JP2020032317A - Final treatment device of wastewater containing high concentration of persistent organic matter and system using the device and final treatment method of wastewater containing high concentration of persistent organic matter - Google Patents

Abstract

To provide a final treatment device, system, and method of wastewater containing a high concentration of persistent organic matter which enables treatment of the persistent organic matter and also ammonium sulphate and nitrogen fixation matter such as ammonium nitrogen, nitrite nitrogen, or nitrate nitrogen with low running cost.SOLUTION: A final treatment system of wastewater containing a high concentration of persistent organic matter comprises: a decomposition reaction treatment with an ozone microbubble and/or nanobubble and ozone gas; and also a catalytic reaction treatment reacting in an active carbon catalyst an ozone microbubble and/or nanobubble and a free radical generated by crushing of the ozone microbubble with the persistent organic matter of an acrylic type, etc. and an organic matter-based minute solid substance.SELECTED DRAWING: None

Description

  The present invention provides a method for producing a high-concentration hardly decomposable organic substance using water containing ozone gas-containing microbubbles (hereinafter referred to as “ozone microbubbles”) and / or ozone gas-containing nanobubbles (hereinafter referred to as “ozone nanobubbles”). The present invention relates to a final treatment device for wastewater, a system using the device, and a final treatment method for wastewater of high-concentration hardly decomposable organic matter.

  Ozone has the strongest oxidizing power next to fluorine, and is used for sterilization, inactivation of viruses, deodorization, decolorization, removal of organic substances, etc. in the fields of medicine, food, agriculture, livestock, and cleaning of semiconductor products. It is generally well known that Further, it is known that ozone is used not only in the fields described above but also in the fields of wastewater treatment such as industry, agriculture, and living.

  An advantage of using ozone in the field of wastewater treatment is that not only oxidation treatment of metals but also oxidation treatment of organic substances can be performed as described above. For example, Japanese Patent No. 3468414 (Patent Document 1) discloses a method and a system for wastewater treatment of contained equipment utilizing the property.

  The method and system described in Patent Document 1 treats wastewater containing organic substances and hardly decomposable substances by ozone treatment in a two-stage negative pressure type separation tank, and after ozone treatment, further performs aeration of microorganisms and sedimentation separation. It is to do. When ozone treatment is performed in a negative pressure type separation tank, that is, when wastewater and ozone are gas-liquid condensed and mixed, the ozone treatment is efficiently performed using a vortex.

  However, in the method and system described in Patent Literature 1, even if the wastewater is treated with ozone, sterilization is sufficient, but the hardly decomposable substance is changed from hardly decomposable to easily decomposable. Depends on microbial aeration and sedimentation. It is not known whether wastewater having a large BOD (biochemical oxygen demand) or COD (chemical oxygen demand) value, that is, wastewater containing a high concentration of organic matter can be treated.

  Here, when performing wastewater treatment using ozone, microbubbles (microbubbles) in the order of tens to hundreds of μm containing ozone gas in the wastewater and / or tens to hundreds of nm in order to contain ozone gas are included. Japanese Patent Application Laid-Open No. 2012-106212 and Japanese Patent Application Laid-Open No. 2012-106212 disclose a method of treating organic matter in wastewater using the adsorbability of the microbubbles and / or nanobubbles. Japanese Patent Application Laid-Open No. 2012-106213 (Patent Document 4). The method described in Patent Literature 2 is a wastewater pretreatment method that enables efficient subsequent wastewater treatment by removing high molecular weight (molecular weight 10,000 or more) organic fine solid substances. Further, the method described in Patent Document 3 decomposes organic substances in wastewater by ozone microbubbles and free radicals generated by forced crushing of ozone microbubbles, and renders them harmless by further processing with an inorganic coagulant. The wastewater is treated by precipitation as sediment. In addition, the method described in Patent Document 4 passes, for example, the final residual organic matter that cannot be completely treated by the method described in Patent Document 3, that is, an organic fine solid substance, together with ozone microbubbles and / or ozone nanobubbles through activated carbon. That is, it is processed. The methods described in Patent Documents 2 to 4 are effective for wastewater having a relatively high concentration of COD value of 1000 mg / L or more.

Japanese Patent No. 3468414 JP 2012-106211 A JP 2012-106212 A JP 2012-106213 A

  However, according to the method and system described in Patent Literature 1, as described above, only a substance that is hardly degradable is changed from a hardly degradable substance to a readily decomposable substance. I do. In addition, it is unknown whether it is possible to decompose acrylic wastewater, glass wastewater, aldehyde wastewater, etc. as hardly decomposable substances, and it is also unknown whether it is possible to treat wastewater containing high concentrations of hardly decomposable substances. It is.

  Further, in Patent Document 2, the organic matter is not completely treated in view of the pretreatment method of the wastewater treatment. In the method of Patent Document 2, since the foam separation is used, it is sufficient that the foam can be efficiently generated. However, it is conceivable that the generation of the foam is not confirmed or the organic matter does not move to the foam.

  Further, in Patent Document 3, it is difficult to treat organic matter in wastewater without removing suspended matters, and COD is not reduced without relying not only on ozone microbubbles and / or ozone nanobubbles but also on a coagulant. These are concerns. Patent Literature 4 is directed to a high-molecular-weight (molecular weight of 10,000 or more) organic substance-based minute solid substance, and it is unclear whether the above-mentioned hard-to-decompose substances such as acrylic and glass-based substances can be decomposed. In addition, as for the activated carbon used as a catalyst, since the backwashing step is performed with water (excluding water containing microbubbles and / or nanobubbles), the life of the activated carbon may be shortened. Even if it is possible to react organic substances other than organic substance-based micro solid substances with ozone under an activated carbon catalyst, adsorption is prioritized unless the COD value is low (40-100 mg / L), Catalytic reactions could no longer occur.

  In addition, Patent Documents 2 to 4 disclose that all kinds of organic substances can be treated. However, when the techniques described in these documents are combined, even if organic substance-based minute solid substances can be removed, It is unknown whether it is possible to treat hardly decomposable substances such as acrylic wastewater, glass wastewater, and aldehyde wastewater, and nitrogenous fixed substances such as ammonium sulfate, ammoniacal, nitrite, or nitrate nitrogen.

  Therefore, in view of the above-described circumstances, the present invention enables the treatment of hardly decomposable organic substances and further nitrogen-fixed substances such as ammonium sulfate, ammoniacal, nitrite, or nitrate nitrogen, and has a low running cost. It is an object of the present invention to provide a high-concentration hard-to-decomposable organic matter wastewater final treatment apparatus using ozone microbubbles and / or ozone nanobubbles, a system using the apparatus, and a high-concentration hard-to-decompose organic matter wastewater final treatment method. And

  The purpose of the waste water final treatment device according to the present invention is an ozone generation device, an ozone decomposition reaction device and a high concentration hardly decomposable organic matter waste water final treatment device equipped with an ozone catalyst reaction device, wherein the ozone decomposition reaction device, An ozone decomposition reaction tank, a raw water inlet, a first microbubble generator, an ejector pump, a first transformer, a first circulation pump, and a first activated carbon tower are provided. The ozone generator includes a microbubble generator, a second circulation pump, a second transformer, a third circulation pump, and a second activated carbon tower. And the ozone decomposition reaction tank and the ozone catalyst decomposition tank are connected by an overflow pipe, and are connected to the ozone catalyst. Inside the decomposition tank, the first activated carbon layer and the second activated carbon layer is disposed, and that characterized the backwash water outlet is provided, is effectively achieved.

