KR100954028B1 - Apparatus for treating wastewater using electrochemical reactor with immobilized peroxidase and method thereof - Google Patents

Abstract

Disclosed is a wastewater treatment apparatus and method for efficiently treating hardly decomposable aromatic organic substances contained in wastewater through a continuous process while increasing operational efficiency. Wastewater treatment equipment is an anode for generating hydrogen ions through an oxidation reaction, a cathode for generating hydrogen peroxide using hydrogen and ions generated from oxygen and an anode, and a cathode for supplying oxygen to the cathode The aeration device is filled between the anode and the cathode, and has a porous structure fixed with peroxidase to decompose an aromatic organic material. Therefore, it is possible to effectively decompose the aromatic organic material by the decomposition of the peroxidase immobilized on the porous structure.

Aromatic organic substance, porous structure, peroxidase, immobilization

Description

Apparatus for treating wastewater using electrochemical reactor with immobilized peroxidase and method

The present invention relates to a wastewater treatment method and apparatus using an electrochemical reactor in which peroxidase is introduced, and more particularly, to a wastewater treatment method using an electrochemical reactor in which peroxidase is introduced to effectively remove hardly decomposable aromatic organic substances. And to the apparatus.

Due to the increase in industrial activity, a large amount of aromatic organic substances such as benzene, phenol, and aniline are produced and widely used in industrial processes. For this reason, not only the exposure of the workers to the aromatic organic materials but also environmental pollution due to the discharge to the surrounding environment has become a problem. As the concern about environmental pollution and the adverse effects of these aromatic organic substances on the environment and human health is increasing, methods for purifying aromatic organic substances have been continuously developed.

Among them, penton oxidation, ozonation, UV oxidation and photochemical decomposition are used as physicochemical treatment methods.

Fenton oxidation method is to decompose organic matter by strong oxidizing power of Fenton's reagent by generating hydroxy radical (OH ·) by reacting hydrogen peroxide and divalent iron ion. Can be divided into However, there is a disadvantage in that a large amount of sludge in the form of hydroxide is generated by iron used as a reaction catalyst.

The ozone oxidation method refers to oxidative decomposition by the strong oxidizing power of ozone. When ozone in water reacts with organic matter, it may be directly oxidized by ozone, and the oxidation by hydroxy radical (OH ·) generated during ozone decomposition process. There is a case. In particular, hydroxy radical (OH ·) reacts evenly with most organics, and because of the high reaction rate with organics that do not react with some ozone, it has a great effect on organic oxidation and removal. However, there is a problem that the production rate of hydroxy radical (OH ·) is low, the reaction is slow with some organic matter, and the ozone generator is relatively expensive.

UV oxidation method is divided into homogeneous method and heterogeneous method. Homogeneous method increases the production efficiency of hydroxy radical (OH ·) by using iron salt as a catalyst. Wiper system to prevent this because fouling occurs in quartz tube by iron salt. This is necessary. In addition, it is difficult to apply when the concentration of contaminants or turbidity is high, and there are disadvantages in that toxic by-products are generated in a specific pH range.

The heterogeneous method forms hydroxy radicals (OH ·) using titanium dioxide (TiO ₂ ). Compared to the conventional method, sludge is hardly generated by completely oxidizing contaminants and requires a cleaning process or a membrane replacement. No energy consumption. However, a separate apparatus for recovering and reusing titanium dioxide (TiO ₂ ), which is a catalyst, is required, and the efficiency is inferior when there is a component of the nature adsorbed on the surface of the catalyst.

The physicochemical treatment method has a high efficiency, but there is a problem that only batch operation or small scale operation is possible.

In general, biological treatment is widely used for large-scale wastewater treatment, which is a method of removing organic matter decomposable by living organisms using microorganisms. Biological treatment methods can be classified into aerobic treatment methods such as activated sludge method, water spraying method, rotating disc method, and oxidation paper method, and anaerobic treatment methods such as decay method, lagoon method, and stock solution method.

The biological treatment method has the disadvantages of operating constraints and site requirements and long processing time which are related to microorganisms, and the microorganisms are not efficient for some aromatic substances, and the degradation products are sludge and the activity of residual microorganisms in the system. It has the disadvantage of reducing the overall efficiency by inhibiting.

In order to solve the above problems, it is a first object of the present invention to provide a wastewater treatment apparatus which increases the operational efficiency while effectively treating the aromatic organic material contained in the wastewater through a continuous process in a short time.

In addition, a second object of the present invention is to provide a wastewater treatment method for achieving the first object.

The wastewater treatment apparatus for achieving the first object of the present invention described above uses an electrode for generating hydrogen ions through an oxidation reaction, opposing the anode, and using oxygen and hydrogen ions generated from the anode. A reduction electrode for generating hydrogen peroxide, an aeration device for supplying the oxygen to the reduction electrode and a porous structure filled between the anode and the reduction electrode, and fixed to the peroxide enzyme to decompose the aromatic organic material.

