KR20180075923A - Treatment Apparatus of Non-biodegradable Organic Wastewater or Anaerobic Digestion Effluent - Google Patents

Abstract

The present invention relates to a treatment apparatus for non-degradable organic wastewater or digestion tank effluent and, more specifically, to a treatment apparatus for non-degradable organic wastewater or digestion tank effluent comprising a nanocatalyst electroflotation tank and a nanocatalyst electrolysis oxidation tank for removing COD and nitrogen. In the treatment apparatus for non-degradable organic wastewater or digestion tank effluent according to the present invention, the nanocatalyst electroflotation tank can float and separate solid matters contained in organic wastewater or digestion tank effluent, and in the nanocatalyst electrolysis oxidation tank including an iridium-ruthenium-titanium based nanocatalyst alloy plate, COD and nitrogen can be removed. In addition, the treatment apparatus of the present invention can reliably treat dissolved algae in effluents, which are difficult to remove without a chemical treatment, and COD, nitrogen, and phosphorus; due to the non-use of chemicals, can reduce the amount of sludge formation; due to a good water quality of drain water, does not require a separate filtration facility; and can be conveniently maintained and managed with a low maintenance and management cost.

Description

[0001] The present invention relates to an apparatus for treating organic wastewater or a digestion tank,

More particularly, the present invention relates to an apparatus for treating degradation organic wastewater or digestion tank effluent, and more particularly, to an apparatus for treating degradation organic wastewater or digestion tank desalination liquid containing COD, a nanocatalyst electrolytic flocculation tank for removing nitrogen, ≪ / RTI >

BioGasPlant (BGP), an application of food waste treatment as an anaerobic digestion technology, is on the rise due to the ban on marine emissions from the London Convention and the reduction of greenhouse gases. In order to discharge food wastewater, a large amount It is necessary to treat the anaerobic digestion desalination liquid containing salinity, nitrogen, organic matter and the like.

In addition, biogasification technology of organic matter such as food is developed, and there is a high concentration of refractory substance and nitrogen, and it is difficult to flow into the sewage treatment plant or to discharge the waste water, so that the need to treat the anaerobic digestion effluent is increasing. In particular, since the food waste anaerobic digestion tank desalin has a high COD, nitrogen concentration and a large amount of salinity, it is difficult to obtain a stable treatment efficiency with the present simple microbial treatment method, so that a method combining both physico-chemical treatment and biological treatment is required.

Although organic wastes such as food are high in concentration, organic wastes treated by anaerobic digestion are being tried, but studies are under way to lower the quality of discharged water due to high concentration of COD and T-N. As a prior art related to the technology of treating excess sludge by the electrolysis described above, Korean Patent No. 10-0319022 discloses a wastewater treatment apparatus using an electrolytic floating method using two consecutive electrolytic floating floats in which cathodes and anodes are alternately arranged Korean Patent No. 10-1651080 discloses a sewage and sludge resource treatment system including a pretreatment process of a sludge digestion tank. Korean Patent Registration No. 10-0644758 discloses a treatment method of excess activated sludge generated after biological treatment of wastewater, And discloses the apparatus. In addition, Korean Patent No. 10-1102275 discloses an electrolytic solubilization (electrolytic solution) including electrodes of a multi-layer matrix type structure and a multi-layer matrix type structure in which organic sludge generated in a biological treatment process of waste water and wastewater is solubilized by electrolysis And Korean Patent Registration No. 10-0593497 discloses an advanced wastewater treatment system using counter current water electrolysis, in which electrolytic treatment of reflux water comprising an enriched tank supernatant and a dehydrator desalination solution is introduced into a bioreactor will be. It is possible to effectively remove effluent containing high concentrations of organic substances and nutrients, thereby increasing the efficiency of wastewater treatment. Korean Patent No. 10-1618757 discloses a process for preparing an iridium alloy nanocatalyst for removing COD, ammonia nitrogen, nitrate nitrogen and nitrogen, and a process for producing an iridium alloy nanocatalyst for removing algae, COD, nitrogen and phosphorus, Discloses an electrolyzed flocculation type effluent treatment apparatus including a device. Korean Patent Nos. 10-0425954, 10-0490307, and 10-0533246 use iridium alloy nanocatalyst as a plate electrode to generate an iridium alloy nanocatalyst ion or a hydrogen ion and a hydroxy radical (.OH), and the iridium alloy nanocatalyst ion Or a method of removing nitrogen with a hydrogen ion and a hydroxyl radical. However, there is a problem that it is difficult to efficiently remove COD and nitrogen at a high concentration by a simple nano catalyst plate.

Accordingly, the present inventors have made intensive efforts to effectively treat degradation-resistant organic wastewater or digestion tank desolvation solution containing high COD, high concentration nitrogen, and a large amount of salt, and as a result, have found that the nano-catalytic electrolytic flocculation bath and the nano- It is possible to treat COD, nitrogen and phosphorus stably without chemical treatment by using organic wastewater or digestion tank desalination treatment system and it is possible to reduce the amount of sludge to be generated by using chemical agent without using chemical agent. And the present invention has been completed.

It is an object of the present invention to provide an apparatus for treating refractory organic wastewater or digesters.

In order to accomplish the above object, (a) a facility for flotation and separation of solid matter contained in refractory organic wastewater or digestion tank desalination liquid, a nanocatalyst type micro-bubble generator is installed in the lower part, A nanocatalyst electrolytic floating tank 30 provided with a scum removing part; And (b) a nano-catalytic electrolytic oxidation vessel containing iridium-ruthenium-titanium at the bottom and a nano-catalytic alloy plate of an anode and a cathode for removing COD and nitrogen remaining in the crude treated water on the nano- 70) which is provided in the digester tank.

In the refractory organic wastewater or digestion tank desolvation treatment apparatus according to the present invention, the nanocatalyst electrolytic flocculation tank is constructed such that the solid matter contained in the organic wastewater or the digestion tank desolvate is flashed off, and the nanocatalyst electrolysis including the iridium-ruthenium- COD and nitrogen can be removed from the oxidation tank. In addition, it is possible to treat the dissolved algae and COD, nitrogen and phosphorus of discharged water that is difficult to remove without chemical treatment, and it is possible to reduce the amount of sludge to be generated by the use of chemicals without use of chemicals, and a separate filtration facility The maintenance of the apparatus is simple and the maintenance cost is low.

1 shows a digester tank storage tank 10 according to an embodiment of the present invention; A nano-catalyst electrolytic floating tank (30); AGS-SBR 50; And a nano-catalytic electrolytic oxidation tank (70).
FIG. 2 is a schematic diagram of a digester tank storage tank 10 according to an embodiment of the present invention; AGS-SBR 50; A nano-catalyst electrolytic floating tank (30); And a nano-catalytic electrolytic oxidation tank (70).
FIG. 3 shows a mass balance of a digester tank decanting apparatus according to an embodiment of the present invention.
FIGS. 4 through 7 illustrate an aerobic granular sludge and an AGS-SBR process according to an embodiment of the present invention.
FIG. 8 shows a mechanism of generation of a hydroxyl radical (.OH) in a nanocatalytic electrolytic oxidation reactor according to an embodiment of the present invention.

