CN114797457A - Electrochemical-multiphase ozone catalysis system and method for gas-water cooperative treatment - Google Patents
Electrochemical-multiphase ozone catalysis system and method for gas-water cooperative treatment Download PDFInfo
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Abstract
The invention provides an electrochemical-multiphase ozone catalysis system and method for gas-water cooperative treatment. The system consists of an oxygen generator, an ozone generator, a gas-water cooperative treatment device and an oxygen recycling device. The gas-water cooperative treatment device is formed by sequentially connecting three-stage electrochemical-ozone catalytic reactors in series. The oxygen recovery device consists of an electrochemical system filled with a hydrophobic carbon particulate filler. The invention can realize the high-efficiency treatment of the organic matters difficult to degrade by constructing the gas-water co-treatment device, simultaneously, the ozone tail gas is completely utilized and treated in a co-operation way, and the most oxygen is recovered by the oxygen recovery deviceHigh efficiency conversion of end oxygen tail gas into H 2 O 2 Recycled to the water inlet end to realize the ozone/H at the water inlet end 2 O 2 High-efficiency homogeneous catalysis, water inlet load reduction and system decontamination performance improvement. Finally, the invention efficiently solves the problems of ozone tail gas emission, secondary pollution, oxygen waste and unbalanced wastewater-ozone supply and demand in the traditional ozone catalysis process.
Description
Technical Field
The invention relates to the fields of sewage treatment and waste gas treatment, in particular to an electrochemical-multiphase ozone catalytic system and method for gas-water cooperative treatment.
Background
Ozone is widely applied in the fields of industrial wastewater and the like by virtue of the characteristics of high-efficiency oxidation property, no drug residue and the like. However, the existing ozone water treatment methods have the key problems of low ozone gas utilization rate, a large amount of ozone tail gas and the like in the practical application process, on one hand, the oxidation potential of ozone is wasted, and the sustainable development capability of the ozone water treatment technology is reduced. For ozone tail gas generated in the ozone water treatment process, the existing treatment method mainly comprises the steps of adding an ozone quenching device, converting ozone into oxygen through a catalytic filler loaded by a metal oxide, and finally discharging the oxygen into the atmosphere. Although the method can realize high-efficiency tail gas treatment, the method still belongs to a typical terminal treatment mode, ozone tail gas is treated as waste gas, a large amount of catalysts are consumed in the process, and meanwhile, the oxidation potential in ozone is converted into heat energy (exothermic reaction) to cause great waste. More importantly, the ozone gas usually contains more than 95% of pure oxygen, and even after the ozone tail gas is treated by the quenching agent, a large amount of pure oxygen is further wasted and is directly discharged into the atmosphere. In addition, ozone is generally added in an excessive manner in the ozone water treatment process, and even when the pollutant concentration is very low in the later stage of the reaction, the positive correlation does not exist between the ozone concentration and the pollutant concentration, so that the ozone resource waste is caused; meanwhile, toxic byproducts such as bromate and the like are easily generated due to overhigh ozone exposure in a liquid phase at the later stage of the reaction, so that gradient addition of ozone from high to low is realized along with gradual reduction of organic pollutants, a gas addition mode conforming to a pollutant degradation rule is established, and the ozone water treatment method has important significance for ozone water treatment and application.
In response to the above problems, CN113792260A proposes a mode of recycling exhaust gas, in which oxygen in the exhaust gas is recycled to the air inlet end of the ozone generator through an ozone quenching device. However, in the prior art, on one hand, the ozone is quenched to waste the oxidation potential, and the ozone tail gas treatment is not efficiently cooperated with the wastewater treatment. Although the patent CN106335998B previously granted by the applicant proposes an electrochemical-multiphase ozone catalytic system based on a porous titanium aeration electrode, the problem of ozone tail gas discharged by the system, the problem of balancing of wastewater advanced treatment and ozone supply and demand, are not effectively solved. More importantly, the electrochemical-ozone catalytic reactor can utilize the carbon-coated cathode to reduce the oxygen in the ozone/oxygen mixed gas in situ to generate H 2 O 2 The catalyst is used for catalyzing ozone in situ to generate active oxygen substances, but a large amount of oxygen in tail gas is not completely recycled, so that oxygen resource waste is caused.
