JP2000301175A - Method and apparatus for mineralizing agricultural chemical waste solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To discharge treated water to rivers or the sea or to reutilize the same without polluting organisms or the environment by reacting ozone with an agricultural chemical waste soln. over a predetermined residence time. SOLUTION: An agricultural chemical waste soln. flows in a raw water tank 1 through a piping 10 after refuse in the waste soln. is removed by a refuse removing filter to be stored in the raw water tank 1. An oxidation reaction accelerating agent (alkali agent, hydrogen peroxide) is added to the agricultural chemical waste soln. in the raw water tank 1 from a chemical tank 5. In the case of batchwise treatment, ozone is introduced into treated water by an ozone generator 2 while treated water is circulated between the raw water tank 1 and a reaction tower 3 through the piping 25 allowing the raw water tank 1 and the reaction tower 3 to communicate with each other and the stored waste soln. is subjected to oxidation reaction over about 1 hr. In the case of continuous treatment, a waste soln. amt (m3/hr) 1/2 ozone generation mass (g/hr) is treated. Succeedingly, the oxidized/decomposed soln. is passed through an activated carbon adsorbing column to adsorb and remove an org. compd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for mineralizing pesticide waste liquid by detoxifying the pesticide waste liquid by the strong oxidizing power of ozone.

[0002]

2. Description of the Related Art Until now, the disposal of pesticide residual effluents has been slow to spread in this field and, due to the high cost of the processing equipment, has often been discharged untreated or permeated underground. . For example, a commercial seed and seedling disinfecting waste liquid treatment apparatus mainly uses a coagulation treatment method using a chemical. Dehydrate things,
It is configured to adsorb and remove the pesticide from the dehydrated aggregate, decolorize it with activated carbon, and then discharge treated water.

[0003]

However, in the above-mentioned treatment method, the conventional water treatment form is simply spread for agrochemical waste liquid, such as drying the excess sludge after dehydration treatment or disposing it as a wet cake. However, the cohesiveness based on the residual concentration and the amount of chemicals used must be properly set each time, and it must be determined whether the treatment is completed by always relying on the result analysis. Processing.

[0004] A treatment method such as coagulation of a thick or diluted seedling waste liquid by administering a large amount of a coagulant does not satisfy the environmental conservation demanded in the future era and does not solve the problem. Also, from the viewpoint of zero emission, treated water should be reused in the same place as much as possible. The present invention has been made in view of such circumstances, and makes a waste liquid of a pesticide used for each application mineral (detoxification) treatment, and treats the treated water to rivers and seas without polluting organisms and the environment. It is an object of the present invention to provide a method and an apparatus for mineralizing a pesticide waste liquid, which can be discharged to waste water and reused.

[0005]

In order to achieve the above object, a method for mineralizing a pesticide waste liquid according to claim 1 of the present invention comprises:
By causing a retention reaction of ozone on pesticide waste liquid,
It is characterized by mineralizing residual pesticides. This method
Ozone is used for mineralization treatment of pesticide waste liquid. As a result of the reaction between the waste liquid and ozone due to the strong oxidizing power of ozone,
Hydroperoxy radical (H
O _2. ) Is generated, and further, a hydroxyl radical (OH.) Is generated by a chain reaction, and the waste liquid is mineralized in a short time.

According to a second aspect of the present invention, there is provided a method for mineralizing a pesticide waste liquid, wherein ozone is injected into the pesticide waste liquid, a residence reaction is performed while applying pressure thereto, and the residual pesticide is mineralized. It is characterized by removing organic matter. This method removes residual organic matter from the liquid after the ozone treatment in addition to the ozone treatment, so that the liquid after the ozone treatment becomes more clean.

