JP2009039705A - Air cell type waste water treatment apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a waste water treatment apparatus capable of both removing phosphorus by an electrochemical reaction means and decomposing organic matter by a biochemical reaction means over a long period of time in treatment of organic electrolyte waste water containing phosphate ions and phosphate compounds, while only phosphorus removal has been carried out conventionally by an electrochemical reaction means having a cell function. <P>SOLUTION: The waste water treatment apparatus comprises an air cell having a metal anode and a cathode of a carbon material such as black coal, hard charcoal, graphite or the like, which functions as both an electrochemical reaction means and a biochemical reaction means with the charcoal cathode serving as an organism carrier for an aerobic biological treatment tank in the treatment of organic electrolyte waste water containing phosphate ions or phosphorus compounds. The apparatus is also provided with a dissolved oxygen feeding means and a stirring means for efficiently continuing the electrochemical reaction and biochemical reaction, and a solid-liquid separating means for post treatment of the electrochemical reaction and biochemical reaction. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an organic aerobic biological treatment function and an electrochemical reaction function in the treatment of phosphate ion, phosphorous phosphorus or phosphorus compound-containing organic wastewater, and an oxygen supply means, a stirring means, a metal anode, black coal, and white coal. In addition, the present invention relates to an organic electrolyte wastewater treatment apparatus having an aerobic biological treatment tank equipped with an air battery as a carbonaceous cathode such as graphite or graphite, and is provided with a heating means if necessary, and further, if necessary, air The present invention relates to an organic electrolyte air battery type wastewater treatment apparatus that integrates electric power generated by battery power generation and electric power generated by solar battery power generation.

Organic electrolyte wastewater containing phosphorus has been treated by electrochemical reaction means based on electrolysis provided with a power source (for example, Patent Document 1).
Moreover, the method of heating and processing organic electrolyte wastewater in the electrolysis which provided the power supply is disclosed (for example, patent document 2).
Moreover, the knowledge which processes by the electrochemical reaction means by the primary battery comprised by the dissimilar metal electrode is disclosed (for example, patent document 3).
Moreover, the apparatus which heats and processes the wastewater process by electrolysis is disclosed. (For example, Patent Document 4).
Moreover, the knowledge of the primary battery power generation device of electrolyte is also disclosed (for example, patent document 5).
Moreover, the knowledge which comprises a primary battery with the electrolyte waste water and the dissimilar metal which are agitated and agitated and removes phosphorus, and the knowledge to generate electric power are also disclosed (for example, patent document 6).
In addition, the knowledge of air batteries using metal anodes and semiconducting charcoal cathodes is also disclosed. (For example, Patent Document 7).
In addition, the knowledge that charcoal has a wide surface area of micropores per gram per gram, has high adsorptivity, water permeability, and air permeability, and is a comfortable place for microbial growth is disclosed. (For example, Patent Document 8)
Moreover, the manufacturing method and utilization method of a high intensity | strength porous carbon molded object are disclosed using carbonaceous powder. (For example, patent document 9).
Further, it is disclosed that the life of an aluminum air battery is extended by using a depolarizer and an aluminum ion conductor. (For example, patent document 10).
Also disclosed is a method of oxidatively decomposing organic matter, ammonia, etc. with hypochlorous acid, ozone or active oxygen by electrochemical method or chemical addition. (For example, patent document 11).
However, there is no organic electrolyte wastewater treatment device that is made efficient by using an air battery having a metal anode and a semiconducting carbonaceous cathode. Moreover, there is no power generation device that integrates an air battery and a solar battery, which have the functions of aerobic biological treatment of organic matter in wastewater and phosphorus removal.
JP 2001-252668 A JP 10-323672 A JP 2001-252668 A JP 10-323672 A JP 2001-252668 A JP 2004-66223 A JP 2005-85719 A JP 2000-61452 A JP-A-10-45483 (Porous carbon molding) JP2006-147442. JP2004-330182A.

  In electrolyte wastewater treatment equipment for phosphorus removal using electrochemical reaction means by a primary battery method with a metal as an anode, the electrochemical reaction rate is slow at a low water temperature of about 10 ° C or less, which is not practical. No means for effectively removing phosphate ions and phosphorus compounds has been disclosed.

  And, in the electrochemical reaction means by the different metal primary battery in the primary battery method using the conventional metal as the anode, the phosphate ion, the phosphorous phosphorus or the phosphorus compound in the organic waste water is removed and the different metal primary battery is used. No means for aerobic biodegradation treatment of organic matter has been disclosed.

  In addition, in the treatment of organic electrolyte wastewater containing phosphate ions, phosphorous phosphorus, or phosphorus compounds near room temperature, the electrochemical reaction rate and biochemical reaction rate increase as the temperature rises. The conductivity of the anode decreases as the temperature rises, but the semiconducting carbon body whose conductivity increases as the temperature rises is used as the cathode of the air battery, and the semiconducting carbon body is used as a biological carrier in organic wastewater treatment. No means has been disclosed.

  In addition, in the primary battery wastewater treatment method using different metals as anode and cathode, the reaction rate is high in the low pH range and the reaction persists well, but the reaction rate in the vicinity of neutrality is slow. There was a problem of short duration of reaction.

  In addition, the primary battery wastewater treatment method using a metal as a cathode has a problem of low current density.

  In addition, the electrolysis method having a power source has a problem that it requires electric equipment costs and electric power costs.

