CN111138009B - Water treatment recovery device based on metal-air battery and method thereof - Google Patents
Water treatment recovery device based on metal-air battery and method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
Abstract
The invention provides a water treatment recovery device based on a metal-air battery and a method thereof, wherein the water treatment recovery device comprises the following steps: the system comprises an electricity generation system, an energy storage system and a water treatment and recovery system; the power generation system comprises a corrosive metal cathode, an air diffusion anode and a cavity, wherein the corrosive metal cathode and the air diffusion anode are oppositely arranged and form a closed container together with the cavity, and the outer side of the air diffusion anode is in contact with air; the power generation system is respectively connected with the energy storage system circuit through a corrosive metal cathode and an air diffusion anode, and a switch is arranged between the power generation system and the energy storage system and used for switching the anode and the cathode of the power generation system and adjusting the charging and discharging states; the power generation system is connected with a water treatment recovery system through a pipeline, and the water treatment recovery system comprises a circulating pump, a tank body and a crystallization filter. The device can realize self-supply of electric energy and water treatment and resource recovery without adding external chemical substances.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a water treatment recovery device based on a metal-air battery and a method thereof.
Background
In recent years, the development of new sustainable water treatment technologies is a research hotspot in the field of water pollution control. The key point is how to realize the high-efficiency recovery of potential nutrient elements such as ammonia nitrogen, phosphate and the like in the wastewater and effectively remove refractory organic matters in the wastewater. The ammonia nitrogen and the phosphate are key indexes for controlling water pollution and are main reasons for causing water eutrophication, and meanwhile, the ammonia nitrogen and the phosphate are important chemical fertilizers or raw materials in the agricultural and chemical industries. Therefore, if high-concentration nitrogen and phosphorus in the wastewater are efficiently recovered, sustainable development of wastewater treatment can be realized. Extensive research has been carried out in the chemical industry and the industry aiming at the recovery of nitrogen and phosphorus in wastewater, and a great deal of innovation and progress are obtained. Among the most widely studied methods are: magnesium ammonium phosphate coprecipitation method. The method realizes the synchronous removal of nitrogen and phosphorus in the wastewater by adding the magnesium salt into the wastewater containing nitrogen and phosphorus and regulating and controlling the process. Meanwhile, magnesium ammonium phosphate is commonly called struvite, is an excellent slow-release fertilizer, has excellent fertilizer efficiency, is an important target product for recycling nitrogen and phosphorus resources, and has higher economic value. In addition, for the wastewater only containing high phosphate, iron ions are added to generate ferric phosphate crystallization products, and the ferric phosphate crystallization products are finally recovered in a form of vivianite, so that the method has wide prospects in phosphate recovery due to the special mineral dye. However, this method requires a large amount of foreign metal salt substances, a large amount of added chemicals, continuous manual input, and regular maintenance, and thus, in order to improve the metal salt adding efficiency, patent application No. 201610259921.9 proposes that metal ions are added electrochemically. Corrosive metals can release metal cations into a solution under the action of current, but the whole system of the device still needs additional electric energy to meet the continuous reaction; xi Chen et al (Self-stabilizing advanced water treatment and simultaneous anaerobic in situ recovery in a novel biochemical system, Chem Eng J,2017, 692) propose that the microbial fuel cell technology is adopted to remove organic matters and simultaneously recover ammonia nitrogen and phosphate in liquid form through an anion-cation membrane arranged in the cell, and under the condition of not adding electric energy and chemical agents, nitrogen and phosphorus in the wastewater are efficiently recovered, organic pollutants are effectively removed, and simultaneously electric energy can be generated. However, the microbial fuel cell is limited by the inherent conditions of microbes, is sensitive to the environmental temperature and water quality conditions, particularly takes organic matters in wastewater as main fuel, and if the organic matters in the wastewater are not biodegradable or have strong biological toxicity, the electricity generation performance of a cell system is greatly influenced. Meanwhile, if the wastewater contains less organic matters or no organic matters, the microbial fuel cell cannot remove nitrogen and phosphorus; in addition, the patent (application No. 201510372998.2) realizes the recovery of nitrogen and phosphorus in the aquaculture wastewater and simultaneously generates electric energy by using a seawater battery, and obtains higher recovery effect. However, the seawater battery only aims at nitrogen and phosphorus in the wastewater, and cannot effectively remove potential other organic matters in the wastewater.