  In the wastewater final treatment apparatus according to the present invention, the first transformer is installed so as to circulate raw wastewater containing ozone microbubbles between the ozone decomposition reaction tank through a plurality of pipes. Alternatively, the first transformer tower is provided with a punching plate inside, or the first transformer tower is provided with an orifice inside, or the first activated carbon tower is provided with a plurality of pipes. , Ozone gas, ozone microbubbles and / or ozone nanobubbles are installed so as to circulate the wastewater to and from the ozonolysis reaction tank, or the second transformer is provided with a plurality of pipes through By being installed so as to circulate the raw wastewater containing microbubbles between the ozone catalytic reactor and the second transformer, By installing a punching plate inside, or by installing an orifice inside the second transformer column, or by installing the second activated carbon tower through a plurality of pipes, ozone gas, ozone microbubbles and / or Activated carbon filled in the first activated carbon tower and the second activated carbon tower by being installed so as to circulate raw water wastewater containing ozone nanobubbles between the ozone catalyst reaction tank or the activated carbon granules is granular activated carbon The activated carbon having a diameter of 1 to 2 mm, or the activated carbon filled in the first activated carbon layer is a pellet type activated carbon having a diameter of 6 to 7 mm, and the activated carbon filled in the second activated carbon layer. Is a pellet-type activated carbon having a diameter of 3 to 4 mm, or the still another ozonolysis reactor and the coagulation sedimentation tank By Bei is achieved more effectively.

  Further, an object of the wastewater final treatment system according to the present invention is a wastewater final treatment system for high-concentration hardly decomposable organic matter using the above-mentioned device, wherein the wastewater final treatment system converts the raw wastewater into an ozone decomposition reaction tank and a raw water. An ozonolysis treatment system that performs treatment using an ozonolysis reactor having an inlet, a first microbubble generator, an ejector pump, a first transformer, a first circulation pump, and a first activated carbon tower, and the ozonolysis treatment The raw wastewater treated by the system is provided with an ozone catalyst decomposition tank, a second microbubble generator, a second circulating pump, a second transformer, a third circulating pump, and a second activated carbon tower. (2) An ozone catalytic decomposition system for treating with an ozone catalytic reactor in which an activated carbon layer is installed is provided. Water effectively be achieved by characterized by passing the first activated carbon layer and the second activated carbon layer at a flow rate of 10 to 100 cm / sec.

  Further, the purpose of the wastewater final treatment system according to the present invention is to further provide at least one or more of the above-mentioned ozone decomposition treatment system, coagulation treatment system, filtration treatment system, and / or at least the above-mentioned ozone catalyst decomposition system. Alternatively, the activated carbon filled in the first activated carbon layer is a pellet type activated carbon having a diameter of 6 to 7 mm, and the activated carbon filled in the second activated carbon layer is a pellet type activated carbon having a diameter of 3 to 4 mm. Is achieved more effectively.

  Further, the object of the waste water final treatment method according to the present invention is effectively achieved by providing a waste water final treatment method using the above waste water final treatment system, comprising a step of performing ozone decomposition treatment and a step of performing ozone catalyst decomposition. Is done.

  Further, an object of the wastewater final treatment method according to the present invention is to provide at least one or more of the above-described ozone decomposition treatment step, coagulation treatment step, filtration treatment step, and / or the ozone catalyst decomposition step. Is achieved more effectively.

  ADVANTAGE OF THE INVENTION According to the waste water final treatment apparatus which concerns on this invention, it becomes possible to process hard-to-decompose organic substances and also nitrogen-state fixed substances, such as ammonium sulfate, ammonia, nitrite, or nitrate nitrogen, and does not require running cost. Thus, a wastewater final treatment device for high-concentration hard-to-decompose organic substances using ozone microbubbles and / or ozone nanobubbles has become possible.

  In addition, according to the wastewater final treatment system and the wastewater final treatment method using the high-concentration hardly decomposable organic matter wastewater final treatment apparatus according to the present invention, a decomposition reaction treatment using ozone microbubbles and / or nanobubbles and ozone gas; COD is provided by providing a catalytic reaction process in which free radicals generated by the crushing of microbubbles and / or nanobubbles and ozone microbubbles react with hardly decomposable organic substances such as acrylics and organic solid fine solid substances under an activated carbon catalyst. 5,000 (100,000) mg / L or more of wastewater treatment became possible.

BRIEF DESCRIPTION OF THE DRAWINGS It is the schematic which shows the wastewater final-treatment apparatus of the high concentration hardly decomposable organic substance which concerns on this invention. It is the schematic which shows another aspect of the waste water final treatment apparatus of the high concentration hardly decomposable organic substance which concerns on this invention. It is a system outline figure showing one mode concerning the waste water final treatment system concerning the present invention. 9 is a flowchart illustrating a wastewater treatment system according to a third embodiment.

  First, a wastewater final treatment apparatus for highly concentrated hardly decomposable organic matter according to the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a schematic diagram showing a wastewater final treatment device for high-concentration hardly decomposable organic matter according to the present invention. As shown in FIG. 1, the wastewater final treatment device 1 includes an ozone generator 2, an ozonolysis reactor 3, and an ozone catalyst reactor 4. Next, the ozonolysis reactor 3 includes an ozonolysis reaction tank 31, a raw water inlet 32, a first microbubble generator 33, an ejector pump 34, a first transformer 35, a first circulation pump 36, and a first activated carbon tower 37. Have. Next, the ozone catalyst reactor 4 includes an ozone catalyst decomposing tank 41, a second microbubble generator 42, a second circulation pump 43, a second transformer 44, a third circulation pump 45, and a second activated carbon tower 46. A first activated carbon layer 47 and a second activated carbon layer 48 are provided inside the ozone catalyst decomposition tank 41, and a backwash water outlet 49 is provided. The ozone gas is supplied from the ozone gas generator 2 through an ozone gas supply pipe Ts connected to the ejector pump 34, the first microbubble generator 33, and the second microbubble generator 42. The supply amount of the ozone gas is 150 to 600 g / h (hour). When the supply amount of the ozone gas is less than 150 g / h, the waste water is hardly treated, and even when the supply amount is more than 600 g / h, the treatment capacity does not change much.