On the other hand, an apparatus for mineralizing an agricultural chemical waste liquid according to claim 6 comprises a waste liquid tank for storing the agricultural chemical waste liquid, an ozone generator,
A reaction tank for injecting ozone from an ozone generator into the waste liquid from the waste liquid tank to cause a stagnation reaction between the waste liquid and ozone, and an organic substance removal tank for removing residual organic substances from the liquid after the ozone treatment from the reaction tank It is characterized by. This apparatus is for carrying out the method of the present invention, and if this apparatus is used, the mineralization treatment of the agricultural chemical waste liquid with ozone can be performed efficiently and in a short time.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described based on embodiments. FIG. 1 (side view) and FIG. 2 (a front view as viewed from an arrow A in FIG. 1) show an appearance and a schematic structure of a mineralizer for pesticide waste liquid according to the embodiment. This apparatus includes a raw water tank (waste liquid tank) 1 for storing agrochemical waste liquid, an ozone generator 2 having a built-in oxygen concentrator, and an ozone generator 2 for injecting ozone into the waste liquid from the raw water tank 1 to generate a waste liquid. A reaction tower (reaction tank) 3 for causing a retention reaction of ozone, an activated carbon adsorption tower (organic matter removal tank) 4 for removing residual organic matter from the liquid after the ozone treatment from the reaction tower 3, and a pesticide waste liquid in the raw water tank 1. A chemical tank 5 for adding an oxidation reaction accelerator (alkali agent, hydrogen peroxide), and a mixing pump for stirring the waste liquid to which the oxidation reaction accelerator has been added and pressurizing the gas-liquid mixed fluid in the raw water tank 1 6 is provided. However, the capacity of the raw water tank 1, the reaction tower 3, the activated carbon adsorption tower 4, the chemical tank 5, the mixing pump 6, and the amount of ozone generated by the ozone generator 2 are appropriately changed depending on the waste liquid treatment capacity.

An agrochemical waste liquid flows into the raw water tank 1 through a pipe 10, and the agrochemical waste liquid is accumulated in the raw water tank 1 after dust is removed by a dust filter 11. An oxidation reaction accelerator is added to the agricultural chemical waste liquid in the raw water tank 1 from the chemical tank 5. The raw water tank 1 has a drain 12 at the lower part. The ozone generator 2 has an oxygen concentrator, and further has a pressure gauge and a flow meter. A control box 7 is arranged on the ozone generator 2 and the control box 7
Has a power switch, a changeover switch, an adjustment volume, a timer, and the like.

The mixing pump 6 has a pump housing. In the pump housing, the agrochemical waste liquid in the raw water tank 1 to which the oxidation reaction accelerator has been added is introduced through a pipe 20, and the mixing pump 6 is supplied from the ozone generator 2. Of ozone is introduced through a pipe 21. This mixing pump 6
It has a function of expanding the pesticide waste liquid and ozone, a function of promoting mixing while crushing bubbles in a gas-liquid mixed fluid of waste liquid and ozone, and a function of pressurizing the gas-liquid mixed fluid. The mixing pump 6 having these three functions is disclosed in Japanese Patent Application No. Hei.
No. 34527. The gas-liquid contact between the waste liquid and the ozone in the mixing is 2 seconds or more, which is realized by, for example, a pipe of an appropriate length. Further, the dissolving efficiency of the waste liquid and ozone is maintained at 90% or more (preferably 95% or more).

The lower part of the reaction tower 3 communicates with the mixing pump 6 via a pipe 22, and a gas-liquid mixed fluid of waste liquid and ozone from the mixing pump 6 is introduced into the reaction tower 3. The reaction tower 3 has a level sensor 30 for detecting the liquid level of the gas-liquid mixed fluid in the reaction tower 3 and a pressure sensor 31 for detecting the pressure in the reaction tower 3 at the upper part. By the ozone treatment in the reaction tower 3, the waste liquid is mineralized and decolorized.

In the reaction tower 3, in the residence reaction between the waste liquid and ozone, the hydroperoxy radical (HO _2. ) Due to hydrolysis and the hydroxyl radical (OH. The promotion time is 2 minutes or more, and the gas-liquid mixed fluid of waste liquid and ozone is pressurized at a pressure of at least 2 kg / cm ² . Due to the reaction acceleration time and the pressurizing condition, the reaction efficiency is extremely excellent, and the ozone consumption magnification is improved even when the decomposition of the residual organic matter is taken as an example.