Therefore, based on the defects in the conventional research, it is urgently needed to develop a water treatment and resource recovery device which can realize self-supply of electric energy and does not need to add foreign chemical substances in the treatment process aiming at the complex water quality of nitrogen, phosphorus, organic matters and the like in the wastewater.
Disclosure of Invention
The invention provides a water treatment recovery device based on a metal-air battery and a method thereof, which aim to solve the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme.
The invention provides a water treatment recovery device based on a metal-air battery, which comprises: the system comprises an electricity generation system, an energy storage system and a water treatment and recovery system;
the power generation system comprises a corrosive metal cathode, an air diffusion anode and a cavity, wherein the corrosive metal cathode and the air diffusion anode are oppositely arranged and form a closed container together with the cavity, and the outer side of the air diffusion anode is in contact with air;
the power generation system is respectively connected with the energy storage system through a corrosive metal cathode and an air diffusion anode and used for storing electric energy generated in the power generation system into the energy storage system, and a reverse pole switch is arranged between the power generation system and the energy storage system and used for switching the anode and the cathode of the power generation system and adjusting the charging or discharging state;
the power generation system is connected with the water treatment recovery system through a pipeline, the water treatment recovery system comprises a circulating pump, a tank body and a crystallization filter, the circulating pump is used for pumping water in the tank body into the power generation system, and the crystallization filter is used for filtering and intercepting treated water.
Preferably, the corrosive metal negative electrode is a magnesium, iron, aluminum plate, or an alloy plate of any two or three thereof; the air diffusion positive electrode comprises a carbon diffusion electrode substrate and a positive electrode catalyst layer loaded on the substrate.
Preferably, the carbon diffusion electrode substrate is of a sandwich structure consisting of a carbon active substance, a current collector and an air diffusion layer; the anode catalyst layer is one of Ir oxide, Ru oxide, Co oxide, Mn oxide, Fe oxide, Pt and carbon black, or a compound of any of a plurality of components.
Preferably, the anode catalyst layer is in the shape of an array arrangement of nanospheres, nanowires, nanorods, nanotubes or nanoflowers, and a circular hole is formed in one side of the cavity parallel to the air diffusion anode and used for contacting with air.
Preferably, the energy storage system is a chargeable and dischargeable battery.
Preferably, the circulating pump is a peristaltic pump, the cavity is an organic glass cavity, and the tank body is an organic glass container or a plastic container; the metal filter head of the crystallization filter is made of stainless steel or titanium material, and the filtering aperture of the crystallization filter is 1-5 μm.
Preferably, the electrode spacing between the corrosive metal negative electrode and the air diffusion positive electrode is 0.5-2 cm.
Preferably, the current collector is a mesh structure having electrical conductivity; the carbon active substance comprises one or more of activated carbon, carbon black, graphene and graphite powder; the air diffusion layer is a polytetrafluoroethylene coating.
Preferably, the current collector is a mesh structure having electrical conductivity; the carbon active substance is carbon cloth or carbon paper.
Another aspect of the present invention provides a water treatment and recycling method applied to the above apparatus, comprising:
the first stage is as follows: placing wastewater to be treated in a tank body of a water treatment recovery system, starting a circulating pump, pumping the wastewater to be treated into a closed container of an electricity generation system, spontaneously utilizing the wastewater to be treated as electrolyte by a corrosive metal cathode to generate a galvanic cell reaction and release metal cations into the wastewater, and utilizing oxygen in air by an air diffusion anode to generate an oxygen reduction reaction to generate current which is stored in an energy storage system as electric energy;
the released metal cations enter a tank body of a water treatment recovery system, generate phosphate-form crystals with ammonia nitrogen and phosphate in the residual wastewater to be treated, and are separated by a crystallization filter;
and a second stage: changing the positive and negative polarities of electrodes in the original power generation system through a reverse pole switch, electrolyzing waste water by using collected electric energy as a direct current power supply, oxidizing chloride ions in the waste water into active chlorine by using a catalyst loaded on an air diffusion positive pole, and degrading organic matters in the waste water by using the active chlorine as an oxidizing agent; meanwhile, the generated active chlorine reacts with residual ammonia nitrogen in the wastewater in the first stage to further oxidize the ammonia nitrogen into nitrogen.
