CN115010226B - Membrane electrolysis treatment high-chlorine organic wastewater device - Google Patents
Membrane electrolysis treatment high-chlorine organic wastewater device Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
- C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to a device for treating high-chlorine organic wastewater by membrane electrolysis, which comprises a treatment tank, a first anode plate, a second anode plate and a membrane assembly. The first anode plate and the second anode plate are oppositely arranged in the treatment tank, and the membrane assembly is arranged between the first anode plate and the second anode plate. The membrane assembly is provided with a first side and a second side which are composed of conductive micro-filtration membranes. The first anode plate and the second anode plate are connected with the positive pole of a power supply, and the first side face and the second side face are connected with the negative pole of the power supply. The membrane component forms a closed filter chamber by virtue of the first side surface, the second side surface, the peripheral side surface or the inner wall surface of the treatment tank. The closed filter chamber is provided with a water outlet. After the power is switched on, the chlorine ions in the wastewater lose electrons at the anode plate and are oxidized into hypochlorous acid, and the hypochlorous acid oxidizes and degrades organic matters in the water. The surface of the conductive micro-filtration membrane is negatively charged, and the negative electricity repulsion enables some micelles or particles which are also negatively charged to be trapped. The conductive microfiltration membrane also utilizes microfiltration pores to retain some macromolecules or micelles. The invention realizes the removal of chlorine and organic matters in the high-chlorine organic wastewater and improves the effluent quality.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a device for treating high-chlorine organic wastewater through membrane electrolysis.
Background
The membrane electrolysis technology is a new technology which combines a membrane separation method and an electrochemical method for development. The core material of the membrane separation method is a thin membrane, and the separation of the pollutants from water is performed by utilizing the selective permeability of the membrane, but the method has the defect that part of organic pollutants cannot be trapped. Electrochemical techniques can be classified into electrochemical oxidation, electro-adsorption, electrochemical reduction, and electrodialysis, etc. from their action processes. The electrochemical technology has the advantages of high efficiency, no pollution, no need of additional reagent and the like, and is widely used for treating wastewater of pharmacy, printing and dyeing, spinning and the like. The high-chlorine organic wastewater has wide sources, high chloride ion concentration and strong corrosivity, has great inhibition effect on microorganisms for biological treatment, and particularly has high chloride ion concentration in pharmaceutical wastewater discharged from pharmaceutical factories. High-chlorine wastewater is one of the great problems faced in the current water treatment industry. Therefore, the membrane electrolysis device aiming at the degradation of the high-chlorine organic wastewater is of great significance.
Disclosure of Invention
In view of the above disadvantages and shortcomings of the prior art, the present invention provides a membrane electrolysis apparatus for treating high-chlorine organic wastewater, which has a simple structure, can operate continuously, and can efficiently remove organic pollutants in organic wastewater.
In order to achieve the purpose, the invention adopts the main technical scheme that:
in a first aspect, the present invention provides a membrane electrolysis apparatus for treating high chlorine organic wastewater, comprising:
the treatment tank is used for accommodating high-chlorine organic wastewater, a water inlet is formed in one end of the treatment tank, and the high-chlorine wastewater enters the treatment tank from the water inlet;
the first anode plate and the second anode plate are arranged in the treatment tank at a certain distance and are immersed in the high-chlorine organic wastewater;
the membrane assembly is arranged between the first anode plate and the second anode plate and comprises a first side surface and a second side surface, wherein the first side surface is arranged opposite to the first anode plate, and the second side surface is arranged opposite to the second anode plate; the first side and the second side of the membrane component are plane membrane structures formed by conductive micro-filtration membranes;
a space is reserved between the first side surface and the second side surface of the membrane module, and the first side surface and the second side surface and the inner wall of the treatment tank or the peripheral side surfaces of the membrane module form a closed filter chamber; the closed filter chamber is separated from the rest of the treatment tank;
a water outlet is arranged on the closed filter chamber and is connected with a water outlet pump;
the first anode plate and the second anode plate are connected with a positive electrode of a power supply, and the first side surface and the second side surface of the membrane assembly are connected with a negative electrode of the power supply.
