CN110124735B - Hydrophilic conductive hydrogel cathode catalytic membrane and preparation method and application thereof - Google Patents
Hydrophilic conductive hydrogel cathode catalytic membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a hydrophilic conductive hydrogel cathode catalytic membrane and a preparation method and application thereof, wherein the hydrophilic conductive hydrogel cathode catalytic membrane is prepared by coating hydrophilic conductive hydrogel loaded with nano iron particles, has a regular three-dimensional network structure and has a pore size of 100-1000 nm; the tensile strength is more than or equal to 1600MPa, and the bearing capacity is more than or equal to 1.5 MPa. According to the invention, a base film is not needed, the hydrogel cathode catalytic film with a three-dimensional network structure is prepared by adopting an emulsion polymerization direct film-forming method, and the ionizable functional group and the nano catalyst are introduced into the polymer network, so that the conductivity and the catalytic performance of the cathode catalytic film are improved; the hydrogel cathode catalytic membrane is applied to the cathode catalytic process of the EMBR, can promote the oxygen reduction reaction, improve the ORR activity and improve the electricity generation efficiency of a reaction system; the membrane electrode has good hydrophilicity, high conductivity, high membrane electrode stability and mechanical property with adjustable height.
Description
Technical Field
The invention relates to the technical field of new materials and organic wastewater treatment, in particular to a hydrophilic conductive hydrogel cathode catalytic membrane for purifying high-concentration refractory organic industrial wastewater.
Background
The coking wastewater is wastewater generated in coke refining, gas purification and chemical product recovery processes of a coking plant, main pollutants are phenol, heterocyclic compounds, polycyclic aromatic hydrocarbon, ammonia nitrogen, cyanogen, sulfides and the like, and the coking wastewater is typical high-concentration refractory organic wastewater which has complex components, high pollutant concentration, high chromaticity, high toxicity and poor biodegradability. At present, most coking plants adopt the traditional activated sludge method to treat coking wastewater, can effectively remove pollutants such as phenol, ammonia nitrogen and the like, but have poor effect of removing some heterocyclic or polycyclic aromatic organic polymer pollutants, and the COD of the effluent is 200-400mg/L, which is difficult to reach the national discharge standard. The main problems in the coking wastewater treatment process are as follows: firstly, the removal effect of the refractory organic matters is poor, the COD content is still high after biochemical treatment, and the effluent quality is poor; secondly, the simple physical and chemical method is used as a pretreatment process and a subsequent treatment process, the required conditions are harsh, and the problems of medicament addition, high operation cost and secondary pollution exist at the same time; thirdly, a series of high-tech treatment experimental equipment researched at present has high requirements and high cost, is not suitable for industrial production and is not suitable for treating bulk wastewater. Therefore, a treatment process which has a good treatment effect and low cost and can quickly realize engineering is required to be developed for the coking wastewater.
A Membrane Bioreactor (MBR) is an advanced wastewater treatment method combining membrane technology and biotechnology, and mainly removes biodegradable organic pollutants in water by utilizing the biotechnology, and then filters suspended matters and water-soluble macromolecular substances by utilizing the membrane technology to reduce water turbidity and play double roles of biochemical treatment and reverse osmosis treatment. MBR has the advantages of high treatment efficiency, small floor area, high automation degree and the like, is a sewage treatment and reclaimed water recycling technology with the greatest development prospect in the 21 st century, and is applied to the treatment of coking wastewater at home and abroad to a certain extent in recent years. However, the biggest challenge of MBR is membrane fouling, and only by solving the membrane fouling, the operation cost and the cleaning frequency can be reduced, and the manual operation can be reduced. In order to realize the zero emission requirement of the coking wastewater recycling, the MBR becomes the key technology in the future wastewater treatment field, and the key of the membrane process achievement is how to effectively control the membrane pollution. The traditional methods for controlling membrane pollution mainly comprise chemical cleaning, aeration scouring, hydraulic shearing, chemical reagent adding and the like, the methods only have a temporary relieving effect, and medicament adding or membrane removing cleaning is needed, so that the method consumes manpower and material resources, has unstable effect and higher cost, influences the continuous operation of a reactor, and cannot radically solve the problem of membrane pollution.