According to the technical scheme provided by the water treatment and recovery device based on the metal-air battery and the method thereof, the device takes the metal-air battery as a core, does not depend on microorganisms as a catalyst, has strong adaptability of a system to the environment and water quality, and is suitable for various water qualities; the device fully utilizes the characteristics that the metal air battery can release cations in situ and generate high electricity, and finally realizes the feeding of different metal cations and the recovery of electric energy according to the characteristics of wastewater to be treated, such as the treatment of wastewater containing nitrogen and phosphorus, by adopting a magnesium electrode as a negative electrode, such as the treatment of wastewater containing phosphorus, and by adopting an iron electrode and an aluminum electrode as negative electrodes, the metal cations entering the electrolyte (wastewater to be treated) can be subjected to crystallization precipitation reaction with nitrogen and phosphorus in water, so that the high-efficiency recovery of nutrient elements is realized; the metal-air battery can be used as an electricity generating device and an electrolysis device at the same time, the positive electrode (cathode) has double catalytic activities of efficient oxygen reduction and efficient chlorine electroanalysis, the positive electrode accelerates the oxygen reduction to improve the electricity generating power in the electricity generating stage, and the electrode is used as the anode to electrolyze chloride ions in wastewater to generate active chlorine substances in the electrolysis stage and has the sterilization effect when being used for degrading pollutants and removing ammonia nitrogen; the electric energy in the electricity generation stage is efficiently stored, and is utilized sparingly in the electrolysis stage, so that net electricity productivity is realized, the whole system promotes efficient recovery of nitrogen and phosphorus in the wastewater and effective degradation of organic matters only through self-corrosion electricity generation of a metal battery, and meanwhile, the electric energy can be generated, and organic combination of wastewater treatment recycling and energy generation is realized.
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 embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a water treatment and recovery device based on a metal-air battery according to an embodiment;
description of reference numerals:
the corrosive metal negative pole, air diffusion positive pole and organic glass cavity of crystal filter are formed by the water inlet on the cavity, the water outlet on the cavity, the corrosive metal negative pole, the air diffusion positive pole and the organic glass cavity.
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.
To facilitate an understanding of embodiments of the present invention, several specific embodiments are described below in conjunction with the accompanying drawings.
Example 1
Fig. 1 is a schematic structural diagram of a water treatment recycling device based on a metal-air battery provided in this embodiment, and referring to fig. 1, the device includes: the system comprises an electricity generating system, an energy storage system and a water treatment and recovery system.
The electrogenesis system comprises a corrosive metal cathode (R), an air diffusion anode (ninx) and an organic glass cavity (R), parts of the corrosive metal cathode (R) and the air diffusion anode (ninx) are arranged in the organic glass cavity (R), the corrosive metal cathode (r) and the air diffusion anode (ninx) are oppositely arranged and form a closed container together with the organic glass cavity (R), the outer side of the air diffusion anode (ninx) is contacted with air, and one side of the organic glass cavity (R) parallel to the air diffusion anode (ninx) is respectively provided with a round hole for contacting with the air.
The power generation system (I) is respectively connected with the energy storage system (2) through a corrosive metal negative electrode (C) and an air diffusion positive electrode (C) in a circuit mode and is used for storing electric energy generated in the power generation system (I) into the energy storage system (II), and a reverse pole switch (IV) is arranged between the power generation system (I) and the energy storage system (II) and is used for switching the positive pole and the negative pole of the power generation system (I) and adjusting the charging or discharging state.
The electric generating system is connected with the water treatment and recovery system through a pipeline, the water treatment and recovery system comprises a peristaltic pump, a tank body and a crystallization filter, a water inlet and a water outlet are respectively arranged on the organic glass cavity and the tank body, the water inlet on the cavity is connected with the water outlet on the tank body, the water outlet on the cavity is connected with the water inlet on the tank body, and the peristaltic pump is arranged on the pipeline between the water inlet of the cavity and the water outlet on the tank body. Pumping the waste water pre-placed in the water treatment and recovery system into the power generation system through a peristaltic pump, returning the waste water to the water treatment and recovery system through a cavity of the power generation system, filtering and trapping the treated water through a crystallization filter, and enabling the filtered water to enter the power generation system again after the crystal sediment generated in the water treatment and recovery system is trapped through the crystallization filter.
The corrosive metal cathode adopts a pure magnesium plate, and the air diffusion anode comprises a carbon diffusion electrode substrate and a catalyst layer loaded on the substrate and having high-performance oxygen reduction and electrochemical chlorine evolution capabilities. The air diffusion positive electrode of this embodiment is composed of carbon paper, an air diffusion layer, and a catalyst supported on the carbon paper. The catalyst is a composite oxide of Ir and Ru with high-performance oxygen reduction and electrochemical chlorine evolution capacity, and the shape of the catalyst is a nanowire array. The energy storage system is a chargeable and dischargeable battery, specifically, a lithium battery. And the electrode distance between the corrosive metal negative electrode (r) and the air diffusion positive electrode (nini) is 1 cm.