Disclosure of Invention
The embodiment of the invention provides an electrochemical-multiphase ozone catalysis system and method for gas-water cooperative treatment, which are used for establishing a set of ozone-based gas-water cooperative sustainable treatment system.
In order to achieve the purpose, the invention adopts the following technical scheme.
According to one aspect of the invention, an electrochemical-multiphase ozone catalytic device based on gas-water cooperative treatment is provided, which comprises: the device comprises an oxygen generator, an ozone generator, a gas-water cooperative treatment device, an oxygen recycling device, a water pump and a three-way pipeline, wherein the ozone generator is communicated with an ozone gas distribution device of a first-stage electrochemical-ozone catalytic reactor of the gas-water cooperative treatment device, the water pump is communicated with a liquid transfer device between the electrochemical-ozone catalytic reactors of the gas-water cooperative treatment device, the three-way pipeline is connected with the tail end of a third-stage electrochemical-ozone catalytic reactor of the gas-water cooperative treatment device, one part of water is directly discharged, and the other part of water is communicated into the oxygen recycling device through the water pump.
In a preferred embodiment, the ozone generating system further comprises an oxygen generator for generating oxygen, an ozone generator for generating ozone, a rotameter for adjusting the flow rate of the ozone intake air, and an ozone detector for detecting the concentration of ozone; the devices are connected in sequence and arranged in front of a first-stage electrochemical-ozone catalytic reactor of the gas-water cooperative treatment device.
In a preferred embodiment, the gas-water cooperative treatment device comprises a cavity, a carbon-coated titanium mesh cathode and a porous titanium aeration anode.
In a preferred embodiment, the bottom of the cavity of the gas-water cooperative processing device is provided with an air inlet, the lower part of the side wall of the cavity is provided with a water inlet, the top of the cavity is provided with an air outlet, and the upper part of the side wall of the cavity is provided with a water outlet.
In a preferred embodiment, the gas-water co-processing electrochemical-multiphase ozone catalytic device is characterized in that one to three stages of gas-water co-processing devices are established, each stage is provided with a constant current, and a current gradient is established in stages.
In a preferred embodiment, the oxygen recycling device comprises means for establishing oxygen recycling with H 2 O 2 And (5) preparing the device.
In a preferred embodiment, the gas-water co-processing device is a carbon-coated titanium mesh cathode which mainly comprises a titanium mesh and a carbon coating, wherein the carbon coating comprises: one or more of carbon black, graphite powder, carbon nano tubes and graphene.
In a preferred embodiment, the gas-water cooperative treatment device is characterized in that the porous titanium aeration anode consists of a porous titanium substrate and TiO 2 The oxide intermediate layer and the catalyst layer of one or more metal oxide compounds of Sn, Ir, Ru, Zn, Mn, Fe and Ce.
In a preferred embodiment, the hydrophobic carbon particle filler is a granular filler which is prepared by mixing, pressing, granulating and sintering polytetrafluoroethylene and carbon black at 250-350 ℃, and the particle size is 5-50 mm.
According to another aspect of the invention, a treatment method related to an electrochemical-ozone catalytic reaction system using the gas-water co-treatment is provided, and comprises the following steps:
air generates pure oxygen through an oxygen generator (1), the pure oxygen enters an ozone generator (2) to generate ozone/oxygen mixed gas, the mixed gas enters a first-stage electrochemical-ozone catalytic reactor of the air-water cooperative treatment device (3) through a porous titanium aeration anode (9), and mixed gas tail gas is introduced into a second-stage electrochemical-ozone catalytic reactor through a pipeline and the porous titanium aeration anode (9); the secondary tail gas of the mixed gas is introduced into a third-stage electrochemical-ozone catalytic reactor through a pipeline through a porous titanium aeration anode (9); wastewater passes through a first, a second and a third-stage electrochemical-ozone catalytic reactors in sequence through a water pump;
a step power supply method with the gradual decrease from high to low is adopted to apply the current density of 5mA/cm between the porous titanium aeration anode (9) and the carbon coating titanium net cathode (8) of the first, second and third-stage electrochemical-ozone catalytic reactors respectively 2 –30mA/cm 2 The ozone of the mixed gas and the ozone of the refractory organic matters in the wastewater are gradually removed after passing through each stage of electrochemical-ozone catalytic reactor in sequence.
