Hollow plate type carbon membrane water treatment device and water treatment method thereof

Abstract

The application discloses a kind of hollow plate carbon membrane water treatment device and water treatment method thereof.Hollow plate carbon membrane is parallelly assembled in the order of anode and cathode, and membrane assembly is immersed in water tank when operating.Anode carbon membrane is connected with water pump through permeate pipe, and cathode carbon membrane is connected with aeration device through aeration pipeline.Water treatment method is as follows: wastewater to be treated is added into reaction tank through water inlet, power supply is started, and aeration device is opened to carry out cathode carbon membrane aeration.Cathode generates electrofenton reaction, generates ·OH to degrade organic pollutants in water.Then water pump is started, and wastewater is permeated from anode carbon membrane surface to channel, and further oxidizes and degrades pollutants under the action of anode electrocatalytic oxidation.Processed water reaches water outlet through filtration from anode carbon membrane channel.The water treatment device is suitable for advanced treatment of organic wastewater, and has the characteristics of easy assembly, easy cleaning and easy scale use.

Description

Technical Field

[0001] This invention relates to the field of water treatment technology, and specifically discloses a hollow plate carbon membrane water treatment device and its water treatment method. Background Technology

[0002] With the booming development of industry, agriculture, and medical fields, a large amount of recalcitrant organic wastewater containing organic pollutants such as antibiotics, dyes, and phenols is generated. If this wastewater is discharged into natural water bodies without effective treatment, it will inevitably cause widespread organic pollution of water bodies, posing a threat to the ecological environment and human health and safety.

[0003] Traditional water treatment processes struggle to efficiently treat recalcitrant organic wastewater. Membrane separation technology, due to its high efficiency, lack of chemical additives, and ease of operation, is considered a promising water treatment technology. However, single-membrane separation technologies are typically based on size screening, making it difficult to remove pollutants smaller than the membrane pores and prone to membrane fouling, thus limiting their application in treating organic wastewater. Catalytic membrane processes, combining membrane separation with advanced oxidation technologies, can achieve both high-efficiency pollutant removal and resistance to membrane fouling. Among advanced oxidation technologies, electrochemical advanced oxidation mainly includes anodic electrochemical oxidation and cathodic electro-Fenton oxidation. Anodic electrochemical oxidation degrades organic pollutants through direct and indirect oxidation pathways by applying direct current to the reaction anode; cathodic electro-Fenton oxidation continuously generates H₂O₂ and maintains Fe²⁺ through electrochemical methods. 3+ To Fe 2+ The continuous conversion between the two leads to the immediate reaction of highly oxidizing active substances such as hydroxyl radicals (·OH), which effectively degrade organic pollutants. Combining membrane separation technology with electrochemical advanced oxidation technology is a highly efficient and energy-saving water treatment technology that can degrade organic pollutants, eliminate their toxicity, and even completely mineralize them, showing great promise for application in the field of water treatment.

[0004] Carbon-based membrane materials combine the properties of both carbon and membrane materials, exhibiting good conductivity, high porosity, and excellent physical and chemical stability. By functionalizing carbon-based membrane materials to impart anodic electrocatalytic oxidation capabilities and cathodic electro-Fenton capabilities, oxidation capacity can be maximized and electrical energy can be efficiently utilized within an electric field system, thereby achieving highly efficient removal of organic pollutants from water. Traditional carbon membrane materials are generally configured in tubular or plate-like structures. Tubular carbon membrane modules are easy to install and have simple devices, but due to the brittle nature of carbon materials, tubular carbon membranes have relatively low mechanical strength. Furthermore, when used as electrocatalytic membranes, electrode arrangement is difficult, the electric field distribution is uneven, and regeneration and cleaning are not convenient. Plate-like carbon membranes have higher strength, easier electrode arrangement, and are easier to regenerate and clean, but the packing density is lower, and the module sealing is more complex. Summary of the Invention

[0005] This invention addresses the advanced treatment and recycling of organic wastewater by developing a hollow plate carbon membrane water treatment device and method that couples anodic oxidation and cathodic electro-Fenton oxidation. This water treatment device is suitable for the advanced treatment of organic wastewater and features easy assembly, easy cleaning, and easy large-scale application.

