a monomer solution and an initiator solution of the conductive high molecular polymer according to a preset sequence to perform oxidative polymerization reaction, thereby obtaining the conductive high molecular polymer.
And loading the conductive high molecular polymer on the carbon nanotube layer to obtain the conductive functional layer.
And carrying out crosslinking treatment on the conductive functional layer to obtain the electric response film.
According to the embodiment of the invention, before the carbon nano tubes are loaded on the supporting layer in a preset mode, the carbon nano tubes are pretreated; the preset mode comprises vacuum filtration or spraying.
According to an embodiment of the present invention, the molar concentration ratio of the monomer solution of the conductive high molecular polymer to the initiator solution is 1: 0.5 to 1: 3.
According to the embodiment of the invention, the conductive functional layer is subjected to crosslinking treatment, and the crosslinking treatment comprises crosslinking for 8-15 hours by dipping in hydrochloric acid solution of glutaraldehyde or heating at 120-200 ℃.
According to the embodiment of the invention, doping acid is added into the monomer solution of the conductive high molecular polymer; the mass fraction of the doping acid is 0-5% of the mass fraction of the monomer solution corresponding to the conductive polymer; the doping acid comprises at least one of: hydrochloric acid, sulfuric acid, camphorsulfonic acid, dodecylbenzenesulfonic acid, but also acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinylsulfonic acid, styrenesulfonic acid, propylenesulfonic acid, allylsulfonic acid, methacrylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and their corresponding polymeric acids.
According to another aspect of the invention, an application of an electric response membrane is provided, which is used for combining membrane separation and electrochemical water treatment to realize regulation and control of ion transmission in acidic wastewater, wherein the electric response membrane is obtained according to the embodiment of the invention or prepared according to any preparation method of the embodiment of the invention.
According to an embodiment of the invention, an electric response film is provided and applied to acidic wastewater treatment. The membrane separation technology and the electrochemical technology are combined through the electric response membrane consisting of the carbon nanotube layer and the conductive functional layer, the electrochemical properties (such as charge property, surface charge density and the like) of the surface of the electric response membrane are regulated and controlled under the action of an external electric field, and the electrophoresis, the electrostatic action and the DouNan effect are cooperated, so that the 'trade-off' effect in the traditional membrane separation technology is broken, the selective regulation and control of ion transmission in the filtering process are realized, and the ion interception rate is improved under the condition of not reducing the membrane flux.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent from the following description of the embodiments of the present invention with reference to the accompanying drawings, in which:
FIG. 1 is a schematic structural diagram of an electric responsive film according to an embodiment of the present invention;
FIG. 2 is a flow chart of a method of making an electrically responsive film according to an embodiment of the present invention;
FIG. 3 is a schematic flow chart of a method for manufacturing an electric response film according to an embodiment of the present invention;
FIG. 4 is a graph showing the effect of an electrically responsive membrane on the rejection of ions under acidic conditions according to an embodiment of the present invention;
FIG. 5 is a graph showing the effect of an electrically responsive membrane on the trapping of ions under an applied electric field according to an embodiment of the present invention; and
fig. 6 is a graph showing the retention effect of the electric responsive membrane according to the embodiment of the present invention on different ions under acidic conditions.
[ instruction of reference ]
100-an electrically responsive film;
1-a support layer;
a 2-carbon nanotube layer;
3-a conductive functional layer;
4-conductive high molecular polymer.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. It is to be understood that such description is merely illustrative and not intended to limit the scope of the present invention. In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the embodiments of the invention. It may be evident, however, that one or more embodiments may be practiced without these specific details. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The terms "comprises," "comprising," and the like, as used herein, specify the presence of stated features, steps, operations, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, or components.
All terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise defined. It is noted that the terms used herein should be interpreted as having a meaning that is consistent with the context of this specification and should not be interpreted in an idealized or overly formal sense.
Where a convention analogous to "at least one of A, B, and C, etc." is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., "a system having at least one of A, B, and C" would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.). In those instances where a convention analogous to "at least one of A, B, or C, etc." is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., "a system having at least one of A, B, or C" would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.).
It should also be noted that directional terms, such as "upper", "lower", "front", "rear", "left", "right", etc., used in the embodiments are only directions referring to the drawings, and are not intended to limit the scope of the present invention. Throughout the drawings, like elements are represented by like or similar reference numerals. Conventional structures or constructions will be omitted when they may obscure the understanding of the present invention. And the shapes and sizes of the respective components in the drawings do not reflect actual sizes and proportions, but merely illustrate the contents of the embodiments of the present invention.