  In the treatment of organic electrolyte wastewater containing phosphate ions, phosphate phosphorus or phosphorus compounds, the present invention does not require a power source and efficiently continues the electrochemical reaction for removing phosphorus over a long period of time. Let it be the first issue. Further, as a function of the electrode material, a second problem is to have not only a function of removing phosphorus but also a function deeply related to the ability to decompose and remove organic substances. In addition, the third issue is to make the electrochemical reaction and the biochemical reaction more efficient by preventing the decrease in the electrochemical reaction rate and the biochemical reaction rate with the decrease in water temperature in winter. . As a fourth problem, not only the electric equipment cost and the electric power cost are hardly required, but also an object is to produce electric power while removing phosphorus and decomposing the organic matter.

  In order to achieve the above object, the present invention has a technical configuration as described below. That is, in the treatment of organic electrolyte wastewater containing phosphate ions, phosphorous phosphorus, or phosphorus compounds, an air battery comprising a metal anode and a carbonaceous cathode such as black charcoal, white charcoal, graphite or graphite and the black charcoal, white charcoal, Electrochemical reaction means using a carbonaceous cathode such as graphite or graphite as a biological carrier for an aerobic biological treatment reaction tank, and provided with dissolved oxygen supply means and stirring means in order to continue electrochemical reaction and biochemical reaction efficiently And biochemical reaction means. In an aerobic biological treatment reaction tank, since it is common to provide dissolved oxygen supply means and stirring means by air aeration or oxygen aeration in water or mechanical surface aeration, they can be used together. Alternatively, a semiconducting ceramic plate-like porous white charcoal powder re-fired body obtained by mixing and pressure-molding a binder with carbonaceous powder and re-firing can be configured as a cathode. The organic electrolyte wastewater treatment containing phosphate ion, phosphate phosphorus or phosphorus compound includes treatment of seawater or lake water containing phosphate ion, phosphate phosphorus or phosphorus compound. As the metal anode, it is not preferable to contain harmful heavy metals and harmful metal compounds in the treated effluent due to the nature of organic wastewater treatment, so aluminum or aluminum alloy, magnesium or magnesium alloy, iron or iron alloy, etc. Preferably, the electrochemical reaction rate is the magnesium or magnesium alloy having the greatest ionization tendency, followed by aluminum or aluminum alloy, iron or iron alloy. However, there are many types of wastewater, and the solutes contained in the wastewater are solutes that suppress the electrochemical reaction or inhibit or interfere with each of these metals having anodes such as aluminum or aluminum alloys, iron or iron alloys, etc. Since it may be different from the case where it becomes the solute which becomes the same with respect to each of the said aluminum or aluminum alloy, iron, or an iron alloy, confirmation work may be required.

  In addition, in the treatment of organic wastewater containing phosphate ions, phosphoric acid phosphorus or phosphorus compounds that are solid-liquid separated as metal phosphates and metal hydroxides that are sparingly soluble in water, the electrochemical reaction by the air battery is continued efficiently. Therefore, an electrochemical reaction means provided with a dissolved oxygen supply means and a stirring means and a carbonaceous cathode such as black coal, white coal, graphite or graphite are used as a biological carrier for an aerobic biological treatment reaction tank.

  In addition, near the room temperature, the electrical conductivity of the semiconducting carbon body is different from the electrical conductivity of the metal in which the electrical conductivity of the metal decreases with increasing temperature. On the other hand, the electrochemical reaction rate and the biochemical reaction rate also increase with the temperature rise, so that the water to be treated in the aerobic biological treatment reaction tank is heated by heating means with a low-temperature heat source such as factory waste heat. It is. However, since the optimal temperature for aerobic organisms is around 30 ° C., it is not preferable to overheat.

  Also, an air battery module that uses phosphate electrolyte, phosphoric acid phosphorus, or phosphorus compound-containing organic electrolyte wastewater as an aerobic biological treatment reactor with a metal anode and a carbonaceous cathode such as black charcoal, white charcoal, graphite or graphite In addition, the carbonaceous cathode is used as a biological carrier for the aerobic biological treatment reaction tank, and the air battery modules are connected in series and parallel to form an air battery string. In addition, an electrochemical reaction by an air battery generates a poorly soluble metal phosphate salt and a highly cohesive metal hydroxide particle, and generates electric power. If necessary, voltage adjusting means is added to the air battery module system. Wiring integration means for connecting and integrating the plurality of air cell strings and the plurality of solar cell strings, a charge / discharge controller, and a power conditioner are disposed. Further, a power storage means is provided if necessary. The aerobic biological treatment reaction tank also includes sea areas and lakes that are natural aeration resources.

  In addition, oxygen is effectively supplied to the internal micropores of the porous carbon body by providing the porous carbon body with a diffuser function as well as a cathode function and a microorganism carrier function.

  In addition, in the treatment of organic electrolyte wastewater, only an air battery using a metal anode and a carbonaceous cathode such as black coal, white coal, graphite or graphite has a low voltage and current, and an electrochemical reaction in the organic electrolyte wastewater is insufficient. When there is a need for a stronger electrochemical reaction, an air battery formed of a stronger electrolyte and an electrode than the organic electrolyte waste water is connected in series or in parallel.

  Also, an air battery in which an air battery made of a carbonaceous cathode such as black coal, white coal, graphite or graphite having both an electrolyte solution contacting means and air or oxygen gas contact means is formed by a stronger electrolyte and an electrode than an organic electrolyte is used. An aerobic biological treatment reaction tank, oxygen supply means, stirring means and metal anode and carbonaceous cathode such as black charcoal, white charcoal, graphite or graphite in the treatment of organic electrolyte wastewater containing phosphate ion, phosphorous phosphorus or phosphorus compound Connect in series or parallel to the air battery.