[0006] The objective of this invention is achieved as follows: a hollow plate carbon membrane water treatment device, mainly comprising: a reaction tank, an aeration device, a water pump and a catalytic module power supply, wherein an immersion carbon membrane module and a stirring device are provided in the reaction tank, and the entire membrane module is immersed in the water tank during operation.

[0007] The carbon membrane in the submersible carbon membrane module has a hollow plate structure;

[0008] The carbon membrane in the submerged carbon membrane assembly can serve as both an anode and a cathode, including an anode carbon membrane and a cathode carbon membrane. The submerged carbon membrane assembly is assembled in parallel from top to bottom in the order of anode carbon membrane and cathode carbon membrane. The anode carbon membrane and cathode carbon membrane are connected to the positive and negative electrodes of the catalytic modular power supply.

[0009] The anode carbon membrane is connected to a water pump via a permeate pipe for producing treated water; the cathode carbon membrane is connected to an aeration device via an aeration pipe for aeration.

[0010] Based on the above technical solution, furthermore, the reaction tank is provided with a water inlet on one side and the water pump is provided with a water outlet.

[0011] Based on the above technical solution, further, the anode carbon membrane is connected to the positive terminal of the catalytic module power supply via a wire, and the cathode carbon membrane is connected to the negative terminal of the catalytic module power supply via a wire.

[0012] Based on the above technical solution, furthermore, the aeration device and the water pump are connected to the power supply of the aeration device / water pump module.

[0013] Based on the above technical solution, furthermore, the permeate pipe and the aeration pipe are located on both sides of the carbon membrane.

[0014] Based on the above technical solutions, furthermore, the carbon membrane in the immersion carbon membrane assembly can be arbitrarily disassembled and assembled.

[0015] Based on the above technical solution, further, the spacing between the anode carbon film and the cathode carbon film in the immersion carbon film module is 5-100mm, the number of carbon films in a single membrane module unit is an even number, wherein the number of anode carbon films and cathode carbon films each accounts for half, and they are arranged in sequence.

[0016] Based on the above technical solutions, further, the precursor of the carbon membrane is one or more of activated carbon, petroleum coke, coal, semi-coke, graphite, graphene, carbon nanotubes, MOF and polymers.

[0017] Based on the above technical solution, furthermore, the hollow plate carbon membrane has two or more hollow channels, making it a porous hollow plate carbon membrane (e.g., Figure 2 Taking a five-hole hollow plate carbon membrane as an example, it has five hollow channels with rectangular cross-sections. The hollow plate carbon membrane has the following dimensions: length 20-5000mm, thickness 4-50mm, width 10-1000mm, and wall thickness 1-20mm. Preferred ranges are as follows: length 100-2000mm, thickness 10-40mm, width 100-500mm, and wall thickness 5-15mm.

[0018] Based on the above technical solutions, furthermore, the hollow plate anode carbon film and cathode carbon film are carbon films that have undergone targeted modifications.

[0019] The anodic carbon film is a functional carbon film material with high anodic oxidation activity, which is loaded with active electrocatalysts including BDD (boron-doped diamond), SnO2-Sb, PbO2, TiO2, etc., by means of sol-gel, electrodeposition, etc.

[0020] The cathode carbon membrane is a functional carbon membrane material with high hydrogen peroxide production and Fenton catalytic activity, prepared through processes such as activation and loading of active materials. The active materials loaded onto the cathode carbon membrane include polyaniline, polypyrrole, nano-zero-valent iron, ferric chloride, ferric hydroxyl oxide, and iron-based metal-centered MOFs, etc.

[0021] Based on the above technical solution, furthermore, the flow rate range of the submerged carbon membrane module in actual operation is 20-500 L / (m³). 2 The preferred range for ·h) is 50-300 L / (m 2 ·h).

[0022] Based on the above technical solution, furthermore, both the power supply for the catalytic module and the power supply for the aeration device / water pump module are purchased commercially and can provide 0-20V / 0-220V voltage. The catalytic module power supply is effectively connected to the hollow plate carbon membrane, which serves as the cathode / anode, by connecting the positive and negative terminals on both sides of the module assembly.