  Next, the ozone reactor 3 will be described more specifically. First, in the embodiment shown in FIG. 1, the raw water inlet 32 is provided in a column shape above the ozone decomposition reaction tank 31, but the shape is not particularly limited. In addition, since the inlet 32 only needs to be able to inject wastewater containing high-concentration hardly decomposable organic matter (hereinafter referred to as “raw water”) into the ozonolysis reaction tank 31, the upper part of the ozonolysis reaction tank 31 is opened. It does not have to be provided separately. Next, in the embodiment shown in FIG. 1, the first microbubble generator 33 is provided above the ozonolysis reaction tank 31, but the microbubbles may be uniformly distributed from the outlet to the raw water. May be slightly shifted from the center of the ozonolysis reaction tank 31. The shape and type of the first microbubble generator 33 are not particularly limited as long as the ozone gas can be introduced (supplied) from the ozone generator 2. The raw water is mixed with an ozone microbubble-containing gas-liquid mixture (hereinafter referred to as “ozone microbubble-containing raw water”) by the ozone microbubbles (about 20 to 200 μm in diameter) supplied from the first microbubble generator 33. Become.

  As shown in FIG. 1, the first transformer 35 circulates the ozone microbubble-containing raw water described above in the order of the pipe Ta, the pipe Tb, and the pipe Tc (see the arrow) through the pipe Ta, the pipe Tb, and the pipe Tc. It is set up to make it. In this case, the pipes Ta, Tb, and Tc may be made of any material such as metal and plastic, as long as raw water containing microbubbles can be circulated. In addition, the pipe is not subject to any particular object such as laminar flow or turbulent flow. Here, when the ozone microbubble-containing raw water is circulated between the first transformer 35 and the ozonolysis reaction tank 31, an ejector pump 34 is required. The reason for adopting this configuration is not only the circulation of the ozone microbubble-containing raw water described above, but also the introduction of ozone gas directly into the raw water from the ozone gas generator 2 (hereinafter, in order to distinguish this raw water from the ozone microbubble-containing raw water). The raw water is referred to as “ozone gas introduction raw water.” The purpose of passing the ozone microbubble-containing raw water and the ozone gas-introduced raw water through the first transformer 35 is to ozone microbubble contained in the ozone microbubble raw water by crushing the ozone microbubbles contained in the raw water. If the raw water is an ozone gas-introduced raw water, a gas-liquid (ozone-raw water) mixed water is generated and circulated to further make the gas-liquid mixed water the same as the ozone microbubble-containing raw water. . In other words, the purpose is to continuously generate ozone microbubbles and ozone nanobubbles. Although not shown, a punching plate or an orifice (perforated plate) for crushing microbubbles is inserted in the transformer column. Incidentally, the hole diameter and shape of the punching plate, the orifice, and the like are not particularly limited in a system and a method described below, as long as the microbubbles can be crushed.

  Next, as shown in FIG. 1, the first activated carbon tower 37 also contains the above-mentioned ozone gas (ozone microbubbles and / or ozone nanobubbles) through the pipes Td, Te, and Tf as shown in FIG. Is disposed so as to circulate the gas-liquid mixed raw water in the order of the pipe Td, the pipe Te, and the pipe Tf (see the arrow). The pipes Td, Te, Tf in this case are also of any material, such as metal or plastic, as long as the raw water can be circulated. In addition, the pipe is not particularly limited in its object such as laminar flow or turbulent flow. Here, when circulating the microbubble-containing raw water between the first activated carbon tower 37 and the ozonolysis reaction tank 31, a circulation pump 36 is required. As for the circulating pump 36, if the pump can circulate waste water (raw water or the like) between the activated carbon tower 37 and the ozonolysis reaction tank 31 at a circulating rate of 100 to 200 L / min, the type is as follows. There is no particular limitation. The amount of circulation by the ejector pump 34 when the microbubble-containing raw water described above is circulated between the first transformer 35 and the ozonolysis reaction tank 31 is also 100 to 200 L / min. The reason and effect of employing the circulation amount of 100 to 200 L / min will be described later.

  The first activated carbon tower 37 is used to remove compounds due to the reaction between organic matter in raw water and ozone, and to remove microorganisms and the like in raw water. As the activated carbon to be filled in the tower, granular activated carbon having a diameter of 1 to 2 mm is desirable. If the diameter of the activated carbon is less than 1 mm, these compounds and microorganisms cannot be removed. If the diameter of the activated carbon is more than 2 mm, the raw water may not be circulated and may be clogged in the tower. In addition, about 70 to 80% of the volume of the first activated carbon tower 37 may be filled with the activated carbon.

  By pre-treating the raw water in the ozone reactor 3 configured as described above, most of the organic substances are treated, and the COD value is reduced to about 1/2 to 1/5 of the raw water.

  Next, the ozone catalytic reactor 4 will be described more specifically. First, in the embodiment shown in FIG. 1, the overflow pipe To is shown so as to connect (connect) the upper part of the ozone decomposition reaction tank 31 and the upper part of the ozone catalyst decomposition tank 41. The raw water pretreated by the reactor 3 (hereinafter referred to as “pretreated raw water”) only needs to be able to be introduced into the ozone catalyst decomposition tank 41, and there is no particular limitation on the piping method and the installation location. Next, in the embodiment shown in FIG. 1, the second microbubble generator 42 is provided above the ozone catalyst decomposition tank 41. However, the second microbubble generator 42 may be installed as long as the microbubbles can uniformly reach the pretreated raw water from the outlet. The location may be slightly shifted from the center of the ozone catalyst decomposition tank 41. The shape and type of the second microbubble generator 42 are not particularly limited as long as the ozone gas can be introduced (supplied) from the ozone generator 2. The pretreatment raw water becomes a gas-liquid mixture containing ozone microbubbles by the ozone microbubbles (about 20 to 200 μm in diameter) supplied from the second microbubble generator 42. Incidentally, the second microbubble generator 42 may be the same as the first microbubble generator 33.

  Next, as shown in FIG. 1, the second transformer column 44 transmits the microbubble-containing pretreated raw water described above through the pipes Ta ′, Tb ′, and Tc ′ to the pipes Ta ′, Tb ′, and Tc ′. It is installed so as to circulate in the order of Tc '(see arrow). In this case, the pipe may be of any material such as metal or plastic, as long as the pretreated raw water containing microbubbles can be circulated. In addition, the pipe is not subject to any particular object such as laminar flow or turbulent flow. Here, when circulating the microbubble-containing raw water between the second transformer column 44 and the ozone catalyst decomposition tank 41, a second circulation pump 43 is required. The purpose of passing the pretreated raw water containing microbubbles through the second transformer column 44 is to crush the ozone microbubbles contained in the raw water into ozone nanobubbles (100 to 500 nm order). In other words, the purpose is to continuously generate ozone microbubbles and ozone nanobubbles. Although not shown, a punching plate or an orifice (perforated plate) for microbubble crushing is inserted in the second transformer tower 44 as in the first transformer tower 35. Incidentally, the hole diameter and shape of the punching plate, the orifice, and the like are not particularly limited when they are used in the method described later, as long as the microbubbles can be crushed.