Similarly, it should be appreciated that in the description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the invention and aiding in the understanding of one or more of the various aspects. However, the method of the invention should not be construed to reflect the intent: rather, the invention as claimed requires more features than are expressly recited in each claim.
In the related technology, the traditional nanofiltration membrane has deteriorated micro-morphology in a strong acid environment, so that the membrane separation performance is reduced, the selective permeability of the traditional nanofiltration membrane is difficult to regulate and control in the operation process, and the 'trade-off' effect between the membrane flux and the rejection rate still exists. In view of this, the electro-responsive membrane has attracted a great deal of attention among those skilled in the art, but those skilled in the art have not yet applied the electro-responsive membrane to the field of acidic wastewater treatment.
The invention provides an electric response membrane and a preparation method thereof, aiming at regulating and controlling the interception of ions in acidic wastewater by the electric response membrane, applying the electric response membrane to the field of acidic wastewater treatment and enhancing the desalination performance of the membrane by electricity.
According to an embodiment of the present invention, there is provided an electric response membrane for acidic wastewater treatment, including: the carbon nanotube layer comprises a supporting layer, a carbon nanotube layer and a conductive functional layer; wherein, the carbon nanotube layer is loaded on the support layer. And the conductive functional layer is loaded on the carbon nanotube layer, wherein the conductive functional layer is obtained by loading a conductive high-molecular polymer on the carbon nanotube layer in situ, and the conductive high-molecular polymer is obtained by performing oxidative polymerization reaction on a monomer of the conductive polymer adsorbed on the carbon nanotube layer and an initiator.
Fig. 1 schematically shows a structural composition diagram of an electric responsive film according to an embodiment of the present invention.
As shown in fig. 1, the electric responsive film 100 may include: a support layer 1, a carbon nanotube layer 2 and a conductive functional layer 3.
The support layer 1 is a substrate of the electric response film 100, and plays a supporting role in the whole electric response film, and the mechanical strength thereof is an important factor determining the mechanical strength of the electric response film 100. The carbon nanotube layer 2 is loaded on the support layer 1 for conducting electrons and enhancing the electrochemical performance of the electric response film 100, and simultaneously, the surface of the support layer 1 is roughened to support the conductive high molecular polymer 4. The conductive functional layer 3 is provided with different functional groups and used for regulating and controlling ion transmission in the water treatment process, and is obtained by loading a conductive high molecular polymer 4 on the carbon nanotube layer 2 in situ. Specifically, the conductive polymer monomer is adsorbed on the carbon nanotube layer 2, and undergoes an oxidative polymerization reaction with an initiator, and a conductive high molecular polymer 4 is loaded on the surface of the carbon nanotube layer 2, thereby forming a conductive functional layer 3.
According to the embodiment of the invention, the membrane separation technology and the electrochemical water treatment technology are combined through the electric response membrane consisting of the carbon nanotube layer and the conductive functional layer, the electrochemical properties (such as charge property, surface charge density and the like) of the surface of the electric response membrane are regulated and controlled under the action of an external electric field, and the electrophoresis, the electrostatic action and the southward effect are cooperated, so that the 'trade-off' effect in the traditional membrane separation technology is broken, the selective regulation and control on ion transmission in the filtering process are realized, and the rejection rate of ions is improved under the condition of not reducing the membrane flux. It should be understood that under the electrically assisting action, the electrostatic repulsion of the electrically responsive membrane 100 to the same ions is increased, the attraction to the counter ions is enhanced, and the counter ions partially adsorbed in the electrically responsive membrane 100 generate the repulsive force to the ions with the same electric property in the solution, so that the interception performance of the electrically responsive membrane is further improved.
It should be noted that the above examples only illustrate the operation principle of the electric responsive film and the composition thereof provided by the present invention to help those skilled in the art understand the technical content of the present invention, and it is not meant that the electric responsive film of the present invention is limited to the treatment of the above ions.
In addition, it should be noted that fig. 1 is only an example of the structural composition of the embodiment of the present invention to help those skilled in the art understand the technical content of the present invention, but it is not meant that the electric response film and the composition thereof of the present invention are limited to the shape shown in fig. 1, and the electric response film, the support layer, the carbon nanotube layer, and the conductive function layer of the present invention may be any shape that can meet the acid waste liquid treatment, such as a rectangle, an ellipse, an irregular pattern, etc., according to the actual needs.
It should be understood that the numbers of the supporting layer, the carbon nanotube layer and the conductive functional layer in fig. 1 are only schematic, and any number of the supporting layer, the carbon nanotube layer and the conductive functional layer may be provided according to actual needs.