[0023] Based on the above technical solution, the stirring device is further defined as a stirrer.

[0024] Based on the above technical solution, furthermore, the stirring device is located near the aeration pipeline side.

[0025] Based on the above technical solution, the reaction tank is further divided into left and right sides by a middle partition. The left side reaction tank is equipped with an immersion carbon membrane module and a stirrer, and the right side reaction tank is equipped with an aeration device and a water pump. The left side reaction tank is equipped with a catalytic module power supply above it, and the right side reaction tank is equipped with an aeration device / water pump module power supply above it.

[0026] Based on the above technical solution, further, the aeration pipeline is connected to the cathode carbon membrane through a pipeline, and the permeate pipeline is connected to the anode carbon membrane through a pipeline.

[0027] Based on the above technical solution, furthermore, the bottom of the permeate pipe is kept sealed, and the top is connected to a water pump.

[0028] Based on the above technical solution, furthermore, the aeration device and water pump mentioned above are purchased commercially and can effectively adjust the aeration volume and operating flow rate.

[0029] Based on the above technical solution, a negative pressure gauge is further provided between the permeate pipe and the water pump.

[0030] Based on the above technical solution, furthermore, the negative pressure gauge is purchased through commercial channels and can provide pressure indication.

[0031] Based on the above technical solution, furthermore, the membrane module is immersed in a water tank during operation.

[0032] Based on the above technical solution, furthermore, all pipelines, membrane modules, reaction tanks, etc., in the water treatment device are made of corrosion-resistant materials, such as polytetrafluoroethylene (PTFE), which can be purchased commercially. Moreover, the structure of each component can adopt standard engineering interfaces, facilitating disassembly or replacement at any time and simplifying maintenance.

[0033] The water treatment device has an inlet on its left side. Water enters the reaction tank under the pressure of an external water pump, and the solution completely submerges the carbon membrane module. At this point, the agitator is turned on, and the aeration device is simultaneously operated. After the aeration device has been running for 5-30 minutes, anodizing and cathodic electro-Fenton processes are performed. Simultaneously, the water pump is turned on to synergistically remove organic pollutants from the wastewater. The treated filtrate enters the permeate pipe and flows to the outlet under the action of the water pump.

[0034] The hollow plate carbon membrane water treatment device described above utilizes a water treatment method that couples anodic oxidation and cathode electro-Fenton oxidation. The specific process is as follows: First, the wastewater to be treated is added to the reaction tank through the inlet, and the stirring device and catalytic module power are turned on. After the submerged carbon membrane module is powered on, the aeration device is turned on to aerate the cathode carbon membrane, causing an electro-Fenton reaction on the cathode surface. H2O2 is generated online and then activated by the loaded active material to generate ·OH, which degrades organic pollutants in the water. Subsequently, the water pump is turned on, and under pressure, the wastewater in the reaction tank passes through the anode carbon membrane (permeating from the surface of the anode carbon membrane into the channels). Electrocatalytic oxidation occurs on the surface and in the pores of the anode carbon membrane, further oxidizing and degrading the pollutants in the water. The filtered water is then immersed in the channels inside the anode carbon membrane and pumped out to the outlet to obtain the treated permeate.

[0035] Based on the above technical solution, further, the aeration rate is 10-100 L / (m³). 2 Within the range of ·h);

[0036] The electric field strength at the two electrodes of the carbon film is 2-20V;

[0037] The water treatment throughput of the device is 20-500 L / (m²). 2 ·h);

[0038] The suction pressure of the water pump is 5-100 kPa; when the negative pressure gauge in front of the water pump is higher than 100 kPa, backwashing and regeneration are performed.

[0039] The hollow plate carbon membrane water treatment method described above is mainly used for the deep treatment of organic wastewater (such as dyes, phenols, antibiotics, environmental hormones, drugs, etc.).

[0040] Beneficial effects:

[0041] (1) By designing the carbon membrane as a hollow plate structure, setting both the anode and cathode as carbon membranes, and carrying out targeted modification, the electrocatalytic anodic oxidation and cathode electro-Fenton can be effectively coupled together, improving the oxidation capacity of the system and alleviating membrane fouling, thereby effectively treating the recalcitrant organic pollutants in the water body to achieve the harmless discharge standard.