  Next, as shown in FIG. 1, the second activated carbon tower 46 also feeds the above-mentioned ozone microbubble-containing pretreated raw water through a pipe Td ′, a pipe Te ′, and a pipe Tf ′, as shown in FIG. It is installed so as to circulate in the order of Td, tube Te, and tube Tf (see arrow). In this case, the pipe may be made of any material such as metal and plastic, as long as the pretreated raw water containing ozone microbubbles (and / or ozone nanobubbles) can be circulated. In addition, the pipe is not subject to any particular object such as laminar flow or turbulent flow. Here, when circulating the pretreated raw water containing ozone microbubbles (and / or ozone nanobubbles) between the second activated carbon tower 46 and the ozone catalyst decomposition tank 41, a third circulation pump 45 is required. As for the third circulation pump 45, a pump capable of circulating waste water (raw water or the like) between the second activated carbon tower 46 and the ozone catalyst decomposition tank 41 at a circulation rate of 100 to 200 L / min. There are no particular restrictions on the type and the like. The amount of circulation by the third circulation pump 45 when circulating the microbubble-containing raw water described above between the second transformer 44 and the ozone catalyst decomposition tank 41 is also 100 to 200 L / min. The reason and effect of employing the circulation amount of 100 to 200 L / min will be described later.

  The purpose of the second activated carbon tower 46 is to remove compounds due to the reaction between organic matter and ozone in the raw water and remove microorganisms and the like in the raw water as in the first activated carbon tower 37. As the activated carbon to be filled in the tower, granular activated carbon having a diameter of 1 to 2 mm is desirable. If the diameter of the activated carbon is less than 1 mm, these compounds and microorganisms cannot be removed. If the diameter of the activated carbon is more than 2 mm, the raw water may not be circulated and may be clogged in the tower. As for the filling of the activated carbon, 70 to 80% of the volume of the second activated carbon tower 46 may be filled as in the case of the first activated carbon tower 37.

  Next, the first activated carbon layer 47, the second activated carbon layer 48, and the backwash water outlet 49 in the ozone catalytic reactor 4 will be sequentially described.

  However, most of organic matter and harmful microorganisms contained in the raw water and the pre-treated raw water are treated (removed or removed) by the ozone gas, the ozone microbubble and / or the ozone nanobubble, and the first activated carbon tower 37 and the second activated carbon tower 46. Harmless). However, when treating wastewater containing a high concentration of hardly decomposable organic substances as in the present invention, a part of high molecular weight (molecular weight of 10,000 or more) organic fine solid substances, hardly decomposable organic substances, nitrogen The removal of most of the fixed matter (ammonia-form, nitrite-form nitrogen, etc.) (hereinafter referred to as “final residue”) is performed by removing ozone gas, ozone microbubbles and / or ozone nanobubbles, the first activated carbon tower 37 and The second activated carbon tower 46 alone does not work. Here, the first activated carbon layer 47 and the second activated carbon layer 48 are important components in the apparatus, system and processing method according to the present invention. Generally, as the role of activated carbon, applications such as deodorants, adsorbents, and catalysts utilizing the surface area of pores are known. However, in the conventional method, when used as a catalyst, if the concentration of the reaction substrate is not considerably low (for example, about 40 to 100 mg / L in the case of wastewater), the adsorption is superior to the catalytic reaction. In the field of wastewater (purified water) treatment, the role as an adsorbent was more numerous.

  Here, in the device according to the present invention, the role of the first activated carbon layer 47 and the second activated carbon layer 48 is that the hydroxyl (hydroxyl group) radicals generated from the ozone nanobubbles, the ozone gas itself, etc., and the final residue contained in the raw water for pretreatment. Plays a role as a reaction field, a so-called catalyst. By the way, the pre-treated raw water can be treated even if the COD is 5000 mg / L or more (up to about 100,000 mg / L).

  First, the first activated carbon layer 47 and the second activated carbon layer 48 will be described. Pellet-type activated carbon is used for the first activated carbon layer 47, and the activated carbon has a diameter (effective diameter) of 6 to 7 mm. This setting range is set to be longer (longer) than the second activated carbon layer 48. On the other hand, pellet type activated carbon is used for the second activated carbon layer 48, and the diameter (effective diameter) of the activated carbon is 3 to 4 mm. This set range is set smaller (shorter) in diameter (effective diameter) than the first activated carbon layer 48. The reason for this is that if the catalytic reaction in the first activated carbon layer 47 could not be successfully processed, the second activated carbon layer 48 should have a larger specific surface area so that the catalytic reaction can be performed almost quantitatively. That is, the diameter of the pellet type activated carbon filled in the layer 48 is smaller than the diameter of the pellet type activated carbon filled in the first activated carbon layer 47. In addition, if the diameter of the pellet type activated carbon is less than 3 mm, the adsorption reaction will be superior to the catalyst, and if it is larger than 7 mm, the pretreated raw water can pass at a sufficient speed when passing through each layer. May be gone.

  When passing the pretreated raw water containing the final residue through the first activated carbon layer 47 and the second activated carbon layer 48, it is desirable to pass each layer at a flow rate of 10 to 100 cm / sec. If the flow rate is less than 10 cm / sec, the adsorption reaction will be superior to the catalyst. If the flow rate is faster than 100 cm / sec, neither the adsorption nor the catalytic reaction will be achieved. Note that the flow rate may be adjusted by the circulation amount of the second circulation pump 43 or the third circulation pump 45, or any flow rate adjusting means may be used.

  Next, the backwash water outlet 49 will be described. The purpose of using the backwash water outlet 49 is to backwash the pellet type activated carbon of the first activated carbon layer 47 and the second activated carbon layer 48 with ozone microbubble-containing water and / or ozone nanobubble-containing water. . In addition, as a method of backwashing, water containing ozone microbubbles and / or water containing ozone nanobubbles prepared in advance is stored in an arbitrary container (not shown), and backwashed through a pump P. That is, the contained water is blown out from the water outlet 49 to backwash.

  The number of backwashing is not particularly limited as long as the number of backwashing is set to once a week as a minimum. Incidentally, by backwashing the pellet-type activated carbon according to the first activated carbon layer 47 and the second activated carbon layer 48 with ozone microbubble-containing water and / or ozone nanobubble-containing water, it is more effective than backwashing with water (tap water). The life of the pellet type activated carbon is extended about 8 to 20 times. For backwashing, batch processing is desirable.

  With reference to FIG. 1, the embodiment of the final treatment apparatus for wastewater of high-concentration hard-to-decompose organic substances using ozone microbubbles according to the present invention has been described. Another embodiment of the wastewater final treatment device will be described. In addition, about the code | symbol, the part which overlaps with FIG. 1 is the same. In this description, the description of the portions that overlap with the embodiment shown in FIG. 1 will be omitted.

  FIG. 2 is a schematic view showing another embodiment of the wastewater final treatment apparatus for high-concentration hardly decomposable organic substances using ozone microbubbles according to the present invention. The embodiment shown in FIG. 2 is, in other words, further provided with another ozonolysis reactor and a coagulation sedimentation tank in order to further carefully perform the pretreatment in the apparatus shown in FIG.

  In this alternative embodiment, the wastewater treatment device 1 ′ further includes an ozone decomposition reaction device 3 ′ and a coagulation sedimentation tank 50 in addition to the ozone generation device 2, the ozone decomposition reaction device 3 and the ozone catalyst reaction device 4.