The present invention can be all accomplished by the following description. It is to be understood that the following description is only illustrative of preferred embodiments of the invention, but the invention is not necessarily limited thereto. It is to be understood that the accompanying drawings are included to provide a further understanding of the invention and are not to be construed as limiting the present invention. The details of the individual components may be properly understood by reference to the following detailed description of the related description.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

In the present invention, the solids contained in the refractory organic wastewater or the digestion tank desolvation solution are separated by flotation in a nanocatalyst electrolytic bath and the residual COD and nitrogen in the nano-catalytic electrolytic oxidation tank containing iridium-ruthenium- Can be removed. In addition, it is possible to treat the dissolved algae and COD, nitrogen and phosphorus of discharged water that is difficult to remove without chemical treatment, and it is possible to reduce the amount of sludge to be generated by the use of chemicals without use of chemicals, and a separate filtration facility It is possible to provide a device that does not.

Accordingly, in one aspect, the present invention provides a facility for float separation of (a) solids contained in refractory organic wastewater or digestion tank desalination liquid, a nanocatalyst type micro-bubble generator at the lower part, A nano-catalyst electrolytic floating tank 30 provided with a scum removing portion; And (b) a nano-catalytic electrolytic oxidation vessel containing iridium-ruthenium-titanium at the bottom and a nano-catalytic alloy plate of an anode and a cathode for removing COD and nitrogen remaining in the crude treated water on the nano- 70). The present invention also relates to an apparatus for treating waste water of a digestion tank.

The apparatus for treating a desalting tank desalination liquid according to an embodiment of the present invention comprises: (a) a digester turgor reservoir 10 including an agitator type stirring apparatus for storing a food digestion tank desorption solution and preventing precipitation of solids; (b) a facility for floating and separating the solid matter contained in the digestion tank desorbing liquid discharged from the storage tank, a nano-catalytic microbubbles generator installed at the lower part, a skimmer for collecting floating solids, A nano-catalyst electrolytic bath 30 provided with a scum collector; (c) a continuous batch reactor (AGS-SBR) 50 fed with an aerobic granular sludge which repeats the processes of influent-anoxic-aerobic-discharge to remove COD and nitrogen contained in the electrolytic flotage treated water; And (d) iridium-ruthenium-titanium in the lower part to remove COD and nitrogen remaining in the AGS-SBR treated water, and a nano-catalytic electrolytic oxidation vessel 70 comprising a nano- . ≪ / RTI >

(E) a food supernatant reservoir 150 containing an organic carbon source necessary for the denitrification reaction in the AGS-SBR; (f) an organic acid reaction tank 130 for producing an organic acid using the food supernatant 160 supplied from the reservoir; And (g) means 140 for supplying the prepared organic acid to the AGS-SBR.

(H) the sediment sludge and scum 120 generated in the nano-catalytic electrolytic bath, the excess sludge 100 generated in the AGS-SBR, and the sediment generated in the nano-catalytic electrolytic oxidation tank A sludge treatment tank (90) for treating sludge and scum (80); And (i) means 110 for supplying the sludge treatment tank supernatant 110 to the AGS-SBR.

FIG. 1 is a schematic view of a digester tidal liquid treatment apparatus according to an embodiment of the present invention. Referring to FIG. 1, a digester tidal liquid 20 discharged from a digester tidal liquid reservoir 10 is discharged from the nocatalyst electrolytic floating tank 30, And the removed sediment sludge and the scum 120 are sent to the sludge treatment tank 90. The treated water 40 treated in the nanocatalyst electrolytic floating tank 30 is sent to a continuous batch reactor (AGS-SBR) 50 in which aerobic granular sludge is injected to treat COD and nitrogen, and AGS-SBR treated water 60 ) Treats the remaining COD and nitrogen by sending it to the nano-catalytic electrolytic oxidation unit 70 using a nano-catalytic alloy plate composed mainly of iridium-ruthenium-titanium. The excess sludge 100 generated in the AGS-SBR is sent to the sludge treatment tank 90 and the supernatant 110 is sent to the AGS-SBR 50 for reprocessing. In order to supply the organic carbon source necessary for the denitrification reaction in the AGS-SBR, the food supernatant 160 is received in the food supernatant reservoir 150, and the organic supernatant 160 is prepared in the organic acid reaction tank 130 and supplied to the AGS- Is used as a carbon source to remove carbon dioxide.

The apparatus for treating a desalting tank desalination liquid according to an embodiment of the present invention comprises: (a) a digester turgor reservoir 10 including an agitator type stirring apparatus for storing a food digestion tank desorption solution and preventing precipitation of solids; (b) a continuous batch reactor (AGS-SBR) 50 injected with an aerobic granular sludge which repeats the processes of inlet-anoxic-aerobic-discharge to remove COD and nitrogen contained in the desalination tank discharged from the storage tank; (c) a facility for float separation of the solid matter contained in the AGS-SBR treated water, a nanocatalyst type micro-bubble generator at the lower part, a skimmer and a scum remover for collecting floating solids A nano-catalyst electrolytic floating tank 30 provided with a scum collector; And (d) a nano-catalytic electrolytic oxidation vessel containing iridium-ruthenium-titanium in the lower portion and a nano-catalytic alloy plate of an anode and a cathode for removing COD and nitrogen remaining in the crude treated water on the nano- 70).

(E) a food supernatant reservoir (150) containing an organic carbon source necessary for the denitrification reaction in the nanocatalyst electrolytic bath; (f) an organic acid reaction tank 130 for producing an organic acid using the food supernatant 160 supplied from the reservoir; And (g) means 140 for supplying the prepared organic acid to the nanocatalyst electrolytic bath.

(H) the sediment sludge and scum 120 generated in the nano-catalytic electrolytic bath, the excess sludge 100 generated in the AGS-SBR, and the sediment generated in the nano-catalytic electrolytic oxidation tank A sludge treatment tank (90) for treating sludge and scum (80); And (i) means 110 for supplying the sludge treatment tank supernatant 110 to the nanocatalyst electrolytic bath.