An electrically assisted membrane bioreactor (EMBR) couples a Microbial Fuel Cell (MFC) and a membrane bioreactor together, can generate electricity while treating wastewater, can degrade organic pollutants by using the metabolism of microorganisms, can decompose carbon dioxide, electrons and protons by using the anaerobic respiration of the microorganisms, and transmits the electrons to a cathode by an external circuit to generate a potential difference to form current so that the cathode and activated sludge, colloid and the like with negative electricity generate near electrostatic repulsive force, thereby controlling membrane pollution and solving the practical engineering problem of the MBR; in addition, the mode of recycling and utilizing the chemical energy of the organic matters in the form of electric energy by utilizing the microorganisms in the mild environment has huge potential, and has important practical significance for sustainable energy sources and environmental problem treatment in the future. At present, researchers have studied the coupling technology, for example, a chinese patent with application number 201210081071.X discloses a "reactor and wastewater treatment method for directly coupling a bioreactor and a microbial fuel cell", which uses a conductive material as a filter medium of a membrane bioreactor and simultaneously as a cathode of a microbial fuel cell to realize direct coupling of the MBR and the MFC, and can realize better control of effluent quality and membrane pollution, thus showing that the coupling technology has better development prospect.
In recent years, with the continuous development of material science, the modification of the membrane surface gradually enters the sight of researchers, and hydrophilic groups and other functional modifications can be added on the surface by utilizing the modification of a membrane component, so that the membrane pollution resistance is improved, and the service life is prolonged.
At present, a great part of polymeric membranes for water treatment are prepared from polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl chloride, polyarylethersulfone and other materials, and the materials have the common advantages of high mechanical strength, chemical corrosion resistance and high thermal stability. For example, chinese patent No. 201610141239.X discloses a "polytetrafluoroethylene electrocatalytic porous membrane and a method for preparing the same", which uses polytetrafluoroethylene prepared by biaxial stretching as a base membrane, and deposits a mixture of multi-walled carbon nanotubes, graphene and the like thereon by vacuum filtration to prepare a conductive layer, and the obtained membrane has good flexibility and low cost. However, because of the strong hydrophobicity of the polytetrafluoroethylene materials, the separation membrane is very easy to adsorb protein, oil drops, colloid or other organic substances in water when being applied to water treatment, so that the membrane pores are blocked, and the long-term treatment operation of high-concentration refractory wastewater is not facilitated.
In addition, the cathode catalytic membrane is required to have a high oxygen reduction activity (ORR activity). Because the cathode is always in an aeration state during the operation of the reactor and the oxygen reduction reaction occurs at the cathode, the higher the oxygen mass transfer efficiency of the cathode is, the higher the obtained battery potential is, and the higher the electricity generation efficiency is. At present, the research on the oxygen sensitivity of the cathode membrane is less, and researchers research the oxygen adsorption performance of the fuel cell, for example, the Chinese patent with the application number of 201711474770.X discloses that2A fuel cell membrane electrode and a preparation method thereof are characterized in that a titanium source, a doping agent and a stabilizing agent are stirred in a water bath to prepare a mixed solution, then an auxiliary agent is added to carry out hydrothermal reaction to prepare a gel material, and then the gel material and a catalyst are compounded and hot-pressed to form, so that the obtained fuel cell membrane electrode has better oxygen sensitivity, strong adsorption capacity to oxygen and high cathode oxygen catalytic capacity; but the membrane electrode has stronger hydrophobicity and is more suitable for being used as an air cathode of a fuel cell.
In addition, the preparation method of the cathode catalytic membrane mainly adopts the idea of attaching a conductive layer or a catalytic layer on a base membrane, such as a sol-gel method, a dip coating method or an electrodeposition method, and the like, so that the obtained electrocatalytic membrane has many defects, the acting force of nano catalytic particles and the base membrane is weak, agglomeration is easy to occur, and the stability of the membrane electrode is poor, thereby causing low current efficiency of the cathode, poor ORR activity and low electron transmission efficiency.