According to the preferred embodiment of the invention, cerium phosphate modified active coke is filled in the treatment tank between the first anode plate and the first side surface of the membrane module and between the second anode plate and the second side surface of the membrane module; the cerium phosphate modified active coke is obtained by mixing cerium phosphate and active coke, ball-milling, and roasting at 400-600 ℃ under the protection of inert atmosphere.
According to the preferred embodiment of the invention, activated coke modified by iron manganese copper vanadium or iron manganese copper tungsten is filled between the first anode plate and the first side surface of the membrane component and between the second anode plate and the second side surface of the membrane component in the treatment tank; the iron-manganese-copper-vanadium or iron-manganese-copper-tungsten modified active coke is prepared by firstly soaking the active coke in an aqueous solution containing soluble iron salt, manganese salt, copper salt and vanadium salt/tungsten salt by an impregnation method, taking out and drying the active coke, and finally roasting the active coke at a high temperature of 550-900 ℃ under the protection of an inert atmosphere.
According to the preferred embodiment of the present invention, the conductive micro-filtration membrane is a membrane structure embedded with a silver-plated stainless steel mesh; the preparation method comprises the following steps: preparing a casting solution of aromatic polyamide, scraping and coating the casting solution on a silver-plated stainless steel mesh and a non-woven fabric of 300-400 meshes by using a film scraping machine, overlapping the silver-plated stainless steel mesh and the non-woven fabric, and curing to obtain the conductive microfiltration membrane.
The casting solution comprises 30-35 parts by mass of aromatic polyamide, 15-35 parts by mass of good solvent (dimethyl sulfoxide or dimethylacetamide) and 30-50 parts by mass of additive; wherein the additive is one of polyethylene glycol, polyvinylpyrrolidone or Tween.
According to a preferred embodiment of the present invention, the membrane module comprises a hexahedral mold frame, and the first side, the second side, and the peripheral sides fixed to the mold frame; the first side and the second side are both connected to a negative pole of a power supply; the first side surface, the second side surface and the peripheral side surfaces enclose a closed filter chamber; or the membrane module comprises two separated plane modules, the first side surface and the second side surface are respectively fixed on the two plane modules, and the first side surface, the second side surface and the inner wall of the treatment pool together enclose a closed filter chamber.
According to the preferred embodiment of the invention, the bottom of the treatment pool is provided with an ultrasonic transducer which works intermittently.
According to a preferred embodiment of the present invention, the membrane module comprises a hexahedral mold frame, and the first side, the second side, and the peripheral sides fixed to the mold frame; the first side surface, the second side surface and the peripheral side surfaces enclose a closed filter chamber; the lower part of the membrane component is arranged at the bottom of the treatment tank through a vibrating spring, the membrane component is connected with a vibrating device, and the vibrating device works intermittently.
According to the preferred embodiment of the invention, the closed filter chamber is filled with 1/3-2/3 volume of modified activated carbon-zeolite material; the preparation method of the modified activated carbon-zeolite material comprises the following steps: sieving active carbon with the particle size of 1-2mm and zeolite, and mixing according to the mass ratio of the active carbon to the zeolite of 1; preparing 0.5-1g/L aluminum sulfate solution, putting active carbon and zeolite into the solution to be immersed, heating to 40-60 ℃ for treatment for 2-4h, filtering and drying.
According to the preferred embodiment of the invention, the water inlet is connected with a water inlet pump for introducing the high-chlorine organic wastewater into the treatment tank.
The beneficial effects of the invention are:
the invention utilizes the characteristic of high chlorine ion concentration in the wastewater to lead the chlorine ions to lose electrons near the anode plate to generate strong oxidizing substances such as hypochlorous acid or hypochlorite, and the strong oxidizing substances can oxidize and degrade partial organic matters in the treatment tank. The conductive microfiltration membrane not only has the characteristics of a polymer microporous membrane, but also has good conductive property (negative electricity), can retain colloid particles with negative electricity due to the action of electricity, and also retains some macromolecules by using microfiltration pores. The organic small molecules which can not be intercepted are degraded into smaller molecules by the oxidation of hypochlorous acid in the treatment tank and enter the atmosphere or enter the closed filter chamber.