[0042] (2) The device has the characteristics of simple structure, easy cleaning, small footprint and uniform electric field distribution. It has a wide range of applications and is easy to use in multiple scenarios. Attached Figure Description

[0043] The structures, proportions, and sizes depicted in these accompanying drawings are merely for illustrative purposes and are not intended to limit the implementation of the invention. Any modifications to the structure, proportions, or sizes, without affecting the effectiveness and objectives of the invention, are within the scope of this invention. For those skilled in the art, obtaining other drawings based on these drawings without inventive effort is also within the scope of protection of this invention.

[0044] Figure 1 A schematic diagram of a hollow plate carbon membrane water treatment device that couples anodic oxidation and cathodic electro-Fenton.

[0045] Figure 2 This is a schematic diagram of a hollow plate carbon membrane.

[0046] Figure 3 A schematic diagram of the hollow plate carbon membrane module layout, where a) is a front view of the membrane module layout; b) is a diagram of the electrode layout sequence.

[0047] Figure 4 Schematic diagram of each component of the hollow plate carbon film module, where a) cathode carbon film; b) anode carbon film; c) cathode power supply connection; d) anode power supply connection; e) overall side view; f) overall top view.

[0048] The relevant markings in the diagram are as follows: 1. Inlet, 2. Reaction tank, 3. Catalytic modular power supply, 4. Aeration device / water pump module power supply, 5. Stirrer, 6. Submerged carbon membrane module, 7. Aeration pipeline, 8. Aeration device, 9. Permeate pipe, 10. Water pump, 11. Negative pressure gauge, 12. Outlet. Detailed Implementation

[0049] The specific operational scheme of this invention will be described in detail through accompanying drawings and textual description. The following examples are only listed as the preferred embodiments, mainly for illustrative and guiding purposes to help familiarize oneself with the operation of this invention, and should not be construed as limiting the invention. Based on the technical solution of this invention, any adjustments, modifications, or equivalent substitutions that can be made by those skilled in the art without creative effort are still within the protection scope of this invention.

[0050] Example 1

[0051] like Figure 1-4As shown, the hollow plate carbon membrane water treatment device coupled with anodic oxidation and cathodic electro-Fenton in this embodiment includes a reaction tank 2, an aeration device 8, a water pump 10, a catalytic module power supply 3, and an aeration device / water pump module power supply 4. The reaction tank is divided into left and right sides by a middle partition. The left side of the reaction tank 2 is equipped with an immersion carbon membrane assembly 6 and a stirrer 5. The left side of the reaction tank 2 is equipped with an aeration device 8 and a water pump 10. The catalytic module power supply 3 is located above the left side of the reaction tank 2, and the aeration device / water pump module power supply 4 is located above the right side of the reaction tank 2. The carbon membrane in the submerged carbon membrane module 6 has a hollow plate structure. The carbon membrane in the submerged carbon membrane module 6 includes an anode carbon membrane and a cathode carbon membrane. The submerged carbon membrane module 6 is assembled in parallel from top to bottom in the order of anode carbon membrane and cathode carbon membrane, with each accounting for half of the total number. The anode carbon membrane is connected to the positive terminal of the catalytic module power supply 3 via a wire, and the cathode carbon membrane is connected to the negative terminal of the catalytic module power supply 3 via a wire. The anode carbon membrane is connected to the water pump 10 via a permeate pipe 9, and the cathode carbon membrane is connected to the aeration device 8 via an aeration pipe 7. An inlet 1 is located on the left side of the reaction tank 2, and water is discharged through the outlet 12 of the water pump 10. The aeration device 8 and the water pump 10 are respectively connected to the power supply 4 of the aeration device / water pump module. The permeate pipe 9 and the aeration pipe 7 are located on both sides of the carbon membrane, and the stirrer 5 is located near the aeration pipe 7. An inlet 1 is located on the left side of the reaction tank 2, and an outlet 12 is located on the water pump 10. Aeration pipe 7 is connected in series with the cathode carbon membrane via a pipeline. Oxygen is transported through aeration device 8 via a pipeline connected to the aeration pipe. The bottom of the permeate pipe 9 is sealed, and the top is connected to the water pump 10. A negative pressure gauge 11 is installed between the permeate pipe 9 and the water pump 10. The permeate pipe 9 is connected in series with the anode carbon membrane via a pipeline. The treated water is discharged through the permeate pipe 9, the water pump 10, and the outlet 12.