According to an embodiment of the present invention, in the electric responsive film, the material of the support layer includes at least one of: polyvinylidene fluoride (PVDF), polyethersulfone (PES), phenolphthalein type non-sulfonated polyarylethersulfones, polyacrylonitrile (PAN) or bisphenol A type polysulfones.
In the embodiment of the invention, the material adopted as the support layer material has the advantages of chemical corrosion resistance, high mechanical strength, high toughness, difficult damage in the using process and better material compatibility. However, it should be understood that the material of the supporting layer is not limited to the above materials, and other materials with good compatibility, acid and alkali resistance, and high mechanical strength, such as Polytetrafluoroethylene (PTFE), etc. (for example only), may be substituted according to the actual use requirement.
According to the embodiment of the invention, in the electric response film, the carbon nano tube layer is formed by loading the carbon nano tubes on the supporting layer in a preset mode. The preset mode comprises a vacuum filtration or spraying mode.
According to an embodiment of the present invention, the carbon nanotube may include: the carbon nanotube comprises a single-walled carbon nanotube, a double-walled carbon nanotube or a multi-walled carbon nanotube, wherein groups carried on the surface of the carbon nanotube comprise: an amino group, a hydroxyl group, or a carboxyl group.
In the embodiment of the invention, the carbon nano tube is loaded on the supporting layer 1, so that the carbon nano tube has good conductivity, chemical corrosion resistance and mechanical strength, can effectively promote electron transfer, and improves the response capability of the membrane to electric stimulation; meanwhile, the formed carbon nanotube layer 2 has a rough surface and contains large voids to support the conductive high molecular polymer.
It should be understood that the composition of the electric response film provided by the present invention is not limited to the form of carbon nanotubes, and may be replaced by one or more carbon nanomaterials such as carbon nanofibers and carbon nanospheres according to actual use requirements, so as to effectively support the conductive polymer. Similarly, the groups on the surface of the carbon nanotube are not limited to the above groups, and can be modified according to the actual processing requirements.
According to an embodiment of the present invention, in the electro-responsive film, the conductive polymer includes one of: polyaniline (PANI), polyaniline derivatives, polypyrrole (PPy), polypyrrole derivatives, polythiophene (PT), polythiophene derivatives.
According to an embodiment of the present invention, the initiator may comprise an oxidizing agent comprising: ammonium persulfate, hydrogen peroxide, potassium dichromate, potassium iodate, ferric trichloride, ferric tetrachloride, aluminum trichloride, manganese dioxide, or benzoyl peroxide.
In the embodiment of the invention, the conductive functional layer is formed by adopting the conductive high molecular polymers such as polyaniline and the like, so that the conductive functional layer has good conductivity and electrochemical performance, and meanwhile, the conductive high molecular polymers can be provided with different functional groups so as to realize the regulation and control of the electrochemical performance of the surface of the electric response membrane; meanwhile, the oxidative polymerization mode is adopted, and the free radicals generated by the redox reaction initiate the polymerization of the polymer monomer, so that a large amount of conductive high molecular polymer can be obtained under mild conditions.
It should be understood that the above-mentioned conductive high molecular polymer is only illustrative of the embodiments of the present invention, and any high molecular polymer having conductivity and capable of supporting different functional groups, such as polyphenylacetylene and its derivatives, etc., can be used as the conductive functional layer according to actual needs. The above-mentioned initiator is not limited to the oxidizing agent, and any radical initiator such as a water-soluble azo initiator and a polyfunctional initiator may be used instead depending on the polymerization system.
According to an embodiment of the present invention, a method of manufacturing an electro-responsive film is disclosed for manufacturing the electro-responsive film as described above.
Fig. 2 schematically shows a flow chart of a method for preparing an electrically responsive film according to an embodiment of the present invention.
As shown in fig. 2, the method for preparing the electro-responsive film includes steps S1 to S4:
and S1, loading the carbon nano tube on the supporting layer in a preset mode to form a carbon nano tube layer.
And S2, respectively soaking the carbon nanotube layer in a monomer solution and an initiator solution of the conductive high molecular polymer according to a preset sequence to perform oxidative polymerization reaction, thereby obtaining the conductive high molecular polymer.
And S3, loading the conductive high molecular polymer on the carbon nanotube layer to obtain the conductive functional layer.
And S4, performing cross-linking treatment on the conductive functional layer to obtain the electric response film.
The corresponding features of the support layer 1, the carbon nanotube layer 2, the conductive functional layer 3, and the conductive high molecular polymer are as described in the electric response film section, and are not described herein again.