The upper part of the activated carbon adsorption tower 4 communicates with the reaction tower 3 via a pipe 23, and the liquid ozone treated in the reaction tower 3 is introduced into the activated carbon adsorption tower 4. The activated carbon adsorption tower 4 uses activated carbon as a remover for residual organic substances, and is configured so that the liquid from the reaction tower 3 passes through the activated carbon while flowing down from the upper part to the lower part. By the treatment in the activated carbon adsorption tower 4, the residual organic matter, that is, the chemical oxygen demand (CO 2
The component related to D) is adsorbed and removed, and the purified liquid is discharged from the lower part of the activated carbon adsorption tower 4 and is discharged or reused.

In the case of batch processing, this apparatus circulates treated water between the raw water tank 1 and the reaction tower 3 through a pipe 25 communicating the raw water tank 1 and the reaction tower 3, and collects waste liquid. Over about 1 hour to cause an oxidation reaction with ozone, or in the case of continuous treatment, the mass of ozone generated (g
/ Hr) of the waste liquid (m ³ / hr).

The apparatus has a base 40, and the base 40
A raw water tank 1, an ozone generator 2, a reaction tower 3, an activated carbon adsorption tower 4, a chemical tank 5, a mixing pump 6, and the like are provided thereon. The base 40 has casters 41 and fixing bolts 42, and the casters 41 facilitate movement of the device.
After the movement, the device is fixed immovably by the fixing bolt 42.

Next, a description will be given of a specific example in which the agrochemical waste liquid is mineralized with ozone using the mineralizing apparatus configured as described above. As shown in the table of FIG. 3 as typical examples, the pesticides to be treated include Trifmine emulsion, Techlead C flowable, Sportac emulsion, Vigit emulsion, Sumithion emulsion, Stana wettable powder, and Helseed emulsion (all trade names). The waste liquid after using each of these commercially available pesticides for seed disinfection was used.

The compound names, structural formulas and main components of each of the above pesticides are as follows. (1) Trihumin emulsion (triflumizole 15%, organic solvent, surfactant, etc.) Triflumizole: CAS No.68694-11-1, C ₁₅ H ₁₅ ClF
_{3 N 3 O, mw 345.75 (} E) -4- chloro - α, α, α- trifluoro-N-(1-imidazol-1-yl-2-propoxy-ethylidene) -O- toluidine

[0018]

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(2) Techlead C Flowable (5% ipconazole, 4.6% cupric hydroxide, water, surfactant, etc.) Ipconazole: CAS No. 125225-28-7, C ₁₈ H ₂₄ ClN
₃ O, mw 333.86 (1RS, 2SR, 5RS; 1RS, 2SR, 5SR) -2- (4-chlorobenzyl) -5-isopropyl-1- (1H-1,2,4-triazol-1-ylmethyl) cyclo Pentanol

[0020]

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(3) Sportac emulsion (Prochloraz
25%, organic solvent, surfactant, etc.) Prochloraz: CAS No. 67747-09-5, C ₁₅ H ₁₆ Cl ₃ F ₃
N ₃ O ₂ , mw 376.67 N-propyl-N-2- (2,4,6-trichlorophenoxine) ethyl imidazole-1-carboxamide

[0022]

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(4) Visit emulsion (MPP 50%,
Organic solvent, emulsifier, etc.) MPP: CAS No. 55-38-9, C ₁₀ H ₁₅ O ₃ PS ₂ , mw 278.3
3O, O-dimethyl-O- (3-methyl-4- (methylthio) phenyl)
Thiophosphate

[0024]

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(5) Sumithion emulsion (50% MEP,
Organic solvent, emulsifier, etc.) MEP: CAS No. 122-14-5, C ₉ H ₁₂ NO ₅ PS, mw 277.
24O, O-dimethyl-O- (3-methyl-4-nitrophenyl) thiophosphate

[0026]