Further, the depolarizer is brought into contact with or carried on the carbonaceous cathode. As the depolarizer, manganese dioxide is preferable and does not exclude manganese nodules, hydrogen peroxide, and the like.
An aluminum ion conductor is brought into contact with the aluminum anode. As the aluminum ion conductor, a ceramic solid electrolyte, a polymer ion conductor, or the like can be applied.
In addition, depending on the electrochemical reaction function, water phosphates and metal hydroxide particles that are hardly soluble in water are produced, and depending on the biochemical reaction function, the air cells for aerobic biodegradation treatment of organic substances are connected in series and parallel. The power source generated by the constructed air battery power generation means energizes the electrode pair consisting of an insoluble anode and a cathode capable of reducing water to hydrogen gas, and is immersed in an organic wastewater containing chloride ions pretreated by solid filtration. The action of the first problem solving means for oxidizing and decomposing organic matter, ammonia, etc. with the generated hypochlorous acid, ozone or active oxygen is as follows. That is, in the dissolved oxygen supply means and the stirring means, the method of aeration by aeration of the air supplied by the blower from the aeration device is the most common and easy method, but the mechanical aeration of the surface aeration method should be used It is also possible to diffuse oxygen gas from the diffuser, and there is no restriction other than economic efficiency. Furthermore, natural aeration in a lake, river or sea may be used. By aeration and agitation, dissolved oxygen necessary for the electrochemical reaction of the air battery is supplied and the reaction product and the reaction material in the electric double layer or in the vicinity of the electric double layer in the electrode are quickly exchanged. In the case of disposing an air battery in an aeration tank or the like in organic biological treatment, the dissolved oxygen supply means and the stirring means are generally disposed in the aeration tank or the like. It is not necessary to provide separate dissolved oxygen supply means and stirring means.

  In general, electrolyte reaction water containing orthophosphoric acid ions is composed of magnesium, aluminum or iron as an anode, and a carbon cell such as black charcoal, white charcoal, graphite or graphite is used as a cathode, and an electrochemical reaction treatment is performed. For example, in the case of an aluminum anode, oxygen molecules adsorbed on the microporous wall of the carbonaceous material are dissociated into oxygen atoms, and the electrons ionized by the aluminum dissolution reaction are received together with water molecules via the cathode. Dissolves as ions.

At the anode, aluminum atoms leave three electrons in the metal and dissolve in the electrolyte as trivalent aluminum ions, and the three electrons move from the anode to the cathode through an external circuit in which the anode and the cathode are connected by a wire. As a result, current flows from the cathode to the anode through an external circuit connected by electric wires.

  And it reacts with the trivalent aluminum ion melt | dissolved in water, a hydroxide ion, and an orthophosphate ion, and produces | generates the aluminum hydroxide and aluminum phosphate which are the hardly soluble and have good sedimentation shown by the following Reaction Formula.

Furthermore, aluminum hydroxide produces alumina by a dehydration reaction.

  In addition, the action of the means for solving the second problem is that the electrochemical reaction rate is extremely lowered in a low water temperature environment in winter. Therefore, by heating the wastewater to be treated as necessary, a water temperature of less than 80 ° C. If it is higher, the electrochemical reaction rate becomes larger, the reaction product particle shape becomes larger and the viscosity of the waste water becomes smaller, so that the electrochemical reaction is promoted and particles having good sedimentation properties are produced.

  In addition, the water temperature in the aerobic biological treatment is preferably around 30 ° C., but generally the waste water temperature is often around 15 ° C. or more, and therefore, a low waste heat is often sufficient as a heating source.

  Therefore, if there is a need for good treated water having a low water temperature, heating the treated water with the heating means effectively acts on the electrochemical reaction and the biochemical reaction.

  Further, in the semiconducting carbon body used in the present invention, the free electron density excited in the conduction band and the free hole density generated as an electron shell in the valence band increase as the temperature rises. Increases exponentially. Further, the semiconducting carbon body also has a function as an aerobic biological carrier. Generally, an aerobic organism has an optimum temperature around 30 ° C. Therefore, an air battery using a semiconducting carbon body as a cathode is useful as a cathode of an air battery by heating water to be treated with factory waste heat or the like.

  Also, the third problem solving means is that the open voltage of the single air battery is about 0.6 V and the current is only several mmA to several tens of mmA, so that a voltage and current suitable for the purpose of use can be obtained. The aerobic biological treatment reaction tank is partitioned by a partition plate having a plurality of flow holes, and a plurality of unit air batteries are arranged in each partition tank, and the unit air batteries are connected in parallel to increase the amount of current. Battery module. And if necessary, voltage adjustment, backflow prevention, DC / AC conversion, and the like are incorporated in the same manner as the solar cell. For example, if necessary, a plurality of air battery modules connected in parallel and a backflow prevention diode are connected in series to form an air battery string. In addition, an automatic booster unit is connected to the output side of the air cell strings and the solar cell strings so as not to cause any trouble even if the air cell strings and the solar cell strings are connected in parallel as necessary. The voltage can be adjusted. Of course, each of the solar cell strings is composed of each module, a backflow prevention diode and a bypass diode, and an electric wire combining an array circuit in series and parallel. Furthermore, the output side of the primary battery strings and the solar cell strings is connected to the input side of a power conditioner incorporating DC power conversion means and system linkage protection means, and the output of the power conditioner Connect the side to the input side of the distribution board. A commercial power supply is connected to the input side of the distribution board. By wiring in this way, the power generated by the primary battery can be handled as the same power generated by the solar battery. In addition, although the aerobic biological treatment tank provided with an air battery was divided with a partition plate to make an air battery here, a plurality of compartments may be connected in parallel to form an air battery module. An air battery module may be connected in series. In addition, it is possible to perform a self-sustained operation by adding a storage battery, to switch between commercial and private power generation, or to be an independent system not linked to a commercial power source. In other words, all of the power generation systems, charge / discharge systems, power conversion systems, protection systems, and wiring works that have been conventionally performed by solar cell strings alone can be applied except for mobility.