The tank body of the water treatment recovery system (c) in this embodiment is a plastic reaction tank body, and the crystallization filter is a stainless steel crystallization filter with a filter pore size of 1 μm.
The embodiment also provides a water treatment and recovery method applied to the device, and the wastewater treated by the method mainly aims at organic wastewater containing high ammonia nitrogen and phosphate, such as urine. The method comprises two stages: the power generation nitrogen and phosphorus recovery stage and the electrolysis water purification stage are as follows:
the first stage is as follows: and (5) recovering nitrogen and phosphorus in the power generation stage.
Waste water (urine) to be treated is placed in a tank body of a water treatment and recovery system III, a peristaltic pump is started, the waste water to be treated is pumped into a closed container of an electricity generation system I, and then returns to the water treatment and recovery system III to be circulated and reciprocated. During the period, a corrosive metal cathode (magnesium cathode) spontaneously utilizes the wastewater to be treated as electrolyte to generate a galvanic cell reaction and release magnesium ions into the wastewater, and an air diffusion anode generates an oxygen reduction reaction by utilizing oxygen in the air to generate current which is stored in an energy storage system II as electric energy;
the released magnesium ions enter a tank body of a water treatment recovery system III, generate magnesium ammonium phosphate sediment together with ammonia nitrogen and phosphate in the residual wastewater to be treated, and are separated through a crystallization filter.
In the process, ammonia nitrogen and phosphate are effectively recovered in a crystal form, and electric energy is generated for storage.
And a second stage: and (5) electrolyzing water to purify water.
Changing the positive and negative polarities of electrodes in an original electricity generating system (a magnesium electrode is changed into a cathode, an original air diffusion positive electrode is changed into an anode, an original electricity generating system is changed into a discharging system, so that the whole system is changed into an electrolytic system), electrolyzing waste water by using collected electric energy as a direct current power supply, oxidizing chlorine ions in the waste water into active chlorine by using a catalyst loaded on the air diffusion positive electrode, and degrading organic matters in the waste water by using the catalyst as an oxidant; meanwhile, the generated active chlorine reacts with residual ammonia nitrogen in the wastewater in the first stage to further oxidize the ammonia nitrogen into nitrogen. The stage achieves the purpose of complete denitrification. Meanwhile, the magnesium cathode can generate continuous hydrogen evolution reaction, so that the falling of the scaling layer on the surface of the original electrode is accelerated, and the self-cleaning of the surface of the electrode is promoted.
And finally, effective recovery of ammonia nitrogen and phosphate in the wastewater is realized, organic matters are efficiently removed, the surface of the electrode is kept to be continuously clean, and surplus electric energy in the first stage and the second stage is finally stored in an energy storage system. Finally, the wastewater can generate extra electric energy while realizing the high-efficiency recovery of nitrogen and phosphorus and the high-efficiency removal of organic matters by the method, so that the purpose of self-power supply is finally realized without external electric energy input.
Example 2
Referring to fig. 1, a schematic structural diagram of a water treatment and recovery device based on a metal-air battery provided in this embodiment includes: the system comprises an electricity generating system, an energy storage system and a water treatment and recovery system.
The electrogenesis system comprises a corrosive metal cathode (R), an air diffusion anode (ninx) and an organic glass cavity (R), parts of the corrosive metal cathode (R) and the air diffusion anode (ninx) are arranged in the organic glass cavity (R), the corrosive metal cathode (r) and the air diffusion anode (ninx) are oppositely arranged and form a closed container together with the organic glass cavity (R), the outer side of the air diffusion anode (ninx) is contacted with air, and one side of the organic glass cavity (R) parallel to the air diffusion anode (ninx) is respectively provided with a round hole for contacting with the air.
The power generation system (I) is respectively connected with the energy storage system (2) through a corrosive metal negative electrode (C) and an air diffusion positive electrode (C) in a circuit mode and is used for storing electric energy generated in the power generation system (I) into the energy storage system (II), and a reverse pole switch (IV) is arranged between the power generation system (I) and the energy storage system (II) and is used for switching the positive pole and the negative pole of the power generation system (I) and adjusting the charging or discharging state.