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(6) Sturna wettable powder (20% oxolinic acid, mineral substance, surfactant, etc.) Oxolinic acid: CAS No.14698-29-4, C ₁₃ H ₁₁ N
O ₅ , mw 261.235-Ethyl-5,8-dihydro-8-oxo 1,3
Dioxolo 4,5-g quinoline-7-carboxylic acid

[0028]

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(7) Healthy seed emulsion (pefurazoate
15%, organic solvent, surfactant, etc.) Pefurazoate: CAS No., C ₁₈ H ₂₃ N ₃ O ₄ , mw 345.4
Penta-4-enyl = N-furfuryl-N-imidazole-1-
Ilcarbonyl-DL-homoalaninate

[0030]

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<Experimental Example> A raw water tank 1 (40 in the test) containing the undiluted waste liquid after each of the undiluted agricultural chemicals was used for disinfecting seeds and seedlings.
Liters), take 40 liters of each pesticide waste liquid diluted 1000 times with water, add sodium hydroxide as an oxidation reaction accelerator until the pH reaches 10, and then add
20 ml of hydrogen peroxide (H ₂ O ₂ ) was injected.

Next, while the pesticide stock solution is circulated between the raw water tank 1 and the reaction tower 3 by the mixing pump 6, ozone (1 g / hr, gas phase concentration of 11,6) is obtained by the ozone generator 2.
(00 ppm) and oxidized and decomposed by pesticides with ozone and hydroxyl radicals for 1 hour. Subsequently, the oxidized / decomposed liquid was passed through an activated carbon adsorption tower 4 to adsorb and remove organic compounds.

The effect of oxidizing and decomposing and removing pesticides by ozone and hydroxyl radicals was evaluated by measuring the concentration of residual pesticide components in the decomposed liquid by high performance liquid chromatography (HPLC) of the activated carbon adsorption treatment liquid. The mechanism of oxidation and decomposition of pesticides by ozone and hydroxyl radical was estimated from the infrared absorption spectrum of organic compounds in the oxidized and decomposed liquid.

In this experiment, the dechlorinated clean water was reacted in the mineralizer, the time required for the oxidation-reduction potential to reach equilibrium was measured by an oxidation-reduction potentiometer, and the unreacted gas phase on the water surface was measured. The ozone concentration was measured and performed under optimized conditions. The experimental results are shown in a table in FIG. According to the table of FIG. 4, it can be seen that according to the present invention, the concentration of the residual pesticide component is greatly reduced as compared with the conventional art.

FIGS. 5 to 12 show oxidation and ozone by ozone.
Tables show the measurement results of pH and oxidation potential (ORP) in the decomposition treatment. The graphs in each table are plots of changes in ORP during the oxidation / decomposition treatment against pH.
5 is a Trifmin emulsion, FIG. 6 is Teclead C flowable, FIG. 7 is a Sportac emulsion, FIG. 8 is a Visit emulsion, FIG. 9 is a Sumithion emulsion, and FIG. 10 is a Sumithion emulsion.
(2), FIG. 11 relates to a stearner wettable powder, and FIG. 12 relates to a healthy seed emulsion.

In any of the graphs in the tables of FIGS. 5 to 12, the pH decreases with the lapse of the ozone treatment time.
ORP is higher. 5, 9, and 11.
In, the reason why the graph is not continuous is that sodium hydroxide was added during the treatment due to a drastic decrease in pH. Generally, ORP is an index indicating the oxidation / reduction state of a solution. In this treatment test, ORP is completely correlated with a change in pH, and a change in ORP of a solution is not necessarily a change in the oxidation / reduction state of a solution due to ozone oxidation. Not shown. For example, especially in FIGS. 5, 9, 10 and 11,
ORP continues to increase significantly, and the longer the treatment time, the more the organic compounds in the solution are degraded.

Further, the relationship between ORP and pH for each pesticide is shown in graphs in FIGS. On the other hand, FIG.
Is a table showing the results of measurement of pesticide components by high-performance liquid chromatography. The formula for calculating the concentration of pesticide in the treatment liquid was calculated as follows: C = c × (a / A) [unit: mg / l] .