The invention realizes the high-efficiency removal of organic matters in the organic wastewater through the electrochemical and membrane separation effects, and overcomes the defects that floc substances and toxic organic pollutants generated by the coagulation effect cannot be intercepted. The device has simple and novel structure, less pipeline connection and high removal rate of organic matters in the wastewater. The device of the invention realizes the dual purposes of removing chlorine and degrading organic matters.
The invention further adds cerium phosphate modified active coke in the treatment tank, and organic matters which cannot be intercepted by the conductive micro-filtration membrane stay in the treatment tank for a longer time without entering the closed filtration chamber by utilizing the ketone group on the surface of the active coke and the strong adsorption effect, so that the organic matters can be oxidized and degraded by hypochlorous acid and the like. In addition, the invention also adds ferro manganese copper vanadium or ferro manganese copper tungsten modified active coke for promoting the speed of hypochlorous acid oxidizing organic matters into the treatment tank, and the active coke is used as a catalyst for the hypochlorous acid oxidizing organic matters, thereby greatly improving the effect of degrading the organic matters. Finally, the invention also fills modified active carbon-zeolite material in the closed filter chamber composed of membrane components to further remove organic matters, thereby greatly improving the quality of effluent. The stainless steel mesh in the conductive microfiltration membrane is made of silver-plated materials, so that the resistance is reduced, the energy consumption is saved, the corrosion resistance is realized, and the chlorine resistance of the conductive microfiltration membrane is improved by adopting aromatic polyamide in the casting solution. The ultrasonic transducer or the vibration device works intermittently and is used for removing micelles adsorbed on the surface of the membrane component, reducing the water outlet resistance and ensuring the continuity of the outlet water.
Drawings
FIG. 1 is a schematic structural diagram of a device for treating high-chlorine organic wastewater by membrane electrolysis in example 1.
FIG. 2 is a schematic structural diagram of the apparatus for membrane electrolysis treatment of high-chlorine organic wastewater in example 3.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
Example 1
As shown in fig. 1, the present embodiment provides an apparatus for treating high-chlorine organic wastewater by membrane electrolysis, which comprises: the treatment tank 1 is used for containing the high-chlorine organic wastewater, one end of the treatment tank 1 is provided with a water inlet 11, and the water inlet 11 is connected with a water inlet pump 12 and used for guiding the high-chlorine organic wastewater into the treatment tank 1. Two first anode plates 21 and two second anode plates 22 are arranged in the treatment tank 1 and are immersed in the high-chlorine organic wastewater. The membrane assembly 30 is disposed between the first anode plate 21 and the second anode plate 22, and the membrane assembly 30 includes a hexahedral mold frame, and a first side 31, a second side 32, and a peripheral side 33 fixed to the mold frame, where the peripheral side 33 connects the first side 31 and the second side 32, so that the first side 31, the second side 32, and the peripheral side 33 enclose a closed filter chamber 70. The closed filter chamber 70 is provided with a water outlet 34, and the water outlet 34 is connected with a water outlet pump 35.
Wherein, the first side 31 of the membrane assembly 30 is arranged opposite to the first anode plate 21, the second side 32 is arranged opposite to the second anode plate 22, and the first side 31 and the second side 32 are respectively planar membrane structures formed by conductive micro-filtration membranes. The conductive micro-filtration membrane is of a membrane structure embedded with a silver-plated stainless steel mesh. The preparation method comprises the following steps: preparing a membrane casting solution of aromatic polyamide, scraping and coating the membrane casting solution on a silver-plated stainless steel mesh and a non-woven fabric of 300-400 meshes by using a membrane scraping machine, overlapping the silver-plated stainless steel mesh and the non-woven fabric, and curing to obtain the conductive microfiltration membrane. Specifically, in this embodiment, the preparation method of the conductive microfiltration membrane is as follows: (1) preparing a casting solution: placing 30g of aromatic polyamide in a 500mL three-neck round-bottom flask, adding 30g of dimethylacetamide as a solvent and 30g of polyethylene glycol (additive), stirring at 80 ℃ for 24h (400 r/m), performing ultrasonic treatment for 15min, and standing at 60 ℃ for defoaming for 48h to obtain a casting solution; (2) film scraping: and (3) scraping and coating the casting film liquid on a silver-plated stainless steel mesh and a non-woven fabric of 300 meshes by using a film scraping machine, scraping the film with the thickness of 200 mu m with the stainless steel mesh above and the non-woven fabric below, immediately placing the scraped film in a coagulating bath (distilled water at 30 ℃) for 48h, and continuously changing water during the period to obtain the conductive microfiltration membrane.