In a preferred embodiment, the wastewater treated by the gas-water co-treatment device (3) is used as electrolyte to enter the oxygen recycling device (4) according to the flow proportion of 20% -50%, the residual oxygen in the tail gas is used as resource and is uniformly introduced into the cavity of the oxygen recycling device (4) through the carbon coating porous titanium aeration cathode (12) component, and under the electrochemical action, the oxygen firstly performs two-electron reduction reaction with the carbon coating on the surface of the porous titanium aeration cathode (12) to generate H 2 O 2 The oxygen entering the liquid phase main body contacts with the hydrophobic carbon particle filler (13) filled in the cavity body, and further fully reacts under the electrochemical action to generate H 2 O 2 ；
The effluent of the oxygen recycling device (4) is rich in H 2 O 2 The reagent is mixed with the water inlet of a first-stage electrochemical-ozone catalytic reactor of the gas-water cooperative treatment device (3) through a return pipeline, and H in the return water 2 O 2 Reacts with ozone in the first-stage electrochemical-ozone catalytic reactor to promote ozone decomposition and simultaneously generate active oxygen.
Compared with the prior art, the invention has the following advantages:
the ozone tail gas is utilized step by step and is efficiently coupled with the step-by-step purification of the wastewater: according to the invention, the multistage series-connected gas-water cooperative treatment device is arranged, and the last stage of ozone tail gas is introduced into the next stage of reactor, so that fresh ozone gas is not introduced into each stage of reactor, the ozone consumption is reduced, and the power consumption is saved. Meanwhile, the characteristics that the requirements of ozone tail gas treatment and wastewater advanced treatment agents are reduced step by step are fully exerted, the current application amount of each stage of gas-water cooperative treatment device is reduced through gradient power supply, and efficient cooperation, energy conservation and consumption reduction of tail gas treatment and wastewater advanced treatment are realized.
The high-efficient utilization of pure oxygen tail gas and the high-efficient retrieval and utilization of waste water: according to the invention, by constructing a filling type oxygen recovery device, by arranging the multi-stage carbon coating porous titanium cathode and the hydrophobic carbon particle filler, oxygen is firmly locked in the device, and under the electrochemical action, the oxygen is efficiently converted into H through the porous electrode and the hydrophobic cathode particles 2 O 2 . More importantly, the invention also takes the fully and deeply treated wastewater as a resource, and a part of the wastewater enters the oxygen recovery device to generate the H-enriched wastewater 2 O 2 The water solution is used as a supplementary medicament and is recycled to the water inlet end of the gas-water cooperative treatment device and is recycled to the H of the water inlet end 2 O 2 Not only can accelerate the decomposition of ozone-H 2 O 2 The homogeneous reaction of (2) promotes the utilization of ozone gas, promotes the conversion of ozone into active oxygen substances and the rapid degradation of pollutants. More importantly, the recycled water reduces the pollution load of the inlet water, improves the load impact resistance of the whole ozone water treatment system, and provides technical support for the system to adapt to more complex industrial wastewater.
According to the technical scheme provided by the embodiment of the invention, the invention realizes the high-efficiency purification of the ozone tail gas and the high-efficiency resource production of H from oxygen 2 O 2 The high-efficiency and low-consumption treatment of the wastewater and the effective reuse of the wastewater realize the gas-water cooperative treatment and disposal. The invention establishes a set of ozone-based gas-water cooperative sustainable treatment system, and provides green development for ozone water treatmentProvides a new idea.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic structural diagram of an electrochemical-multiphase ozone catalytic system for gas-water co-treatment provided by an embodiment of the present application;
FIG. 2 is a front view of the co-processing of gas and water in an electrochemical-ozone catalytic reactor for co-processing of gas and water provided by an embodiment of the present application;
fig. 3 is a front view of an oxygen recycling device provided in an embodiment of the present application;
icon: 1-an oxygen generator; 2-an ozone generating device; 3-a gas-water cooperative treatment device; 4-an oxygen recycling device; 5, a water pump; 6-three-way pipeline.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
As used herein, the singular forms "a", "an", "the" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. It will be understood that when an element is referred to as being "connected" or "coupled" to another element, it can be directly connected or coupled to the other element or intervening elements may also be present. Further, "connected" or "coupled" as used herein may include wirelessly connected or coupled. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
For the convenience of understanding the embodiments of the present invention, the following description will be further explained by taking several specific embodiments as examples in conjunction with the drawings, and the embodiments are not to be construed as limiting the embodiments of the present invention.