Next, as an explanation of the measurement of the pesticide component in the oxidized / decomposed liquid, the concentration of the pesticide component in the oxidized / decomposed liquid was measured by a high-performance liquid chromatography method. Measuring equipment High-performance liquid chromatograph (HPLC) Pump: Tosoh Corporation PU880 Detector: Otsuka Electronics Co., Ltd. MCPD-3500 (3D
Detector) Measurement conditions Separation column: TSKgel ODS 80Ts 4.6
φ × 150mm Eluent: methanol + water (4 + 1) 1ml / mi
n Measurement Method A standard solution for a calibration curve was prepared by dissolving a commercially available pesticide drug substance in methanol to prepare a 1 mg / l solution. However, the Techlead emulsion and the visit emulsion were dissolved in water and then filtered, and the filtrate was diluted with methanol. Under the measurement conditions described above, 20 μl of each of the standard solution and the processing solution was injected, and the HPLC chromatogram and the UV spectrum of the main peak were measured with a 3D detector.

HPL of each pesticide standard solution and treatment solution
From the C chromatogram and the UV spectrum, a wavelength (measurement wavelength described above) having no interference with the measurement component due to the coexisting component was selected. The concentration was calculated by comparing the peak areas of the components in the HPLC chromatograms of the standard solution and the treatment solution. 16 to 22 show triflumizole standard solution and trifumin emulsion, ipconazole standard solution and techlead emulsion, prochloraz standard solution and sportac emulsion, MPP standard solution and bidit emulsion, MEP standard solution and Sumithion emulsion, The HPLC chromatogram of the oxidized / decomposed liquid and the UV spectrum of the main peak of each of the oxolinic acid standard solution and the Starna wettable powder, the pefurazoate standard solution and the healthy seed emulsion are shown, respectively. The peak of each pesticide component is HPL
Indicated by “↓” in the C chromatogram. In FIGS. 16 to 22, the left side is the standard solution, and the right side is the HPLC of the processing solution.
It is a chromatogram.

In the HPLC chromatogram of the treatment solution, almost no peak marked with “↓” was observed, indicating that the pesticide components were almost completely removed by the oxidation / decomposition with ozone and the adsorption treatment with activated carbon. This can also be understood from the fact that all the concentrations of the pesticide components in the treatment liquid are 0.1 mg / l or less, as shown in the rightmost column of FIG. next,
A description will be given of a decomposition mechanism of a component compound of a pesticide by ozone oxidation / decomposition. Degradation mechanism of pesticide components by ozone oxidation and decomposition was estimated by infrared spectroscopy. The absorption peaks of the infrared absorption spectrum before and after the treatment of the pesticide are compared, and from the substituents identified, C—C and —C = N of the pesticide component are determined.
It is presumed that bonds and the like are oxidized and decomposed by ozone or (HO · radical) and further cleaved to generate amino groups (—NH ₂ ), carbonyl groups (—CHO), carboxyl groups (—COOH), and the like. it can. Sample preparation method-Sample stock solution To about 1.5 ml of the pesticide emulsion, 5 ml each of n-hexane and distilled water were added, and the mixture was suspended by shaking and then centrifuged.
Separate the hexane layer. Further, 5 ml each of n-hexane and distilled water are added, and the same operation is repeated twice.

The obtained n-hexane layer was washed three times with about 2 ml of distilled water (using a separating funnel), dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain an extract at a temperature of 30 ° C. Obtained. This extract was vacuum-dried overnight to obtain an infrared measurement sample. -Agrochemical sample solution after ozone treatment About 300 ml of ozone oxidation / decomposition solution is concentrated under reduced pressure at a temperature of 30 ° C to about 5 ml, and n-hexane and distilled water are added in 5 ml each, and the same operation as the sample stock solution is performed. , An extract was obtained. This extract was vacuum-dried overnight to obtain an infrared measurement sample. Infrared spectroscopy Measurement device: Fourier transform infrared spectrophotometer Perkin Elmer System-2000 Resolution: 4 cm ^-1 Measuring method: KBr tablet transmission method Detector: TGS detector Integration: 64 times (Averaging process) Test result <Trihumin Effect of ozone treatment on emulsion> Infrared absorption spectra before and after ozone oxidation / decomposition treatment of trihumin emulsion are shown in FIG. 23 [trihumin emulsion (hexane extract)] and FIG. 24 [after trihumin emulsion O ₃ treatment (hexane extract)]
Shown in According to this spectrum, 32
An absorption peak of an amine not present in the stock solution is observed around 00 to 3600 cm ^-1 . This is because the imidazole ring or the C = N bond of triflumizole is cleaved at the position indicated by the dotted line and the primary or secondary amine (R ₁ R
₂ NH).