Fig. 3 schematically shows a flow chart of a method for manufacturing an electric response film according to an embodiment of the present invention.
As shown in fig. 3, in the embodiment of the present invention, the support layer 1 supports the carbon nanotubes to form the carbon nanotube layer 2, and the support layer 1 and the carbon nanotube layer 2 form a composition (i.e., a carbon nanotube film). The carbon nanotube film is immersed in an acidic monomer solution corresponding to the conductive polymer, so that the polymer monomer in the acidic monomer solution is attached to the carbon nanotube layer 2 or in the voids thereof. And (3) soaking the carbon nanotube film with the conductive polymer monomer on the carbon nanotube layer 2 or in the gap of the carbon nanotube film in an initiator solution, and initiating the monomer polymerization by using free radicals obtained through redox reaction to form a compact conductive high molecular polymer 4. The carbon nanotube layer 2 is used as a bearing platform of the conductive high molecular polymer 4 in the polymerization process, and a conductive functional layer 3 is formed on the basis of the bearing platform. Through further cross-linking treatment of the conductive functional layer 3, a stable covalent cross-linking structure is formed between polymer chains of the conductive functional layer 3, and stripping of the conductive functional layer 3 in the using process is avoided.
In the examples of the present invention, the preparation of the membrane is carried out by dipping operation, but it is understood that the dipping is intended to fully react the oxidative polymerization process, and any operation that can fully react, such as coating, casting, etc., may be substituted.
In addition, the monomer solution is obtained by adding a polymer monomer to a solvent. The present invention is not limited to the choice of solvent for the monomer solution, and the solvent for the monomer solution may be ultrapure water (as an example only) or any organic solvent that meets the dissolution requirements. The kind of the added monomer is not single, and when two or more monomers are added, the finally prepared conductive high molecular polymer is a copolymer of the two monomers.
In an exemplary embodiment, the monomer solution is an aqueous solution of aniline and pyrrole, and after oxidative polymerization, the prepared conductive high molecular polymer is an aniline-pyrrole copolymer, and the obtained electric response membrane still has good conductivity and ion selective permeability.
Accordingly, the kind of solvent of the initiator solution and the kind of initiator need to be adaptively changed according to the kind of the monomer solution. In the above exemplary embodiment, when the initiator is ammonium persulfate, the aniline and pyrrole can be initiated to be oxidized and polymerized to obtain the aniline-pyrrole copolymer. However, this example is merely illustrative, and the kind of the initiator is not limited, and two or more kinds of the initiator may be added according to actual needs.
Similarly, the conductive polymer is obtained by oxidative polymerization in the present embodiment, but it should be understood that the oxidative polymerization is only an example, and the polymerization manner of the monomer and the corresponding initiator can be modified according to actual needs, such as emulsion polymerization, microemulsion polymerization, etc. (just an example).
In the embodiment of the invention, the membrane separation technology and the electrochemical water treatment technology are combined by the electric response membrane consisting of the carbon nanotube layer and the conductive functional layer, the electrochemical properties (such as charge property, surface charge density and the like) of the surface of the electric response membrane are regulated and controlled under the action of an external electric field, and the electrophoresis, the electrostatic action and the southward effect are cooperated, so that the 'trade-off' effect in the traditional membrane separation technology is broken, the selective regulation and control on ion transmission in the filtering process are realized, the interception rate of ions is improved under the condition of not reducing the membrane flux, and the membrane separation membrane has wide application prospect in the field of water treatment.
According to the embodiment of the invention, the carbon nanotubes are easy to agglomerate into bundles or twine, and are insoluble in any organic solvent and aqueous solution due to the inertia of the surface, so that the carbon nanotubes are difficult to uniformly disperse in the process of being loaded on the supporting layer, and the bonding force with the conductive high molecular polymer also has space for improvement.
In the embodiment of the invention, the carbon nano tube is pretreated before being loaded on the supporting layer in a preset mode; wherein the preset mode comprises vacuum filtration or spraying.
Specifically, the embodiment of the invention pretreats the carbon nanotubes, removes amorphous carbon and carbon nanoparticles on the surface, reduces the activation energy of the surface of the carbon nanotubes, enables the carbon nanotubes to be uniformly dispersed in a solution, and is loaded on the support layer in a vacuum filtration or spraying manner. Meanwhile, the surface of the carbon nano tube after pretreatment can be soaked, which is beneficial to the monomer and the conductive high molecular polymer in the monomer solution to be attached to the carbon nano tube layer 2.