Example 1
The structural schematic diagram of the electrochemical-multiphase ozone catalytic system for gas-water co-treatment provided by the embodiment of the application is shown in fig. 1, and the front view of the electrochemical-multiphase ozone catalytic system for gas-water co-treatment provided by the embodiment of the application is shown in fig. 2. As shown in fig. 1 and fig. 2, the electrochemical-ozone catalytic reactor for gas-water co-treatment according to the embodiment of the present invention comprises an oxygen generator 1, an ozone generating device 2, a gas-water co-treatment device 3, an oxygen recycling device 4, a water pump 5 and a three-way pipe 6.
The gas-water cooperative treatment device 3 is formed by connecting three-stage electrochemical-ozone catalytic reactors in series, wastewater sequentially flows through the electrochemical-ozone catalytic reactors through a water pump 5, a part of treated effluent is discharged after reaching the standard, and a part of water enters an oxygen recycling device 4 to be used as electrolyte to absorb oxygen to generate H 2 O 2 And by refluxingThe pipeline enters the water inlet end of the first-stage electrochemical-ozone catalytic reactor of the gas-water cooperative treatment device 3 and is fully mixed with inlet water. Air generates pure oxygen through the oxygen generator 1, generates ozone/oxygen mixed gas after entering the ozone generator 2, sequentially enters the three-stage electrochemical-ozone catalytic reactor of the air-water cooperative treatment device 3, and the outlet air of the upper stage is used as the inlet air of the next-stage electrochemical-ozone catalytic reactor. The tail gas (pure oxygen) of the third-stage electrochemical-ozone catalytic reactor enters an oxygen recycling device 4.
An electrochemical-ozone catalytic reactor is arranged in the gas-water cooperative treatment device 3 and consists of an organic glass cavity 7 and a load TiO 2 A porous titanium aeration anode 9 of nanometer flower and a titanium net cathode 8 loaded by graphite powder. An air inlet is arranged at the bottom of the cavity 7, an air outlet is arranged at the top of the cavity, a water inlet is arranged at the lower part of the side wall, and a water outlet is arranged at the upper part of the side wall.
Fig. 3 is a front view of the oxygen recycling device 4 provided in the embodiment of the present application, in which an organic glass cavity 10, a carbon black coated porous titanium aerated cathode 12, a titanium mesh anode 11, and a hydrophobic carbon particle filler 13 filled between the cathode and the anode are disposed in the oxygen recycling device 4, and the particle size is 10 mm.
In this embodiment, the water treatment method using the gas-water co-processing electric multi-phase ozone catalytic apparatus includes:
air generates pure oxygen through the oxygen generator 1, generates ozone/oxygen mixed gas after entering the ozone generator 2, enters the first-stage electrochemical-ozone catalytic reactor of the air-water cooperative treatment device 3 through the porous titanium aeration anode 9, and the tail gas of the mixed gas is introduced into the second-stage electrochemical-ozone catalytic reactor through the porous titanium aeration anode 9 through a pipeline; the secondary tail gas of the mixed gas is introduced into the third-stage electrochemical-ozone catalytic reactor through a pipeline through the porous titanium aeration anode 9; wherein, the lower part of the porous titanium aeration anode 9 is connected with the ozone generator 2 and the voltage-stabilizing direct-current power supply and is used as an ozone aerator and an anode. Wastewater passes through a first, a second and a third-stage electrochemical-ozone catalytic reactors in sequence through a water pump; wastewater enters from the upper part of the cavity, passes through the reactor from top to bottom and is discharged from a water outlet at the lower part of the cavity, wherein residual ozone is discharged from the top of the cavityDischarging from the outlet, and sequentially introducing into the first three stages of gas-water cooperative treatment devices; the liquid discharged by the third stage gas-water cooperative treatment device is partially treated by the three-way pipeline to directly discharge the wastewater reaching the standard, and partially introduced into the oxygen recycling device to be used as H 2 O 2 The aquatic products are output and flow back to the first-stage device, so that efficient pollution degradation and resource utilization are realized. Wherein the first to third stages are applied with 10mA/cm 2 ,5mA/cm 2 ,2mA/cm 2 Constant current, ozone gas removing rate up to 95.74%, difficultly degradable pollutant p-chlorobenzoic acid removing rate up to 95%, mineralization rate 90%, oxygen recovery and H 2 O 2 Application of 5mA/cm in the preparation apparatus 2 Current density, in one hour to H 2 O 2 The yield is 50mg/L-100 mg/L.