The electric generating system is connected with the water treatment and recovery system through a pipeline, the water treatment and recovery system comprises a peristaltic pump, a tank body and a crystallization filter, a water inlet and a water outlet are respectively arranged on the organic glass cavity and the tank body, the water inlet on the cavity is connected with the water outlet on the tank body, the water outlet on the cavity is connected with the water inlet on the tank body, and the peristaltic pump is arranged on the pipeline between the water inlet of the cavity and the water outlet on the tank body. Pumping the waste water pre-placed in the water treatment and recovery system into the power generation system through a peristaltic pump, returning the waste water to the water treatment and recovery system through a cavity of the power generation system, filtering and trapping the treated water through a crystallization filter, and enabling the filtered water to enter the power generation system again after the crystal sediment generated in the water treatment and recovery system is trapped through the crystallization filter.
Wherein the corrosive metal cathode is a pure iron plate, and the air diffusion anode is composed of carbon paper, an air diffusion layer and a catalyst loaded on the carbon paper. The catalyst is a composite oxide of Ir and Co and is in a nanorod array shape. The energy storage system is a chargeable and dischargeable battery, specifically, a lithium battery. And the electrode distance between the corrosive metal negative electrode and the air diffusion positive electrode is 0.5 cm.
The tank body of the water treatment recovery system (c) in this embodiment is a plastic reaction tank body, and the crystallization filter is a stainless steel crystallization filter with a filtration pore size of 2 μm.
The embodiment also provides a water treatment and recovery method applied to the device, and the wastewater treated by the method mainly aims at organic wastewater containing high ammonia nitrogen and phosphate, such as urine. The method comprises two stages: the power generation nitrogen and phosphorus recovery stage and the electrolysis water purification stage are as follows:
the first stage is as follows: and (5) recovering nitrogen and phosphorus in the power generation stage.
Waste water (urine) to be treated is placed in a tank body of a water treatment and recovery system III, a peristaltic pump is started, the waste water to be treated is pumped into a closed container of an electricity generation system I, and then returns to the water treatment and recovery system III to be circulated and reciprocated. During the period, a corrosive metal cathode (iron cathode) spontaneously utilizes the wastewater to be treated as electrolyte to generate a galvanic cell reaction and release iron ions into the wastewater, and an air diffusion anode ninthly utilizes oxygen in the air to generate an oxygen reduction reaction to generate current which is stored in an energy storage system II as electric energy;
the released iron ions enter a tank body of a water treatment recovery system III, generate iron phosphate precipitation with phosphate in the residual wastewater to be treated, and are separated through a crystallization filter.
In this process, phosphate is effectively recovered in crystalline form, producing electrical energy for storage.
And a second stage: and (5) electrolyzing water to purify water.
The positive and negative polarities of electrodes in the original electricity generating system are changed through a reverse electrode switch (the iron electrode is changed into a cathode, the original air diffusion positive electrode is changed into an anode, the original electricity generating system is changed into a discharging system, so that the whole system is changed into an electrolytic system), the collected electric energy is used as a direct current power supply to electrolyze wastewater, and the catalyst loaded on the air diffusion positive electrode is used for oxidizing chlorine ions in the wastewater into active chlorine and degrading organic matters in the wastewater as an oxidant. Meanwhile, the continuous hydrogen evolution reaction of the iron cathode can accelerate the desquamation of the scaling layer on the surface of the original electrode and promote the self-cleaning of the surface of the electrode. And finally, the effective recovery of phosphate in the wastewater is realized, the organic matters are efficiently removed, and the continuous cleanness of the electrode surface is kept.
The surplus electrical energy in the first and second phases is finally stored in the energy storage system. Finally, the wastewater can generate extra electric energy while realizing efficient recovery of phosphorus and efficient removal of organic matters through the method, and the purpose of self-power supply is finally realized without external electric energy input.
And finally, effective recovery of ammonia nitrogen and phosphate in the wastewater is realized, organic matters are efficiently removed, the surface of the electrode is kept to be continuously clean, and surplus electric energy in the first stage and the second stage is finally stored in an energy storage system. Finally, the wastewater can generate extra electric energy while realizing the high-efficiency recovery of nitrogen and phosphorus and the high-efficiency removal of organic matters by the method, so that the purpose of self-power supply is finally realized without external electric energy input.
It will be appreciated by those skilled in the art that the foregoing is illustrative only, and that other types of applications, whether presently existing or later to be developed, that may be suitable for use with the embodiments of the present invention, are also encompassed within the scope of the present invention and are hereby incorporated by reference.