The prepared conductive micro-filtration membranes are fixed on two sides of a mold frame of the membrane module 30, so as to prepare the first side 31 and the second side 32. Because the first side surface 31 and the second side surface 32 have a distance, the peripheral side surface 33 connects the first side surface 31 and the second side surface 32 to form a closed filter chamber 70; the closed filter chamber 70 is separated from the rest of the treatment tank 1.
As shown in FIG. 1, the first anode plate 21 and the second anode plate 22 are connected to the positive electrode of the regulated power supply, and the first side surface 31 and the second side surface 32 of the membrane assembly are connected to the negative electrode of the regulated power supply. When the electricity is supplied, the chlorine ions in the high-chlorine organic wastewater lose electrons at the first anode plate 21 and the second anode plate 22 to generate hypochlorous acid or hypochlorite, and the hypochlorous acid and the hypochlorite have strong oxidizability, so that some organic matters in the water are oxidized and decomposed. Some large molecular organic substances that cannot be decomposed and some charged colloidal particles are trapped outside the membrane module 30. Some organic matter that cannot be trapped by membrane assembly 30 is in turn oxidatively degraded into smaller small molecules. Thus, the water entering closed filter chamber 70 contains only a small number of small organic molecules.
In order to slow down the organic molecules which cannot be trapped by the membrane module 30 from rapidly entering the closed filter chamber 70 and being discharged from the water outlet 34, the invention also fills the treatment tank 1 with the cerium phosphate modified active coke 40 between the first anode plate 21 and the first side 31 of the membrane module 30, and between the second anode plate 22 and the second side of the membrane module. The cerium phosphate modified active coke 40 is obtained by mixing cerium phosphate and active coke, ball milling, and roasting at 400-600 ℃ under the protection of inert atmosphere.
For example, in this embodiment, the preparation method of the cerium phosphate modified activated coke 40 is as follows: (1) 1 part by mass of cylindrical active coke particles with the particle size of 1-2mm are cleaned by 1mol/L sodium hydroxide solution, then are mixed with 2 parts by mass of cerium phosphate solid powder in a ball milling way for 30min, and then are subjected to heat preservation treatment at 500 ℃ for 3h under the protection of nitrogen, so as to prepare the cerium phosphate modified active coke 40. The surface of the cerium phosphate modified active coke 40 is provided with a large number of oxygen-containing functional groups, and the active coke has a large number of active bonds which can combine some organic molecules (particularly acidic substances), and the self-pore structure of the active coke can also fix some organic molecules, so that some molecules which cannot be intercepted by the membrane component 30 can be fixed and retained in the treatment tank 1 for a longer time through the combination and adsorption action of the cerium phosphate modified active coke 40, and the molecules have enough time to be further degraded by the oxidation action of hypochlorous acid or sodium hypochlorite. The cerium phosphate in the cerium phosphate modified active coke 40 can generate a large number of structures such as ketone groups on the surface of the active coke for organic molecule combination, and compared with some organic active functional group modified materials, the cerium phosphate has good thermal stability and oxidation resistance, and the modified groups are prevented from being oxidized by hypochlorous acid. Wherein the mass ratio of the active coke to the cerium phosphate can be 1-2. The cerium phosphate also has mercury adsorption properties, and is helpful for purifying wastewater.
