CN108217861B - Internal circulation type electrocatalytic oxidation reactor and sewage purification treatment method - Google Patents

Internal circulation type electrocatalytic oxidation reactor and sewage purification treatment method Download PDF

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CN108217861B
CN108217861B CN201810322997.0A CN201810322997A CN108217861B CN 108217861 B CN108217861 B CN 108217861B CN 201810322997 A CN201810322997 A CN 201810322997A CN 108217861 B CN108217861 B CN 108217861B
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shell
sewage
layer
reaction
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CN108217861A (en
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孙淼
延善玉
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Liaoning Qingduo Environmental Protection Technology Co ltd
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Liaoning Qingduo Environmental Protection Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • C02F1/46109Electrodes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • C02F1/46109Electrodes
    • C02F2001/46133Electrodes characterised by the material
    • C02F2001/46138Electrodes comprising a substrate and a coating
    • C02F2001/46142Catalytic coating

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
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Abstract

The invention discloses an internal circulation type electrocatalytic oxidation reactor and a sewage purification treatment method, comprising at least one circulation device, wherein the circulation device comprises a reaction cabin, the reaction cabin comprises an inner reaction cabin surrounded by an inner shell and an outer reaction cabin surrounded by an outer shell, an inner electrode plate is arranged in the inner reaction cabin, the inner reaction cabin is embedded in the outer reaction cabin, and a filler layer is arranged between the inner reaction cabin and the outer reaction cabin; the inner electrode plate and the inner shell are used as cathodes, the outer shell is used as a cathode, a first electrocatalytic reaction zone is formed between the electrified inner electrode plate and the inner shell, and a second electrocatalytic reaction zone is formed between the electrified outer shell and the inner shell. The invention utilizes the characteristics of effective ring opening and chain breaking of the three-dimensional electrode and high energy efficiency of the two-dimensional electrode to jointly degrade pollutants, and has high electrocatalytic efficiency; the sewage purification treatment method realizes multi-stage external circulation purification of the sewage in the circulating device for multiple times, and ensures that effluent reaches the standard and is discharged.

Description

Internal circulation type electrocatalytic oxidation reactor and sewage purification treatment method
Technical Field
The invention relates to water treatment equipment, in particular to an internal circulation type electrocatalytic oxidation reactor and a sewage purification treatment method.
Background
The electrocatalytic oxidation technology is a novel high-efficiency clean wastewater treatment technology, and a plurality of domestic and foreign scholars apply the electrocatalytic oxidation technology to the treatment of organic wastewater which is difficult to degrade. Electrocatalytic oxidation is the generation of hydroxyl radicals (.oh) or other radicals and radicals with strong oxidizing power through electrochemical processes by using metal oxide electrodes with catalytic properties to attack organic matters in wastewater solution, so that they are decomposed into carbon dioxide, water and simple organic matters. In the whole electrocatalytic oxidation process, hydroxyl free radicals (OH) react with organic matters in the wastewater solution directly without selection, so that the electrocatalytic oxidation technology has the remarkable advantages of high decontamination efficiency, strong sterilization and bacteriostasis activity, few byproducts, low toxic action, environmental friendliness, strong adaptability, simple operation, good controllability, easiness in realizing automatic control and the like, and has attracted wide attention in the field of water treatment in recent years.
Although electrocatalytic oxidation technology has many advantages and has shown attractive prospects in the field of water treatment and is considered as the water treatment technology with the most development prospect at present, the electrocatalytic oxidation technology is still in a laboratory stage, and for the reason, the existing electrocatalytic oxidation reactor has the defect that the existing electrocatalytic technology is low in electrocatalytic efficiency due to the fact that a single two-dimensional electrode without filler or a three-dimensional electrode with filler is adopted. The current electrocatalytic oxidation reactor is used for treating sewage and wastewater, so that the concentration of pollutants in discharged water is reduced, the standard discharge of the discharged water is ensured, and a large amount of electric energy is consumed.
Because the electricity consumption for realizing the industrial sewage treatment on a large scale is too high, if the electrocatalytic oxidation technology is applied to industrial production, common enterprises can not bear the electricity consumption, so that the efficiency of the sewage treatment of the existing electrocatalytic oxidation reactor is improved, the electricity consumption of the electrocatalytic oxidation reactor is reduced, and the hot spot and the difficulty of the research of the existing electrocatalytic oxidation reactor are formed.
Disclosure of Invention
The invention aims to provide an internal circulation type electrocatalytic oxidation reactor and a sewage purification treatment method, which are used for solving the problem of low sewage treatment efficiency of the existing electrocatalytic oxidation reactor.