[0052] The hollow plate carbon membrane water treatment device consists of six five-hole hollow plate petroleum coke-based carbon membranes connected in series. The dimensions of each hollow plate petroleum coke-based carbon membrane are: length 300mm, thickness 20mm, width 150mm, and wall thickness 10mm. In the submerged carbon membrane module 6, the spacing between the anode and cathode carbon membranes is 10mm, and the aeration rate is 30L / (m³). 2 The flow rate of the membrane module is 200 L / (m³). 2The pumping pressure of the water pump is 25 kPa. The hollow plate carbon membrane at the anode is pre-modified with a PbO2 catalyst layer by immersing the carbon membrane in a mixed solution containing ethylene glycol, citric acid, and PbCl2 (ethylene glycol concentration: 140 mM, citric acid: 30 mM, PbCl2: 10 mM), followed by drying and calcination at 450°C for 1 hour. The hollow plate carbon membrane at the cathode is pre-modified with zero-valent iron by immersing the carbon membrane in a 0.1 g / L Fe(NO3)3·9H2O solution, drying, and then reducing it at 1100°C for 1 hour under an argon atmosphere. Sulfamethoxazole at 5 mg / L is selected as the target pollutant.

[0053] The working process is as follows: First, the wastewater to be treated is added to the reaction tank 2 through the inlet 1), and the stirrer 5 and the power supply 3 of the catalytic module are turned on; after the submerged carbon membrane module 6) is powered by 2.0V, the power supply 4) of the aeration device 8 is turned on to aerate the cathode carbon membrane, and an electro-Fenton reaction occurs on the cathode surface, generating H2O2 online. After being activated by the loaded active material, it generates ·OH to degrade the organic pollutants in the water; then the water pump 10 is turned on, and under pressure, the antibiotic wastewater in the reaction tank 2 passes through the anode carbon membrane, and an electrocatalytic oxidation reaction occurs on the surface and pores of the anode carbon membrane, further oxidizing and degrading the pollutants in the water; the filtered water is immersed in the channels inside the anode carbon membrane, and then pumped out to the outlet 12 by the water pump 10 to obtain the treated water, in which the removal rate of sulfamethoxazole can reach 99.5% and the removal rate of TOC is 59.8%.

[0054] Example 2

[0055] like Figure 1-4As shown, the hollow plate carbon membrane water treatment device coupled with anodic oxidation and cathodic electro-Fenton in this embodiment includes a reaction tank 2, an aeration device 8, a water pump 10, a catalytic module power supply 3, and an aeration device / water pump module power supply 4. The reaction tank is divided into left and right sides by a middle partition. The left side of the reaction tank 2 is equipped with an immersion carbon membrane assembly 6 and a stirrer 5. The left side of the reaction tank 2 is equipped with an aeration device 8 and a water pump 10. The catalytic module power supply 3 is located above the left side of the reaction tank 2, and the aeration device / water pump module power supply 4 is located above the right side of the reaction tank 2. The carbon membrane in the submerged carbon membrane module 6 has a hollow plate structure. The carbon membrane in the submerged carbon membrane module 6 includes an anode carbon membrane and a cathode carbon membrane. The submerged carbon membrane module 6 is assembled in parallel from top to bottom in the order of anode carbon membrane and cathode carbon membrane, with each accounting for half of the total number. The anode carbon membrane is connected to the positive terminal of the catalytic module power supply 3 via a wire, and the cathode carbon membrane is connected to the negative terminal of the catalytic module power supply 3 via a wire. The anode carbon membrane is connected to the water pump 10 via a permeate pipe 9, and the cathode carbon membrane is connected to the aeration device 8 via an aeration pipe 7. An inlet 1 is located on the left side of the reaction tank 2, and water is discharged through the outlet 12 of the water pump 10. The aeration device 8 and the water pump 10 are respectively connected to the power supply 4 of the aeration device / water pump module. The permeate pipe 9 and the aeration pipe 7 are located on both sides of the carbon membrane, and the stirrer 5 is located near the aeration pipe 7. An inlet 1 is located on the left side of the reaction tank 2, and an outlet 12 is located on the water pump 10. Aeration pipe 7 is connected in series with the cathode carbon membrane via a pipeline. Oxygen is transported through aeration device 8 via a pipeline connected to the aeration pipe. The bottom of the permeate pipe 9 is sealed, and the top is connected to the water pump 10. A negative pressure gauge 11 is installed between the permeate pipe 9 and the water pump 10. The permeate pipe 9 is connected in series with the anode carbon membrane via a pipeline. The treated water is discharged through the permeate pipe 9, the water pump 10, and the outlet 12.