In addition, activated coke 50 modified by iron manganese copper vanadium or iron manganese copper tungsten is filled between the first anode plate 21 and the first side 31 of the membrane assembly 30 and between the second anode plate 22 and the second side 32 of the membrane assembly 30. The iron-manganese-copper-vanadium or iron-manganese-copper-tungsten modified active coke 50 is prepared by soaking the active coke in an aqueous solution containing soluble iron salt, manganese salt, copper salt and vanadium salt/tungsten salt by adopting an impregnation method, taking out and drying the active coke, and finally roasting the active coke at a high temperature of 550-900 ℃ under the protection of an inert atmosphere.
For example, in the embodiment, firstly, the activated coke is washed by 1mol/L sodium hydroxide solution, washed to be neutral by deionized water, then dipped into 1mol/L ferrous sulfate solution for 5 hours, taken out, dried at 120 ℃, then roasted for 2 hours at 700 ℃ in a tubular furnace under the condition of filling nitrogen, and cooled; then soaking the mixture into a solution containing 0.5mol/L manganese nitrate, 1mol/L copper nitrate, 0.4mol/L ammonium metavanadate and 2mol/L oxalic acid, and taking out the mixture after soaking for 3 hours. The impregnated catalyst precursor was dried in an oven at 120 ℃ for 2h. And (3) taking out the dried catalyst, placing the catalyst in a muffle furnace, roasting at 650 ℃ for 4h, taking out the catalyst, and naturally cooling to obtain the iron-manganese-copper-vanadium modified active coke. The iron manganese copper vanadium or iron manganese copper tungsten modified active coke 50 is helpful for catalyzing sodium hypochlorite to catalyze and oxidize organic matters.
In addition, because the filter membrane on the membrane module 30 is a conductive microfiltration membrane with a pore size of 0.1 to 10 microns, some large micelles or particles are easy to attach to the conductive microfiltration membrane to block the filter pores, so that the water production resistance of the closed filter chamber 70 is too high. In order to solve the technical problem, the ultrasonic transducer 13 is arranged at the bottom of the treatment pool 1, and the ultrasonic transducer 13 works intermittently. By applying ultrasonic waves to the high chlorine organic wastewater in the treatment tank 1 at regular intervals, micelles or particles adhering to the membrane module 30 can be removed, and the membrane module 30 is cleaned, so that the dropped particles or micelles or the like are deposited on the bottom of the treatment tank 1. The ultrasonic wave can also stir the wastewater in the treatment tank 1, so that the active coke can be uniformly distributed in the treatment tank 1. And meanwhile, a stirring device is arranged in the matching treatment pool 1. Of course, as an alternative, when the membrane module 30 is configured as a closed filter chamber 70, the bottom of the membrane module 30 is connected with the bottom of the treatment tank 1 by the vibration spring 36, and the vibration device 37 is provided at the bottom of the membrane module 30. The intermittent operation of the vibration device 37 also achieves the function of peeling off particles or micelles adhered to the membrane module 30, so as to reduce the resistance of water production.
The device for treating high-chlorine organic wastewater by membrane electrolysis of the embodiment utilizes the characteristics of extremely high concentration of chloride ions in wastewater, etc., so that the chloride ions lose electrons near the anode plate to generate strong oxidizing substances such as hypochlorous acid or hypochlorite, and the strong oxidizing substances can be used for oxidizing and degrading partial organic matters in the treatment tank, especially organic matters which cannot be intercepted by the membrane assembly 30.