In order to achieve the above purpose, the technical scheme of the invention is that an internal circulation type electrocatalytic oxidation reactor is provided, the internal circulation type electrocatalytic oxidation reactor comprises at least one circulation device, the circulation device comprises a circulation water tank, a water inlet pump and a reaction cabin, the circulation water tank is provided with a water inlet pipe, and the circulation water tank, the water inlet pump and the reaction cabin are communicated through pipelines;
the reaction chamber comprises an inner reaction chamber and an outer reaction chamber, wherein,
the inner reaction cabin is a cavity surrounded by an inner shell and a bottom plate arranged at the bottom of the inner shell, an inner cabin water inlet pipe is arranged at the bottom of the inner reaction cabin, and the inner cabin water inlet pipe is communicated with the water inlet pump through a pipeline; an inner electrode plate is arranged in the inner reaction chamber;
the outer reaction cabin is a cavity surrounded by an outer shell and a bottom plate arranged at the bottom of the outer shell, the bottom of the outer reaction cabin is communicated with the circulating water tank through a circulating water pipe, and the top of the outer reaction cabin is provided with a water outlet pipe; the inner reaction cabin is embedded in the outer reaction cabin, and a packing layer is arranged between the inner reaction cabin and the outer reaction cabin;
the inner layer shell is an inner layer electrode, the outer layer shell is an outer layer electrode, the polarities of the inner layer electrode plate and the electrode of the outer layer shell are the same, the polarities of the inner layer electrode plate and the electrode of the inner layer shell are different, a first electrocatalytic reaction area is formed between the inner layer electrode plate and the inner layer shell after the inner layer electrode plate and the inner layer shell are electrified, and a second electrocatalytic reaction area is formed between the outer layer shell and the inner layer shell after the inner layer shell is electrified.
Preferably, the inner electrode plate and the outer shell are cathodes, and the inner shell is an anode; the inner electrode plate comprises an inner cathode substrate plate and an inner cathode catalytic layer, and the inner cathode catalytic layer is coated on the front surface and the back surface of the inner cathode substrate; the inner layer shell comprises an anode substrate shell and an anode shell catalytic layer, and the anode shell catalytic layer is coated on the surface of the anode substrate shell; the outer shell comprises a cathode substrate shell and a cathode shell catalytic layer, and the cathode shell catalytic layer is coated on the surface of the inner layer of the cathode substrate shell.
Preferably, the anode casing catalytic layer is a layer of homogeneous graphene with the thickness of 1mm to 2 mm; the inner cathode catalytic layer and the cathode shell catalytic layer are both metal oxides plated with platinum, iridium, manganese, zinc or palladium.
Preferably, the bottom plates of the inner reaction chamber and the outer reaction chamber are all insulating plates, and the insulating plates are UPVC plates, PVC plates, PP plates or polytetrafluoroethylene plates.
Preferably, the packing layer is a honeycomb porous packing layer, the honeycomb porous packing layer is filled with spherical particles with the particle size of 2mm to 6mm, and the dielectric constant of the spherical particles is more than 100.
As another preferable technical scheme, the internal circulation type electrocatalytic oxidation reactor comprises more than two circulation devices, and a water outlet pipe of each front circulation device is communicated with a water inlet pipe of a rear circulation device.
The invention also discloses a sewage purification treatment method, which adopts the internal circulation type electrocatalytic oxidation reactor, and comprises the following steps:
step 1: sewage flows into the circulating water tank from the water inlet pipe, and is mixed and homogenized in the circulating water tank;
step 2: the mixed and homogenized sewage is pumped into an inner cabin water inlet pipe by a water inlet pump;
step 3: the sewage flows into the inner reaction cabin through the inner cabin water inlet pipe, the inner electrode plate is used as a cathode, the inner shell is used as an anode, a first electrocatalytic reaction zone is formed between the inner electrode plate and the inner shell after the cathode and the anode are electrified, and the sewage is subjected to electrocatalytic action of the first electrocatalytic reaction zone, so that refractory organic matters in the sewage are primarily treated;
step 4: the sewage continues to rise until the sewage overflows the inner reaction cabin and flows into the outer reaction cabin, the inner shell is used as an anode, the outer shell is used as a cathode, and a second electrocatalytic reaction zone is formed between the outer shell and the inner shell after the cathode and the anode are electrified;
step 5: macromolecular organic matters in the sewage are enriched in the filler layer, and the ring chain of the organic matters which are difficult to degrade in the sewage is further opened under the cracking ring-opening electrocatalytic effect of the second electrocatalytic reaction zone;
step 6: the sewage flow in the outer reaction cabin penetrates through the whole packing layer and flows from high to low to the bottom of the outer reaction cabin;
step 7: sewage at the bottom of the outer reaction cabin flows into the circulating water tank again through the circulating water pipe to form sewage circulation in a circulating device;
step 8: repeating the steps 2 to 7, and repeating the sewage circulation in the circulation device until the sewage flows to the water outlet pipe of the outer reaction cabin, and overflowing and discharging supernatant water from the top of the reaction cabin through the water outlet pipe;
step 9: detecting the pollutant content in the sewage flowing out of the water outlet pipe of the circulating device, and if the pollutant content does not reach the standard yet, continuing to flow the sewage into the water inlet pipe of the rear circulating device;
step 10: and (5) repeating the steps 1 to 9 until the pollutant content in the sewage reaches the standard.