[0056] The hollow plate activated carbon membrane water treatment device consists of six eight-hole hollow plate activated carbon membranes connected in series. The dimensions of each hollow plate activated carbon membrane are: length 1000mm, thickness 30mm, width 250mm, and wall thickness 15mm. In the submerged activated carbon membrane module 6, the spacing between the anode and cathode carbon membranes is 15mm, and the aeration rate is 50L / (m³). 2 The flow rate of the membrane module is 400 L / (m³). 2The pumping pressure of the water pump is 60 kPa. The hollow plate carbon film of the anode is pre-modified with BDD. Diamond is deposited on the carbon film by hot-wire chemical vapor deposition, using methane as the carbon source, hydrogen as the etching gas, and boron trioxide as the boron source. The volume ratio of methane, hydrogen, and boron trioxide is 1:2:0.1. The substrate temperature is 800℃, the hot wire temperature is 2200℃, the reaction pressure is 80 Pa, and the reaction time is 8 h. The hollow plate carbon membrane of the cathode was pre-modified with pyrolysis-polyaniline by immersing the carbon membrane in a mixed solution containing hydrochloric acid (0.50M), potassium oxalate (0.25M), and aniline (0.05M), followed by electrochemical polymerization (based on cyclic voltammetry, with a potential window of -0.2 to 0.5V and a scan rate of 50mV / s) and further high-temperature pyrolysis treatment at 900℃ under a nitrogen atmosphere for 30 min. Phenol at 10 mg / L was selected as the target pollutant.

[0057] The work process is as follows: Figure 1 As shown, the phenolic wastewater to be treated is first poured into the reaction tank (2) through the inlet 1, and the stirring device 5 and the power supply 3 of the catalytic module are turned on. After the submerged carbon membrane module (6) is powered by 3.0V, the power supply 4 of the aeration device 8 is turned on to aerate the cathode carbon membrane. An electro-Fenton reaction occurs on the cathode surface, and H2O2 is generated online. After being activated by the metal-free Fenton reaction of the loaded polyaniline material, ·OH is generated to degrade the organic pollutants in the water. Then, the water pump 10 is turned on. Under pressure, the phenolic wastewater in the reaction tank 2 passes through the anode carbon membrane and undergoes an electrocatalytic oxidation reaction on the surface and pores of the anode carbon membrane to further oxidize and degrade the pollutants in the water. The filtered water enters the channel inside the anode carbon membrane and is then pumped out to the outlet 12 by the water pump 10 to obtain the treated water. The removal rate of phenol can reach 98.6%, and the removal rate of TOC is 68.5%.