Disclosure of Invention
The invention provides a hydrophilic conductive hydrogel cathode catalytic membrane and a preparation method and application thereof, wherein a base membrane is not needed, the hydrogel cathode catalytic membrane with a three-dimensional network structure is prepared by adopting an emulsion polymerization direct film-forming method, and an ionizable functional group and a nano catalyst are introduced into a polymer network, so that the conductive performance and the catalytic performance of the cathode catalytic membrane are improved; the hydrogel cathode catalytic membrane is applied to the cathode catalytic process of the EMBR, can promote the oxygen reduction reaction, improve the ORR activity and improve the electricity generation efficiency of a reaction system; the membrane electrode has good hydrophilicity, high conductivity, high membrane electrode stability and mechanical property with adjustable height.
In order to achieve the purpose, the invention adopts the following technical scheme:
the hydrophilic conductive hydrogel cathode catalytic membrane is prepared from a nano iron particle-loaded hydrophilic conductive hydrogel by a coating mode, has a regular three-dimensional network structure, and has a pore diameter of 100-1000 nm; the tensile strength is more than or equal to 1600MPa, and the bearing capacity is more than or equal to 1.5 MPa.
A preparation method of a hydrophilic conductive hydrogel cathode catalytic membrane comprises the steps of carrying out emulsion polymerization on an N- (4-chlorophenyl) acrylamide monomer, an acrylic acid monomer and an acrylamide monomer according to the mass ratio of 5-15: 2-9 to generate a terpolymer hydrogel; introducing conductive polymer aniline into the terpolymer hydrogel through an emulsion polymerization method to obtain conductive polymer hydrogel, wherein the mass ratio of the terpolymer hydrogel to the aniline is 1.25-5: 1; then adding iron salt into the conductive polymer hydrogel, wherein the mass ratio of the conductive polymer hydrogel to the iron salt is 5-35: 9, heating in a water bath to obtain the hydrophilic conductive hydrogel loaded with the nano iron catalyst, and finally preparing the hydrophilic conductive hydrogel loaded with the nano iron particles into a flat membrane in a coating mode.
A preparation method of a hydrophilic conductive hydrogel cathode catalytic membrane specifically comprises the following steps:
(1) preparation of the terpolymer flexible material:
synthesis of N- (4-chlorophenyl) acrylamide: dissolving 1-5 g of an acrylic acid reagent in an organic solvent to prepare an acrylic acid solution with the mass fraction of 0.1-5 wt%; taking 10-100 mL of acrylic acid solution, and then adding 1-30mL of dichloroSulfoxide solution, reaction to form C2H5A COCl solution; weighing 10-100 g of p-phenylenediamine solid, and putting into 20-150 mL of C2H5In a COCl solution, N- (4-chlorphenyl) acrylamide is generated after reaction;
synthesis of a terpolymer: synthesizing an N- (4-chlorphenyl) acrylamide monomer, an acrylic acid monomer and an acrylamide monomer into a terpolymer by adopting an emulsion polymerization method; putting 5-15 g of N- (4-chlorophenyl) acrylamide monomer, 2-9 g of acrylic acid monomer, 2-9 g of acrylamide monomer, 0.1-5 g of OP-10 emulsifier and 0.1-10 g of ammonium persulfate into a four-neck flask, adding 50-300 mL of deionized water for dissolution, then mechanically stirring, adjusting the reaction temperature to 60-70 ℃, cooling to 20-40 ℃ after 1-6 h, and sealing for later use;
(2) preparation of conductive polymer hydrogel:
weighing 10-200 g of terpolymer, diluting the terpolymer into a hydrogel solution with the mass fraction of 1-5 wt%, weighing aniline according to the proportion of 20-80 wt% of the terpolymer, adding the aniline into the hydrogel solution, synthesizing by using an emulsion polymerization method, adjusting the reaction temperature to 60-70 ℃, cooling to 20-40 ℃ after 1-6 h, obtaining conductive polymer hydrogel after the reaction is finished, and sealing and storing for later use;
(3) introduction of a nano catalyst:
placing 1-10 g of conductive polymer hydrogel in a 500mL four-neck flask, adding 30-300 mL of 0.1-0.5 mol/L ferric nitrate aqueous solution, and stirring at room temperature for 6-24 h to fully embed iron ions in an adhesive layer of the conductive polymer hydrogel; washing with deionized water for many times, and placing in 50-300 mL of NaBH with concentration of 0.3-1.5 mol/L4Heating in water bath in the aqueous solution, wherein the temperature of the water bath is 35-45 ℃, and the heating time is 2-6 h; meanwhile, removing oxygen in the solution by bubbling nitrogen, keeping the room temperature under the nitrogen atmosphere, and slowly stirring for 6-10 hours to complete the reduction reaction of iron ions, wherein the generated iron simple substance is attached to the conducting polymer hydrogel to form the metal nano catalyst;
(4) preparing a hydrophilic conductive hydrogel cathode catalytic membrane:
and (3) taking 10-15 g of the hydrophilic conductive hydrogel loaded with the nano iron particles in the step (3), preparing a flat membrane in a coating scraping mode, quickly putting the flat membrane into ultrapure water for phase conversion for 4-8 h, and drying at the temperature of 70-80 ℃ to obtain the hydrophilic conductive hydrogel cathode catalytic membrane.
The mass concentration of the thionyl chloride solution is 37 wt%.
The mass ratio of the N- (4-chlorphenyl) acrylamide monomer to the acrylic acid monomer to the acrylamide monomer is 6: 2.
The mass ratio of the terpolymer to the aniline is 3: 1.
An application of a hydrophilic conductive hydrogel cathode catalytic membrane is used in an EMBR system for purifying high-concentration organic wastewater difficult to degrade.
The high-concentration degradation-resistant organic wastewater is coking wastewater.
Compared with the prior art, the invention has the beneficial effects that:
1) the hydrophilic conductive hydrogel cathode catalytic membrane has a three-dimensional network structure of cross-linked polymer chains, has the mechanical property, the thermodynamic property, the ion diffusion property and the liquid transportation property which are highly adjustable, can increase the membrane flux of the cathode membrane, improves the hydrophilicity, the oxygen adsorption capacity and the conductivity of the membrane, is suitable for treating high-concentration organic wastewater, can improve the anti-pollution property, reduce the cleaning frequency and prolong the service life;
2) the hydrophilic conductive hydrogel cathode catalytic membrane provided by the invention has the advantages that the electronic conductive polymer chain is crosslinked through emulsion polymerization, so that continuous electronic transmission can be realized, and the conductivity of the membrane material is increased; meanwhile, the introduction of the nano catalytic particles increases the ORR activity of the cathode film, promotes the proceeding of the cathode oxygen reduction reaction, increases the cathode potential and improves the electricity generation efficiency of the reactor;
3) the hydrophilic conductive hydrogel cathode catalytic membrane disclosed by the invention is formed by integrating the hydrogel polymer, and compared with the traditional cathode membrane material preparation process, the hydrophilic conductive hydrogel cathode catalytic membrane does not need a base membrane, the whole polymer network is combined with each other through chemical bond interaction, and the membrane electrode has high stability.
Drawings
Fig. 1 is a schematic diagram of a synthesis process of the hydrophilic conductive hydrogel cathode catalytic membrane of the present invention.
Fig. 2 is a schematic diagram of a system for coupling a hydrophilic conductive hydrogel cathode catalytic membrane with an EMBR according to an embodiment of the present invention.
In the figure: 1. anode carbon rod 2, resistor 3, hydrophilic conductive hydrogel cathode catalytic membrane 4, aeration head 5, aeration pump 6, voltage and current data collector 7, water quality monitor
FIG. 3 shows the effluent COD and NH of the coking wastewater after treatment in the embodiment of the invention4 +-N removal rate profile.