It should be noted that the present invention is not limited to the predetermined manner of loading the carbon nanotubes on the supporting layer, and other loading methods may be used to form the carbon nanotube layer according to the actual requirement, such as dip coating, electrochemical deposition, self-assembly, floating-catalyzed chemical vapor deposition, and the like.
According to an embodiment of the present invention, the manner of pre-treating the carbon nanotubes may include strong acid treatment or strong alkali treatment.
According to the embodiment of the present invention, in the process of preparing the electro-responsive film, the molar concentration ratio of the monomer solution of the conductive high molecular polymer to the initiator solution is 1: 0.5 to 1: 3.
According to an embodiment of the present invention, the molar concentration ratio of the monomer solution of the conductive high molecular polymer and the initiator solution may be 1: 0.5, 1: 0.6, 1: 0.7, 1: 0.8, 1: 0.9, 1: 1, 1: 1.1, 1: 1.2, 1: 1.3, 1: 1.4, 1: 1.5, 1: 1.6, 1: 1.7, 1: 1.8, 1: 1.9, 1: 2, 1: 2.1, 1: 2.2, 1: 2.3, 1: 2.4, 1: 2.5, 1: 2.6, 1: 2.7, 1: 2.8, 1: 2.9, 1: 3.
The above-described process of oxidative polymerization will be described only as a preferred embodiment of the molar concentration ratio between the monomer solution and the initiator solution.
According to the embodiment of the invention, only the carbon nanotubes are pretreated, the conductive high molecular polymer formed by monomer polymerization is loaded on the carbon nanotube layer 2 in the form of linear high molecular chains, and in the use process of the electric response film, the possibility of stripping off the conductive high molecular polymer part still exists, so that the separation performance of the electric response film is reduced.
In the embodiment of the invention, the conductive functional layer 3 is subjected to cross-linking treatment, and the cross-linking treatment may include immersing in hydrochloric acid solution of glutaraldehyde, or may include cross-linking for 8-15 hours by heating at 120-200 ℃.
According to an embodiment of the present invention, the heating temperature may be 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃; the crosslinking time can be 8h, 9h, 10h, 11h, 12h, 13h, 14h and 15h.
According to the embodiment of the invention, through a crosslinking treatment mode, on one hand, the connection of the structures among the high molecular chains in the conductive high molecular polymer can be realized, and a stable network structure is formed; on the other hand, covalent crosslinking of the conductive high molecular polymer and the carbon nanotube layer 2 can be realized, so that the chemical and mechanical stability of the electric response film is improved.
In the above examples, the crosslinking treatment was performed using a hydrochloric acid solution of glutaraldehyde as a crosslinking agent, but the selection of the crosslinking agent is not limited thereto, and other types of crosslinking agents, such as polyhydric alcohols, may be used instead as needed.
The crosslinking temperature and the crosslinking time in the above examples are only described as a preferred embodiment of the process of the crosslinking treatment.
According to the embodiment of the present invention, in order to regulate and control the loading of different functional groups on the conductive functional layer 3, the doping acid may be added to the monomer solution.
Wherein, the mass fraction of the doping acid can be the mass fraction of the monomer solution corresponding to the conductive polymer and can be 0-5%.
According to an embodiment of the present invention, the mass fraction of the doping acid may be: 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%.
According to embodiments of the invention, the doping acid may comprise at least one of: hydrochloric acid, sulfuric acid, camphorsulfonic acid, dodecylbenzenesulfonic acid, but also acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinylsulfonic acid, styrenesulfonic acid, propylenesulfonic acid, allylsulfonic acid, methacrylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and their corresponding polymeric acids.
In the embodiment of the invention, different doping acids are added into the monomer solution of the conductive high molecular polymer to prepare the electric response membrane with different functional groups, so that the surface electrochemical property of the electric response membrane is regulated and controlled under the action of an electric field, and the interception of ions is further regulated and controlled.
It should be noted that the dopant is not limited to doping acid, and the mass fraction and the type of the dopant are not limited, and any dopant and mass fraction thereof can be selected to meet the requirements according to the requirements of loading different functional groups on the conductive functional layer.
According to an embodiment of the invention, the invention further provides application of the electric response membrane, which is used for combining membrane separation and electrochemical water treatment to realize regulation and control of ion transmission in acidic wastewater, wherein the electric response membrane is obtained according to the embodiment of the invention or prepared according to any preparation method of the embodiment of the invention.
When the electric response film provided by the embodiment of the invention is applied to acid wastewater treatment, the prepared electric response film 100 is used as a positive/negative electrode necklace of a working electrode and a direct current power supply, a two-electrode system is constructed by the electric response film electrode and a counter electrode, the electrode is connected by a lead, and the working voltage range is 0 to +/-5V.