  In addition, oxygen is infiltrated into the pores of the porous carbon body by providing the porous carbon body with a diffuser function as well as a cathode function and a biological carrier function.

In addition, in the treatment of organic electrolyte wastewater, only an air battery using a metal anode and a carbonaceous cathode such as black coal, white coal, graphite or graphite has a low voltage and current, and an electrochemical reaction in the organic electrolyte wastewater is insufficient. When a primary battery formed of a stronger electrolyte and an electrode than the organic electrolyte wastewater is connected in series when there is a more or more powerful electrochemical reaction, the voltage and current of the electric circuit increase and the organic electrolyte The electrochemical reaction in the wastewater becomes stronger. The electrolyte other than the organic electrolyte waste water is preferably a strong electrolyte.
Also, an air battery in which an air battery made of a carbonaceous cathode such as black coal, white coal, graphite or graphite having both an electrolyte solution contacting means and air or oxygen gas contact means is formed by a stronger electrolyte and an electrode than an organic electrolyte is used. Aerobic bioreactor, oxygen supply means, agitation means and metal anode and carbonaceous cathode such as black charcoal, white charcoal, graphite or graphite in the treatment of organic electrolyte wastewater containing phosphate ion, phosphorous phosphorus or phosphorus compound If the battery is connected in series or in parallel, the aerobic organisms will not be able to survive or the survival activity will be suppressed in liquids of strong electrolytes rather than organic electrolytes. Ingestion is insignificant, whether by air batteries alone or by aerobic organisms. Accordingly, by disposing a part of the porous carbonaceous cathode exposed in the air or oxygen gas, it can be replenished as long as it exceeds the amount of oxygen consumed by the electrochemical reaction of the air battery.
Electrons flowing from the anode and hydrogen ions combine to prevent the progress of the electrode reaction. However, when an oxidizing agent such as manganese dioxide, hydrogen peroxide, or potassium dichromate is in contact with or supported on the carbonaceous cathode, an electrode reaction is generated. Oxidizes the hydrogen of the product to suppress the decrease in electrode reaction.
In addition, when an aluminum ion conductor is brought into contact with the aluminum anode, aluminum ions generated by oxidation of aluminum are combined with the aluminum ions and hydroxide ions on the surface of the aluminum anode to form aluminum hydroxide. Although discharge by reaction is inhibited, when an aluminum ion conductor is brought into contact with the aluminum anode, aluminum ions and hydroxide ions are combined in the aluminum ion conductor, so that aluminum hydroxide is contained in the aluminum ion conductor. Generated in a distributed manner. Due to such a mechanism, it is presumed that aluminum hydroxide, which has been a problem in the past, suppresses discharge inhibition due to adhesion to the surface of the aluminum anode, and suppresses discharge inhibition due to the aluminum hydroxide.

  Since the present invention is configured as described above, the following effects can be obtained.

  Constructing an air battery comprising an organic electrolyte wastewater containing phosphate ions, phosphorous phosphorus or phosphorus compounds in an aerobic biological treatment reaction tank and using a metal anode and a carbon material cathode such as black coal, white coal, graphite or graphite A carbonaceous cathode such as black charcoal, white charcoal, graphite or graphite is used as a biological carrier for the aerobic biological treatment reaction tank, and dissolved oxygen supply means and stirring means are installed to continue the electrochemical reaction and biochemical reaction efficiently. By using the electrochemical reaction means and the biochemical reaction means as well as post-processing the solid-liquid separation means as a post-treatment of the electrochemical reaction means and the biochemical reaction, a power source is not required as in the electrolysis method, While removing phosphorus, the carbonaceous cathode such as black charcoal, white charcoal, graphite or graphite also serves as a biological carrier, so the installation area can be reduced. There is a low effect of suppressing the cost of equipment it is possible to fence. Carbon body such as black charcoal, white charcoal, graphite or graphite is an extremely porous material having a fine pore surface area of 100 to 400 square meters per gram, and has high adsorptivity, water permeability and air permeability, and is comfortable for microorganisms. Since the mineral content to be eluted becomes a eutrophic source of microorganisms, it has an effect of increasing the processing efficiency. Then, metal phosphates, metal hydroxides and metal oxides are produced by oxidation / reduction with anodes and cathodes of air batteries, but these are hardly soluble and have good sedimentation, so that they also have the effect of facilitating solid-liquid separation. is there.

  Semiconducting charcoal is produced by using sawdust or large sawdust generated when sawing various kinds of wood, drying the large sawdust, compressing it from powder to a hard bulk shape, and firing it. Moreover, the semiconducting charcoal used for the wastewater treatment can be used as a fuel by adding a chlorine sterilization treatment and a drying treatment. Therefore, since unused resources can be used effectively, the effect of preventing global warming, the effect of energy saving, and the effect of reducing wastewater treatment costs are exhibited.

  When the water temperature is low, such as in winter, the electrochemical reaction rate and the biochemical reaction rate are slow and the conductivity of the semiconducting carbonaceous material decreases, so when the water temperature is raised by heating, the electrochemical reaction rate and the biochemical reaction As the speed increases, the conductivity of the semiconducting carbonaceous material increases, and the phosphorus removal efficiency and the BOD removal efficiency are improved. Further, when the water temperature rises, the viscosity is lowered, and there is an effect that the particles are easily separated or separated by filtration.

  In the treatment of organic electrolyte wastewater containing phosphate ion, phosphorous phosphorus or phosphorus compound, the black charcoal having a large current density while constituting an air battery with a metal anode and a carbonaceous cathode such as black charcoal, white charcoal, graphite or graphite, Electricity provided with carbonaceous cathodes such as white coal, graphite or graphite as the biological carrier of the aerobic biological treatment reaction tank, and further provided with dissolved oxygen supply means and stirring means in order to continue the electrochemical reaction and biochemical reaction efficiently. Since the wastewater treatment having chemical reaction means and biochemical reaction means can be used together with the generated electric power, there are effects of preventing global warming, reducing fossil fuel power generation and nuclear power, and improving economic efficiency.