The cerium phosphate modified active coke 40 filled in the treatment tank 1 enables organic matters which cannot be intercepted by the conductive microfiltration membrane to stay in the treatment tank for a longer time without entering a closed filter chamber, so that the organic matters can be oxidized and degraded by hypochlorous acid and the like, and the filling amount of the cerium phosphate modified active coke 40 is 1/5 of the volume of the treatment tank. The iron-manganese-copper-vanadium or iron-manganese-copper-tungsten modified active coke 50 can also be used as a catalyst for oxychlorination of organic matters by hypochlorous acid, so that the degradation efficiency and speed are greatly improved. The filling amount of the iron-manganese-copper-vanadium or iron-manganese-copper-tungsten modified activated coke 50 can also be 1/5 of the volume of the treatment tank. The stainless steel meshes in the conductive microfiltration membranes used for the first side surface 31 and the second side surface 32 of the membrane assembly 30 are made of silver plating materials, so that the resistance is reduced, the chlorine corrosion is prevented, and the aromatic polyamide is adopted in the casting solution to improve the chlorine resistance of the conductive microfiltration membranes.
Example 2
The difference between this example and example 1 is: the interior of the closed filter chamber 70 is further filled with 1/2 volume of a modified activated carbon-zeolite material. The preparation method of the modified activated carbon-zeolite material comprises the following steps: sieving active carbon with the particle size of 1-2mm and zeolite, and mixing according to the mass ratio of the active carbon to the zeolite of 1; preparing 0.5-1g/L aluminum sulfate solution, putting activated carbon and zeolite into the solution to be immersed, heating to 40-60 ℃ for treatment for 2-4h, filtering and taking out the activated carbon and zeolite, and drying. By filling the modified activated carbon-zeolite material in the closed filter chamber 70, the quality of the effluent is greatly improved, and the content of organic matters in the effluent is reduced. The aluminum sulfate modified activated carbon-zeolite material can greatly improve the specific surface area of the material and the adsorption performance to organic micromolecules.
Example 3
The difference between this embodiment and embodiment 2 is that, as shown in fig. 2, the closed filter chamber 70 in this embodiment is composed of the first side surface 31 and the second side surface 32 and the inner wall surface of the processing tank 1. At this time, four sides of the first side surface 31 and the second side surface 32 of the membrane module 30 are joined to the inner wall surface of the treatment tank 1. At this time, in order to prevent a large amount of glue lumps or particles from gathering on the membrane module 30, an ultrasonic transducer 13 is mainly arranged at the bottom of the treatment tank 1, and the ultrasonic transducer 13 works intermittently, so that the effect of shaking off and depositing the intercepted matters on the surface of the membrane module 30 to the bottom of the treatment tank 1 is achieved, and the continuity of the effluent is ensured. The conductive micro-filtration membranes and the like arranged on the first side surface 31 and the second side surface 32 are connected to the negative electrode of the regulated power supply.
Application example
The water quality of high-salt pharmaceutical wastewater from a pharmaceutical factory of Shijiazhuang is as follows: the COD of the inlet water is 15950.50mg/L, the pH is 8.31, the SS is 198.69mg/L, the content of chloride ions is high and is 21160mg/L, and the biodegradability of the water quality is poor. A small-sized membrane electrolysis high-chlorine organic wastewater treatment device with a treatment pool volume of 3L and a closed filter chamber volume of 1L is built in a laboratory, and the voltage between an anode plate and a conductive microfiltration membrane is controlled to be 40V. Adjusting the water outlet speed to be 0.4L/min, and obtaining a water outlet result: the removal rate of chloride ions is 93.51 percent, and the removal rate of COD reaches 94.02 percent. Therefore, the treatment effect is good, and the treatment speed is high.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. The utility model provides a membrane electrolysis handles organic waste water device of perchloride which characterized in that, it includes:
the treatment tank is used for accommodating high-chlorine organic wastewater, a water inlet is formed in one end of the treatment tank, and the high-chlorine wastewater enters the treatment tank from the water inlet;
the first anode plate and the second anode plate are arranged in the treatment tank at a certain distance and are immersed in the high-chlorine organic wastewater;
the membrane assembly is arranged between the first anode plate and the second anode plate and comprises a first side surface and a second side surface, wherein the first side surface is arranged opposite to the first anode plate, and the second side surface is arranged opposite to the second anode plate; the first side surface and the second side surface of the membrane component are planar membrane structures formed by conductive microfiltration membranes;