Example 2
As shown in fig. 1 and fig. 2, an electrochemical-ozone catalytic reactor for gas-water co-processing in the embodiment of the present invention includes an oxygen generator 1, an ozone generating device 2, a gas-water co-processing device 3, and an oxygen recycling device 4. The gas-water cooperative treatment device 3 is formed by connecting three-stage electrochemical-ozone catalytic reactors in series, wastewater sequentially flows through the electrochemical-ozone catalytic reactors through a water pump 5, a part of treated water is discharged after reaching the standard, and a part of treated water enters an oxygen recycling device to be used as H generated by absorbing oxygen by electrolyte 2 O 2 And reflows to the water inlet end of the gas-water cooperative treatment device through the reflow system. Ozone gas passes through the three-stage electrochemical-ozone catalytic reactor in sequence, and the outlet gas of the previous stage is used as the inlet gas of the next-stage electrochemical-ozone catalytic reactor. And introducing tail gas (pure oxygen) of the third-stage electrochemical-ozone catalytic reactor into an oxygen recycling device. The latter-stage electrochemical-ozone catalytic reactor fully utilizes ozone in tail gas of the electrochemical-ozone catalytic reactor as an oxidant and synchronously serves as a former-stage wastewater advanced treatment device and a tail gas treatment device to realize efficient purification of tail gas and efficient treatment of wastewater, and ozone tail gas and refractory organic matters in mixed gas are completely removed after three-stage series reaction.
The electrochemical-ozone catalytic reactor in the gas-water cooperative treatment device consists of an organic glass cavity 7 and a doping agentSnO 2 Supported TiO of (2) 2 A porous titanium aeration anode 9 and a titanium mesh cathode 8 loaded with graphite powder. The oxygen recycling device 4 comprises an organic glass cavity 10, a carbon black coating porous titanium aeration cathode 12, a titanium mesh anode 11 and a hydrophobic carbon particle filler 13 filled between the cathode and the anode, wherein the particle size is 5 mm. An air inlet is arranged at the bottom of the cavity 7, an air outlet is arranged at the top of the cavity, a water inlet is arranged at the lower part of the side wall, and a water outlet is arranged at the upper part of the side wall. Under the electrochemical action, oxygen firstly generates two-electron reduction reaction with the surface carbon coating of the porous titanium aeration cathode to generate a large amount of H 2 O 2 The oxygen entering the liquid phase main body contacts with the hydrophobic carbon particle cathode filled in the cavity, and further fully reacts under the electrochemical action to generate a large amount of H 2 O 2 And the high-efficiency recovery and resource utilization of pure oxygen are realized.