  The ozonolysis reactor 3 'has basically the same configuration as the ozonolysis reactor 3, and includes an ozonolysis reactor 31', a raw water inlet 32 ', a first microbubble generator 33', an ejector pump 34 ', A first transformer column 35 ', a first circulation pump 36' and a first activated carbon tower 37 'are provided. The role of each component is also omitted because the ozonolysis reactor 3 ′ is basically the same as the ozonolysis reactor 3.

  Next, the coagulation sedimentation tank 50 will be described. The coagulation and sedimentation tank 50 feeds a sedimentation coagulant to the raw water that could not be pretreated by the ozonolysis reactor 3 ′ to lower the COD and to reduce organic matter-based micro solid substances contained in the raw water as sediment. The purpose is to treat organic substances that could not be pretreated by the ozonolysis reactor 3 '. When performing coagulation sedimentation, an inorganic coagulation sedimentation agent is added to the raw water introduced into the coagulation sedimentation tank 50. As the inorganic coagulant, a polyaluminum chloride or sulfuric acid band can be used as a liquid, and a polymer coagulant can be used as an auxiliary.

  The sediment and the supernatant (raw water) are separated in the coagulation sedimentation tank 50, and the supernatant raw water is separated from the ozonolysis reaction tank 31 of the ozonolysis reaction apparatus 3 through an appropriately connected introduction pipe (not shown). '. On the other hand, regarding the sediment, the sediment can be compressed and dried by any method and discarded, or the sediment can be reused as sludge. Then, the supernatant (raw water) is sequentially treated in the ozonolysis reactor 3 and the ozone catalyst reactor 4.

  Although the wastewater final treatment apparatus according to the present invention has been described above, for example, the wastewater final treatment apparatus shown in FIG. 1 is connected as a single unit, and a plurality of units are connected. The introduction of a means, a device, or an apparatus enables the final wastewater treatment system according to the present invention. Further, the wastewater final treatment system according to the present invention is possible even if an arbitrary process, means, or device is inserted between the ozone decomposition reaction device 3 and the ozone catalyst reaction device 4 shown in FIG. Hereinafter, a wastewater final treatment system and a wastewater treatment method according to the present invention will be described with reference to the drawings. The description will be given with reference to FIG. 1 or FIG. 2 as necessary.

  FIG. 3 is a system schematic diagram showing one embodiment of the wastewater final treatment system according to the present invention. In the embodiment shown in FIG. 3, first, raw waste water (hereinafter simply referred to as “raw water”) is diluted. Incidentally, the dilution may be about 2 to 12 times with water. If the ratio is less than twice, various components contained in the wastewater may deteriorate the device or system. Even if the dilution is 12 times or more, the effect does not change much.

  Next, the diluted raw water is treated by the ozonolysis treatment system S10. In the case of the present invention, the ozone decomposition treatment system S10 performs decomposition treatment with ozone microbubbles and ozone microbubble crushing treatment, that is, decomposition treatment with ozone nanobubbles, using an ozone decomposition reaction device 3 as shown in FIG. First, the raw water containing ozone microbubbles is subjected to crushing of the ozone microbubbles by the transformer tower, and a part of the raw water is converted into ozone nanobubbles by the embodiment according to FIG. Since the ozone gas is directly blown from the ejector pump while receiving the treatment, the raw water also becomes a gas-liquid mixture containing the ozone gas. That is, as an image, an organic substance in a rough part is oxidized and decomposed by ozone gas, and a small part of the organic substance is oxidized and decomposed by an ozone microbubble and / or an ozone nanobubble, and finally, most of the organic substance is oxidized. It works. Therefore, when the ozonolysis treatment system S10 ends, the value of COD becomes about 1/2 to 1/5 of the raw water.

  Incidentally, in the ozonolysis treatment system S10, the supply amount of ozone gas is desirably 150 to 600 g / h (hour). When the supply amount of the ozone gas is less than 150 g / h, the waste water is hardly treated, and even when the supply amount is more than 600 g / h, the treatment capacity does not change much. Further, in the ozonolysis treatment system S10, the circulation rate of the raw water in the ozonolysis reactor 3 is 100 to 200 L / min. If the circulation rate is less than 100 L / min, the ozone microbubbles will not be crushed or ozone gas will not be introduced into the raw water, and the raw water will not be sufficiently treated. Or, on the contrary, it causes the processing capacity to decrease. The processing in the ozonolysis processing system S10 is preferably performed for about 2 to 72 hours. If the treatment time is less than 2 hours, the treatment is not sufficiently performed. If the treatment time is more than 72 hours, the treatment is sufficient. May return to substance.

  Next, in the ozone decomposition processing system S10, after performing ozone decomposition processing using ozone microbubbles, ozone nanobubbles, and ozone gas, an aggregation processing system S11 is performed. The coagulation processing system S11 is a process performed in the coagulation settling tank 50 in the schematic diagram shown in FIG. Here, the coagulation treatment is performed by adding a precipitating coagulant to the raw water that could not be pretreated as described above, thereby lowering the COD and, at the same time, the organic micro solid substance contained in the raw water as a precipitate. And the purpose of treating organic substances that could not be pretreated. When performing coagulation sedimentation, an inorganic coagulation sedimentation agent is added to the raw water introduced into the coagulation sedimentation tank 50. As the inorganic coagulant-precipitating agent, aluminum-based or iron-based ones can be used, and among them, a sulfate band (aluminum sulfate) and PAC (polyaluminum chloride) are suitable. In addition, a polymeric coagulant / precipitant can be used as an auxiliary agent for the inorganic coagulant / precipitant. Incidentally, the coagulation treatment system S11 is not always an essential requirement, but if it is desired to more efficiently and completely treat the organic minute solid substance, the coagulation treatment system S11 may be provided. The sediment generated in the coagulation treatment system S11 can be used as sludge, and the sludge can be used as a building material, a fertilizer, and the like.

  Regarding the dropping of the flocculant, if the pH (hydrogen ion concentration) of the raw water is about 8.5 ± 1.5 in the ozonolysis treatment system S10, it may be added without considering the pH control. If the pH is out of the range of 8.5 ± 1.5, the pH of the raw water may be controlled to fall within the range by an arbitrary method.

  In addition, the coagulation treatment system S11 may be connected to a coagulation / sedimentation tank and / or an ozone decomposition reaction apparatus and / or an ozone catalyst reaction apparatus, or may be provided with a separate and independent coagulation / sedimentation tank.

  Next, after the aggregation processing system S11, the filtration processing system S12 is performed. The sand filtration system S12 is for removing, by sand filtration, sediment that has not been removed by coagulation and settling. As in the case of the sand filtration, sand is used as a filtering material, and the particle size of the sand is preferably about 50 μm.

  The filtration system S12 may be connected to the ozonolysis reactor and / or the ozone catalyst reactor by a conduit or the like, or may be separately and independently provided with a sand filtration apparatus or means for processing.