Fig. 4 is a graph schematically showing the effect of the electric response membrane on the retention of ions in an acidic environment according to the embodiment of the present invention.
As shown in fig. 4, when the electric response membrane provided by the embodiment of the present invention is applied to an acidic environment, the membrane flux and the rejection rate of ions of the electric response membrane after soaking for 0, 1, 3, 7, 15, 21, and 30 days, respectively. Column data representation in FIG. 4In response to the permeability of the membrane (i.e., membrane flux), the line data represents the rejection of ions by the electrically responsive membrane. As can be seen from fig. 4, after the electric response membrane is soaked in an acidic environment for 30 days, the rejection rate of the electric response membrane to ions is kept above 90%; compared with the initial use (namely the soaking time is 0 day), the change of the membrane flux of the electric response membrane after 30 days of soaking is maintained at 3L/m under the unit pressure and the unit time 2 In the meantime.
The electric response membrane provided by the embodiment of the invention is applied to acidic wastewater treatment, a membrane separation technology and an electrochemical water treatment technology are combined through the electric response membrane consisting of the carbon nanotube layer and the conductive functional layer, the electrochemical properties (such as charge property, surface charge density and the like) of the surface of the electric response membrane are regulated and controlled under the action of an external electric field, and the electrophoresis, the electrostatic action and the Tao-nan effect are cooperated, so that the 'trade-off' effect in the traditional membrane separation technology is broken, the selective regulation and control on ion transmission in the filtering process are realized, and the rejection rate of ions is improved under the condition of not reducing the membrane flux. Has wide application prospect in the field of acid wastewater treatment.
In the above embodiments, the connection mode of the wires and the range of the operating voltage are only examples, and may be adaptively changed according to actual needs. Similarly, the use of cross-flow filtration is merely illustrative of the process and other forms of filtration, including dead-end filtration (by way of example only), may be substituted.
According to an embodiment of the present invention, during the application of the electric response membrane 100, the counter electrode of the electric response membrane electrode may be made of one or two or more materials of titanium, platinum, stainless steel, graphite sheet or carbon fiber cloth, but is not limited thereto.
The preparation method and application of the conductive catalytic hydrophobic membrane of the present invention are further illustrated by the following specific examples. It should be noted, however, that the following specific examples are illustrative only, and the scope of the present invention is not limited thereto.
The chemicals and raw materials used in the following examples were either commercially available or were prepared by a known preparation method.
Example 1
The preparation method of the electric response film of the embodiment is specifically implemented according to the following steps:
1. pretreatment of the carbon nano tube: adding a certain amount of Carbon Nano Tubes (CNT) into HNO with a volume ratio of 1: 3 3 ：H 2 SO 4 And cleaning the mixed solution with ultrapure water, and drying the cleaned mixed solution for later use.
2. Preparing a carbon nanotube layer: and dispersing the acidified CNT into ultrapure water to prepare 0.5g/L dispersion liquid, and performing suction filtration on a polyvinylidene fluoride film substrate to prepare the CNT film.
3. Preparing a conductive functional layer: 3.36mL of polystyrenesulfonic acid (PSSA) solution and 0.14mL of aniline were dissolved in ultrapure water, stirred well, and stored in a refrigerator at 4 ℃ until use. And soaking the prepared CNT film in the solution for 20min, taking out, and naturally airing at room temperature. Subsequently, it was immersed in a 0.15M aqueous solution of ammonium persulfate, reacted for 20min and taken out. The residual solution on the surface of the membrane is discarded, and the reaction is continued for 6 hours at the temperature of 4 ℃.
4. And (3) crosslinking treatment: preparing a glutaraldehyde hydrochloric acid solution with the mass fraction of 1%, immersing the prepared electric response membrane in the glutaraldehyde acid solution for reaction for 3 hours, taking out the electric response membrane, cleaning the electric response membrane by using ultrapure water, and drying the electric response membrane.
According to the embodiment of the invention, the carbon nanotubes are uniformly distributed on the surface of the membrane through suction filtration, and after polymerization reaction occurs, polyaniline generates compact polymer skin layers on the surface and inside of the carbon nanotube layer, so that the surface of the carbon nanotube layer is completely covered, and the surface of the electric response membrane becomes smoother and smoother. Through crosslinking, the connection of the structures among the polymer chains is realized, a stable double-chain structure is formed, and the chemical and mechanical stability of the membrane is improved.