In addition, in order to achieve the second object of the present invention, the present invention is the hydrogen peroxide generated from the cathode by the peroxidase immobilized on the porous structure decomposes the aromatic organic material and the activity is lost through the step It provides a wastewater treatment method comprising the step of activating by continuously decomposing the aromatic organic material.

By using the wastewater treatment apparatus of the present invention, the aromatic organic material can be effectively treated in a short time through a continuous process. In addition, because fixed peroxidase oxidizes pollutants and is activated by hydrogen peroxide and reduced to its original form, it does not generate secondary pollutants, and is 'environmentally sound and sustainable development' (ESSD). It can contribute to the establishment of base technology for industrialization of clean technology in various fields pursuing

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description.

Prior to this, terms or words used in this specification and claims should not be construed as limiting in their usual or dictionary sense, and the inventors will appropriately define the concept of terms in order to best describe their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that it can. Therefore, the illustrated configuration of the embodiments and drawings described herein are only the most preferred embodiment of the present invention and do not represent all of the technical idea of the present invention, various equivalents that may be substituted for them at the time of the present application It should be understood that there may be water and variations.

Hereinafter, with reference to the accompanying drawings, it will be described in detail a preferred embodiment of the present invention.

Example

1A and 1B are a perspective view and an exploded view of a wastewater treatment apparatus according to an embodiment of the present invention.

1A and 1B, the wastewater treatment apparatus of the present invention includes an anode electrode 110, a cathode electrode 120, an aeration device 130, and a porous structure 140.

The anode 110 is disposed on one side of the wastewater treatment device and oxidizes water to generate hydrogen ions (H ⁺ ).

The reduction electrode 120 is disposed at positions opposite to the anode 110. In addition, the space between the anode 110 and the cathode 120 is filled with a porous structure 140.

The reduction electrode 120 generates hydrogen peroxide through a 2-electron reaction between oxygen supplied from the aeration device 130 and hydrogen ions (H ⁺ ) generated from the anode.

The aeration device 130 is provided to supply oxygen to the cathode 120. Therefore, when the aeration device 130 supplies oxygen to the reduction electrode 120, it will be apparent to those skilled in the art that the arrangement may be provided in various ways in addition to the positions shown in FIGS. 1A and 1B.

The porous structure 140 fills a space between the anode 110 and the cathode 120. In addition, the porous structure 140 is fixed peroxidase.

The peroxidase immobilized on the porous structure 140 decomposes aromatic organic materials contained in the introduced wastewater. In addition, the peroxide enzyme fixed to the porous structure 140 is activated by hydrogen peroxide generated from the cathode 120. For example, an active peroxidase loses its activated state when it decomposes the aromatic organic material of the introduced wastewater. Therefore, the deactivated peroxidase is activated by hydrogen peroxide generated in the cathode 120, and the decomposition of the aromatic organic material is possible. The peroxidase may be used a variety of peroxidases that exhibit a decomposition action on the aromatic organic material.

Hereinafter, the operation of the wastewater treatment apparatus according to the present embodiment will be described.

First, the introduced wastewater passes through the packed layer of the porous structure 140 in which the peroxidase is fixed between the anode 110 and the cathode 120. In addition, oxygen is supplied through the aeration device 130. As the oxygen reacts, hydrogen peroxide is generated in the cathode 120 by the following (Scheme 1) and (Scheme 2). The hydrogen peroxide serves to activate the peroxidase in the wastewater treatment device.

Anode: H ₂ O → 2e- + 2H + + 1 / 2O ₂ (Scheme 1)

Reduction electrode: O ₂ + 2H + + 2e + → H ₂ O ₂ (Scheme 2)

Hydrogen ions (H ⁺ ) are generated by water dissociation on the surface of the anode 110 (Scheme 1), and in the cathode 120, the oxygen and the anode 110 supplied from the aeration device 130. Hydrogen peroxide is produced by a 2-electron reaction of hydrogen ions transferred at (Scheme 2). Hydrogen peroxide generated at this time can be calculated by using a divalent copper ion and 2,9-dimethyl-1,10-phenanthroline (DMP, Aldrich, US) and measuring the absorbance at 453 nm to calculate its concentration.

In addition, as the voltage applied between the anode 110 and the cathode 120 increases, the amount of hydrogen peroxide increases, but decreases under a certain voltage or more, which is lower than (Scheme 2) for the generation of hydrogen peroxide. This is because water molecules are regenerated by the 4-electron reaction.

O ₂ + 4H + + 4e + → 2H ₂ O (Scheme 3)

Between the anode electrode 110 and the reduction electrode 120 of the wastewater treatment device is filled with a porous structure 140 in which the peroxide enzyme is fixed. As the porous structure 140, various kinds of inert porous structures are preferably used. For example, a celite carrier (R-646) may be used.

The celite carrier is a diatomaceous earth compound used in various industrial processes such as a filter, an adsorbent, an abrasive, has a large specific surface area and many micropores, and has excellent chemical durability. In particular, the celite carrier produced for catalyst immobilization is a low cost, practical construct suitable for inducing efficient enzyme immobilization.