The present invention relates to an apparatus and method for disposing of a digester tannery liquid according to an embodiment of the present invention. The digester tannery effluent 20 discharged from the digester tannery effluent storage tank 10 is introduced into a continuous batch reactor (AGS-SBR) 50 fed with aerobic granular sludge, And the AGS-SBR treated water 170 is sent to the nanocatalyst electrolytic floating tank 30 to flocculate and remove solids and scum on the electrolytic solution, and the removed sediment sludge and the scum 100 are treated with sludge And sends it to the treatment tank 90. The nano-catalytic electrolytic solution-based pretreatment water 180 is fed to a nano-catalytic electrolytic oxidation tank 70 using a nano-catalytic alloy sheet containing iridium-ruthenium-titanium as a main component to treat residual COD and nitrogen. The surplus sludge 100 generated in the AGS-SBR is sent to the sludge treatment tank 90 and the supernatant 110 is sent to the nanocatalyst electrolytic flocculation tank 30 for reprocessing. The food supernatant 160 is received in the food supernatant reservoir 150 to supply the organic carbon source necessary for the nano catalytic electrolytic flocculation denitrification reaction and is then made into an organic acid in the organic acid reaction tank 130 and then supplied to the nanocatalyst electrolytic bath ) It is used as a carbon source to remove nitrogen.

According to an embodiment of the present invention, a digester tank desalination apparatus having the following configuration can be used.

(a) an agitator-type agitator for storing the food digestion tank desalination solution and preventing solid matter precipitation;

(b) A facility for float separation of solids in a digestion liquor so as to be suitable for a continuous batch biological apparatus (AGS-SBR) injected with aerobic granular sludge. A nanocatalytic micro-basal generator is installed in the lower part, A nano-catalytic electrolytic flotation device consisting of a Skimmer and a Scum Collector for collecting solids;

(c) an SBR reactor forming an aerobic granular sludge (AGS) type microorganism that repeats the process of influx - anoxic - aerobic - discharge for the purpose of removing COD and nitrogen;

(d) Facilities for transporting surplus sludge generated from AGS-SBR to the reservoir after storage;

(e) a facility for removing COD and nitrogen remaining after AGS-SBR reaction, a nano-catalytic oxidation apparatus using a nano-catalyzed alloy sheet comprising iridium-ruthenium-titanium as a main component;

(f) a ventilator for installing a skimmer and a collector for removing the solid material floating on the upper part, the scum, and discharging the gaseous component generated in the oxidation reaction;

(g) To provide a method of removing the anaerobic digestion tank desolvation solution through an organic acid reaction tank for producing and supplying the organic carbon source necessary for the denitrification reaction of AGS-SBR and a device for supplying AGS-SBR.

In the present invention, it is a facility for transferring the food digestion liquid to the raw water storage tank of the treatment facility, and is controlled in connection with the level of the waste liquid storage tank. It is a facility to smoothly feed the transferred digesters tannery liquid into the nano catalytic flotation separation tank. It consists of an agitator-type agitator for preventing precipitation of solids and a propellant-type pump connected to the water level meter. The retention time is 2 hours and the electrode area is 0.76m2 or more. The nanocatalyst flotation separator separates the solids in the digestion liquor into 500 mg / L of the solids to be suitable for the continuous batch biological apparatus (AGS-SBR) injected with aerobic granular sludge The system consists of a nano-catalytic microstructure generator at the bottom and a skimmer and a scum collector at the top to collect suspended solids. In order to smoothly supply the separated water to the raw water supply cycle of the AGS-SBR, the residence time is 48 hours, which is composed of a feed pump facility connected to the water level meter. In the electrolytic flotation device, COD of 3500ppm and T-N of 500ppm or less which can biological treatments were treated and treated with COD of 2500ppm and nitrogen concentration of 216ppm and COD of 760ppm and nitrogen concentration of 140ppm in the nano-catalytic redox system. The steps of the process for treating anaerobic digesters desolvate are as follows. The raw water intake facility is a facility for transferring 1.03 m3 / day of food anaerobic digestion decontamination, which has a COD of 5000 ppm and a nitrogen concentration of 800 ppm or more, to the raw water reservoir and is controlled in connection with the level of the effluent reservoir. The nano catalytic flotation separator is a facility to remove 3500ppm of COD and 500ppm of TN by floatation of the influent water so that the anaerobic digestion tank desalination solution is suitable for AGS-SBR, and a nano-catalytic micro- It consists of a skimmer and a collector that collect the separated solids. The AGS-SBR reactor repeats the anaerobic-aerobic-evacuation process with an SBR reactor that forms AGS-type microorganisms for the purpose of removing nitrogen. An agitation facility for anoxic condition and an aeration facility for exhalation reaction are constituted, and raw water is sequentially supplied in the anaerobic reaction, and then the treated water is discharged after settling in a certain period. For the purpose of removing nitrogen, anaerobic-aerobic-discharging process is repeated in an SBR reactor forming an aerobic granular sludge (AGS) type microorganism. An agitation facility for anoxic condition and an aeration facility for exhalation reaction are constituted, and raw water is sequentially supplied in the anaerobic reaction, and then the treated water is discharged after settling in a certain period. As an example, an agitator type (0.4 kW), a paddle for an agitation type, a membrane disk type for an acid type facility, a root type blower (1.5 kW) for a blowing facility, and an ultrasonic water level meter can be used as a water level gauge. The AGS-SBR reaction tank has a retention time of 7.2 days, a required capacity of 7.2㎥, an agitator type (1.5 kW), a membrane plant of a membrane disk type, and an excess sludge generated from AGS-SBR This is a facility for temporarily storing the microorganisms in the reaction tank when operating conditions are changed during the experiment, and it is constructed in connection with the transfer pump of the floating separation treatment tank. A facility for oxidizing residual organic matter after AGS-SBR reaction is equipped with a nano catalytic oxidation unit at the bottom, a skimmer and a collector to remove the solid substances and scum floating on the upper part, And a ventilation device for discharging the air. It is a facility to produce and supply organic carbon source needed for denitrification reaction of AGS-SBR. It uses organic deionized water as the raw water to induce organic acid reaction and constitutes agitation facility for smooth reaction inside. The reaction time is 2-24 hours and it is composed of electric power of 0.1KW or more and electrode area is 4-10m2. The produced organic acid is transferred to the raw water storage tank to remove solids in the reaction solution and then supplied to the AGS-SBR. An inorganic membrane can be installed to enable the AGS-SBR to be supplied separately. The nanocatalyst floatation, the biofilm reaction tank, the nano oxidation catalyst device, the treatment process chart and the mass balance of the treated water are as shown in FIG.

Hereinafter, the aerobic granular sludge and the AGS-SBR process will be described in more detail with reference to FIGS.