Preferably, during the steps 2 to 7, the reflux ratio of the sewage circulation in the circulation device is controlled between 3:1 and 5:1, and the residence time of the sewage in the internal circulation type electrocatalytic oxidation reactor is controlled between 0.5h and 1h.
The invention has the following advantages:
(1) The invention relates to a sewage purification treatment method using an internal circulation type electrocatalytic oxidation reactor, which adopts the internal circulation type electrocatalytic oxidation reactor for sewage purification treatment: after the sewage enters the circulating water tank for homogenization, the sewage is pumped to an inner cabin water inlet pipe in the reaction cabin through a water inlet pump of the inner cabin, flows into the inner reaction cabin through a water inlet pipe of the inner cabin, takes an inner electrode plate as a cathode, takes an inner shell as an inner electrode, forms a first electrocatalytic reaction zone of a two-dimensional electrode without a filler layer between the inner electrode plate and the inner shell after the cathode and the anode are electrified, and obtains primary treatment on refractory organic matters in the sewage through the electrocatalytic effect of the first electrocatalytic reaction zone. The sewage is treated by electrocatalytic treatment and continuously rises, and after the sewage overflows the inner reaction cabin, the sewage slowly enters the outer reaction cabin. The cellular porous structure of the packing layer increases the contact area with sewage, facilitates the enrichment of macromolecular organic matters in the packing layer, and simultaneously, after the outer shell and the inner shell are electrified, a second electrocatalytic reaction zone of a three-dimensional electrode of the packing layer is formed between the outer shell and the inner shell, the organic macromolecules in the sewage are enriched in the packing layer to crack and open loop electrocatalytic effect, a loop chain of refractory organic matters in the sewage is further opened, most of sewage flows into a circulating water tank through a circulating water pipe to form an internal circulation loop, and supernatant water is overflowed from the top of a reaction cabin through a water outlet pipe to be discharged. Detecting the pollutant content in the liquid flowing out of the water outlet pipe, if the pollutant content does not reach the standard, flowing into the second circulating device again, detecting the water flowing out of the water outlet pipe in the second circulating device again after the circulating, and flowing into the third circulating device again if the pollutant content does not reach the standard, until the pollutant content reaches the standard, and discharging directly. The sewage purification treatment method not only realizes the repeated circulation purification of sewage in the circulating device, but also realizes the multistage external circulation purification of sewage outside the circulating device, greatly improves the sewage purification capability of the internal circulation type electrocatalytic oxidation reactor, reduces the concentration of pollutants in discharged water, and ensures the standard discharge of the discharged water.
(2) The invention relates to an internal circulation type electrocatalytic oxidation reactor, which is different from the existing electrocatalytic technology in designing a single two-dimensional electrode without filler or a three-dimensional electrode with filler.
(3) The internal circulation type electrocatalytic oxidation reactor disclosed by the invention has the advantages that the packing layer is designed into a honeycomb porous structure, the contact area with sewage is increased, macromolecular organic matters in the sewage are enriched in the packing layer, and in the second electrocatalytic reaction zone, the ring-opening electrocatalytic effect is realized by the cracking of the organic macromolecules enriched in the packing layer in the sewage, so that the ring chain of the organic matters which are difficult to degrade in the sewage is further opened, and the sewage purifying capacity and efficiency of the internal circulation type electrocatalytic oxidation reactor are further improved.
(4) The internal circulation type electrocatalytic oxidation reactor has reasonable design and strong practicability, improves the electrocatalytic efficiency of the electrocatalytic oxidation reactor, and realizes the efficient utilization of electric energy; the use method of the internal circulation type electrocatalytic oxidation reactor is used for purifying sewage, has strong sewage purifying capacity and good effect, and solves the problems of hot spots and difficulties of the current electrocatalytic oxidation applied to sewage treatment research.
Drawings
Fig. 1 is a schematic structural view of an internal circulation type electrocatalytic oxidation reactor provided in example 1.
Fig. 2 is a schematic structural view of the internal circulation type electrocatalytic oxidation reactor provided in example 2.
Fig. 3 is a schematic structural view of the internal circulation type electrocatalytic oxidation reactor provided in example 3.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
Example 1
This embodiment 1 provides an internal circulation type electrocatalytic oxidation reactor, and the structure of the internal circulation type electrocatalytic oxidation reactor provided in this embodiment 1 is described in detail below.
Referring to fig. 1, the internal circulation type electrocatalytic oxidation reactor comprises a circulation device, wherein the circulation device comprises a circulation water tank 2, a water inlet pump 3 and a reaction chamber 100, the circulation water tank 2 is provided with a water inlet pipe 1, and the circulation water tank 2, the water inlet pump 3 and the reaction chamber 100 are communicated through pipelines.