  In the organic electrolyte wastewater containing phosphate ion, phosphate phosphorus or phosphorus compound, an air battery with a metal anode and a carbonaceous cathode such as black charcoal, white charcoal, graphite or graphite is disposed and a solar cell is also provided. By integrating with the wiring integration means, it is possible to share electric equipment such as a power conditioner, automatic voltage regulator, transmission / reception substation equipment, etc., so there is an effect of reducing power generation cost.

  In addition, oxygen is supplied into the pores of the porous carbon body by providing the porous carbon body with the cathode function and the microbial carrier function as well as the diffuser function, so that the electrochemical reaction at a high current density. Can be sustained.

  In addition, in the treatment of organic electrolyte wastewater, only an air battery using a metal anode and a carbonaceous cathode such as black coal, white coal, graphite or graphite has a low voltage and current, and an electrochemical reaction in the organic electrolyte wastewater is insufficient. If a primary battery formed of a strong electrolyte and an electrode is connected in series to the organic electrolyte wastewater when there is or a stronger electrochemical reaction is required, the electrochemical reaction rate in the organic electrolyte wastewater is increased. As a result, the rate of formation of poorly soluble phosphate is increased, and phosphorus removal is promoted. Moreover, since the voltage and current of the electric circuit increase, the amount of generated power increases.

  In addition, the breakdown of dissolved oxygen consumption in carbonaceous cathode air cells using saturated saline, saturated saline and ammonium sulfate, strong acidic water, strong alkaline water, etc. as the electrolyte other than organic electrolyte wastewater is the aerobic organism. There is little or no consumption due to air, and since dissolved oxygen consumption by the air battery is sufficient for natural replenishment, there is no need to diffuse air or oxygen, thus saving energy.

  Further, when an oxidizing agent such as manganese dioxide, hydrogen peroxide, potassium dichromate or the like is brought into contact with or supported on the carbonaceous cathode, hydrogen of the electrode reaction product is oxidized to suppress a decrease in the electrode reaction. There is an effect of suppressing a decrease in current density.

  Further, when the aluminum ion conductor is brought into contact with the aluminum anode, discharge inhibition due to aluminum hydroxide is suppressed, so that there is an effect of suppressing electromotive force and current density reduction.

  In addition, an insoluble anode and an electrode pair composed of a cathode having the ability to reduce water to hydrogen gas by a power source generated by an air battery power generation means are electrolyzed and are subjected to solid matter filtration pretreatment chlorine ion-containing organic waste water. By removing the phosphorus as a metal phosphate that is hardly soluble in water by the electrochemical reaction function of the air battery that oxidizes and decomposes organic substances, ammonia, etc. with hypochlorous acid, ozone or active oxygen generated by immersion in water. Compared to wasted use of available electricity, it is an effective use of resources, and it is energy saving compared to electrolysis with a power source.

  In addition, the amount of current in electrolysis is not proportional to the amount of electrochemical reaction alone, but the current in a primary battery such as an air battery is a phenomenon physical quantity as a result of the amount of electrochemical reaction. Since the state of the electrochemical reaction of the air battery can be monitored by measuring and monitoring the current, the current can be used as a management index of the wastewater treatment state.

  Embodiments will be described with reference to the drawings. In the first embodiment according to the first invention shown in FIG. 1, FIG. 2, FIG. 3, FIG. 4 and FIG. 5, organic electrolyte wastewater containing at least phosphate ions, phosphorous phosphorus or phosphorus compounds is used. An electrically insulating mesh material comprising a flat aluminum anode 3 and a flat charcoal cathode 4 in the organic electrolyte waste water at the upper part of the contact material bed 2 in the catalytic oxidation reaction tank 1 for aerobic biological treatment. The flat aluminum anode 3 and the flat charcoal cathode 4 are electrically connected by an electric conductor 6 in the vicinity of 5 to form a unit air cell 7 and 42 units. The air battery type waste water treatment apparatus 9 is configured by supporting the air battery 7 with a support frame 8. The air diffuser 10 supplies air for aerobic organisms and oxygen necessary for the oxidation reaction of the air battery and diffuses and agitates to promote the oxidation reaction. The support frame 8 is provided with a large number of lattice-shaped flow holes 8a each having a thin member so as not to obstruct the flowing water as much as possible. In addition, the treated water is transferred to a precipitation tank 11 placed after the catalytic oxidation reaction tank 1 to form a water-insoluble aluminum phosphate, metal hydroxide, alumina, biological solids in the catalytic oxidation reaction tank 1. And other settled solids are separated by precipitation to discharge clear water. The organic electrolyte wastewater treatment includes seawater or lake water treatment, and of course, organic electrolyte wastewater treatment containing at least phosphate ions or phosphorus compounds described below. Also apply to. In this embodiment, the flat aluminum anode 3 and the flat charcoal cathode 4 are immersed in close proximity with the electrically insulating mesh material 5 interposed therebetween. Even when the door 3 and the plate-like charcoal cathode 4 are separated by up to about 10 cm, the electrochemical reaction occurs sufficiently without any practical problem. In this example (the same applies to the other examples below), an air battery type wastewater treatment device is provided together with the contact material bed 2, but the standard activated sludge method, the carrier fluidized biological filtration method, the long-time aeration method, etc. It can be installed together with other aerobic biological treatments, or can be provided alone.