Further, sharp absorption of the substituted benzene is observed at around 750 cm ^{-1 of the} ozonized solution. This is due to the fact that the bond of triflumizole was cleaved at the position indicated by the dashed line, and a substituted benzene was formed.

[0043]

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[0044] Figure 25 [Tekurido emulsion (hexane extract)] The infrared absorption spectra before and after ozone oxidation and decomposition process Tekurido emulsion <Tekurido effect ozone treatment emulsion> and 26 [Tekurido Emulsion O ₃ processed (hexane Extract)]. According to this spectrum, the absorption peak around 3200 to 3600 cm ^{−1 of the} ozone-treated solution is sharper than that of the undiluted solution. This is because, as shown in the following [Chemical formula 9], the bond of ipconazole was cleaved at the position indicated by the dotted line to generate an amine.

In the case of the ozone treatment liquid, 750 cm ^-1
The absorption in the vicinity is increased, which is due to the fact that the bond of ipconazole was cleaved at the position indicated by the dashed line, and a substituted benzene was formed.

[0046]

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[0047] Figure 27 [Suporutakku emulsion (hexane extract)] The infrared absorption spectra before and after ozone oxidation and decomposition process Suporutakku emulsion <Suporutakku emulsions effect by ozone treatment> and 28 [Suporutakku Emulsion O ₃ processed (hexane Extract)]. According to this spectrum, the absorption of the aromatic ring C—H is clearly observed around 3000 to 3100 cm ^{−1 of the} ozonized solution, and the 750c
Absorption is also observed near m ^-1 . This is represented by the following
As shown in [0], the bond of prochloraz was cleaved at the position shown by the dotted line to generate substituted benzene.

The absorption of the carbonyl group observed around 1690 cm ^-1 before the ozone treatment was 1730 cm ^-1 after the treatment.
It is observed around cm ^-1 . This is because the prochloraz bond was cleaved at the position indicated by the dashed line, and an ester bond was formed.

[0049]

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[0050] Figure 29 [Baijitto emulsion (hexane extract)] The infrared absorption spectra before and after ozone oxidation and decomposition process Baijitto emulsion <Baijitto effect ozone treatment emulsion> and 30 [Baijitto Emulsion O ₃ processed (hexane Extract)]. According to this spectrum, the aromatic ring C—H is located around 3100 to 3200 cm ^{−1 of the} ozonized solution.
Is observed.

The ozone treatment liquid 2800-2900c
While absorption of the alkyl group is strongly observed around m ⁻¹ ,
A carbonyl group around 1670 cm ^-1 and 1720 cm ^-1 ,
An absorption peak of the ester group is observed. This is considered to be because the benzene ring of MPP was decomposed at the position indicated by the dashed line as shown in the following [Chemical formula 11]. Further, absorption by the substituted benzene is observed at around 700 cm ^{-1 of the} ozonized solution. This is because MPP was decomposed at the position indicated by the dotted line to generate substituted benzene.