Example 2
In the application of the electric response film in the embodiment, the electric response film provided in example 1 is adopted, and the regulation and control effect of an external electric field on ion transmission is investigated through a self-made film assembly, and the electric response film is implemented according to the following specific process:
1. connecting a wastewater treatment component: the electric response film is connected with a conductive material to form a working electrode, the working electrode is connected with a negative electrode of a direct current power supply, and a titanium plate is used as a counter electrode and is placed in parallel with the working electrode.
2. Carrying out wastewater treatment: the distance between the working electrode and the counter electrode is set to be 1cm, and the applied voltage is 0-2.5V. An aqueous solution of sodium sulfate was used as a solution to be treated, and the concentration of the salt solution was 2mmol/L. The filtration mode in the system is cross-flow filtration, the filtration flow rate of the simulated salt solution is 1.2L/min, and the pressure in the system is 5bar. The wastewater treatment is realized by collecting the recovery liquid on two sides of the electric response membrane, and the ion concentration in the recovery liquid is used as a parameter for inspecting the ion transmission effect of the electric response membrane.
Fig. 5 is a graph schematically showing the ion trapping effect of an electrically responsive membrane according to an embodiment of the present invention under an applied electric field.
As shown in fig. 5, the column data represents the permeability (i.e., membrane flux) of the electro-responsive membrane, and the line data represents the rejection of sodium sulfate by the electro-responsive membrane. Due to experimental error, the membrane flux of the electroresponsive membrane is considered to remain constant within the error range. When the applied voltage is 0V, namely under the condition of no application, the rejection rate of the electric response membrane to the sodium sulfate is between 80 and 90 percent; under the condition of power application, the retention rate of the membrane on sodium sulfate is obviously improved, and when the applied voltage is-2.5V, the retention rate of the electric response membrane on sodium sulfate reaches the maximum value (> 95%).
In the embodiment, under the action of an external electric field, the surface charge density of the surface of the electric response membrane is greatly improved, the interaction between the membrane and ions in the solution is improved, and the interception performance of the electric response membrane to the ions is further improved. In addition, under the electrically-assisted effect, the adsorption capacity of the membrane to ions is improved, and the ions adsorbed in the electrically-responsive membrane can generate repulsion force to the same ions in the solution, so that the interception performance of the electrically-responsive membrane is further improved.
Example 3
The application of the electric response membrane in the embodiment adopts the electric response membrane provided in example 1, inspects the acid resistance and the regulation and control condition of ions of the electric response membrane through a self-made membrane module, and is implemented according to the following specific procedures:
1. simulating a working environment: and respectively soaking the electric response film in a hydrochloric acid solution with the mass fraction of 3% for 1 day, 3 days, 7 days, 15 days, 21 days and 30 days.
2. Connecting a wastewater treatment component: the electric response film is connected with a conductive material to form a working electrode, the working electrode is connected with the negative electrode of a direct current power supply, and the titanium plate is used as a counter electrode and is placed in parallel with the working electrode.
3. Carrying out wastewater treatment: the distance between the working electrode and the counter electrode is 1cm, and the applied voltage is 0-2.5V. Sodium chloride, sodium sulfate and magnesium chloride are respectively used as the liquid to be treated, and the concentration of the salt solution is 2mmol/L. The filtration mode in the system is cross-flow filtration, the filtration flow rate of the simulated salt solution is 1.2L/min, and the pressure in the system is 5bar. The wastewater treatment is realized by collecting the recovery liquid on two sides of the electric response membrane, the ion concentration in the recovery liquid is used as a parameter for inspecting the ion transmission effect of the electric response membrane, and the electric response membrane is respectively operated under the condition of electrification and non-electrification so as to realize the evaluation of the separation performance.
Fig. 6 is a graph schematically showing the ion rejection effect of the electric responsive membrane according to the embodiment of the present invention under acidic conditions.
As shown in fig. 6, the electric response membrane provided by the embodiment of the present invention still shows a good separation effect on different salt solutions (80-85% of sodium sulfate, 50-60% of sodium chloride, and 85-90% of magnesium sulfate) after being soaked for 30 days under an acidic condition; when the applied voltage is-2.5V, the rejection rate of the electric response membrane to sodium sulfate is increased to 90-95%, the rejection rate to sodium chloride is increased to 65-70%, and the rejection rate to magnesium sulfate is increased to 90-95%, which shows that the electric response membrane has improved rejection effects on different salt solutions under the condition of electrification.
In the embodiment, the polyaniline has good electrochemical stability and mechanical strength, and has good applicability to strong acid conditions, so that the polyaniline can still maintain excellent performance after being soaked for a long time. In addition, because polystyrene sulfonic acid and polyaniline have strong intermolecular interaction force, a stable double-chain structure can be formed, and the stability of the conductive high polymer under a strong acid condition is favorably enhanced.