In the second embodiment according to the first invention shown in FIG. 6, the contaminant removal tank 12, the anaerobic filter bed tank 13, the carrier fluid biological filtration tank 14, the treated water tank 15, and the disinfection tank 16 are processed in this order. The carrier fluid biological filtration tank 14 of the carrier fluid biological filtration system arranged in the water flow direction is disposed in the carrier fluid biological filtration tank 14 with the aluminum anode 3 and the charcoal cathode 4 sandwiched between the electrically insulating mesh material 5. Air in which a plurality of unit air cells 7 that are immersed in close proximity and electrically connected to each other by the electric conductor 6 and the flat aluminum anode 3 and the flat charcoal cathode 4 are supported by a support frame 8. A battery unit 9 is provided.
In the third embodiment according to the first invention shown in FIG. 7, the air battery unit disposed in the middle of the circulation pipe 19 of the circulation device 18 of the carrier flow biological filtration system combined treatment purification tank 17 shown in FIG. An air battery unit 9 is disposed in the storage tank 20. The circulation device 18 is provided with an air lift pump 21.

  In the fourth embodiment according to the first invention shown in FIG. 4, FIG. 5, FIG. 8, FIG. 9, FIG. 11, FIG. A plurality of unit air cells 7 shown in FIG. 4 and FIG. 5 are arranged on the support frame 8 in the enclosed lake water to be used as the air cell unit 9, and the support frame 8 is partly immersed in water and the rest is on the water. The float 22 is placed above the contact material floor 2 of the floating tank purifier 23 floated on the water by the float 22. Then, when the outside lake water of the floating tank type purifying device 23 is aerated by the air diffuser 10 and the closed lake water is introduced into the floating type purifying device 23 by the circulating submersible pump 24 and is absorbed so as to be a downward flow. Then, the air passes through the air battery unit 9 and the contact material floor 2, passes through a water collecting hopper and a water collecting pipe, and is discharged to a lake by the circulating submersible pump 24. The closed lake water is purified by repeating this series of operations. The floating tank type purification device 23 in which weights 25 for securing stability against wind and waves are suspended by hangers 26 is moored by an anchor 27. In this embodiment, a closed lake is used, but the present invention can also be applied to a closed sea area. Also in the aeration method, surface mechanical aeration, deep layer aeration, natural aeration, etc. other than the present embodiment can be applied, and any aeration method is not excluded.

  FIG. 13 shows another embodiment of the unit air cell 7 in the first to fourth embodiments according to the first invention, in which the cylindrical hole 28 of the cylindrical charcoal cathode 4 is made of stainless steel. A round rod-shaped ring-shaped aluminum anode in which an aluminum terminal 31 is electrically connected and fixed to the outer periphery of the cylindrical charcoal cathode 4 to which the terminal 29 is fixed with a conductive resin 30 with an electrically insulating mesh 5 interposed therebetween. 3 is disposed.

  FIG. 14 shows another embodiment of the unit air battery 7 in the first to fourth embodiments according to the first invention, in which the cylindrical hole 28 of the cylindrical charcoal cathode 4 is made of stainless steel. A cylindrical aluminum anode 3 in which an aluminum terminal 31 is electrically connected and fixed to the outer periphery of the cylindrical charcoal cathode 4 to which a terminal 29 is fixed with a conductive resin 30 is sandwiched by an electrically insulating mesh 5 is disposed. ing.

  FIG. 15 shows another example of the unit air cell 7 in the first to fourth embodiments according to the first invention, in which the cylindrical charcoal cathode 4 is not shown. A stainless steel terminal 29 with a stopper portion 32 and a male screw portion 33 is inserted into the hole 28 and tightened with a stainless nut 34.

  FIG. 16 shows another example of the unit air battery 7 in the first to fourth embodiments according to the first invention, in which both sides of the flat aluminum anode 3 are electrically insulated. Five sets of unit air cells 7 configured by electrically connecting two flat graphite cathodes 35 sandwiching the mesh 5 and the aluminum anode 3 through electric conductors 6 are accommodated in a support frame 8.

  What is shown in FIG. 17 is one of the other forms of the unit air cell 7 in the first to fourth embodiments according to the first invention, in which two flat plate-like aluminum anodes 3 are arranged on the inside. Five sets of unit air cells 7 configured by disposing flat graphite cathodes 35 apart from each other and being electrically connected by electric conductors 6 are accommodated in a support frame 8.

  What is shown in FIG. 18 is one of the other forms of the unit air cell 7 in the first to fourth embodiments according to the first invention, and is a cylindrical hole 28 of a plurality of cylindrical charcoal cathodes 4. Are electrically connected to each other through a carbon fiber string 36 and housed in a carbon fiber cloth bag 37 to constitute a charcoal cathode unit 38, and two flat plate-like shapes having an electrically insulating mesh 5 sandwiched between both sides of the charcoal cathode unit 38. The unit air cell 7 is configured by electrically connecting the aluminum anodes 3 with electrical conductors 6. As an alternative to the carbon fiber string 36, a stainless steel wire may be used.

  In the fifth embodiment according to the second invention shown in FIG. 19, in addition to the structures in FIGS. 1, 2, 3, 4 and 5, the water to be treated in the catalytic oxidation reaction tank 1 is lower. The heater 39, which uses waste heat from a factory, is heated to promote the electrochemical reaction to increase the phosphorus removal efficiency and the biochemical reaction to increase the BOD removal efficiency. In addition, the treated water is transferred to a precipitation tank 11 placed after the catalytic oxidation reaction tank 1 to form an aluminum phosphate, metal hydroxide, alumina, biological solid which is hardly soluble in the water generated in the catalytic oxidation reaction tank 1. And other settled solids are separated by precipitation to discharge clear water.