[0052]

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[0053]

As described above, according to the method according to the first and second aspects of the present invention and the apparatus according to the sixth aspect, the waste liquid for agricultural chemicals is mineralized with ozone. can get. (1) The pesticide waste liquid can be detoxified in a short time. Therefore, compared with the conventional coagulation and sedimentation treatment using a large amount of chemicals, it does not require specialized knowledge such as setting the amount of chemicals to be used, reducing facility costs, running costs, saving manpower management, and maintaining balance. Excellent in various benefits such as good mechanical efficiency distribution. Moreover, no extra cohesive sludge is generated in the treatment process, and the liquid after treatment is clean, so that it can be discharged to rivers and seas or reused as it is, and it can be used for living organisms including humans and the environment. Safe and secure. (2) Applications include treatment of chemical liquid immersion waste liquid of seed rice, treatment of bulb disinfectant waste liquid, treatment of potato seed potato disinfectant waste liquid, treatment of pesticide waste liquid used at golf courses, residual liquid of agricultural chemical spraying and washing water of spraying equipment Treatment, removal of environmental hormone-like substances brought by pesticides, conversion of hardly decomposable substances to easily decomposable, etc.
It is extremely useful for protecting the water environment. (3) According to the method of the second aspect, in addition to the ozone treatment, the remaining organic matter is removed from the liquid after the ozone treatment, so that the liquid after the ozone treatment becomes cleaner. (4) According to the method of the third aspect, since the oxidation reaction accelerator is injected into the agricultural chemical waste liquid, the oxidation / decomposition of the waste liquid by ozone is further improved. (5) According to the method of the fourth aspect, specific treatment conditions are employed, so that the waste liquid can be oxidized and decomposed by ozone more efficiently and faster. (6) According to the method of the fifth aspect, the removal of residual organic substances can be effectively performed at low cost. (7) According to the device described in claim 7, the effect (4) can be obtained. (8) According to the device described in claim 8, the above effect (6) can be obtained.

[Brief description of the drawings]

FIG. 1 is a side view showing an appearance and a schematic structure of a mineralizing apparatus according to one embodiment.

FIG. 2 is a front view of the device of FIG.

FIG. 3 is a table showing pesticides used in experiments.

FIG. 4 is a table showing experimental results obtained by treating each pesticide by the method of the present invention and the conventional technique.

FIG. 5 pH and oxidation potential (ORP) of a trifumin emulsion
5 is a table showing the measurement results of the above.

FIG. 6 is a table showing measurement results of pH and oxidation potential (ORP) of Techlead C flowable.

FIG. 7 shows the pH and oxidation potential (OR
It is a table | surface which shows the measurement result of P).

FIG. 8: pH and oxidation potential (ORP) of a visit emulsion
5 is a table showing the measurement results of the above.

FIG. 9: pH and oxidation potential (ORP) of Sumithion emulsion
5 is a table showing the measurement results of the above.

FIG. 10 shows the pH and oxidation potential (O) of Sumithion emulsion (2).
9 is a table showing measurement results of (RP).

FIG. 11 shows the pH and oxidation potential (OR
It is a table | surface which shows the measurement result of P).

FIG. 12 shows the pH and oxidation potential (OR) of a healthy seed emulsion.
It is a table | surface which shows the measurement result of P).

FIG. 13 is a graph showing the relationship between pH and oxidation potential (ORP) for each pesticide.

FIG. 14 is another graph showing the relationship between pH and oxidation potential (ORP) for each pesticide.

FIG. 15 is a table showing measurement results of pesticide components by high-performance liquid chromatography.

FIG. 16 is a graph showing an HPLC chromatogram of a triflumizole standard solution and an oxidized / decomposed solution of a trihumin emulsion and a UV spectrum of a main peak.

FIG. 17 is a graph showing HPLC chromatograms and UV spectra of main peaks of an ipconazole standard solution and an oxidized / decomposed solution of a teclead emulsion.

FIG. 18 is a graph showing HPLC chromatograms and UV spectra of main peaks of a prochloraz standard solution and a solution obtained by oxidizing and decomposing Sportac emulsion.

FIG. 19: HPLC chromatograms of MPP standard solution and oxidation / decomposition solution of the visit emulsion, and UV of main peaks
It is a graph which shows a spectrum.

FIG. 20: HPLC chromatograms of MEP standard solution and oxidation / decomposition solution of Sumithion emulsion and UV of main peak
It is a graph which shows a spectrum.