In this embodiment, a water treatment method using an electric multiphase ozone catalytic device with gas-water co-treatment includes:
air generates pure oxygen through the oxygen generator 1, generates ozone/oxygen mixed gas after entering the ozone generator 2, enters the first-stage electrochemical-ozone catalytic reactor of the air-water cooperative treatment device 3 through the porous titanium aeration anode 9, and the tail gas of the mixed gas is introduced into the second-stage electrochemical-ozone catalytic reactor through the porous titanium aeration anode 9 through a pipeline; the secondary tail gas of the mixed gas is introduced into the third-stage electrochemical-ozone catalytic reactor through a pipeline through the porous titanium aeration anode 9; wherein, the lower part of the porous titanium aeration anode 9 is connected with the ozone generator 2 and the voltage-stabilizing direct-current power supply and is used as an ozone aerator and an anode. Wastewater passes through a first, a second and a third-stage electrochemical-ozone catalytic reactors in sequence through a water pump; wastewater enters from the upper part of the cavity, passes through the reactor from top to bottom, is discharged from a water outlet at the lower part of the cavity, wherein residual ozone is discharged from a gas outlet at the top of the cavity, and is sequentially introduced into the first three-stage gas-water cooperative treatment device; the liquid discharged by the third stage gas-water cooperative treatment device is directly discharged after part of the wastewater reaching the standard is treated by the three-way pipeline, and the other part of the wastewater is introduced into the oxygen recycling device to be used as H 2 O 2 The aquatic products are output and flow back to the first-stage device, so that efficient pollution degradation and resource utilization are realized. It is composed ofIn the first to third stages, 10mA/cm was applied respectively 2 ,10mA/cm 2 ,10mA/cm 2 Constant current, ozone gas removing rate up to 99%, nondegradable pollutant p-chlorobenzoic acid removing rate up to 99%, complete mineralization, oxygen recovery and H 2 O 2 Application of 10mA/cm in the preparation apparatus 2 Current density, in one hour to H 2 O 2 The yield is 100mg/L-200 mg/L.
In summary, the electrochemical-ozone catalytic reactor for gas-water cooperative treatment and the water treatment method thereof in the embodiments of the present invention realize an electric multiphase ozone step water treatment process and a pure oxygen tail gas recovery process for gas-water cooperative treatment, and by matching with an ozone generation device, a three-level gas-water cooperative treatment device, and a one-level oxygen recovery and utilization device, the electrochemical-ozone catalytic reactor for gas-water cooperative treatment of the present invention adopts an electrical gradient, an ozone concentration gradient, a pollutant concentration gradient, and an H concentration gradient 2 O 2 The concentration gradient combination adopts a multistage tandem structure, is coupled with a hydrophobic carbon particle electrode, and is combined with a gas-water circulation technology, so that the utilization efficiency of ozone and electric resources is greatly improved, the ozone dosage per ton of water is reduced, and the investment and energy consumption per ton of water are reduced; through the three-way pipeline at the tail end, the electrochemical-ozone catalytic reactor with the gas-water cooperative treatment can solve the problems of secondary pollution of ozone tail gas to the environment and resource waste caused by direct discharge of pure oxygen tail gas by matching with a primary oxygen recycling device and a tertiary gas-water cooperative treatment device.
The ozone tail gas is utilized step by step and is efficiently coupled with the step-by-step purification of the wastewater: according to the invention, the multistage series-connected gas-water cooperative treatment device is arranged, and the last stage of ozone tail gas is introduced into the next stage of reactor, so that fresh ozone gas is not introduced into each stage of reactor, the ozone consumption is reduced, and the power consumption is saved. Meanwhile, the characteristics that the requirements of ozone tail gas treatment and wastewater advanced treatment agents are reduced step by step are fully exerted, the current application amount of each stage of gas-water cooperative treatment device is reduced through gradient power supply, and efficient cooperation, energy conservation and consumption reduction of tail gas treatment and wastewater advanced treatment are realized.
Efficient utilization of pure oxygen tail gas and wastewaterThe efficient recycling of the method comprises the following steps: according to the invention, by constructing a filling type oxygen recovery device, through arranging a multi-stage carbon coating porous titanium cathode and hydrophobic carbon particle filler, oxygen is firmly locked in the device, and under the electrochemical action, the oxygen is efficiently converted into H through the porous electrode and the hydrophobic cathode particles 2 O 2 More importantly, the invention also takes the fully and deeply treated wastewater as a resource, and a part of the wastewater enters the oxygen recovery device to generate H-enriched wastewater 2 O 2 The water solution is used as a supplementary medicament and is recycled to the water inlet end of the gas-water cooperative treatment device and is recycled to the H of the water inlet end 2 O 2 Not only can accelerate the decomposition of ozone-H 2 O 2 The homogeneous reaction of (2) promotes the utilization of ozone gas, promotes the conversion of ozone into active oxygen substances and the rapid degradation of pollutants. More importantly, the recycled water reduces the pollution load of the inlet water, improves the load impact resistance of the whole ozone water treatment system, and provides technical support for the system to adapt to more complex industrial wastewater.