  In the sixth embodiment according to the third invention shown in FIG. 20 and FIG. 21, the catalytic oxidation reaction tank 1 for biologically treating organic electrolyte wastewater containing phosphate ions, phosphate phosphorus or phosphorus compounds is ionized. The partition wall 40A and the partition wall 40B having a flow-inhibiting function are divided into six sections, which are unit contact oxidation reaction tanks 1-1, 1-2, -3 and 1-4, 1-5, 1-6. Each of the six-compartment unit catalytic oxidation reaction tanks 1-1, 1-2, 1-3, 1-4, 1-5, and 1-6 has a set of illustrations for explanation. Only the unit air battery 7 is shown, but six sets of air battery modules 41-1, 41-2, 41-3, 41-4, 41-5 configured by connecting 10 sets of unit air batteries 7 in parallel are shown. And 41-6. And six sets of the air battery modules 41-1, 41-2, 41-3, 41-4, 41-5 and 41-6 are connected in series with electric wires 42A, 42B to form an air battery string 43. Yes. Further, the output side of the air battery string 43 and the output side of the solar cell string 44 are connected and integrated in the connection box 45, and the output side of the connection box 45 is connected to the charge / discharge controller 46, the power conditioner 47, and the distribution board. 48 and a commercial power source are sequentially connected by electric wires 42A and 42B to constitute a power receiving facility 49. Although not shown in the present embodiment, the reference electromotive force determined among the plurality of air battery modules 41-1, 41-2, 41-3, 41-4, 41-5, and 41-6. An automatic booster (not shown) is connected to the output side of any of the air battery modules 41-1, 41-2, 41-3, 41-4, 41-5 and 41-6. You can also.

  In the first embodiment according to the fourth invention shown in FIG. 22, a semiconductive ceramic porous white charcoal grain shaped refired body 50 obtained by mixing and pressure forming a white coal granule with a binder and refiring it. The air supply pipe 51 is inserted into the hole 50-a, and an adhesive is filled and fixed in the gap between the hole 50-a and the air supply pipe 51, and the conductor 6 is electrically fixed to form the cathode diffuser plate 52. The cathode diffuser plate 52 and the aluminum anode 3 are electrically connected by an electric conductor 6 and have the diffuser function as well as the cathode function and the microorganism carrier function, thereby forming the porous white coal particle molding. Oxygen is supplied into the pores of the refired body 50.

  In the first embodiment according to the fifth invention shown in FIG. 23, the aluminum anode 3 is added to the aeration tank water 53 in which the organic electrolyte waste water containing phosphorus is treated by the activated sludge method, and the binder is added to the white coal powder. Are mixed and pressure-molded and re-fired to form an air battery 55 composed of a semiconducting ceramic plate-like porous white charcoal powder re-fired cathode 54, a salt saturated water 56, a magnesium anode 57 and plate-like porous white coal. A booster air battery 58 composed of a powder-molded refired cathode 54 is electrically connected in series. In the present embodiment, the plate-like porous white charcoal powder molded refired cathode 54 made of a semiconducting ceramic material is obtained by mixing and pressure molding a salt saturated water 56, a magnesium anode 57, and white charcoal powder, followed by refiring. The booster air battery 58 is electrically connected in series. As an alternative to the booster air battery 58, for example, an alkaline solution is used as the electrolyte, the anode is aluminum, the cathode is graphite, the catalyst is chloride ion, and the like. Can also be used. As an alternative to the booster air battery 58, any primary battery is not excluded as long as the voltage and current characteristics are superior to the air battery 55 of the phosphorus-containing organic electrolyte wastewater treatment device.

  In the first embodiment according to the sixth invention shown in FIG. 24, an electrolytic gel 59 in which a salt saturated water (not shown) and a superabsorbent polymer (not shown) are mixed is applied to the aluminum anode 3 and stored in the tea bag quality bag 60. The two plate-like porous white charcoal powder molded refired cathodes 54 are in close contact with both sides, and the other surfaces of the two plate-like porous white charcoal powder shaped refired cathodes 54 are exposed to the air to vent. Stored in the storage box 61.

  In the second embodiment according to the sixth invention shown in FIG. 25, six grooves 62a are provided on the surface exposed to the air as an alternative to the semiconductive white charcoal powder plate-shaped refired body 57 shown in FIG. By increasing the contact area with air, the oxygen supply into the pores of the plate-like porous white coal powder refired body 62 is increased. The shape for increasing the contact area with the air is not limited to the groove 62a, and various other shapes such as a punched hole are conceivable.

  In the first embodiment relating to the seventh invention shown in FIG. 26, manganese dioxide particles 63 as a depolarizer are accommodated in a woven bag 64 and brought into contact with a plate-like porous white charcoal powder molded refired cathode 54. Yes.

  In the first embodiment according to the eighth invention shown in FIG. 27, an aluminum ion conductor 65 is in contact with the aluminum anode 3.

The schematic longitudinal cross-sectional view of the waste water treatment apparatus which shows a 1st Example. AA view of FIG. BB view of FIG. The enlarged view of the unit air battery of FIG. CC view of FIG. The schematic longitudinal cross-sectional view of the waste-water-treatment apparatus which shows the 2nd Example of 1st invention. The schematic longitudinal cross-sectional view of the waste-water-treatment apparatus which shows the 3rd Example of 1st invention. The schematic longitudinal cross-sectional view of the waste-water-treatment apparatus which shows 4th Example of 1st invention. DD view of FIG. EE view of FIG. FF view of Fig. 8 GG view of FIG. The schematic perspective view which shows another form of a unit air battery. The schematic perspective view which shows another form of a unit air battery. The schematic perspective view which shows another form of a unit air battery. The schematic perspective view which shows another form of a unit air battery. The schematic perspective view which shows another form of a unit air battery. The schematic perspective view which shows another form of a unit air battery. The schematic longitudinal cross-sectional view of the waste-water-treatment apparatus which shows 5th Example of 2nd invention. The schematic system diagram of the air battery power generation device showing the sixth embodiment of the third invention. HH view of FIG. The schematic perspective view which shows the form of the unit air battery of 7th Example of 4th invention. The schematic system diagram of the wastewater treatment apparatus showing the first embodiment of the fifth invention. The schematic perspective view which shows the form of the unit air battery which shows the 1st Example of 6th invention. The schematic perspective view which shows the form of the unit air battery which shows 2nd Example of 6th invention. Schematic explanatory drawing which shows the form of the depolarizer which shows the 1st Example of 7th invention Schematic explanatory drawing which shows the form of the aluminum ion conductor of 1st Example of 8th invention