Detailed Description
The following further describes embodiments of the present invention with reference to the accompanying drawings:
the hydrophilic conductive hydrogel cathode catalytic membrane is prepared from a nano-iron particle-loaded hydrophilic conductive hydrogel through a coating mode, has a regular three-dimensional network structure, and has a pore size of 100-1000 nm; the tensile strength is more than or equal to 1600MPa, and the bearing capacity is more than or equal to 1.5 MPa.
As shown in figure 1, the preparation method of the hydrophilic conductive hydrogel cathode catalytic membrane comprises the steps of carrying out emulsion polymerization on an N- (4-chlorophenyl) acrylamide monomer, an acrylic acid monomer and an acrylamide monomer according to the mass ratio of 5-15: 2-9 to generate a terpolymer hydrogel; introducing conductive polymer aniline into the terpolymer hydrogel through an emulsion polymerization method to obtain conductive polymer hydrogel, wherein the mass ratio of the terpolymer hydrogel to the aniline is 1.25-5: 1; then adding iron salt into the conductive polymer hydrogel, wherein the mass ratio of the conductive polymer hydrogel to the iron salt is 5-35: 9, heating in a water bath to obtain the hydrophilic conductive hydrogel loaded with the nano iron catalyst, and finally preparing the hydrophilic conductive hydrogel loaded with the nano iron particles into a flat membrane in a coating mode.
The invention relates to a preparation method of a hydrophilic conductive hydrogel cathode catalytic membrane, which comprises the following steps:
(1) preparation of the terpolymer flexible material:
synthesis of N- (4-chlorophenyl) acrylamide: dissolving 1-5 g of an acrylic acid reagent in an organic solvent to prepare an acrylic acid solution with the mass fraction of 0.1-5 wt%; taking 10-100 mL of acrylic acid solution, adding 1-30mL of thionyl chloride solution, and reacting to generate C2H5A COCl solution; weighing 10-100 g of p-phenylenediamine solid, and putting into 20-150 mL of C2H5In a COCl solution, N- (4-chlorphenyl) acrylamide is generated after reaction;
synthesis of a terpolymer: synthesizing an N- (4-chlorphenyl) acrylamide monomer, an acrylic acid monomer and an acrylamide monomer into a terpolymer by adopting an emulsion polymerization method; putting 5-15 g of N- (4-chlorophenyl) acrylamide monomer, 2-9 g of acrylic acid monomer, 2-9 g of acrylamide monomer, 0.1-5 g of OP-10 emulsifier and 0.1-10 g of ammonium persulfate into a four-neck flask, adding 50-300 mL of deionized water for dissolution, then mechanically stirring, adjusting the reaction temperature to 60-70 ℃, cooling to 20-40 ℃ after 1-6 h, and sealing for later use;
(2) preparation of conductive polymer hydrogel:
weighing 10-200 g of terpolymer, diluting the terpolymer into a hydrogel solution with the mass fraction of 1-5 wt%, weighing aniline according to the proportion of 20-80 wt% of the terpolymer, adding the aniline into the hydrogel solution, synthesizing by using an emulsion polymerization method, adjusting the reaction temperature to 60-70 ℃, cooling to 20-40 ℃ after 1-6 h, obtaining conductive polymer hydrogel after the reaction is finished, and sealing and storing for later use;
(3) introduction of a nano catalyst:
placing 1-10 g of conductive polymer hydrogel in a 500mL four-neck flask, adding 30-300 mL of 0.1-0.5 mol/L ferric nitrate aqueous solution, and stirring at room temperature for 6-24 h to fully embed iron ions in an adhesive layer of the conductive polymer hydrogel; washing with deionized water for many times, and placing in 50-300 mL of NaBH with concentration of 0.3-1.5 mol/L4Heating in water bath in the aqueous solution, wherein the temperature of the water bath is 35-45 ℃, and the heating time is 2-6 h; simultaneously removing oxygen in the solution by nitrogen bubbling, keeping the room temperature under the nitrogen atmosphere, and slowly stirring for 6-10 h to finish iron separationCarrying out reduction reaction on the metal nanoparticles, and attaching the generated iron simple substance to the conductive polymer hydrogel to form a metal nano catalyst;
(4) preparing a hydrophilic conductive hydrogel cathode catalytic membrane:
and (3) taking 10-15 g of the hydrophilic conductive hydrogel loaded with the nano iron particles in the step (3), preparing a flat membrane in a coating scraping mode, quickly putting the flat membrane into ultrapure water for phase conversion for 4-8 h, and drying at the temperature of 70-80 ℃ to obtain the hydrophilic conductive hydrogel cathode catalytic membrane.