[0058] Example 3

[0059] like Figure 1-4As shown, the hollow plate carbon membrane water treatment device coupled with anodic oxidation and cathodic electro-Fenton in this embodiment includes a reaction tank 2, an aeration device 8, a water pump 10, a catalytic module power supply 3, and an aeration device / water pump module power supply 4. The reaction tank is divided into left and right sides by a middle partition. The left side of the reaction tank 2 is equipped with an immersion carbon membrane assembly 6 and a stirrer 5. The left side of the reaction tank 2 is equipped with an aeration device 8 and a water pump 10. The catalytic module power supply 3 is located above the left side of the reaction tank 2, and the aeration device / water pump module power supply 4 is located above the right side of the reaction tank 2. The carbon membrane in the submerged carbon membrane module 6 has a hollow plate structure. The carbon membrane in the submerged carbon membrane module 6 includes an anode carbon membrane and a cathode carbon membrane. The submerged carbon membrane module 6 is assembled in parallel from top to bottom in the order of anode carbon membrane and cathode carbon membrane, with each accounting for half of the total number. The anode carbon membrane is connected to the positive terminal of the catalytic module power supply 3 via a wire, and the cathode carbon membrane is connected to the negative terminal of the catalytic module power supply 3 via a wire. The anode carbon membrane is connected to the water pump 10 via a permeate pipe 9, and the cathode carbon membrane is connected to the aeration device 8 via an aeration pipe 7. An inlet 1 is located on the left side of the reaction tank 2, and water is discharged through the outlet 12 of the water pump 10. The aeration device 8 and the water pump 10 are respectively connected to the power supply 4 of the aeration device / water pump module. The permeate pipe 9 and the aeration pipe 7 are located on both sides of the carbon membrane, and the stirrer 5 is located near the aeration pipe 7. An inlet 1 is located on the left side of the reaction tank 2, and an outlet 12 is located on the water pump 10. Aeration pipe 7 is connected in series with the cathode carbon membrane via a pipeline. Oxygen is transported through aeration device 8 via a pipeline connected to the aeration pipe. The bottom of the permeate pipe 9 is sealed, and the top is connected to the water pump 10. A negative pressure gauge 11 is installed between the permeate pipe 9 and the water pump 10. The permeate pipe 9 is connected in series with the anode carbon membrane via a pipeline. The treated water is discharged through the permeate pipe 9, the water pump 10, and the outlet 12.

[0060] The hollow plate carbon membrane water treatment device consists of eight seven-hole hollow plate carbon nanotube-based carbon membranes connected in series (with hollow plate ceramic membranes as the substrate). The dimensions of the hollow plate carbon nanotube-based carbon membranes are: length 2000mm, thickness 40mm, width 350mm, and wall thickness 200mm. In the submerged carbon membrane module 6, the spacing between the anode and cathode carbon membranes is 5mm, and the aeration rate is 80L / (m³). 2 The flow rate of the membrane module is 400 L / (m³). 2The pumping pressure of the water pump is 80 kPa. The hollow plate carbon membrane of the anode is pre-modified by immersing the carbon membrane in a mixed solution containing ethylene glycol, citric acid, SnCl4·5H2O, and SbCl3. The concentrations of ethylene glycol are 140 mM, citric acid is 30 mM, SnCl4·5H2O is 9 mM, and SbCl3 is 1 mM. The immersion time is 30 min, and after drying, the membrane is calcined in a muffle furnace at 500 °C for 2 h, thus pre-modifying the SnO2-Sb catalyst layer. The hollow plate carbon membrane of the cathode was pre-modified with pyrolysis-polypyrrole by immersing the carbon membrane in a mixed solution containing hydrochloric acid (0.25M), potassium chloride (0.10M), and pyrrole (0.10M), followed by electrochemical polymerization (based on cyclic voltammetry, with a potential window of -0.2 to 0.5V and a scan rate of 50mV / s) and further high-temperature pyrolysis treatment at 900℃ under a nitrogen atmosphere for 60 min. Rhodamine B at 10 mg / L was selected as the target pollutant.

[0061] The work process is as follows: Figure 1 As shown, the dye wastewater to be treated is first added to the reaction tank 2 through the inlet 1, and the stirring device 5 and the power supply 3 of the catalytic module are turned on. After the submerged carbon membrane module 6 is powered by 2.5V, the power supply 4 of the aeration device 8 is turned on to aerate the cathode carbon membrane. An electro-Fenton reaction occurs on the cathode surface, generating H2O2 online. After being activated by the metal-free Fenton reaction of the loaded polyaniline active material, ·OH is generated to degrade the organic pollutants in the water. Then, the water pump 10 is turned on. Under pressure, the dye wastewater in the reaction tank 2 passes through the anode carbon membrane, and an electrocatalytic oxidation reaction occurs on the surface and pores of the anode carbon membrane, further oxidizing and degrading the pollutants in the water. The filtered water is immersed in the channels inside the anode carbon membrane, and then pumped out to the outlet 12 by the water pump 10 to obtain the treated water. The water is clear and completely decolorized, with a Rhodamine B removal rate of 100% and a TOC removal rate of 85.3%.