In the present invention, in the case of a continuous batch reactor (AGS-SBR) injected with aerobic granular sludge, high concentration organic matter and nitrogen are removed from the waste water digestion tank remover by repeating the inflow, stirring, aeration, precipitation and outflow. In the raw water inflow stage, agitation is simultaneously carried out to induce denitrification of nitrate nitrogen and oxidation of organic matter and nitrification of ammonia nitrogen are carried out in the aeration step. The raw water treated through repetition of the inflow-desorption step is subjected to solid-liquid separation in the precipitation step and finally to the effluent step. Aerobic Granular Sludge (AGS) refers to activated sludge formed by granulation of microorganisms due to biological, physical and chemical factors. Unlike microbial membranes, aerobic granular sludge is formed by self immobilization of microorganisms without the aid of mediators under aerobic conditions. Aerobic granule sludge is a high density microorganism aggregate composed of various microorganism species. Existing activated sludge has a loose and irregular structure like fluff, whereas aerobic granule sludge has a regular, dense, and rigid structure. Therefore, aerobic granule sludge It has high microbial density and strong internal structure and is excellent in sedimentation. SBR (Sequencing Batch Reactor) advanced treatment system using aerobic granulated sludge instead of general activated sludge based on mass production technology of aerobic granulated sludge and special aerobic granulated sludge production and operation technique of removing organic matter and nitrogen among source technology related to aerobic granulated sludge By minimizing the hydrodynamic residence time and the tank volume, it is possible to reliably remove organic matter and nitrogen by using aerobic granular sludge, in which nitrification and denitrifying microorganisms are dominant. The operating conditions of the SBR process are 1 cycle / 1 day and the total operation time of one cycle is 24 hours. During the operation, the inflow water is injected 14 times in 1 cycle. The operation method is composed of raw water inflow and agitation - abandonment (14 repetitions) - sedimentation - outflow. The total inflow ratio (Vf / Vt) is 0.14, and the injection amount of 1 time is 1% of the volume of the reactor. In the introduction of raw water, external carbon source necessary for denitrification is injected to induce a smooth denitrification reaction. In the surface layer (0 ~ 70um) of the aerobic granule sludge, heterotrophic organisms are ignited to remove organic matter, nitrification occurs by the nitrifying microorganisms as the autotrophic organisms at 70 ~ 100um depth, and anaerobic conditions at 100 ~ And the phosphorus removal and the denitrification reaction occur at the same time. In addition, aerobic granular sludge (AGS) is preferably a dense microorganism aggregate formed by self-immobilization of microorganisms under aerobic conditions without the aid of mediators, unlike microbial membranes.

[Table 1] Aerobic granule sludge main factor and removal efficiency

In the SBR process (AGS-SBR) injected with aerobic granule sludge, organic matter is removed by aerobic granule sludge, organic matter oxidation of the right-burning heterotrophic microorganism is performed on the aerobic granular sludge surface, energy is obtained, Organic matter is converted into new cells (C ₅ H ₇ O ₂ N), CO _2, etc., and is removed. At this time, 0.12 kg of nitrogen and 0.025 kg of phosphorus are consumed in order to synthesize 1 kg of C ₅ H ₇ O ₂ N. This can be expressed as follows.

Organic matter removal reaction

: CHON (organic matter) + O ₂ + nutrients → C ₅ H ₇ O ₂ N + CO ₂ + NH ₃ + other products

Nitrogen removal results in nitrification of ammonia nitrogen in aerobic conditions and oxidation of ammonia nitrogen to nitrite and nitrate nitrogen by autotrophic microorganisms in aerobic granular sludge.

Ammonia Nitrogen Oxidation: NH ⁴⁺ + 1.5O ₂ → NO ₂ ^- + H ₂ O + 2H ⁺ + Energy

Nitrite Nitrogen Oxidation: NO ₂ ^- + 0.5O ₂ → NO ₃ ^- + Energy

In the case of nitrate nitrogen produced under aerobic condition, denitrification is carried out by anaerobic conditions at the time of influent agitation. The denitrification reduces NO ₃ ^- or NO ₂ ^- to N ₂ gas using an organic or inorganic electron donor.

Nitrate nitrogen denitrification

: NO ₃ ^- + 1.08 CH ₃ OH + H ⁺ ? 0.065 C ₅ H ₇ O ₂ N + 0.47 N ₂ + 0.76 CO ₂ + 2.44 H ₂ O

The optimum operating condition of AGS-SBR is to ensure that the MLSS concentration is over 10,000 mg / L and that simultaneous removal of BOD and TN using autotrophic microorganisms on the surface of AGS and heterotrophic microorganisms in the sludge is possible. If necessary, the reaction time (aeration / non-aeration) can be controlled. When the carbon source is insufficient, the amount of methanol injected can be controlled and the sludge disposal amount can be adjusted for sludge residence time. When smoothly operating the AGS-SBR design value the look ^{_{SNR: 0.09 kg NH 4 + -N}} / kg MLVSS · day or more ^{_{secure, SDNR: 0.2 kg NO 3 -}} -N / kg MLVSS · day or more secure, MLVSS / MLSS: 0.8 (8,000 mg / L / 10,000 mg / L), SRT: 45.7 days or more, and HRT: 7.2 days. The characteristics of the SBR process (AGS-SBR) injected with aerobic granule sludge is that it can maintain high concentration of microbial concentration compared to existing activated sludge, has a high resistance to impact load due to high concentration of influent water, and low excess sludge generation. It is possible to design a compact reactor due to the short residence time and to secure a nitrogen removal rate of over 200% compared to other processes.

The carbon source for the nitrogen removal of AGS-SBR is a carbon source by the organic acid fermentation. The organic acid such as acetic acid, propionic acid, and butyric acid is produced by using the anaerobic digestion raw water and utilized as an external carbon source of the AGS-SBR process. The organic acid reaction tank has a retention time of 5-6 days and constitutes a heating facility for maintaining the temperature. The resulting organic acid is transferred to the raw water tank of the PILOT PLANT, and then treated with an amount of less than 500 mg / L of solids in the floatation separation process and supplied during the anoxic process of AGS-SBR. The amount of organic acid supplied is determined based on the C / N ratio 5 and is controlled to 0.01-0.02 (0.015) ㎥ / day.

In the iridium-ruthenium-titanium nanocatalyst device, when water (H ₂ O) on the surface of the nanocatalyst plate composed of iridium and the like receives energy above a bandgap, electrons move to generate an electron- Hydroxy radicals (ÂOH) and oxygen radicals (Â O ₂ ), which have strong oxidizing properties, break down the covalent bonds of pollutants and decompose them into carbon dioxide and water, and convert ammonia (NH ₃ ) into nitrate nitrogen, Gas. In addition, formaldehyde, which is a toxic substance, is also converted into water and carbon dioxide by the hydroxyl radical (.OH) and the oxygen radical (.O ₂ ) (see FIG. 8). The structure of the iridium-ruthenium-titanium nano-alloy catalyst device is an iridium-ruthenium-titanium nano alloy catalyst plate which generates oxygen radicals by coating a catalyst such as iridium and ruthenium on the titanium by electrolysis; (b) an electrolytic bath (electrolytic bath) which breaks down the poorly decomposable COD of the raw water into which oxygen radicals and hydroxyl radicals generated in the nano-alloy catalyst plate of the electrolytic bath are introduced; (c) a hydrogen gas generated in the nanocatalyst plate of the electrolytic bath, And the like, which collects floating scum (contaminated water) by flooding the dissolved organic material with water or the like; (d) a scum storage tank for temporarily storing the floc collected from the electrolytic floating tank and for discharging the floc collected therefrom.