The mass concentration of the thionyl chloride solution is 37 wt%.
The mass ratio of the N- (4-chlorphenyl) acrylamide monomer to the acrylic acid monomer to the acrylamide monomer is 6: 2.
The mass ratio of the terpolymer to the aniline is 3: 1.
An application of a hydrophilic conductive hydrogel cathode catalytic membrane is used in an EMBR system for purifying high-concentration organic wastewater difficult to degrade.
The high-concentration degradation-resistant organic wastewater is coking wastewater.
The invention can solve the problems of poor hydrophilicity, poor mechanical property, poor oxygen adsorption capacity and the like of the traditional cathode; compared with the traditional cathode membrane material, the prepared hydrogel cathode catalytic membrane has the advantages of water absorption swelling but no dissolution, the multi-layer hydrophilic pore channels can promote ion diffusion and liquid transportation, the hydrophilicity is good, and meanwhile, the hydrogel cathode catalytic membrane also has the mechanical properties (such as elasticity and flexibility) with adjustable height to improve other properties of the water treatment membrane material; the hydrogel cathode catalytic membrane is applied to the cathode catalytic process of the EMBR, can promote oxygen reduction reaction and improve ORR activity.
The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation processes are given, but the scope of the invention is not limited to the following examples. The methods used in the following examples are conventional methods unless otherwise specified.
[ examples ] A method for producing a compound
Firstly, preparing a hydrophilic conductive hydrogel cathode catalytic membrane:
(1) preparation of the terpolymer flexible material:
synthesis of N- (4-chlorophenyl) acrylamide monomer: dissolving 2.5g of acrylic acid reagent in a toluene organic solvent to prepare 3 wt% acrylic acid solution, taking 100mL of the solution, adding 20mL of thionyl chloride solution with the mass concentration of 37 wt% for substitution reaction to generate C2H5COCl; 50g of p-phenylenediamine solid is weighed out and put into 80mL of C2H5In a COCl solution, N- (4-chlorphenyl) acrylamide is generated after reaction;
synthesis of a terpolymer: by adopting an emulsion polymerization method, 15g of N- (4-chlorphenyl) acrylamide monomer, 5g of acrylic acid monomer, 5g of acrylamide monomer, 2g of OP-10 emulsifier and 0.5g of ammonium persulfate are placed in a four-neck flask, 200mL of deionized water is added for dissolution, the mechanical stirring is carried out, the reaction temperature is adjusted to 65 ℃, the temperature is reduced to 25 ℃ after 4 hours, and the mixture is sealed and stored for later use.
(2) Preparation of conductive polymer hydrogel:
weighing 36g of terpolymer, diluting into a hydrogel solution with the mass fraction of 2 wt%, weighing 12g of aniline, adding the aniline into the hydrogel solution, synthesizing by an emulsion polymerization method, adjusting the reaction temperature to 65 ℃, cooling to 25 ℃ after 4 hours, obtaining the conductive polymer hydrogel after the reaction is finished, and sealing and storing for later use.
(3) Introduction of a nano catalyst:
10g of conductive polymer hydrogel is placed in a 500mL four-neck flask, 150mL of ferric nitrate aqueous solution with the concentration of 0.15mol/L is added at the same time, and stirring is carried out for 18h at room temperature, so that iron ions can be fully embedded into the conductive polymer hydrogel. After washing the conductive polymer hydrogel for multiple times by deionized water, the conductive polymer hydrogel is placed in 300mL of NaBH with the concentration of 1.2mol/L4Heating in water bath at 40 ℃ for 6h in an aqueous solution, removing oxygen in the solution by nitrogen bubbling, keeping the temperature at room temperature and slowly stirring for 7h in a nitrogen atmosphere to complete the reduction reaction of iron ions, and generating the nano iron catalyst.