Claims

1. A hollow plate carbon membrane water treatment device, characterized in that, The device includes a reaction tank (2), an aeration device (8), a water pump (10), and a catalytic module power supply (3). An immersion carbon membrane assembly (6) and a stirring device (5) are provided in the reaction tank (2). The carbon membrane in the immersion carbon membrane module (6) has a hollow plate structure; The carbon membrane in the submerged carbon membrane assembly (6) includes an anode carbon membrane and a cathode carbon membrane. The submerged carbon membrane assembly is assembled in parallel in an alternating order of anode carbon membrane and cathode carbon membrane. The anode carbon membrane and cathode carbon membrane are respectively connected to the positive and negative terminals of the catalytic module power supply (3). The anode carbon membrane is connected to the water pump through the permeate pipe (9); the cathode carbon membrane is connected to the aeration device (8) through the aeration pipe (7); The aforementioned anode carbon film and cathode carbon film are carbon films that have undergone targeted modifications. The anode carbon film is a functional carbon film material in which an active electrocatalyst is supported by a sol-gel or electrodeposition method; the active electrocatalyst includes at least one of BDD, SnO2-Sb, and PbO2. The cathode carbon film is a functional carbon film material prepared by activating or loading active substances; the active substances include at least one of polyaniline, polypyrrole, nano-zero valent iron, ferric chloride, ferric hydroxyl oxide, and iron-based metal-centered MOF.

2. The hollow plate carbon membrane water treatment device according to claim 1, characterized in that: The spacing between the anode carbon film and the cathode carbon film in the immersion carbon film module (6) is 5-100 mm. The number of carbon films in a single membrane module unit is an even number, with the number of anodes and cathodes each accounting for half, arranged in sequence.

3. The hollow plate carbon membrane water treatment device according to claim 1, characterized in that, The carbon membrane has two or more hollow channels, a length of 20-5000 mm, a thickness of 4-50 mm, a width of 10-1000 mm, and a wall thickness of 1-20 mm.

4. The hollow plate carbon membrane water treatment device according to claim 1, characterized in that, The precursor of the carbon membrane is one or more of activated carbon, petroleum coke, coal, semi-coke, graphite, graphene, carbon nanotubes, MOF and polymers.

5. The hollow plate carbon membrane water treatment device according to claim 1, characterized in that, The reaction tank (2) is provided with an inlet (1) on one side and a water pump (10) is provided with an outlet (12); The aeration device (8) and the water pump (10) are connected to the power supply (4) of the aeration device / water pump module; A negative pressure gauge is provided between the permeate pipe (9) and the water pump (10).

6. The hollow plate carbon membrane water treatment device according to claim 1, characterized in that, The permeate pipe (9) and the aeration pipe (7) are located on both sides of the carbon membrane.

7. The water treatment method of the hollow plate carbon membrane water treatment device according to any one of claims 1-6, characterized in that, Includes the following steps: First, the wastewater to be treated is added to the reaction tank (2) through the inlet (1), and the stirring device (5) and the power supply (3) of the catalytic module are turned on. After the submerged carbon membrane module (6) is powered on, the aeration device (8) is turned on to aerate the cathode carbon membrane. An electro-Fenton reaction occurs on the cathode surface to generate ·OH to degrade the organic pollutants in the water. Then, the water pump (10) is turned on. Under pressure, the wastewater in the reaction tank passes through the anode carbon membrane and undergoes an electrocatalytic oxidation reaction on the surface and in the pores of the anode carbon membrane to further oxidize and degrade the pollutants in the water. The filtered water enters the channel inside the anode carbon membrane and is then pumped out to the outlet (12) by the water pump (10).

8. The water treatment method according to claim 7, characterized in that, Aeration rate is 10~100L / (m³) 2 ·h); The electric field strength at the two electrodes of the carbon film is 2-20V; The water treatment throughput of the device is 20-500 L / (m²). 2 ·h); The suction pressure of the water pump (10) is 5-100 kPa; when the value of the negative pressure gauge (11) in front of the water pump is higher than 100 kPa, the water treatment device is turned off and backwashing and regeneration are performed.

Images