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Contact oxidation reaction tank 2 Contact material bed 1-1, 1-2, 1-3, 1-4, 1-5, 1-6 Unit contact oxidation reaction tank 3 Arminium anode 4 Charcoal cathode 5 Electric insulation mesh 6 Electricity Conductor 7 Unit air battery 8 Support frame 8a Flow hole 9 Air battery type wastewater treatment device 10 Aeration device 11 Precipitation tank 12 Contaminant removal tank 13 Anaerobic filter bed tank 14 Carrier fluid biological filtration tank 15 Treatment water tank 16 Disinfection tank 17 Carrier Fluidized biological filtration system combined treatment purification tank 18 Circulating water device 19 Circulating piping 20 Air battery unit storage tank 21 Air lift pump 22 Float 23 Floating tank type purification device 24 Circulating submersible pump 25 Weight 26 Hanger 27 Anchor 28 Cylindrical hole 29 Stainless steel terminal 30 Conduction Resin 31 Aluminum Terminal 32 Stopper 33 Male Thread 34 Stainless Nut 35 Graphite cathode 36 Carbon fiber string 37 Carbon fiber cloth bag 38 Charcoal cathode unit 39 Heater 40A, 40B Partition wall
41-1, 41-2, 41-3, 41-4, 41-5, 41-
6 Air battery module 42A, 42B Electric wire
43 Air cell strings 44 Solar cell strings 45 Junction box 46 Charge / discharge controller 47 Power conditioner 48 Power distribution panel 49 Power receiving equipment 50 Porous white charcoal grain re-fired body 50-a hole
51 Air supply pipe 52 Cathode diffuser plate 52
53 Water in the aeration tank 54 Plate-like porous white coal powder refired cathode 55 Air battery 56 Salt saturated water 57 Magnesium anode 58 Booster air battery 59 Electrolyte gel 60 Tea bag quality bag 61 Breathable storage box 62a Groove
62 Semiconducting white charcoal powder plate-shaped refired cathode 63 Manganese dioxide grains 64 Woven fabric bag 65 Aluminum ion conductor

Claims (8)

In the treatment of organic electrolyte wastewater containing phosphate ion, phosphate phosphorus or phosphorus compound, oxygen supply means, stirring means and metal anode and air battery made of carbonaceous cathode such as black charcoal, white charcoal, graphite or graphite Air battery type characterized in that depending on the electrochemical reaction function, metal phosphate and metal hydroxide particles that are sparingly soluble in water are generated and organic matter is aerobically biodegraded depending on the biochemical reaction function. Waste water treatment equipment.
  In the treatment of organic electrolyte wastewater containing phosphate ion, phosphorous phosphate or phosphorus compound, oxygen supply means, stirring means, heating means as required, and metal anode and carbonaceous cathode such as black charcoal, white charcoal, graphite or graphite By forming an air battery, it is possible to generate metal phosphates and metal hydroxide particles that are sparingly soluble in water depending on the electrochemical reaction function, and aerobic biodegradation treatment of organic matter depending on the biochemical reaction function The air battery type waste water treatment apparatus according to claim 1.   In the treatment of organic electrolyte wastewater containing phosphate ion, phosphorous phosphorus or phosphorus compound, oxygen supply means, stirring means, heating means as necessary, and metal anode and carbonaceous cathode such as black coal, white coal, graphite or graphite By disposing an air battery, an electrochemical reaction function generates a metal phosphate and metal hydroxide particles that are sparingly soluble in water and an aerobic biodegradation treatment of organic matter depending on the biochemical reaction function, A battery array configured by connecting the air cells and solar cells, which are additionally connected with series-parallel connection means, backflow prevention means, and automatic voltage boosting means for a plurality of the same or different types of air batteries as necessary, by wiring integration means, and necessary The power conditioner is arranged according to the condition, and the power storage means is arranged as necessary. Gas-powered waste water treatment equipment.   The oxygen is effectively supplied to the internal micropores of the porous carbon body by providing the porous carbon body with a diffuser function as well as a cathode function and a microorganism carrier function. The air battery type wastewater treatment apparatus according to 1, 2 or 3.   In the treatment of organic electrolyte wastewater containing phosphate ion, phosphorous phosphorus or phosphorus compound, oxygen supply means, stirring means, heating means as necessary, and metal anode and carbonaceous cathode such as black coal, white coal, graphite or graphite The air battery type wastewater treatment apparatus according to claim 1, 2 or 3, wherein an air battery formed of an electrode and a stronger electrolyte than an organic electrolyte is connected in series or in parallel with the air battery.   It is characterized in that a carbonaceous cathode such as black coal, white coal, graphite or graphite and a metal anode having both an electrolyte solution contacting means and air or oxygen gas contacting means are used as electrodes in contact with a stronger electrolyte than an organic electrolyte. The air battery type wastewater treatment apparatus according to claim 5.   5. The air battery type wastewater treatment apparatus according to claim 1, wherein the depolarizer is in contact with or carried on the carbonaceous cathode. 5. An air battery type wastewater treatment apparatus according to claim 1, wherein an aluminum ion conductor is brought into contact with the aluminum anode.

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