The iridium-ruthenium-titanium nano-alloy catalyst plates were fixed in a unit of 1-10 units by 5-20 sheets, the electrical energy consumption of the insulative brackets was reduced, and the intervals of the nano catalytic plates were minimized within the range of 2 to 10 mm. We want to lower the current density. The scum removing portion of the electrolytic floating tank is provided to scrape flocks, algae, and contaminants that have floated above the water surface, and transfer the flocks to the scum storage tank. The sedimentation tank is constructed in the form of a cone to deposit undiluted flocs and to discharge the supernatant of the effluent water. The feature of the iridium-ruthenium-titanium nano-alloy catalyst plate device is that it does not use coagulant and coagulation device to float phosphorus, algae and suspended matter. The iridium-ruthenium-titanium nano-alloy catalytic plate device generates oxygen and OH radicals generated during electrolysis, generates minute bubbles by intermediate products (OH ·, O ·, O ₃ ), and treats COD, Which is a micro bubble oxidation catalyst device. It is a type of device that immerses the oxidation catalytic plate applied with rated DC voltage and raises suspended substances and algae by nano bubbles released from the oxidation catalyst plate and cools and precipitates water and removes phosphorus and pollutants into the reservoir.

Iridium oxide has been recently studied as a better catalytic material than platinum for the water oxidation process of electrolyzing water to oxygen. Electrolysis causes electrolysis to occur more severely when salts such as electrolytes in water are present. O ₂ ^- , OH ^- , OCl, HOCl, and so on, decompose the organic matters in the wastewater.

The basic electrolysis at the anode of the electrolysis apparatus is as follows.

H ₂ O + M [] + Cl ^- -> M [ClOH] + H ⁺ + 2e ^-

H ₂ O + M [] + Cl ^- -> M [OH ^- ] + H ⁺ + 2e ^-

The secondary electrochemical reaction is as follows.

^{_{12OCl + 6H 2 O + 12e -}} -> 3O 2 + 12H + + 8Cl + 4ClO 3

The basic electrolysis reaction at the cathode is as follows.

2H ₂ O + 2e ^- -> H ₂ + 2OH ^-

Hydrogen ions are discharged from the cathode to generate hydrogen gas, and various kinds of organic substances are reduced, and the pigment and the like are reduced to become colorless. In the reduction process, pH increased from 6.06 to 7.39, indicating that alkalinity was increased.

In cathode, reduction of nitrate nitrogen occurs mainly by electrolysis as follows.

2NO ₃ ^- + 6H ₂ O + 10e N ₂ + 12OH ^- E ⁰ = 0.52V

NO ₃ ^- + 6H ₂ O + 8e NH ₃ + 9OH ^- E ⁰ = -0.12V

Oxygen is generated by the discharge of OH at the anode, and various organic substances are oxidized.

4OH ^- O ₂ ↑ + 2H ₂ O + 4e ^-

The secondary electrochemical reaction is as follows.

OCl + H ₂ O + 2e ^- -> Cl ^- + 2OH ^-

In the closed system, gas bubbles are formed by the hydrogen and oxygen gas generated from the cathode and the anode in the oxidation reaction, and the contaminants are adhered to float, and the flocculated substances are precipitated to remove contaminants.

It removes COD, T-N, Geosmin, 2-MIB, algae, and antibiotics with a hydroxy radical generated in the nano-catalytic alloy plate device. In order to generate micro bubbles, a pressurized tank, a pipe for injecting impacts and bubbles is not necessary, and oxygen and hydrogen gas generated from the nano-alloy catalyst plate can be used as an electrolytic floating device. Removal of COD and total nitrogen, oxidation and reduction reaction by oxidation of nano-catalytic plate due to current density, and removal of ammonia and nitrate nitrogen by oxygen radicals and OH radicals effectively removes amine compounds. The iridium-ruthenium-titanium nano-alloy catalyst plate device is constituted by an insertion structure which can be easily replaced one by one in the apparatus, and the thickness of the oxidation catalyst plate of the oxidation catalyst deposition apparatus is set to 2-10 mm. The oxidation catalyst deposition module installed in the anaerobic digestion tank supernatant is a system in which the positive terminal and the minus terminal are electrically exchanged at intervals of 10 minutes to 1 hour by the electric supply method, thereby removing ionic substances and refractory substances attached to the oxidation catalyst plate Respectively. It consists of a reaction tank, an oxidation catalytic plate module, an oxidation catalyst, and a control panel, which treats the bubbles and suspended substances to raise ionic substances, refractory substances and suspended matters in the anaerobic digestion tank. Each equipment shall be made of iridium-ruthenium-titanium nano-alloy structure that can withstand continuous operation, and shall be rigid so that vibration and noise are few and smooth operation and cavitation phenomenon does not occur.

In the present invention, the substrate of the electrolytic bath may be an iridium-ruthenium-titanium nano-catalytic alloy plate.

The iridium nano-catalytic alloy plate of the anode is made of a titanium alloy plate made of an alloy of at least one selected metal selected from the group consisting of iridium and ruthenium and titanium (Ti), and an iridium nano-catalyst alloy plate of 0.5 to 1.5 M of iridium chloride (IrCl ₃ ) (R) chloride (RuCl ₃ ), and the mixture was heated at a rate of 2-5 ° C / h and heated at 40 ° C to 80 ° C. While 0.1-0.5 M sulfuric acid was added dropwise at a rate of 1-2 ml / (IrO ₂ ) and ruthenium oxide (RuO ₂ ) prepared by coprecipitation for 5 to 10 hours for 30 to 60 minutes, and then dried at room temperature, irradiated with ultraviolet rays (UV) Lt; 0 > C, followed by repeating the coating process 2 to 10 times.

The prepared iridium oxide sol and ruthenium oxide sol may be coated on a titanium alloy plate and coated with a titanium alloy plate. In the method of applying the iridium oxide sol and the ruthenium oxide sol to the titanium alloy sheet, the titanium alloy sheet is immersed in the iridium oxide sol and the ruthenium oxide sol for 1-2 hours, and then taken out and dried to a wavelength of 254-380 nm UV coating is preferred. The coating process is preferably repeated 2 to 10 times in order to increase the bonding strength. If the coating process is repeated 2 to 10 times, the bonding strength between the iridium oxide sol and the ruthenium oxide sol is increased and a bonding surface having a thickness of 5 to 20 um can be obtained. However, It is preferable that the coating process is repeated 2 to 10 times.