in the treatment tank, active coke modified by cerium phosphate is filled between a first anode plate and the first side surface of the membrane module and between a second anode plate and the second side surface of the membrane module; the cerium phosphate modified active coke is obtained by mixing cerium phosphate and active coke, ball-milling, and roasting at 400-600 ℃ under the protection of inert atmosphere;
active coke modified by iron-manganese-copper-vanadium or iron-manganese-copper-tungsten is filled between the first anode plate and the first side surface of the membrane module and between the second anode plate and the second side surface of the membrane module; firstly, soaking the active coke modified by the iron-manganese-copper-vanadium or the iron-manganese-copper-tungsten in an aqueous solution containing soluble iron salt, manganese salt, copper salt and vanadium salt/tungsten salt by adopting an impregnation method, taking out and drying the active coke, and finally roasting the active coke at a high temperature of 550-900 ℃ under the protection of an inert atmosphere to obtain the active coke;
a space is reserved between the first side surface and the second side surface of the membrane module, and the first side surface and the second side surface and the inner wall of the treatment tank or the peripheral side surfaces of the membrane module form a closed filter chamber; the closed filter chamber is separated from the rest of the treatment tank;
a water outlet is arranged on the closed filter chamber and is connected with a water outlet pump;
the first anode plate and the second anode plate are connected with a positive electrode of a power supply, and the first side surface and the second side surface of the membrane assembly are connected with a negative electrode of the power supply.
2. The apparatus for membrane electrolysis treatment of high chlorine organic wastewater according to claim 1, wherein said conductive microfiltration membrane is a membrane structure embedded with silver-plated stainless steel mesh; the preparation method comprises the following steps: preparing a membrane casting solution of aromatic polyamide, scraping and coating the membrane casting solution on a silver-plated stainless steel mesh and a non-woven fabric of 300-400 meshes by using a membrane scraping machine, overlapping the silver-plated stainless steel mesh and the non-woven fabric, and curing to obtain the conductive microfiltration membrane.
3. The apparatus for membrane electrolysis treatment of high chlorine organic wastewater according to claim 2, wherein the membrane casting solution comprises 30-35 parts by mass of aromatic polyamide, 15-35 parts by mass of good solvent, and 30-50 parts by mass of additive; wherein the additive is one of polyethylene glycol, polyvinylpyrrolidone or Tween; the good solvent is dimethyl sulfoxide or dimethyl acetamide.
4. The apparatus for membrane electrolysis treatment of high chlorine organic wastewater according to claim 1, wherein said membrane module comprises a hexahedral mold frame, and said first side, second side and peripheral sides fixed to the mold frame; the first side surface, the second side surface and the peripheral side surfaces enclose a closed filter chamber; or the membrane module comprises two separated plane modules, the first side surface and the second side surface are respectively fixed on the two plane modules, and the first side surface, the second side surface and the inner wall of the treatment pool together enclose a closed filter chamber.
5. The apparatus for membrane electrolysis treatment of high chlorine organic wastewater according to claim 1, wherein the bottom of the treatment cell is provided with an ultrasonic transducer which operates intermittently.
6. The apparatus for membrane electrolysis treatment of high chlorine organic wastewater according to claim 1, wherein said membrane module comprises a hexahedral mold frame, and said first side, second side and peripheral sides fixed to the mold frame; the first side surface, the second side surface and the peripheral side surfaces enclose a closed filter chamber; the lower part of the membrane component is arranged at the bottom of the treatment pool through a vibrating spring, the membrane component is connected with a vibrating device, and the vibrating device works intermittently.
7. The apparatus for membrane electrolysis treatment of high chlorine organic wastewater according to claim 1, wherein the closed filtration chamber is filled with 1/3-2/3 volume of modified activated carbon-zeolite material; the preparation method of the modified activated carbon-zeolite material comprises the following steps: sieving active carbon with the particle size of 1-2mm and zeolite, and mixing according to the mass ratio of the active carbon to the zeolite of 1; preparing 0.5-1g/L aluminum sulfate solution, putting active carbon and zeolite into the solution to be immersed, heating to 40-60 ℃, treating for 2-4h, filtering and drying.
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