It will be appreciated by those skilled in the art that the number of various components shown in fig. 1 for simplicity only may be less than that in a single device, but such omissions are clearly not to be made without affecting the clarity and completeness of the disclosure of the embodiments of the invention.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A water treatment recovery device based on a metal-air battery is characterized by comprising: the system comprises an electricity generation system, an energy storage system and a water treatment and recovery system;
the power generation system comprises a corrosive metal cathode, an air diffusion anode and a cavity, wherein the corrosive metal cathode and the air diffusion anode are oppositely arranged and form a closed container together with the cavity, and the outer side of the air diffusion anode is in contact with air;
the power generation system is respectively connected with the energy storage system through a corrosive metal cathode and an air diffusion anode and used for storing electric energy generated in the power generation system into the energy storage system, and a reverse pole switch is arranged between the power generation system and the energy storage system and used for switching the anode and the cathode of the power generation system and adjusting the charging or discharging state;
the power generation system is connected with the water treatment recovery system through a pipeline, the water treatment recovery system comprises a circulating pump, a tank body and a crystallization filter, the circulating pump is used for pumping water in the tank body into the power generation system, and the crystallization filter is used for filtering and intercepting treated water.
2. The apparatus of claim 1, wherein the corrosive metal negative electrode is a magnesium, iron, aluminum plate, or an alloy plate of any two or three thereof; the air diffusion positive electrode comprises a carbon diffusion electrode substrate and a positive electrode catalyst layer loaded on the substrate.
3. The device according to claim 2, wherein the carbon diffusion electrode substrate is a sandwich structure consisting of a carbon active material, a current collector and an air diffusion layer; the anode catalyst layer is one of Ir oxide, Ru oxide, Co oxide, Mn oxide, Fe oxide, Pt and carbon black, or a compound of any of a plurality of components.
4. The device of claim 3, wherein the positive electrode catalyst layer is in the shape of an array arrangement of nanospheres, nanowires, nanorods, nanotubes or nanoflowers, and a circular hole is formed in one side of the cavity parallel to the air diffusion positive electrode and used for contacting with air.
5. The device of claim 1, wherein the energy storage system is a rechargeable battery.
6. The device of claim 1, wherein the circulation pump is a peristaltic pump, the cavity is an organic glass cavity, and the tank is an organic glass container or a plastic container; the metal filter head of the crystallization filter is made of stainless steel or titanium material, and the filtering aperture of the crystallization filter is 1-5 μm.
7. The device according to claim 1, wherein the electrode distance between the corrosive metal negative electrode and the air diffusion positive electrode is 0.5-2 cm.
8. The apparatus of claim 3, wherein the current collector is a mesh structure having electrical conductivity; the carbon active substance comprises one or more of activated carbon, carbon black, graphene and graphite powder; the air diffusion layer is a polytetrafluoroethylene coating.
9. The apparatus of claim 3, wherein the current collector is a mesh structure having electrical conductivity; the carbon active substance is carbon cloth or carbon paper.
10. A water treatment recovery method applied to the apparatus of any one of claims 1 to 9, comprising:
the first stage is as follows: placing wastewater to be treated in a tank body of a water treatment recovery system, starting a circulating pump, pumping the wastewater to be treated into a closed container of an electricity generation system, spontaneously utilizing the wastewater to be treated as electrolyte by a corrosive metal cathode to generate a galvanic cell reaction and release metal cations into the wastewater, and utilizing oxygen in air by an air diffusion anode to generate an oxygen reduction reaction to generate current which is stored in an energy storage system as electric energy;
the released metal cations enter a tank body of a water treatment recovery system, generate phosphate-form crystals with ammonia nitrogen and phosphate in the residual wastewater to be treated, and are separated by a crystallization filter;
and a second stage: changing the positive and negative polarities of electrodes in the original power generation system through a reverse pole switch, electrolyzing waste water by using collected electric energy as a direct current power supply, oxidizing chloride ions in the waste water into active chlorine by using a catalyst loaded on an air diffusion positive pole, and degrading organic matters in the waste water by using the active chlorine as an oxidizing agent; meanwhile, the generated active chlorine reacts with residual ammonia nitrogen in the wastewater in the first stage to further oxidize the ammonia nitrogen into nitrogen.
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| CN107285435A (en) * | 2017-07-05 | 2017-10-24 | 山东百川集大环境工程有限公司 | Double electrolysis remove the method and apparatus of the phosphorus in organophosphorus pesticide production waste water |
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| CN107285435A (en) * | 2017-07-05 | 2017-10-24 | 山东百川集大环境工程有限公司 | Double electrolysis remove the method and apparatus of the phosphorus in organophosphorus pesticide production waste water |
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