(4) Preparing a hydrophilic conductive hydrogel cathode catalytic membrane:
and taking 10g of the hydrophilic conductive hydrogel loaded with the nano iron particles, preparing a flat membrane in a coating manner, quickly putting the membrane into ultrapure water for phase conversion for 6.5h, and drying at 75 ℃ to obtain the hydrophilic conductive hydrogel cathode catalytic membrane with hydrophilicity, conductivity, catalytic property and ORR activity.
In this embodiment, the hydrophilic conductive hydrogel cathode catalytic membrane is applied to an EMBR system for treating coking wastewater.
The raw water quality of wastewater from a certain coke plant is shown in Table 1.
TABLE 1 raw Water quality of wastewater from certain coking plant
High-concentration coking wastewater of a coking plant is taken as inlet water, the wastewater is subjected to anodic treatment firstly and then reaches a cathode chamber through layers, as shown in fig. 2, the hydrophilic conductive hydrogel cathode catalytic membrane prepared in the embodiment is directly taken as a membrane cathode with the interception and separation effects, an aeration head 4 is arranged at the bottom of the membrane cathode catalytic membrane and connected with an aeration pump 5, and oxygen is provided through aeration. The carbon rod 1 is arranged in the anode chamber to be used as an anode, the carbon rod 1 is connected with the hydrophilic conductive hydrogel cathode catalytic membrane 3 through a lead, and the lead is externally connected with a resistor 2. The water temperature, pH, dissolved oxygen index and the like of the anode chamber are tracked, monitored and data are collected by a water quality monitor 7, the data changes of current, voltage and the like are collected by a voltage and current data collector 6 and are used for monitoring the electricity generation condition of the system, and the membrane front pressure is monitored by a vacuum meter to reflect the membrane pollution condition.
Controlling the flow rate of inlet and outlet water by using a peristaltic pump, controlling the hydraulic retention time to be about 48h, respectively taking out water samples every 24h, and determining COD (chemical oxygen demand) and NH (NH)4 +The removal rate is calculated, the COD concentration is stabilized at about 130mg/L after the continuous operation for 7 days, the removal rate is stabilized at about 96.6 percent, and NH is added4 +The concentration of-N is stabilized at about 20mg/L, the removal rate is stabilized at about 78 percent, and COD and NH in effluent are stabilized4 +the-N removal rate curve is shown in FIG. 3.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (6)
1. The preparation method of the hydrophilic conductive hydrogel cathode catalytic membrane is characterized in that the hydrophilic conductive hydrogel cathode catalytic membrane is prepared by coating hydrophilic conductive hydrogel loaded with nano iron particles, has a regular three-dimensional network structure, and has a pore size of 100-1000 nm; the tensile strength is more than or equal to 1600MPa, and the bearing capacity is more than or equal to 1.5 MPa;
the preparation method of the hydrophilic conductive hydrogel cathode catalytic membrane comprises the steps of carrying out emulsion polymerization on an N- (4-chlorphenyl) acrylamide monomer, an acrylic acid monomer and an acrylamide monomer according to the mass ratio of 5-15: 2-9 to generate a terpolymer hydrogel; introducing conductive polymer aniline into the terpolymer hydrogel through an emulsion polymerization method to obtain conductive polymer hydrogel, wherein the mass ratio of the terpolymer hydrogel to the aniline is 1.25-5: 1; then adding iron salt into the conductive polymer hydrogel, wherein the mass ratio of the conductive polymer hydrogel to the iron salt is 5-35: 9, heating in a water bath to obtain the hydrophilic conductive hydrogel loaded with the nano-iron catalyst, and finally preparing the hydrophilic conductive hydrogel loaded with the nano-iron particles into a flat membrane in a coating manner;
the preparation method of the hydrophilic conductive hydrogel cathode catalytic membrane specifically comprises the following steps:
(1) preparation of the terpolymer flexible material:
synthesis of N- (4-chlorophenyl) acrylamide: dissolving 1-5 g of an acrylic acid reagent in an organic solvent to prepare an acrylic acid solution with the mass fraction of 0.1-5 wt%; taking 10-100 mL of acrylic acid solution, adding 1-30mL of thionyl chloride solution, and reacting to generate C2H5A COCl solution; weighing 10-100 g of p-phenylenediamine solid, and putting into 20-150 mL of C2H5In a COCl solution, N- (4-chlorphenyl) acryloyl is generated after reactionAn amine;
synthesis of a terpolymer: synthesizing an N- (4-chlorphenyl) acrylamide monomer, an acrylic acid monomer and an acrylamide monomer into a terpolymer by adopting an emulsion polymerization method; putting 5-15 g of N- (4-chlorophenyl) acrylamide monomer, 2-9 g of acrylic acid monomer, 2-9 g of acrylamide monomer, 0.1-5 g of OP-10 emulsifier and 0.1-10 g of ammonium persulfate into a four-neck flask, adding 50-300 mL of deionized water for dissolution, then mechanically stirring, adjusting the reaction temperature to 60-70 ℃, cooling to 20-40 ℃ after 1-6 h, and sealing for later use;
(2) preparation of conductive polymer hydrogel:
weighing 10-200 g of terpolymer, diluting the terpolymer into a hydrogel solution with the mass fraction of 1-5 wt%, weighing aniline according to the proportion of 20-80 wt% of the terpolymer, adding the aniline into the hydrogel solution, synthesizing by using an emulsion polymerization method, adjusting the reaction temperature to 60-70 ℃, cooling to 20-40 ℃ after 1-6 h, obtaining conductive polymer hydrogel after the reaction is finished, and sealing and storing for later use;
(3) introduction of a nano catalyst:
placing 1-10 g of conductive polymer hydrogel in a 500mL four-neck flask, adding 30-300 mL of 0.1-0.5 mol/L ferric nitrate aqueous solution, and stirring at room temperature for 6-24 h to fully embed iron ions in an adhesive layer of the conductive polymer hydrogel; washing with deionized water for many times, and placing in 50-300 mL of NaBH with concentration of 0.3-1.5 mol/L4Heating in water bath in the aqueous solution, wherein the temperature of the water bath is 35-45 ℃, and the heating time is 2-6 h; meanwhile, removing oxygen in the solution by bubbling nitrogen, keeping the room temperature under the nitrogen atmosphere, and slowly stirring for 6-10 hours to complete the reduction reaction of iron ions, wherein the generated iron simple substance is attached to the conducting polymer hydrogel to form the metal nano catalyst;
(4) preparing a hydrophilic conductive hydrogel cathode catalytic membrane:
and (3) taking 10-15 g of the hydrophilic conductive hydrogel loaded with the nano iron particles in the step (3), preparing a flat membrane in a coating scraping mode, quickly putting the flat membrane into ultrapure water for phase conversion for 4-8 h, and drying at the temperature of 70-80 ℃ to obtain the hydrophilic conductive hydrogel cathode catalytic membrane.
2. The method for preparing the hydrophilic conductive hydrogel cathode catalytic membrane as claimed in claim 1, wherein the thionyl chloride solution has a mass concentration of 37 wt%.
3. The method for preparing the hydrophilic conductive hydrogel cathode catalytic membrane as claimed in claim 1, wherein the mass ratio of the N- (4-chlorophenyl) acrylamide monomer, the acrylic acid monomer and the acrylamide monomer is 6:2: 2.
4. The method for preparing the hydrophilic conductive hydrogel cathode catalytic membrane as claimed in claim 1, wherein the mass ratio of the terpolymer to the aniline is 3: 1.
5. The method for preparing the hydrophilic conductive hydrogel cathode catalytic membrane according to claim 1, wherein the hydrophilic conductive hydrogel cathode catalytic membrane is used in an electrically assisted membrane bioreactor system for purifying high-concentration organic wastewater difficult to degrade.
6. The preparation method of the hydrophilic conductive hydrogel cathode catalytic membrane as claimed in claim 5, wherein the high-concentration refractory organic wastewater is coking wastewater.
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