  Next, the raw water treated by the filtration processing system S12 (hereinafter referred to as “pre-treated raw water”) is introduced into the ozone catalyst decomposition processing system S13 for processing. In the case of the present invention, the ozone catalyst decomposition treatment system S13 uses an ozone catalyst reactor 4 as shown in FIG. 1 or 2 to perform decomposition treatment with ozone microbubbles and ozone microbubble crushing treatment, that is, decomposition treatment with ozone nanobubbles. Do. First, the pretreated raw water containing ozone microbubbles is subjected to crushing of the ozone microbubbles by the transformer column by the first and second circulating pumps. And undergo microbubble and nanobubble processing. In other words, as an image, a mechanism in which organic substances are oxidized and decomposed to small parts by ozone microbubbles and / or ozone nanobubbles, and finally most organic substances (organic minute solid substances and hardly decomposable substances) are oxidized. become. Therefore, when the ozone catalyst decomposition processing system S13 is completed, the value of COD becomes about 1/5 to 1/10 of the raw water.

  Incidentally, also in the ozone catalyst decomposition treatment system S13, the supply amount of the ozone gas is desirably 150 to 600 g / h (hour). When the supply amount of the ozone gas is less than 150 g / h, the waste water is hardly treated, and even when the supply amount is more than 600 g / h, the treatment capacity does not change much. In the ozone catalyst decomposition treatment system S5, the circulation rate of the raw water in the ozone decomposition reaction device 3 is 100 to 200 L / min. If the circulation rate is less than 100 L / min, the ozone microbubbles will not be sufficiently crushed and the raw water will not be sufficiently treated. Even if the circulation rate is more than 200 L / min, the treatment capacity will not be improved. It may cause a decrease. The processing in the ozone catalyst decomposition processing system S13 is preferably performed for about 1 to 72 hours. If the treatment time is less than 1 hour, the treatment is not sufficiently performed. If the treatment time is more than 72 hours, the treatment is sufficient. May return to substance.

  Further, in the ozone catalyst decomposition treatment system S13, the first and second activated carbon layers installed in the ozone catalyst reaction device 4 are used to remove hydroxyl (hydroxyl) radicals generated from ozone nanobubbles, ozone gas itself, etc. It is important that a reaction field with the final residue contained in the so-called "catalytic reaction" occurs. As described above, pellet-type activated carbon is used for the first activated carbon layer 47, and the activated carbon has a diameter (effective diameter) of 6 to 7 mm. This setting range is set to be longer (longer) than the second activated carbon layer 48. On the other hand, pellet type activated carbon is used for the second activated carbon layer 48, and the diameter (effective diameter) of the activated carbon is 3 to 4 mm. This set range is set smaller (shorter) in diameter (effective diameter) than the first activated carbon layer 48. The reason for this is that when the catalytic reaction in the first activated carbon layer 47 is not successfully performed, the second activated carbon layer is so formed that the catalytic reaction can be performed almost quantitatively in the second activated carbon layer 48 having a larger specific surface area. That is, the diameter of the pellet type activated carbon filled in the first activated carbon layer 47 is smaller than the diameter of the pellet type activated carbon filled in the first activated carbon layer 47. In addition, if the diameter of the pellet type activated carbon is less than 3 mm, the adsorption reaction will be superior to the catalyst, and if it is larger than 7 mm, the pretreated raw water can pass at a sufficient speed when passing through each layer. May be gone.

  When passing the pretreated raw water containing the final residue through the first activated carbon layer 47 and the second activated carbon layer 48, it is desirable to pass each layer at a flow rate of 10 to 100 cm / sec. If the flow rate is less than 10 cm / sec, the adsorption reaction will be superior to the catalyst. If the flow rate is faster than 100 cm / sec, neither the adsorption nor the catalytic reaction will be achieved. The flow rate may be adjusted by the circulation amount of the second circulation pump 43 or the third circulation pump 45 shown in FIG. 1, or an arbitrary flow rate adjusting means may be used.

  In addition, when performing the ozone catalyst decomposition processing system S13 and the later-described ozone catalyst decomposition processing system S14, back washing may be performed. The purpose of the backwash is to backwash the first activated carbon layer 47 and the second activated carbon layer 48 as described above. The number of times of backwashing is not particularly limited as long as once a week is the minimum. Incidentally, by backwashing the pellet-type activated carbon according to the first activated carbon layer 47 and the second activated carbon layer 48 with ozone microbubble-containing water and / or ozone nanobubble-containing water, it is more effective than backwashing with water (tap water). The life of the pellet type activated carbon is extended about 8 to 20 times. For backwashing, batch processing is desirable.

  Next, the ozone catalyst decomposition processing system S14 is performed after the ozone catalyst decomposition processing system S13. The basic operation is the same as that of the ozone catalyst decomposition treatment system S13. However, unless the ozone catalyst decomposition treatment system S14 is provided after the ozone catalyst decomposition treatment system S13, the final concentrations of COD and aldehyde do not become about 1/10 to 1/20 of the raw water. In other words, in this embodiment, if the ozone catalyst decomposition treatment system is completed in one stage, the final concentration of COD and aldehyde will be about 1/10 of raw water. The water (pre-treated raw water) that has been treated in the ozone catalyst decomposition treatment system S14 can be reused as water for diluting the raw water.

  It should be noted that the present invention is not limited to the embodiment shown in FIG. 3, and that the ozone catalyst treatment system is brought after the ozone decomposition treatment system if the system is used, and that the ozone catalyst treatment is performed after the ozone decomposition treatment if the method is used. If so, the order of the filtration treatment, the aggregation treatment and the like may be changed.

  As described above, the system can treat wastewater with a COD of 5000 mg / L or more (up to about 100,000 mg / L) or high-concentration acrylic or glass-based hardly decomposable wastewater. In addition, treatment of hardly decomposable substances such as gas and liquid becomes possible. When performing the pretreatment system, a neutralizing agent such as ammonium chloride may be used in the aldehyde-based wastewater.

  As described above, it is also possible to treat a hardly decomposable substance such as a gas or a liquid. When performing the pretreatment system, a neutralizing agent such as ammonium chloride may be used in the aldehyde-based wastewater. In addition, the waste water final treatment system and the waste water final treatment method according to the present invention are not limited to the embodiments shown in FIGS. 3 and 4, and if the system, an ozone catalyst treatment system is brought after the ozone decomposition treatment system; In the case of the method, if the ozone catalyst treatment is performed after the ozonolysis treatment, the order of the filtration treatment, the aggregation treatment and the like may be changed.

  The embodiments of the high-concentration hardly decomposable organic matter wastewater final treatment apparatus according to the present invention, the system using the apparatus, and the high-concentration hardly decomposable organic matter wastewater final treatment method using ozone microbubbles are described in the embodiments. It goes without saying that various modes can be adopted without departing from the scope of the claims, the specification, the drawings, and the like.

  The above embodiment will be described with reference to examples. The description will be given with reference to FIGS. 1 to 4 according to the contents of the embodiment.

[Example 1] Wastewater treatment of acrylic-based hardly decomposable wastewater In Example 1, the wastewater treatment of acrylic-based hardly decomposable wastewater was performed as follows.