In the present invention, it is preferable that the iridium alloy nanocatalyst device is manufactured by fixing an iridium nano-catalytic alloy plate of a positive electrode and a titanium catalyst alloy plate or an iridium nano catalyst plate of a negative electrode in a unit of 1 to 10, . The iridium alloy nanocatalyst device comprises a titanium catalyst alloy plate including nickel, iron, aluminum, and zinc including titanium, an iridium nano-catalytic alloy plate coated with iridium oxide sol and ruthenium oxide sol, and an insulating bracket (not shown) And the insulative bracket is inserted into an electrolytic module (not shown) by adjusting the distance between the iridium nano-catalytic alloy plate and the titanium catalytic alloy plate, thereby facilitating the iridium nano-catalytic alloy plate and the titanium catalytic alloy plate But it is not limited thereto. In addition, when it is difficult to fix the iridium nano-catalytic alloy plate and the titanium catalytic alloy plate using only the insulating bracket, it is preferable to mix the nickel, manganese, and the like to prevent the corrosion, thereby maintaining the shape of the substrate. The distance between the iridium nano-catalytic alloy plate of the positive electrode and the titanium nano-catalytic alloy plate of the negative electrode is preferably 2 to 10 mm. If the distance between the two iridium nano-catalytic alloy plates and the titanium nano-catalytic alloy plate is close to that of the iridium nano-catalytic alloy plate, the distance between the iridium nano-catalytic alloy plate and the titanium nano- And the water must flow between the iridium nano-catalytic alloy plate and the titanium nano-catalytic alloy plate in order to effectively decompose the pollutant, so that the distance between the nano-catalytic alloy plate and the titanium nano-catalytic alloy plate is preferably 2 to 10 mm or more.

In the present invention, the electrolytic cell allows the inflow water to flow into the lower layer of the iridium alloy nanocatalyst device so that contaminants can be removed while passing through the substrate layer. When the hydraulic retention time of the iridium alloy nanocatalyst device is long, The iridium alloy nanocatalyst device may have a structure capable of repeatedly flowing into the substrate of the iridium alloy nanocatalyst device. If necessary, a flask may be formed by agitating an oxygen radical, a hydroxyl radical, hypochlorous acid, water containing iron and aluminum in a mixing bath. At this time, the mixing tank may be characterized in that the oxygen radical, hydroxyl radical, hypochlorous acid, iron and aluminum react with nitrogen or phosphorus to flocculate nitrogen or phosphorus without chemical substance added thereto. Nitrogen or phosphorus forming flocs is characterized by being easy to remove.

In the present invention, it is preferable that the electrolytic bath apply a direct current to the iridium alloy nanocatalyst device so that the current density is 0.01-1.0 A / cm 2, and more preferably the current density is 0.1-0.5 A / cm 2. When the current density of the iridium alloy nanocatalyst device is less than 0.01 A / cm < 2 >, the efficiency of the iridium alloy nanocatalyst device sharply decreases, and when the current density of the iridium alloy nanocatalyst device exceeds 1.0 A / The current density of the iridium alloy nanocatalyst device is 0.01 to 1.0 A / cm 2, and the more preferable current density is 0.1 to 0.5 A / cm 2, It is preferable to apply an electric current.

In the present invention, the electrolytic flocculation and flocculation bath may be characterized in that flocs float or settle. The electrolytic flocculation and flocculation baths are characterized by flotation of contaminants, inflow algae and nitrogen and phosphorus dissolved in water by microbubbles such as oxygen, hydrogen gas and radical bubbles which are lighter than the air generated in the iridium alloy nanocatalyst device . In the conventional electrolytic floating or floating method, bubbles are supplied by pressurizing with air or by supplying air generated by collision with air, or by adding oxidation water such as H ₂ O ₂ or generating OH radicals composed of a titanium plate. However, In the present invention, the oxidation of the iridium nano-catalytic alloy plate and the titanium catalyst alloy plate, the hydroxyl radical (OH), the oxygen radical (O) and the intermediate product ozone (O ₃ ) generated from the reducing electrode are decomposed COD or nitrogen And carbon dioxide or nitrogen gas is generated while removing it, and microbubbles such as hydrogen gas and radical bubbles which are lighter than air are formed. The microbubbles formed float flocs dissolved in water, incoming algae and nitrogen and phosphorus in the water, and the heights of the electrolytic flocculation and flocculation baths are adjusted with respect to the iridium alloy nanocatalyst device 30 ~ 100cm is raised. The floating flocs and algae may be removed with a scum removing tank. The electrolytic flocculation and coagulation bath may be characterized by supplying a polymer as a polymer coagulant of 0.01 to 1 g / L to float the suspended material and the dissolved substance to remove floating material, dissolved material and phosphorus.

In the present invention, the electrolytic flocculation and flocculation baths may be characterized in that iron, aluminum, and nickel generated (precipitated) from the iridium alloy nanocatalyst device coagulate with suspended matters to form flocs and precipitate flocs with a high weight have. The precipitated iron, aluminum, and nickel act as coagulant to coagulate the suspended material. Flocs formed in the decomposition flotation system have a high sedimentation rate and are difficult to float on the surface of the flocs. The bottom portion of the electrolytic float and the flocculating tank are formed in a cone shape so as to remove precipitated suspended matters in order to remove the flocculated heavy flocculant. The electrolytic floating and the impurities precipitated in the bottom portion of the flocculation tank are transferred to the scum storage tank for treatment.

The scum removing tank may be disposed on the electrolytic bath and on the flocculation tank. The scum removing tank may include, but is not limited to, a pair of rollers, a conveyor chain, a scraper, and a driving motor (not shown). Wherein the pair of rollers are rotatably installed on the electrolytic portion and on the sidewalls of the top of the flocculation tank, the conveyor chain is wound on the pair of rollers, and the scraper is attached to the circumferential surface of the conveyor chain at a predetermined interval, Floating flocks, algae and pollutants can be collected while moving in conjunction with the movement of the conveyor chain. The drive motor drives the pair of rollers. When the drive motor is operated, the pair of rollers rotates counterclockwise to operate the conveyor chain, and the scraper interlocked with the operated conveyor chain moves up Scrape floated flocks, algae and contaminants and transport them to the scum storage tank.

In the present invention, the scum storage tank temporarily stores contaminants such as flocs, algae, and scum that have flowed in from the electrolytic bath and from the flocculation tank and the scum removing tank, and then takes out the water. The recovered pollutants contain a large amount of water, which can lead to secondary pollution if they are discharged as they are, and they are expensive to transport and store. Therefore, it is preferable to temporarily store the recovered flocs to allow the water to separate naturally, and then carry it out.

In the present invention, the settling tank may be characterized by precipitating undrawn flocs and discharging the supernatant of the discharged water. The settling tank has a cone-shaped lower bottom portion attached with a cylindrical swash plate (through-the-tube baffle) to assist in sedimentation and solid-liquid separation of the floating organic matter, and can not float on the surface of the pressurized floating tank, It is possible to precipitate and remove the flock having a heavy weight which is not sufficient. The supernatant discharged from the settling tank can be discharged to the outside as treated water from which pollutants have been removed.