The reaction chamber 100 comprises an inner reaction chamber 11 and an outer reaction chamber 12, wherein the inner reaction chamber 11 is a cavity surrounded by an inner layer shell 6 and a bottom plate arranged at the bottom of the inner layer shell 6, an inner chamber water inlet pipe 4 is arranged at the bottom of the inner reaction chamber 11, the inner chamber water inlet pipe 4 is communicated with a water inlet pump 3 through a pipeline, and an inner layer electrode plate 5 is arranged inside the inner reaction chamber 11; the outer reaction chamber 12 is a cavity surrounded by the outer shell 8 and a bottom plate arranged at the bottom of the outer shell 8, the bottom of the outer reaction chamber 12 is communicated with the circulating water tank 2 through a circulating water pipe 9, the top of the outer reaction chamber 12 is provided with a water outlet pipe 10, the inner reaction chamber 11 is embedded in the outer reaction chamber 12, and a packing layer 7 is arranged between the inner reaction chamber 11 and the outer reaction chamber 12.
Further, the inner layer shell 6 is used as an anode, the outer layer shell 8 and the inner layer electrode plate 5 are used as cathodes, and after the cathodes and the anodes are electrified, a second electrocatalytic reaction zone is formed between the outer layer shell 8 and the inner layer shell 6, and a second electrocatalytic reaction zone is formed between the inner layer electrode plate 5 and the inner layer shell 6. The invention combines the two-dimensional electrode without filler and the three-dimensional electrode with filler, utilizes the characteristic that the three-dimensional electrode can effectively open a loop and break a chain by the circulating action of the two-dimensional electrode and the three-dimensional electrode in the circulating device, plays the characteristic of high energy efficiency of the two-dimensional electrode, realizes the degradation of pollutants together, and improves the electrocatalytic efficiency of the electrocatalytic oxidation reactor.
As a specific embodiment, the inner electrode plate 5 includes an inner cathode substrate plate and an inner cathode catalytic layer, and the inner cathode catalytic layer is coated on both the front and back surfaces of the inner cathode substrate. The outer shell 8 includes a cathode substrate shell and a cathode shell catalytic layer coated on the inner surface of the cathode substrate shell. The inner cathode base material and the shell cathode base material are made of graphite, and the inner cathode catalytic layer and the cathode shell catalytic layer are both made of a layer of metal oxide plated with platinum, iridium, manganese, zinc or palladium. The inner layer casing 6 includes an anode base material casing and an anode casing catalytic layer coated on both the front and outer surfaces of the anode base material casing. The anode shell base material is graphite, titanium, copper or iron, and the anode shell catalytic layer is a layer of homogeneous graphene with the thickness of 1-2 mm. The inner electrode plate 5, the outer shell 8 and the inner shell 6 are used as base materials, and a catalytic layer is smeared on the surface of the base materials, so that the dielectric constant is increased, and the current efficiency of the electrolytic cell is improved.
As a specific implementation mode, the bottom plates of the inner reaction chamber 11 and the outer reaction chamber 12 are all insulating plates, and the insulating plates are UPVC plates, PVC plates, PP plates or polytetrafluoroethylene plates. Since the peripheral walls of the inner and outer reaction tanks 11 and 12 have been used as electrodes, the bottom plates of the inner and outer reaction tanks 11 and 12 are designed as insulating plates in order to ensure the electrolytic effect of the electrolytic cell formed between the two inner and outer annular case electrodes.
As a specific embodiment, the packing layer 7 is a honeycomb porous packing layer, and the honeycomb porous packing layer is filled with filling particles in a spherical, cubic or elliptic shape, and the dielectric constant of the filling particle material is greater than 100. The packing layer 7 is designed into a honeycomb porous structure, the adjustable characteristic of the porous structure is effectively utilized, the contact area with sewage is increased, macromolecular organic matters are enriched in the packing layer, the concentration of the macromolecular organic matters in the sewage is improved, the electrocatalytic reaction rate can be accelerated, the ring chain of the organic compounds difficult to degrade can be opened, the circulating sewage in the second electrocatalytic reaction zone is further oxidized and degraded, the cracking and ring-opening functions of the second electrocatalytic reaction zone are greatly enhanced, the sewage is clean and thorough by utilization, and the homogenized and clean water is finally obtained.
Preferably, the filler particles are spherical particles having a particle size between 2mm and 6 mm. The spherical particles can make contact among particles in the filler layer 7 more uniform, and the particle size is between 2mm and 6mm, so as to ensure that macromolecular organic matters in sewage can be more effectively enriched in the filler layer.
Example 2
This example 2 provides an internal circulation type electrocatalytic oxidation reactor, and the structure of the internal circulation type electrocatalytic oxidation reactor provided in this example 2 is described in detail below.
Referring to fig. 2, the internal circulation type electrocatalytic oxidation reactor comprises two circulation devices which are sequentially arranged into a front circulation device and a rear circulation device according to the sequence of the first circulation device and the second circulation device, each circulation device comprises a circulation water tank 2, a water inlet pump 3 and a reaction chamber 100, the circulation water tank 2 is provided with a water inlet pipe 1, and the circulation water tank 2, the water inlet pump 3 and the reaction chamber 100 are communicated through pipelines.