Finally, the invention realizes the high-efficiency purification of the ozone tail gas and the high-efficiency resource production of H from oxygen 2 O 2 The high-efficiency and low-consumption treatment of the wastewater and the effective reuse of the wastewater realize the gas-water cooperative treatment and disposal. The invention establishes a set of ozone-based gas-water cooperative sustainable treatment system, and provides a new idea for green development of ozone water treatment.
Those of ordinary skill in the art will understand that: the figures are merely schematic representations of one embodiment, and the blocks or flow diagrams in the figures are not necessarily required to practice the present invention.
It will be understood by those skilled in the art that the components of the apparatus in the embodiments of the present invention may be distributed in the apparatus in the embodiments as described in the embodiments, or may be correspondingly modified in one or more apparatuses other than the embodiments. The components of the above embodiments may be combined into one component, or may be further divided into a plurality of sub-components.
The embodiments in the present specification are described in a progressive manner, and the same and similar parts among the embodiments are referred to each other, and each embodiment focuses on the differences from the other embodiments. In particular, for apparatus or system embodiments, since they are substantially similar to method embodiments, they are described in relative terms, as long as they are described in partial descriptions of method embodiments. The above-described embodiments of the apparatus and system are merely illustrative, and the units described as separate parts may or may not be physically separate, and the parts displayed as units may or may not be physical units, may be located in one place, or may be distributed on a plurality of network units. Some or all of the modules may be selected according to actual needs to achieve the purpose of the solution of the present embodiment. One of ordinary skill in the art can understand and implement it without inventive effort.
While the invention has been described with reference to specific preferred embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the following claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. An electrochemical-multiphase ozone catalytic system for gas-water co-treatment, which is characterized by comprising: the device comprises an oxygen generator (1), an ozone generator (2), a gas-water cooperative treatment device (3), an oxygen recycling device (4), a water pump (5) and a three-way pipeline (6);
the gas-water cooperative treatment device (3) is formed by sequentially connecting three stages of electrochemical-ozone catalytic reactors in series, the gas-water cooperative treatment device (3) and the oxygen recycling device (4) are respectively provided with a water inlet, a water outlet, an air inlet and an air outlet, wastewater is pumped into the water inlet of the next stage of reactor through the water outlet of the previous stage of electrochemical-ozone catalytic reactor by a water pump (5), air passes through an oxygen generator (1) to generate ozone-oxygen mixed gas through an ozone generator (2) and is introduced into the gas-water cooperative treatment device (3), and ozone tail gas is introduced into the air inlet of the next stage of water cooperative treatment device (3) from the air outlet of the previous stage of gas-water cooperative treatment device (3) through a pipeline;
one part of the effluent of the gas-water cooperative treatment device (3) is discharged after reaching the standard, the other part of the effluent is connected with the water inlet of the oxygen recycling device (4) through a three-way pipeline (6) and a water pump (5), and the tail gas is connected with the gas inlet of the oxygen recycling device (4) through a pipeline.
2. The system according to claim 1, wherein a return pipeline is arranged at the tail end of the water outlet of the oxygen recycling device (4), and the outlet water enters the water inlet end of the first-stage electrochemical-ozone catalytic reactor of the gas-water cooperative treatment device (3) through the return pipeline and is fully mixed with the inlet water.
3. The system according to claim 1, characterized in that the gas-water cooperative treatment device (3) is provided with a chamber (7), a carbon-coated titanium mesh cathode (8) and a porous titanium aeration anode (9).
4. The system according to claim 1, characterized in that the oxygen recycling device (4) comprises a cavity (10), carbon-coated porous titanium aerated cathodes (12), a titanium mesh anode (11) and hydrophobic carbon particle fillers (13) filled between the cathode and the anode, wherein a plurality of carbon-coated porous titanium aerated cathodes are uniformly arranged.
5. A system according to claim 3, characterized in that said porous titanium aerated anode (9) is made of a porous titanium matrix, TiO 2 The oxide intermediate layer and the catalyst layer of one or more metal oxide compounds of Sn, Ir, Ru, Zn, Mn, Fe and Ce.
6. A system according to claim 3, characterized in that the carbon coated titanium mesh cathode (8) consists of a titanium mesh, a carbon coating, wherein the carbon coating comprises: one or more of carbon black, graphite powder, carbon nano tubes and graphene.