  First, acrylic-based hard-to-decompose wastewater (COD = 11000 mg / L at this point, hereinafter referred to as “acrylic wastewater”) diluted 10-fold with water was subjected to pH control (pH = 7.4), and then acrylic-based. The wastewater was treated with ozone gas, ozone microbubbles and ozone nanobubbles for 2 hours by an ozone decomposition treatment system (ozonation treatment device 3).

  Next, polyaluminum chloride (PAC) and a polymer flocculant were added to carry out a flocculation treatment, and the mixture was filtered by sand filtration, separated into a supernatant and a precipitate of acrylic wastewater, and separated by filtration. At this point, the COD was 9200 mg / L.

  Next, after treating the supernatant liquid for 1 hour with an ozone catalyst decomposition treatment system (ozone catalyst reaction device 4), polyaluminum chloride (PAC) and a polymer flocculant are added again to carry out flocculation treatment. The coagulated precipitate generated by the treatment was filtered again, and the pH was controlled. After pH control of the filtered supernatant, the final COD of the acrylic wastewater (supernatant) was 1500 mg / L.

  Separately, when the treatment was performed for 2 hours by the ozone catalyst decomposition treatment system (ozone catalyst reaction device 4), the COD of the acrylic wastewater (supernatant) was 570 mg / L.

  In Example 1, it was found that the COD of the raw water before treatment could be finally reduced to about 1/20.

[Example 2] Wastewater treatment of glass-based hard-to-decompose wastewater In Example 2, the wastewater treatment of glass-based hard-to-decompose wastewater was performed according to the system shown in Fig. 3.

  The glass-based wastewater (raw water) to be treated was diluted 11-fold to give a COD of 1100 mg / L. This raw water was processed to the ozonolysis treatment system S10, the coagulation treatment system S11, and the filtration treatment system S12. At the end of the filtration treatment system S12, the COD of the glass wastewater was 210 mg / L. Next, when the ozone catalyst decomposition treatment systems S13 and S14 were performed, the value of COD of the glass-based wastewater was 79 mg / L at the end of the ozone catalyst decomposition treatment system S13, and the value of formaldehyde was 16 mg / L. . On the other hand, the COD at the end of the ozone catalyst decomposition treatment system S14 was not different from that at the end of the ozone catalyst decomposition treatment system S13, but the value of formaldehyde was less than 2 mg / L.

  Using the system shown in FIG. 3, it has been found that the COD of raw water before treatment can be finally reduced to about 1/14.

[Example 3] Wastewater treatment of aldehyde-based wastewater In Example 3, as for wastewater treatment of aldehyde-based wastewater, wastewater treatment was performed according to the system shown in Fig. 4. The ozone decomposition processing system S20 and the ozone catalyst decomposition processing systems S21 to S24 in FIG. 4 are the same as the ozone decomposition processing system and the ozone catalyst decomposition processing system shown in FIG.

  First, the raw water of the aldehyde wastewater was diluted 6-fold (235 L) to make COD 10,000 mg / L, the raw water was adjusted to pH = 9.0 with sodium hydroxide, and further 500 g of ammonium chloride (neutralizing agent). Dissolved.

  Then, when processing was performed by the system as shown in FIG. 5, the results as shown in Table 1 were obtained.

  According to the above table, the raw water before the COD treatment was reduced to about 1/14 and the formaldehyde was reduced to about 1/23 after the end of the ozonolysis treatment system S24.

  ADVANTAGE OF THE INVENTION According to this invention, it can be utilized for the final treatment of the wastewater containing every high concentration of organic matter and nitrogen (ammonia state or nitric acid state). Further, not only ozone microbubbles and / or ozone nanobubbles but also microbubbles such as oxygen and nitrogen and / or nanobubbles may be used. In addition, the sediment generated by coagulation sedimentation can be applied as sludge to fertilizers and materials.

DESCRIPTION OF SYMBOLS 1 Waste water final treatment apparatus 2 Ozone gas generator 3 Ozone decomposition reaction apparatus 4 Ozone catalyst reaction apparatus 31 Ozone decomposition reaction tank 33 1st microbubble generation apparatus 35 1st transformer tower 37 1st activated carbon tower 41 Ozone catalyst decomposition tank 42 2nd micro Bubble generator 44 Second transformer column 46 Second activated carbon tower 47 First activated carbon layer 48 Second activated carbon layer

The purpose of the waste water final treatment device according to the present invention is an ozone generation device, an ozone decomposition reaction device and a high concentration hardly decomposable organic matter waste water final treatment device equipped with an ozone catalyst reaction device, wherein the ozone decomposition reaction device, An ozone decomposition reaction tank, a raw water inlet, a first microbubble generator, an ejector pump, a first transformer tower having a punching plate installed therein, a first circulation pump, and a first activated carbon tower; Comprises an ozone catalyst decomposition tank, a second microbubble generator, a second circulation pump, a second transformer having a punching plate installed therein, a third circulation pump, and a second activated carbon tower. And an ozone gas supply pipe connected to the ejector pump, the first microbubble generator, and the second microbubble generator, and the ozone decomposition reaction tank and The ozone catalyst decomposition tank is connected by an overflow pipe, a first activated carbon layer and a second activated carbon layer are provided inside the ozone catalyst decomposition tank, and a backwash water outlet is provided. The feature is effectively achieved. In addition, an object of the wastewater final treatment apparatus according to the present invention is a high-concentration hardly decomposable organic matter wastewater final treatment apparatus including an ozone generator, an ozone decomposition reaction apparatus, and an ozone catalytic reaction apparatus, wherein the ozone decomposition reaction apparatus is used. Comprises an ozone decomposition reaction tank, a raw water inlet, a first microbubble generator, an ejector pump, a first transformer tower having an orifice therein, a first circulation pump, and a first activated carbon tower, wherein the ozone catalytic reaction is carried out. The apparatus includes an ozone catalyst decomposition tank, a second microbubble generator, a second circulation pump, a second transformer having an orifice installed therein, a third circulation pump, and a second activated carbon tower. An ozone gas supply pipe connected to the ejector pump, the first micro-bubble generator and the second micro-bubble generator, and the ozone decomposition reaction tank And the ozone catalyst decomposing tank are connected by an overflow pipe, a first activated carbon layer and a second activated carbon layer are disposed inside the ozone catalyst decomposing tank, and a backwash water outlet is provided. The feature is achieved effectively.

In the wastewater final treatment apparatus according to the present invention, the first transformer is installed so as to circulate raw wastewater containing ozone microbubbles between the ozone decomposition reaction tank through a plurality of pipes. , some have the first activated carbon tower, through a plurality of tubes, the ozone gas, by drainage raw water containing ozone microbubbles and / or ozone nanobubbles is installed to circulate between the ozonolysis reaction vessel , or the second transformer tower, through a plurality of tubes, by drainage raw water containing ozone microbubbles is installed to circulate between the ozone catalytic reactor, some have the second activated carbon tower Circulates waste water containing ozone gas, ozone microbubbles, and / or ozone nanobubbles with the ozone catalyst reaction tank through a plurality of pipes. The activated carbon installed in the first activated carbon tower and the second activated carbon tower is granular activated carbon, and the activated carbon has a diameter of 1 to 2 mm, or 1 The activated carbon to be filled in the activated carbon layer is a pellet type activated carbon having a diameter of 6 to 7 mm, and the activated carbon to be filled in the second activated carbon layer is a pellet type activated carbon having a diameter of 3 to 4 mm, or This is more effectively achieved by providing another ozonolysis reactor and a coagulation sedimentation tank.