FIG. 21 is a graph showing HPLC chromatograms and UV spectra of main peaks of an oxolinic acid standard solution and a solution obtained by oxidizing and decomposing a sterolin wettable powder.

FIG. 22 is a graph showing HPLC chromatograms of a pefurazoate standard solution and an oxidized / decomposed solution of a healthy seed emulsion, and a UV spectrum of a main peak.

FIG. 23 is a graph showing an infrared absorption spectrum of a trifumin emulsion before ozone oxidation / decomposition treatment.

FIG. 24 is a graph showing an infrared absorption spectrum of a trifumin emulsion after an ozone oxidation / decomposition treatment.

FIG. 25 is a graph showing an infrared absorption spectrum of a Techlead emulsion before ozone oxidation / decomposition treatment.

FIG. 26 is a graph showing an infrared absorption spectrum of a Techlead emulsion after an ozone oxidation / decomposition treatment.

FIG. 27 is a graph showing an infrared absorption spectrum of a Sportac emulsion before ozone oxidation / decomposition treatment.

FIG. 28 is a graph showing an infrared absorption spectrum of a Sportac emulsion after ozone oxidation / decomposition treatment.

FIG. 29 is a graph showing an infrared absorption spectrum of a visit emulsion before ozone oxidation / decomposition treatment.

FIG. 30 is a graph showing an infrared absorption spectrum of a visit emulsion after an ozone oxidation / decomposition treatment.

[Explanation of symbols]

 Reference Signs List 1 Raw water tank (waste liquid tank) 2 Ozone generator 3 Reaction tower (reaction tank) 4 Activated carbon adsorption tower (organic matter removal tank) 5 Chemical tank 6 Mixing pump

 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 4D024 AA10 AB11 AB12 AB13 BA02 BC01 CA01 DB24 4D050 AA12 AA20 AB03 AB17 AB18 AB19 AB20 BB02 BB09 BC02 BC10 BD02 BD03 BD04 BD06 BD08 CA06

Claims (8)

[Claims] 1. A method for mineralizing a pesticide waste liquid, wherein the residual pesticide is mineralized by causing a residence reaction of ozone to the pesticide waste liquid. 2. Inorganic pesticide waste liquid, characterized in that ozone is injected into the pesticide waste liquid, a residence reaction is applied thereto while applying pressure, and the residual pesticide is mineralized. Then, residual organic substances are removed from the liquid after the ozone treatment. Method. 3. The method for mineralizing an agricultural chemical waste liquid according to claim 2, wherein an oxidation reaction accelerator is added to the agricultural chemical waste liquid before the ozone injection, and the ozone is injected while stirring. 4. The residence reaction with ozone is performed at a pressure of at least 2 kg / cm ² for 2 minutes or more while maintaining gas-liquid contact between the waste liquid and ozone for 2 seconds or more and maintaining a dissolution efficiency of 90% or more. The method for mineralizing a pesticide waste liquid according to claim 2 or 3, wherein: 5. The method for mineralizing an agricultural chemical waste liquid according to claim 2, wherein the removal of the residual organic substances is performed by passing the liquid after the ozone treatment through activated carbon. 6. A waste liquid tank for storing agrochemical waste liquid, an ozone generator, a reaction tank for injecting ozone from the ozone generator into the waste liquid from the waste liquid tank to cause a stagnant reaction between the waste liquid and ozone, and An organic matter removing tank for removing residual organic matter from the liquid after the ozone treatment. 7. A chemical tank for adding an oxidation reaction accelerator to the agricultural chemical waste liquid in the waste liquid tank, and agitating the waste liquid to which the oxidation reaction accelerator has been added, and mixing the gas-liquid mixed fluid in the reaction tank. The apparatus for mineralizing an agricultural chemical waste liquid according to claim 6, further comprising a pump for pressurizing. 8. The apparatus for mineralizing an agricultural chemical waste liquid according to claim 6, wherein the organic matter removing tank is configured so that the liquid after the ozone treatment passes through activated carbon.