The reaction chamber 100 comprises an inner reaction chamber 11 and an outer reaction chamber 12, wherein the inner reaction chamber 11 is a cavity surrounded by an inner layer shell 6 and a bottom plate arranged at the bottom of the inner layer shell 6, an inner chamber water inlet pipe 4 is arranged at the bottom of the inner reaction chamber 11, the inner chamber water inlet pipe 4 is communicated with a water inlet pump 3 through a pipeline, and an inner layer electrode plate 5 is arranged inside the inner reaction chamber 11; the outer reaction chamber 12 is a cavity surrounded by the outer shell 8 and a bottom plate arranged at the bottom of the outer shell 8, the bottom of the outer reaction chamber 12 is communicated with the circulating water tank 2 through a circulating water pipe 9, the top of the outer reaction chamber 12 is provided with a water outlet pipe 10, the inner reaction chamber 11 is embedded in the outer reaction chamber 12, and a packing layer 7 is arranged between the inner reaction chamber 11 and the outer reaction chamber 12.
Further, the inner layer shell 6 is used as an anode, the outer layer shell 8 and the inner layer electrode plate 5 are used as cathodes, and after the cathodes and the anodes are electrified, a second electrocatalytic reaction zone is formed between the outer layer shell 8 and the inner layer shell 6, and a second electrocatalytic reaction zone is formed between the inner layer electrode plate 5 and the inner layer shell 6. The invention combines the two-dimensional electrode without filler and the three-dimensional electrode with filler, utilizes the characteristic that the three-dimensional electrode can effectively open a loop and break a chain by the circulating action of the two-dimensional electrode and the three-dimensional electrode in the circulating device, plays the characteristic of high energy efficiency of the two-dimensional electrode, realizes the degradation of pollutants together, and improves the electrocatalytic efficiency of the electrocatalytic oxidation reactor.
As a specific embodiment, the inner electrode plate 5 includes an inner cathode substrate plate and an inner cathode catalytic layer, and the inner cathode catalytic layer is coated on both the front and back surfaces of the inner cathode substrate. The outer shell 8 includes a cathode substrate shell and a cathode shell catalytic layer coated on the inner surface of the cathode substrate shell. The inner cathode base material and the shell cathode base material are made of graphite, and the inner cathode catalytic layer and the cathode shell catalytic layer are both made of a layer of metal oxide plated with platinum, iridium, manganese, zinc or palladium. The inner layer casing 6 includes an anode base material casing and an anode casing catalytic layer coated on both the front and outer surfaces of the anode base material casing. The anode shell base material is graphite, titanium, copper or iron, and the anode shell catalytic layer is a layer of homogeneous graphene with the thickness of 1-2 mm. The inner electrode plate 5, the outer shell 8 and the inner shell 6 are used as base materials, and a catalytic layer is smeared on the surface of the base materials, so that the dielectric constant is increased, and the current efficiency of the electrolytic cell is improved.
As a specific implementation mode, the bottom plates of the inner reaction chamber 11 and the outer reaction chamber 12 are all insulating plates, and the insulating plates are UPVC plates, PVC plates, PP plates or polytetrafluoroethylene plates. Since the peripheral walls of the inner and outer reaction tanks 11 and 12 have been used as electrodes, the bottom plates of the inner and outer reaction tanks 11 and 12 are designed as insulating plates in order to ensure the electrolytic effect of the electrolytic cell formed between the two inner and outer annular case electrodes.
As a specific embodiment, the packing layer 7 is a honeycomb porous packing layer, and the honeycomb porous packing layer is filled with filling particles in a spherical, cubic or elliptic shape, and the dielectric constant of the filling particle material is greater than 100. The packing layer 7 is designed into a honeycomb porous structure, the adjustable characteristic of the porous structure is effectively utilized, the contact area with sewage is increased, macromolecular organic matters are enriched in the packing layer, the concentration of the macromolecular organic matters in the sewage is improved, the electrocatalytic reaction rate can be accelerated, the ring chain of the organic compounds difficult to degrade can be opened, the circulating sewage in the second electrocatalytic reaction zone is further oxidized and degraded, the cracking and ring-opening functions of the second electrocatalytic reaction zone are greatly enhanced, the sewage is clean and thorough by utilization, and the homogenized and clean water is finally obtained.
Preferably, the filler particles are spherical particles having a particle size between 2mm and 6 mm. Spherical particles can make contact among particles in the packing layer 7 more uniform, and the particle size between 2mm and 6mm is used for ensuring that macromolecular organic matters in sewage can be more effectively enriched in the packing layer.
Further, the water outlet pipe 10 of the front circulation device is communicated with the water inlet pipe 1 of the rear circulation device. And the pollutant content in the sewage flowing out of the water outlet pipe 10 of the front circulating device is detected, if the sewage does not reach the standard yet, the sewage continuously flows into the water inlet pipe 1 of the rear circulating device to carry out secondary circulating sewage purification treatment, so that the sewage purification capacity of the internal circulating type electrocatalytic oxidation reactor is improved, and the concentration of pollutants in the discharged water is reduced.