The sedimentation tank is installed on the electrolytic float and after the flocculation tank in order to remove the floccs of flocculated and formed flocculent flocculated metal ions, And the flocks of high weight are precipitated and removed.

The electrolyzed flocculation type effluent treatment apparatus including the iridium alloy nanocatalyst device according to the present invention can remove nitrogen by oxidation of ammonia nitrogen with hydroxyl radicals, oxygen radicals and hypochlorous acid generated in the iridium alloy nanocatalyst device , It is possible to remove nitrogen by reducing nitrate and decompose organic materials with hypochlorous acid generated to lower COD concentration. In addition, oxygen and hydrogen gas generated from the iridium alloy nanocatalyst device float organic substances and algae in the water, and iron and aluminum generated from the iridium alloy nanocatalyst device can be removed after forming flocs with the suspended substances .

In the production of the iridium-ruthenium-titanium nano-alloy catalytic plate device, one insert is easily inserted into the device, and the oxidation catalyst deposition module connects the positive plate, the negative plate and the positive plate to the first row, The positive and negative electrodes of the first and second rows are crossed to connect the positive electrode to the positive electrode of the first row and the negative electrode of the second row to the negative electrode of the second row. To remove ionic substances, salts and refractory substances attached to the oxidation catalyst plate. The nanocatalyst plate includes a device for alternating the cathode and the anode at intervals of 10 minutes to 1 hour.

Hydrogen ions are discharged from the cathode, hydrogen gas is generated, various kinds of organic substances are reduced, and the pigment and the like are reduced and reduced. In the course of reduction, the pH is increased from 6.06 to 7.39 to increase alkalinity and reduce nitrate nitrogen, And the generated hypochlorous acid ions oxidize the ammonia nitrogen to nitrogen and oxidize the decomposable organic matter. Gas bubbles are formed by the hydrogen and oxygen gas generated from the cathode and the anode to adhere the contaminants to float, and the aggregated substances are precipitated to remove contaminants.

The iridium nano-catalytic alloy plate and the titanium catalytic alloy plate are inserted into the electrolytic module (not shown) by adjusting the distance between the iridium nano-catalytic alloy plate and the titanium catalytic alloy plate, However, it is not limited thereto. In addition, when it is difficult to fix the iridium nano-catalytic alloy plate and the titanium catalytic alloy plate using only the insulating bracket, it is preferable to mix the nickel, manganese, and the like to prevent the corrosion, thereby maintaining the shape of the substrate.

In the present invention, it is preferable that the electrolytic bath apply a direct current to the iridium alloy nanocatalyst device so that the current density is 0.01-1.0 A / cm 2, and more preferably the current density is 0.1-0.5 A / cm 2. When the current density of the iridium alloy nanocatalyst device is less than 0.01 A / cm < 2 >, the efficiency of the iridium alloy nanocatalyst device sharply decreases, and when the current density of the iridium alloy nanocatalyst device exceeds 1.0 A / The current density of the iridium alloy nanocatalyst device is 0.01 to 1.0 A / cm 2, and the more preferable current density is 0.1 to 0.5 A / cm 2, It is preferable to apply an electric current.

The oxidation of the iridium nano-catalytic alloy plate and the titanium catalyst alloy plate, the hydroxyl radical (OH ·), the oxygen radical (· O ₂ ) and the intermediate product ozone (O ₃ ) The formed micro bubbles float flocs dissolved in water, influent algae and nitrogen and phosphorus in the water, and to prevent mixing again by swirling of water after floating, the heights of electrolytic flocculation and coagulation baths are measured by the iridium alloy nano catalytic device standard 10 ~ 30cm height is raised to produce. The floating flocs and algae may be removed with a scum removing tank. The electrolytic flocculation and coagulation baths are provided with a polymer flocculating agent of 0.01 to 1 g / L to remove floating matters, dissolved substances and phosphorus to float floating matters and dissolved substances, or to occur in iridium alloy nanocatalyst devices ) Iron ions coagulate with the suspended material to form flocs and precipitate the formed flocs with a high weight. The precipitated iron, aluminum, and nickel act as coagulant to coagulate the suspended material. The bottom portion of the electrolytic float and the flocculating tank are formed in a cone shape so as to remove precipitated suspended matters in order to remove the flocculated heavy flocculant. The electrolytic floating and the impurities precipitated in the bottom portion of the flocculation tank are transferred to the scum storage tank for treatment.

The scum removing tank may include, but is not limited to, a pair of rollers, a conveyor chain, a scraper, and a driving motor (not shown). Wherein the pair of rollers are rotatably installed on the electrolytic portion and on the sidewalls of the top of the flocculation tank, the conveyor chain is wound on the pair of rollers, and the scraper is attached to the circumferential surface of the conveyor chain at a predetermined interval, Floating flocks, algae and pollutants can be collected while moving in conjunction with the movement of the conveyor chain. The drive motor drives the pair of rollers. When the drive motor is operated, the pair of rollers rotates counterclockwise to operate the conveyor chain, and the scraper interlocked with the operated conveyor chain moves up Scrape floated flocks, algae and contaminants and transport them to the scum storage tank.

The sedimentation tank equipped with the nano-catalytic alloy plate has a structure in which undoped flocs are precipitated, a rectangular plate having a slope of 1-10 / 100 on the slope is formed, and a bottom is formed in a cone shape to move the sludge to the settling tank hopper It is characterized in that it is installed at the downstream end of the electrolytic floatation and flocculation tank to precipitate and remove floccules having high sedimentation and which can not be collected in the electrolytic floatation and flocculation tank.

(A) A technology for controlling the electrode surface scale formation of a nanocatalytic electrolytic apparatus for removing organic matter and ammonia nitrogen in wastewater, comprising a DC power source A control unit for monitoring / controlling the voltage and current of the rectifier to be supplied, and a management unit for calculating a process value (PV) and a control value of the control unit; (b) A technique of managing the electrode using the set voltage and current during the wastewater treatment. The scale is formed on the surface of the electrode. The formed scale is analyzed by analyzing the tendency of the rate of decrease of current value to prevent the current value from being lowered. To determine the phase change timing, and to determine the phase change timing. (c) The control unit is configured to input and output a digital signal, which is a voltage and a current value, from the rectifier, and the managing unit controls the change of the voltage and current output from the rectifier and supplied to the electrode by the influent flow rate, And a fuzzy specialized program that can determine the phase change timing and the cleaning time of the chemical by analyzing the tendency of the voltage and the current change with a predetermined algorithm.

In order to prevent the contaminants from adhering to the nano-catalytic alloy plate, the direction of the electric current is changed at regular intervals and the nano-catalytic electrolytic oxidation vessel .