7. The system according to claim 4, wherein the hydrophobic carbon particle filler (13) is a granular filler formed by mixing, pressing, granulating and sintering polytetrafluoroethylene and carbon black at 250-350 ℃, and the particle size is 5-50 mm.
8. The system according to claim 1, characterized in that the cathode and the anode of the gas-water cooperative treatment device (3) and the oxygen recycling device (4) are connected with a direct current stabilized power supply through leads.
9. A treatment method related to an electrochemical-ozone catalytic reaction system using gas-water co-treatment according to any one of claims 1 to 8, which is characterized by comprising the following steps:
air generates pure oxygen through an oxygen generator (1), the pure oxygen enters an ozone generator (2) to generate ozone/oxygen mixed gas, the mixed gas enters a first-stage electrochemical-ozone catalytic reactor of the air-water cooperative treatment device (3) through a porous titanium aeration anode (9), and mixed gas tail gas is introduced into a second-stage electrochemical-ozone catalytic reactor through a pipeline and the porous titanium aeration anode (9); the secondary tail gas of the mixed gas is introduced into a third-stage electrochemical-ozone catalytic reactor through a pipeline through a porous titanium aeration anode (9); wastewater passes through a first, a second and a third-stage electrochemical-ozone catalytic reactors in sequence through a water pump;
a step power supply method with the gradual decrease from high to low is adopted to apply the current density of 5mA/cm between the porous titanium aeration anode (9) and the carbon coating titanium net cathode (8) of the first, second and third-stage electrochemical-ozone catalytic reactors respectively 2 –30mA/cm 2 The ozone of the mixed gas and the ozone of the refractory organic matters in the wastewater are gradually removed after passing through each stage of electrochemical-ozone catalytic reactor in sequence.
10. The method of claim 9, comprising:
the wastewater treated by the gas-water cooperative treatment device (3) is used as electrolyte to enter the oxygen recycling device (4) according to the flow proportion of 20-50%, and the residual oxygen in the tail gas is used as resource and is uniformly introduced into the cavity of the oxygen recycling device (4) through the carbon coating porous titanium aeration cathode (12) component in the electrochemical processUnder the chemical action, oxygen firstly generates two-electron reduction reaction with the surface carbon coating of the porous titanium aeration cathode (12) to generate H 2 O 2 The oxygen entering the liquid phase main body contacts with the hydrophobic carbon particle filler (13) filled in the cavity body, and further fully reacts under the electrochemical action to generate H 2 O 2 ；
The effluent of the oxygen recycling device (4) is rich in H 2 O 2 The reagent is mixed with the water inlet of a first-stage electrochemical-ozone catalytic reactor of the gas-water cooperative treatment device (3) through a return pipeline, and H in the return water 2 O 2 Reacts with ozone in the first-stage electrochemical-ozone catalytic reactor to promote ozone decomposition and simultaneously generate active oxygen.
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| CN105800739A (en) * | 2016-05-27 | 2016-07-27 | 长沙华时捷环保科技发展股份有限公司 | 3D-EO three-dimensional peroxidation electrochemical device and application thereof |
| CN111573791A (en) * | 2020-04-09 | 2020-08-25 | 北京交通大学 | Three-dimensional electrochemical-multiphase ozone catalytic reaction device and water treatment method thereof |
| CN214141733U (en) * | 2020-10-29 | 2021-09-07 | 江苏京源环保股份有限公司 | Wastewater treatment device for generating H2O2 in situ by utilizing O3 tail gas in water treatment |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105800739A (en) * | 2016-05-27 | 2016-07-27 | 长沙华时捷环保科技发展股份有限公司 | 3D-EO three-dimensional peroxidation electrochemical device and application thereof |
| CN111573791A (en) * | 2020-04-09 | 2020-08-25 | 北京交通大学 | Three-dimensional electrochemical-multiphase ozone catalytic reaction device and water treatment method thereof |
| CN214141733U (en) * | 2020-10-29 | 2021-09-07 | 江苏京源环保股份有限公司 | Wastewater treatment device for generating H2O2 in situ by utilizing O3 tail gas in water treatment |
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