Example 3
This embodiment 3 provides an internal circulation type electrocatalytic oxidation reactor, and the structure of the internal circulation type electrocatalytic oxidation reactor provided in this embodiment 3 is described in detail below.
Referring to fig. 3, the internal circulation type electrocatalytic oxidation reactor comprises more than two circulation devices which are sequentially arranged in the order of a first circulation device, a second circulation device, a … … circulation device and an nth circulation device, each circulation device comprises a circulation water tank 2, a water inlet pump 3 and a reaction chamber 100, the circulation water tank 2 is provided with a water inlet pipe 1, and the circulation water tank 2, the water inlet pump 3 and the reaction chamber 100 are communicated through pipelines.
The reaction chamber 100 comprises an inner reaction chamber 11 and an outer reaction chamber 12, wherein the inner reaction chamber 11 is a cavity surrounded by an inner layer shell 6 and a bottom plate arranged at the bottom of the inner layer shell 6, an inner chamber water inlet pipe 4 is arranged at the bottom of the inner reaction chamber 11, the inner chamber water inlet pipe 4 is communicated with a water inlet pump 3 through a pipeline, and an inner layer electrode plate 5 is arranged inside the inner reaction chamber 11; the outer reaction chamber 12 is a cavity surrounded by the outer shell 8 and a bottom plate arranged at the bottom of the outer shell 8, the bottom of the outer reaction chamber 12 is communicated with the circulating water tank 2 through a circulating water pipe 9, the top of the outer reaction chamber 12 is provided with a water outlet pipe 10, the inner reaction chamber 11 is embedded in the outer reaction chamber 12, and a packing layer 7 is arranged between the inner reaction chamber 11 and the outer reaction chamber 12.
Further, the inner layer shell 6 is used as an anode, the outer layer shell 8 and the inner layer electrode plate 5 are used as cathodes, and after the cathodes and the anodes are electrified, a second electrocatalytic reaction zone is formed between the outer layer shell 8 and the inner layer shell 6, and a second electrocatalytic reaction zone is formed between the inner layer electrode plate 5 and the inner layer shell 6. The invention combines the two-dimensional electrode without filler and the three-dimensional electrode with filler, utilizes the characteristic that the three-dimensional electrode can effectively open a loop and break a chain by the circulating action of the two-dimensional electrode and the three-dimensional electrode in the circulating device, plays the characteristic of high energy efficiency of the two-dimensional electrode, realizes the degradation of pollutants together, and improves the electrocatalytic efficiency of the electrocatalytic oxidation reactor.
As a specific embodiment, the inner electrode plate 5 includes an inner cathode substrate plate and an inner cathode catalytic layer, and the inner cathode catalytic layer is coated on both the front and back surfaces of the inner cathode substrate. The outer shell 8 includes a cathode substrate shell and a cathode shell catalytic layer coated on the inner surface of the cathode substrate shell. The inner cathode base material and the shell cathode base material are made of graphite, and the inner cathode catalytic layer and the cathode shell catalytic layer are both made of a layer of metal oxide plated with platinum, iridium, manganese, zinc or palladium. The inner layer casing 6 includes an anode base material casing and an anode casing catalytic layer coated on both the front and outer surfaces of the anode base material casing. The anode shell base material is graphite, titanium, copper or iron, and the anode shell catalytic layer is a layer of homogeneous graphene with the thickness of 1-2 mm. The inner electrode plate 5, the outer shell 8 and the inner shell 6 are used as base materials, and a catalytic layer is smeared on the surface of the base materials, so that the dielectric constant is increased, and the current efficiency of the electrolytic cell is improved.
As a specific implementation mode, the bottom plates of the inner reaction chamber 11 and the outer reaction chamber 12 are all insulating plates, and the insulating plates are UPVC plates, PVC plates, PP plates or polytetrafluoroethylene plates. Since the peripheral walls of the inner and outer reaction tanks 11 and 12 have been used as electrodes, the bottom plates of the inner and outer reaction tanks 11 and 12 are designed as insulating plates in order to ensure the electrolytic effect of the electrolytic cell formed between the two inner and outer annular case electrodes.
As a specific embodiment, the packing layer 7 is a honeycomb porous packing layer, and the honeycomb porous packing layer is filled with filling particles in a spherical, cubic or elliptic shape, and the dielectric constant of the filling particle material is greater than 100. The packing layer 7 is designed into a honeycomb porous structure, the adjustable characteristic of the porous structure is effectively utilized, the contact area with sewage is increased, macromolecular organic matters are enriched in the packing layer, the concentration of the macromolecular organic matters in the sewage is improved, the electrocatalytic reaction rate can be accelerated, the ring chain of the organic compounds difficult to degrade can be opened, the circulating sewage in the second electrocatalytic reaction zone is further oxidized and degraded, the cracking and ring-opening functions of the second electrocatalytic reaction zone are greatly enhanced, the sewage is clean and thorough by utilization, and the homogenized and clean water is finally obtained.