In the present invention, the nanocatalytic electrolytic oxidation reactor is manufactured in a cartridge type so that the nano-catalytic alloy sheet can easily be inserted, removed, and replaced, and the portion connected to the catalyst plate and the catalyst plate is made of Teflon. A fixing bracket is attached on the top so that the nano-catalytic alloy plate can be inserted into the fixing bracket base. Several nano-catalytic alloy plates are fixed to the fixing bracket base, and the upper fixing bracket is assembled to the upper base. The nano-catalytic electrolytic oxidation unit is preferably arranged such that the scum or the like floats upwards and the treated water is discharged at an intermediate stage, and the precipitated sludge is introduced into the sludge storage tank through the hopper at the lower end.

Further, the scum removing portion of the present invention includes a roller rotating on the upper end side, a conveyor chain wound on the roller, a skimmer interlocked with the conveyor chain for removing the flock or scum, and a driving motor for driving the roller, It is desirable to remove floated flocs and contaminants with a scum reservoir.

As used herein, the term "degradable organic wastewater" means a wastewater containing high concentrations of organic matter such as food wastes, livestock wastes, domestic wastewater, industrial wastewater and the like, and the degradable organic wastewater has a COD of 5000 ppm, But is not limited thereto.

Hereinafter, the present invention will be described in more detail with reference to Examples. It will be apparent to those skilled in the art that these embodiments are merely illustrative of the present invention and that the scope of the present invention is not limited to these embodiments.

Example 1: Effect of removing contaminants from the digester waste liquid treatment apparatus

In the present embodiment, the effect of removing the pollutants using the digester trollius treatment apparatus of the present invention is confirmed. It is confirmed that the suspended solids (SS), the chemical oxygen demand (COD), the ammonia nitrogen (NH ₃ -N) It was confirmed that the acidic nitrogen (NO ₃ -N) was remarkably reduced through the treatment apparatus of the present invention.

The following Table 2 shows the results of analyzing the concentrations of pollutants by obtaining samples at the outlet of each of the digestion tank desalination tank, the nano catalytic floating separation tank, and the nano-catalytic electrolytic oxidation tank using the digester trolling apparatus of the present invention .

[Table 2] Removal of contaminants using a digester trolley disposal unit

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will readily appreciate that many modifications are possible, will be. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

10: Digestion tank storage tank
20: Digestion talli juice
30: Nano-catalytic electrolytic floating tank
40, 180: Nano-catalytic electrolytic flotation treatment
50: AGS-SBR (Continuous Batch Reactor with Aerated Granule Sludge)
60, 170: AGS-SBR treated water
70: Nano catalytic electrolytic oxidation tank
80: Nano-catalysed electrolysis oxidation-precipitation sludge and scum
90: sludge treatment tank
100: AGS-SBR sludge
110: Sludge treatment tank supernatant
120: Nano-catalytic electrolytic floating sludge and scum
130: organic acid reaction tank
140: Organic acid
150: Food supernatant storage tank
160: Food supernatant
200: drain water

Claims (8)

A refractory organic wastewater or digester effluent treatment apparatus comprising:
(a) a facility for float separation of solids contained in refractory organic wastewater or digestion tank desalination liquid, a nanocatalyst type micro-bubble generator at the lower part, and a nano catalyst having a scum removing part for collecting floating solids An electrolytic floating tank (30); And
(b) a nano-catalytic electrolytic oxidation vessel 70 containing iridium-ruthenium-titanium at the bottom and containing a nano-catalytic alloy plate for the anode and the cathode for removing COD and nitrogen remaining in the crude treated water on the nano- ).
The nanocatalytic electrolytic oxidation reactor according to claim 1, wherein the direct decomposition by the electron potential difference generated by the electrolysis and the indirect decomposition by the hydroxyl radical (.OH) and the oxygen radical (O ₂ ) Characterized in that COD and ammonia nitrogen are oxidized to nitrogen gas, and nitrate nitrogen is reduced to nitrogen and ammonia element.
The nanocatalyst alloy plate of claim 1, wherein the titanium alloy sheet is immersed in an iridium oxide sol and a ruthenium oxide sol for 1 to 2 hours, and then is UV-coated at a wavelength of 254 nm while being taken out and dried. Wherein the coating is made by repeating the above immersion and UV coating processes one or two times, and has a coating thickness of 1-5 [mu] m.
The nano-catalyst alloy plate of claim 1, wherein the anode comprises 0.01 to 0.1 wt% of iridium (Ir), 0.01 to 0.1 wt% of zinc oxide (ZnO), 0.01 to 0.1 wt% of ruthenium (Ru) (IrCl ₃ ) in an amount of 0.1 to 0.5M is added to 50 to 100 ml of 1 to 2M acetic acid, which contains 0.1 to 5 wt% of iron (Fe) and 1 to 5 wt% of titanium (Ti) And 0.1 to 0.5 M of ruthenium chloride (RuCl ₃ ), respectively, and then mixed with 20 to 50 ml of 1 to 2M hydroiodic acid, heated to 100 ° C., and mixed with the iridium oxide (IrO ₂ ) Wherein the titanium nano-alloy plate is immersed in a ruthenium oxide (RuO ₂ ) mixed solution, coated at room temperature and dried, and then fired at 800 to 1200 ° C for 5 to 10 times.
2. The method of claim 1, wherein the nano-catalytic alloy plate has a current density of 0.01 to 1.0 A / cm < ² > in the nano-catalytic electrolytic oxidation reactor, wherein hydrogen ions are discharged from the cathode, Increasing the pH from 7 to 8 during the reduction, increasing the alkalinity and reducing the nitrate nitrogen to nitrogen gas; Wherein a discharge of OH occurs in the anode to generate oxygen to generate hypochlorous acid and hypochlorous acid ions to oxidize ammonia nitrogen to nitrogen and oxidize the refractory organic matter.
The processing apparatus according to claim 1, wherein a direction of a current is changed at regular intervals so that contaminants do not adhere to the nanocatalyst alloy plate, and oxygen gas and hydrogen gas generated from the nanocatalyst alloy plate are used.
The nanocatalytic electrolytic oxidation reactor according to claim 1, wherein the nanocatalytic electrolytic oxidation reactor is formed in a cartridge type so that the nanocatalytic alloy sheet can be easily inserted, removed, and replaced, and a fixing bracket is attached to the top, A plurality of nano-catalytic alloy plates are fixed to the fixing bracket base, and the upper fixing bracket is assembled to the upper base. In the nano-catalytic electrolytic oxidation unit, the scum is lifted up and removed, And the precipitated sludge is introduced into the sludge treatment tank through the hopper at the lower end of the oxidation tank.
The method of claim 1, wherein the nano-catalyst electrolytic floating scoop removing unit comprises: (i) a roller rotating on a side of an upper end; (ii) a conveyor chain wound on a roller; (iii) a skimmer (SKIMER), and (iv) a drive motor for driving the rollers, wherein flocks and contaminants floating above the water surface are removed by a scum storage tank.

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