It will be appreciated by a person skilled in the art that various combinations and/or combinations of features recited in the various embodiments and/or claims of the present invention are possible, even if such combinations or combinations are not explicitly recited in the present invention. In particular, various combinations and/or combinations of the features recited in the various embodiments and/or claims of the present invention may be made without departing from the spirit or teaching of the invention. All such combinations and/or associations fall within the scope of the present invention.
The embodiments of the present invention have been described above. However, these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Although the embodiments are described separately above, this does not mean that the measures in the embodiments cannot be used in advantageous combination. The scope of the invention is defined by the appended claims and equivalents thereof. Various alternatives and modifications can be devised by those skilled in the art without departing from the scope of the invention, and these alternatives and modifications are intended to fall within the scope of the invention.
Claims (10)
1. An electrically responsive membrane for use in acidic wastewater treatment, the electrically responsive membrane comprising: the carbon nanotube layer comprises a supporting layer, a carbon nanotube layer and a conductive functional layer; wherein, the first and the second end of the pipe are connected with each other,
the carbon nanotube layer is loaded on the supporting layer;
the conductive functional layer is loaded on the carbon nanotube layer, wherein the conductive functional layer is obtained by loading a conductive high molecular polymer on the carbon nanotube layer in situ, and the conductive high molecular polymer is obtained by performing oxidative polymerization reaction on a monomer of the conductive polymer adsorbed on the carbon nanotube layer and an initiator.
2. The electrically responsive film of claim 1,
the material of the support layer comprises at least one of the following: polyvinylidene fluoride, polyether sulfone, phenolphthalein type non-sulfonated polyarylethersulfone, polyacrylonitrile or bisphenol A type polysulfone.
3. The electrically responsive film of claim 1,
the carbon nanotube layer is formed by loading carbon nanotubes on the supporting layer in a preset mode;
the carbon nanotube includes: a single-walled carbon nanotube, a double-walled carbon nanotube or a multi-walled carbon nanotube, wherein the groups carried on the surface of the carbon nanotube comprise: an amino group, a hydroxyl group, or a carboxyl group.
4. The electrically responsive film of claim 1,
the conductive polymer comprises one of: polyaniline, polyaniline derivatives, polypyrrole derivatives, polythiophene derivatives;
the initiator comprises an oxidizing agent comprising: ammonium persulfate, hydrogen peroxide, potassium dichromate, potassium iodate, ferric trichloride, ferric tetrachloride, aluminum trichloride, manganese dioxide, or benzoyl peroxide.
5. A method of producing an electric response film according to any one of claims 1 to 4, comprising:
loading the carbon nano tube on the supporting layer in a preset mode to form a carbon nano tube layer;
respectively soaking the carbon nanotube layer in a monomer solution and an initiator solution of the conductive high molecular polymer according to a preset sequence to perform an oxidative polymerization reaction to obtain the conductive high molecular polymer;
loading the conductive high molecular polymer on the carbon nanotube layer to obtain a conductive functional layer;
and carrying out cross-linking treatment on the conductive functional layer to obtain the electric response film.
6. The method of claim 5, wherein,
before the carbon nano tubes are loaded on the supporting layer in a preset mode, pretreating the carbon nano tubes; the preset mode comprises vacuum filtration or spraying.
7. The method of claim 5, wherein,
the molar concentration ratio of the monomer solution of the conductive high molecular polymer to the initiator solution is 1: 0.5-1: 3.
8. The method according to claim 5, wherein the cross-linking treatment comprises cross-linking for 8-15 hours by dipping in a hydrochloric acid solution of glutaraldehyde or heating at 120-200 ℃.
9. The method according to claim 5, wherein a doping acid is added to the monomer solution of the conductive high molecular polymer; the mass fraction of the doping acid is 0-5% of the mass fraction of the monomer solution corresponding to the conductive polymer; the doping acid comprises at least one of: hydrochloric acid, sulfuric acid, camphorsulfonic acid, dodecylbenzenesulfonic acid, but also acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinylsulfonic acid, styrenesulfonic acid, propylenesulfonic acid, allylsulfonic acid, methacrylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and their corresponding polymeric acids.
10. Use of an electrically responsive membrane for the combined membrane separation and electrochemical water treatment for the modulation of ion transport in acidic wastewater, wherein the electrically responsive membrane is obtainable according to any one of claims 1 to 4 or prepared according to the preparation method of any one of claims 5 to 9.
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