Preferably, the filler particles are spherical particles having a particle size between 2mm and 6 mm. The spherical particles can make contact among particles in the filler layer 7 more uniform, and the particle size is between 2mm and 6mm, so as to ensure that macromolecular organic matters in sewage can be more effectively enriched in the filler layer.
Further, among these multiple circulation devices, the water outlet pipe 10 of each of the front circulation devices is communicated with the water inlet pipe 1 of the rear circulation device. The sewage treatment device is provided with a plurality of circulating devices, realizes the multistage treatment of the internal circulation purification of the sewage circulating devices, greatly improves the sewage purification capacity of the internal circulation type electrocatalytic oxidation reactor, can obviously reduce the concentration of pollutants in discharged water, and fully ensures the standard discharge of the discharged water.
Example 4
Embodiment 4 provides a sewage purification treatment method, which adopts the internal circulation type electrocatalytic oxidation reactor provided in embodiment 3, and the sewage purification treatment method comprises the following steps:
step 1: sewage flows into the circulating water tank 2 from the water inlet pipe 1, and is mixed and homogenized in the circulating water tank 2;
step 2: the sewage with homogeneous mixture is pumped into an inner cabin water inlet pipe 4 through a water inlet pump 3;
step 3: sewage flows into the inner reaction chamber 11 through the inner chamber water inlet pipe 4, the inner electrode plate 5 is used as a cathode, the inner layer shell 6 is used as an anode, a first electrocatalytic reaction zone is formed between the inner electrode plate 5 and the inner layer shell 6 after the cathode and the anode are electrified, and the sewage is subjected to the electrocatalytic action of the first electrocatalytic reaction zone, so that refractory organic matters in the sewage are primarily treated;
step 4: the sewage continues to rise until the sewage overflows the inner reaction chamber 11 and flows into the outer reaction chamber 12, the inner shell 6 is used as an anode, the outer shell 8 is used as a cathode, and a second electrocatalytic reaction zone is formed between the outer shell 8 and the inner shell 6 after the cathode and the anode are electrified;
step 5: macromolecular organic matters in the sewage are enriched in the packing layer 7, and the ring chain of the organic matters which are difficult to degrade in the sewage is further opened under the cracking ring-opening electrocatalytic effect of the second electrocatalytic reaction zone;
step 6: the sewage flow in the outer reaction chamber 12 passes through the whole packing layer 7 and flows from high to low to the bottom of the outer reaction chamber 12;
step 7: sewage at the bottom of the outer reaction cabin 12 flows into the circulating water tank 2 again through the circulating water pipe 9 to form sewage circulation in a circulating device;
step 8: repeating the steps 2 to 7, and repeating the sewage circulation in the circulation device until the sewage flows to the water outlet pipe 10 of the outer reaction chamber 12, and overflowing and discharging supernatant water from the top of the reaction chamber 100 through the water outlet pipe 10;
step 9: detecting the pollutant content in the sewage flowing out of the water outlet pipe 10 of the circulating device, and if the pollutant content does not reach the standard yet, continuing to flow the sewage into the water inlet pipe 1 of the rear circulating device;
step 10: and (5) repeating the steps 1 to 9 until the pollutant content in the sewage reaches the standard.
As a preferred embodiment, during steps 2 to 7, the reflux ratio of the sewage circulation in the circulation device is controlled between 3:1 and 5:1, and the residence time of the sewage in the internal circulation type electrocatalytic oxidation reactor is controlled between 0.5h and 1h.
The sewage purification treatment method comprises multiple circulation purification in the circulating device and multiple-stage purification outside the circulating device, so that the multiple circulation purification of sewage in the circulating device is realized, the multiple-stage external circulation purification of sewage outside the circulating device is realized, the sewage purification capacity of the internal circulation type electrocatalytic oxidation reactor is greatly improved, the concentration of pollutants in discharged water is reduced, and the standard discharge of the discharged water is ensured.