Further, an object of the wastewater final treatment system according to the present invention is a wastewater final treatment system for high-concentration hardly decomposable organic matter using the above-mentioned device, wherein the wastewater final treatment system converts the raw wastewater into an ozone decomposition reaction tank, Ozone decomposition performed using an ozonolysis reactor having an inlet, a first microbubble generator, an ejector pump, a first transformer column having a punching plate therein, a first circulation pump and a first activated carbon tower. A treatment system, and an ozone catalyst decomposition tank, a second microbubble generator, a second circulation pump, a second transformer having a punching plate installed therein, and a third circulation. An ozone catalyst comprising a pump and a second activated carbon tower, and treated by an ozone catalytic reactor having a first activated carbon layer and a second activated carbon layer installed therein This is effectively achieved by providing a catalytic cracking system, wherein in the catalytic cracking system, the raw wastewater is passed through the first activated carbon layer and the second activated carbon layer at a flow rate of 10 to 100 cm / sec. You. Furthermore, an object of the wastewater final treatment system according to the present invention is a wastewater final treatment system for high-concentration hardly decomposable organic matter using the above-mentioned device, wherein the wastewater final treatment system converts the raw wastewater into an ozone decomposition reaction tank and a raw water. Ozone decomposition treatment using an ozonolysis reactor equipped with an inlet, a first microbubble generator, an ejector pump, a first transformer tower having an orifice therein, a first circulation pump and a first activated carbon tower. A system, and the wastewater treated by the ozonolysis treatment system, an ozone catalyst decomposition tank, a second microbubble generator, a second circulation pump, a second transformer having an orifice therein, a third circulation pump, Ozone catalytic decomposition provided with a second activated carbon tower and treated by an ozone catalytic reactor having a first activated carbon layer and a second activated carbon layer installed therein This is effectively achieved by providing a stem, and in the catalytic cracking system, characterized in that the wastewater is passed through the first activated carbon layer and the second activated carbon layer at a flow rate of 10 to 100 cm / sec. .

Then, when processing was performed by the system as shown in FIG. 4 , the results as shown in Table 1 were obtained.

Claims (17)

An ozone generator, an ozone decomposition reaction device and an ozone catalyst reaction device, comprising a high-concentration hard-to-decompose organic matter wastewater final treatment device,
The ozonolysis reactor includes an ozonolysis reaction tank, a raw water inlet, a first microbubble generator, an ejector pump, a first transformer, a first circulation pump, and a first activated carbon tower,
The ozone catalyst reactor includes an ozone catalyst decomposition tank, a second microbubble generator, a second circulation pump, a second transformer, a third circulation pump, and a second activated carbon tower,
The ozone generator is connected to the ejector pump, the first microbubble generator, and the second microbubble generator by an ozone gas supply pipe,
The ozone decomposition reaction tank and the ozone catalyst decomposition tank are connected by an overflow pipe,
A first activated carbon layer and a second activated carbon layer are disposed inside the ozone catalyst decomposition tank, and a backwash water outlet is provided. apparatus.   2. The apparatus according to claim 1, wherein the first transformation tower is installed to circulate raw wastewater containing ozone microbubbles with the ozonolysis reactor through a plurality of pipes. 3.   The apparatus according to claim 1, wherein a punching plate is provided inside the first transformer column.   The apparatus according to claim 1 or 2, wherein the first transformer column has an orifice installed therein.   The said 1st activated carbon tower is installed so that the effluent raw water containing ozone gas, an ozone microbubble, and / or an ozone nanobubble may be circulated through the several pipes with the said ozone decomposition reaction tank. An apparatus according to any one of the preceding claims.   The said 2nd transformer column is installed so that the waste water containing ozone microbubble may be circulated between the said ozone catalyst reaction tanks through a several pipe | tube. apparatus.   The apparatus according to any one of claims 1 to 6, wherein a punching plate is installed inside the second transformer column.   The apparatus according to any one of claims 1 to 6, wherein the second transformer column has an orifice installed therein.   The said 2nd activated carbon tower is installed so that the waste water containing ozone gas, an ozone microbubble, and / or an ozone nanobubble may be circulated through a several pipe with the said ozone catalyst reaction tank. An apparatus according to any one of the preceding claims.   The apparatus according to any one of claims 1 to 9, wherein the activated carbon filled in the first activated carbon tower and the second activated carbon tower is granular activated carbon, and the activated carbon has a diameter of 1 to 2 mm.   The activated carbon filled in the first activated carbon layer is a pellet type activated carbon having a diameter of 6 to 7 mm, and the activated carbon filled in the second activated carbon layer is a pellet type activated carbon having a diameter of 3 to 4 mm. The device according to any one of claims 1 to 10.   The apparatus according to any one of claims 1 to 11, further comprising another ozonolysis reactor and a coagulation sedimentation tank. A wastewater final treatment system for high-concentration hardly decomposable organic matter using the apparatus according to any one of claims 1 to 12,
The wastewater final treatment system,
Ozone that treats wastewater raw water using an ozonolysis reactor equipped with an ozonolysis reactor, a raw water inlet, a first microbubble generator, an ejector pump, a first transformer, a first circulation pump and a first activated carbon tower. A decomposition treatment system, and the wastewater treated by the ozone decomposition treatment system is treated with an ozone catalyst decomposition tank, a second microbubble generator, a second circulation pump, a second transformer, a third circulation pump, and a second activated carbon tower. An ozone catalytic decomposition system for treating the first activated carbon layer and the second activated carbon layer with an ozone catalytic reactor installed therein;
In the above-mentioned catalytic cracking system, the raw wastewater for high concentration hardly decomposable organic matter is passed through the first activated carbon layer and the second activated carbon layer at a flow rate of 10 to 100 cm / sec.   The wastewater final treatment system according to claim 13, further comprising at least one or more of the ozonolysis treatment system, the coagulation treatment system, the filtration treatment system, and / or at least the ozone catalytic decomposition system.   The activated carbon filled in the first activated carbon layer is a pellet type activated carbon having a diameter of 6 to 7 mm, and the activated carbon filled in the second activated carbon layer is a pellet type activated carbon having a diameter of 3 to 4 mm. The wastewater final treatment system according to 13 or 14. A wastewater final treatment method using the wastewater final treatment system for high-concentration hardly decomposable organic substances using ozone microbubbles according to claim 13,
A method for final treatment of wastewater of high-concentration hardly decomposable organic matter, comprising a step of performing ozone decomposition treatment and a step of performing ozone catalytic decomposition.   The wastewater final treatment method according to claim 16, further comprising at least one or more of the above-mentioned ozone decomposition treatment step, coagulation treatment step, filtration treatment step, and / or the ozone catalytic decomposition step.

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