While the invention has been described in detail in the foregoing general description and specific examples, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims (5)

1. The internal circulation type electrocatalytic oxidation reactor is characterized by comprising more than two circulation devices, wherein each circulation device comprises a circulation water tank (2), a water inlet pump (3) and a reaction cabin (100), the circulation water tank (2) is provided with a water inlet pipe (1), and the circulation water tank (2), the water inlet pump (3) and the reaction cabin (100) are communicated through pipelines;
the reaction chamber (100) comprises an inner reaction chamber (11) and an outer reaction chamber (12), wherein,
the inner reaction chamber (11) is a cavity surrounded by an inner layer shell (6) and a bottom plate arranged at the bottom of the inner layer shell (6), an inner chamber water inlet pipe (4) is arranged at the bottom of the inner reaction chamber (11), and the inner chamber water inlet pipe (4) is communicated with the water inlet pump (3) through a pipeline; an inner electrode plate (5) is arranged in the inner reaction chamber (11);
the outer reaction cabin (12) is a cavity surrounded by an outer shell (8) and a bottom plate arranged at the bottom of the outer shell (8), the bottom of the outer reaction cabin (12) is communicated with the circulating water tank (2) through a circulating water pipe (9), and a water outlet pipe (10) is arranged at the top of the outer reaction cabin (12); the inner reaction cabin (11) is embedded in the outer reaction cabin (12), and a packing layer (7) is arranged between the inner reaction cabin (11) and the outer reaction cabin (12);
the inner layer shell (6) is an inner layer electrode, the outer layer shell (8) is an outer layer electrode, the polarity of the inner layer electrode plate (5) is the same as that of the outer layer shell (8), the polarity of the inner layer electrode plate (5) is different from that of the inner layer shell (6), a first electrocatalytic reaction area is formed between the inner layer electrode plate (5) and the inner layer shell (6) after electrification, and a second electrocatalytic reaction area is formed between the outer layer shell (8) and the inner layer shell (6) after electrification;
the inner electrode plate (5) and the outer shell (8) are cathodes, and the inner shell (6) is an anode;
the inner electrode plate (5) comprises an inner cathode substrate plate and an inner cathode catalytic layer, and the inner cathode catalytic layer is coated on the front surface and the back surface of the inner cathode substrate;
the inner layer shell (6) comprises an anode substrate shell and an anode shell catalytic layer, and the anode shell catalytic layer is coated on the front surface and the outer surface of the anode substrate shell;
the outer shell (8) comprises a cathode substrate shell and a cathode shell catalytic layer, and the cathode shell catalytic layer is coated on the inner layer surface of the cathode substrate shell;
the anode shell catalytic layer is a layer of homogeneous graphene with the thickness of 1mm to 2 mm; the inner cathode catalytic layer and the cathode shell catalytic layer are both a layer of metal oxide plated with platinum, iridium, manganese, zinc or palladium;
the water outlet pipe (10) of each front circulating device is communicated with the water inlet pipe (1) of the rear circulating device.
2. The internal circulation type electrocatalytic oxidation reactor as claimed in claim 1, wherein the bottom plates of the inner reaction chamber (11) and the outer reaction chamber (12) are both insulating plates, and the insulating plates are UPVC plates, PVC plates, PP plates or polytetrafluoroethylene plates.
3. The internal circulation type electrocatalytic oxidation reactor as claimed in claim 1, wherein the packing layer (7) is a honeycomb porous packing layer, the honeycomb porous packing layer is filled with spherical particles with the particle size of 2mm to 6mm, and the dielectric constant of the spherical particles is more than 100.
4. A sewage purification treatment method adopting the internal circulation type electrocatalytic oxidation reactor as set forth in claim 1, characterized in that the sewage purification treatment method comprises the steps of:
step 1: sewage flows into the circulating water tank (2) from the water inlet pipe (1), and is mixed and homogenized in the circulating water tank (2);
step 2: the sewage with homogeneous mixture is pumped into an inner cabin water inlet pipe (4) through a water inlet pump (3);
step 3: sewage flows into an inner reaction cabin (11) through an inner cabin water inlet pipe (4), an inner electrode plate (5) is used as a cathode, an inner shell (6) is used as an anode, a first electrocatalytic reaction zone is formed between the inner electrode plate (5) and the inner shell (6) after the cathode and the anode are electrified, and the sewage is subjected to electrocatalytic action of the first electrocatalytic reaction zone, so that refractory organic matters in the sewage are primarily treated;
step 4: the sewage continues to rise until the sewage overflows the inner reaction cabin (11) and flows into the outer reaction cabin (12), the inner shell (6) is used as an anode, the outer shell (8) is used as a cathode, and a second electrocatalytic reaction zone is formed between the outer shell (8) and the inner shell (6) after the cathode and the anode are electrified;
step 5: macromolecular organic matters in the sewage are enriched in the packing layer (7), and the ring chain of the organic matters which are difficult to degrade in the sewage is further opened under the cracking ring-opening electrocatalytic effect of the second electrocatalytic reaction zone;
step 6: the sewage flow in the outer reaction cabin (12) passes through the whole packing layer (7) and flows from high to low to the bottom of the outer reaction cabin (12);
step 7: sewage at the bottom of the outer reaction cabin (12) flows into the circulating water tank (2) again through the circulating water pipe (9) to form sewage circulation in a circulating device;
step 8: repeating the steps 2 to 7, and repeating the sewage circulation in the circulation device until the sewage flows to the water outlet pipe (10) of the outer reaction cabin (12), and overflowing and discharging supernatant water from the top of the reaction cabin (100) through the water outlet pipe (10);
step 9: detecting the pollutant content in the sewage flowing out of a water outlet pipe (10) of the circulating device, and if the pollutant content does not reach the standard yet, continuing to flow the sewage into a water inlet pipe (1) of the rear circulating device;
step 10: and (5) repeating the steps 1 to 9 until the pollutant content in the sewage reaches the standard.
5. The wastewater purification treatment method according to claim 4, wherein a reflux ratio of wastewater circulation in the circulation device is controlled to be 3:1 to 5:1 and a residence time of wastewater in the internal circulation type electrocatalytic oxidation reactor is controlled to be 0.5h to 1h during the steps 2 to 7.
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