Figure 2 shows a series of processes for chemically fixing the peroxidase after modifying the surface using the celite carrier as a porous structure.

Referring to FIG. 2, the process of immobilizing peroxidase on the celite carrier, which is a porous structure, consists of three processes. That is, the three processes are composed of a silanization process, a crosslinking reaction, and a fixing process, and a separate process for effectively fixing the peroxidase may be added between the respective processes.

First, the silanization process is a process of introducing an amine group by modifying the surface of the celite carrier which is a porous structure. For example, the celite carrier washed with distilled water was precipitated in a 10% 3-aminopropyltriethoxysilane (3-APTES) solution adjusted to pH 4, heated at 70 ° C. for 3 hours, then discarded the filtrate and washed at 110 ° C. Dry for a day without. The silanized celite carrier thus produced is washed with distilled water and then dried at 80 ° C. for about a day.

Subsequently, a crosslinking reaction is performed in which a carbonyl group is introduced onto the silanized celite carrier surface. The dried silanized celite carrier was precipitated in a glutaraldehyde solution and stirred for 2 hours at room temperature to remove glutaraldehyde remaining on the surface without reacting with the celite carrier. To be washed several times with distilled water.

Finally, the fixation of peroxidase is performed. That is, the crosslinked celite carrier is precipitated in a peroxidase solution, reacted at room temperature for 5 hours, and reacted at 4 ° C. for 19 hours, and then washed with distilled water and stored in a refrigerator.

3 is a cross-linked celite carrier, silanized celite carrier and crosslinking reaction prior to modification to identify functional groups induced in each process during the process of immobilizing peroxide enzymes on the celite carrier which is a porous structure. The FT-IR spectrum of the celite carrier is shown. Oxygen-hydrogen bond (OH bond) was confirmed at 3450 cm ⁻¹ in the carrier obtained after washing through (a) of FIG. 3, and 3-aminopropyltriethoxysilane through (b) of FIG. 3. Nitrogen-hydrogen bonds (NH bonds) derived from the amine group of (3-APTES) were observed at 1480∼1440 cm ⁻¹ . Meanwhile, the ammonium group of the peroxidase and the carbonyl group for the peptide bond were generated by the glutaraldehyde bond, which is a carbon-oxygen double bond (C = O bond) at 1560 cm ⁻¹ as shown in (c) of FIG. 3. Was confirmed by. It can be seen that the carbonyl group necessary for peroxidase fixation was well formed through the silanization process and the glutaraldehyde crosslinking process.

4 is a perspective view showing another modified example of the wastewater treatment apparatus of this embodiment.

In the wastewater treatment apparatus, a platinum plated titanium plate and a reduction plate 120 may be used as the anode 110. It may be composed of a plurality of electrolytic cells arranged to cross each other.

In this case, various flow paths may be formed to maximize the reaction efficiency of the influent wastewater.

For example, a plurality of holes 160 are formed at one end of the anode 110 to form a flow path, and a corresponding number of holes are provided at a position in which the contact electrode 120 can maximize the contact area and the decomposition efficiency of the wastewater. It is possible to form a flow path through which 170 can increase the contact rate between the wastewater and the peroxidase. In addition, the size of the hole 160 of the anode 110 and the hole 170 of the reduction electrode 120 is set smaller than the size of each structure constituting the porous structure 140, each structure is the electrode It is preferable to prevent the problem of penetrating the hole formed in the.

In addition, in the case of installing a mesh, a cap, or the like to prevent the outflow of the porous structure 140 through the holes formed in the electrodes or if there is a separate contrast for the outflow of the porous structure 140, such as a hole or a cut surface The choice of the location, size and shape of the flow path may be more free.

In addition, supply of hydrogen peroxide is required to activate the peroxide enzyme, and an aeration device 140 for oxygen supply is installed to generate the hydrogen peroxide.

In order to increase the efficiency of wastewater treatment in the wastewater treatment apparatus, an electrochemical reactor 200 for causing an oxidation reaction by hypochlorite may be connected to the rear end of the wastewater treatment apparatus. The electrochemical reactor 200 is composed of an anode 210, a cathode 220 and a sodium chloride solution inlet 230 for generating a hypochlorite. The sodium chloride solution supplied through the sodium chloride solution inlet generates hypochlorite through an electrode reaction. The hypochlorite is produced by (Scheme 4), (Scheme 5) and (Scheme 6).

Anode: 2Cl- → Cl ₂ + 2e- (Scheme 4)

Reduction ^{_{electrode: H 2 O + 2e - →}} H 2 + 2OH - ( Reaction Scheme 5)

Total reaction: Cl ₂ + 2NaOH → NaOCl + H ₂ O (Scheme 6)

Through this, it is expected that the system which combines the electroenzyme decomposition by the front end peroxidase and the electrochemical decomposition by the secondary chloride is suitable for the treatment of petrochemical wastewater containing a large amount of aromatic organic pollutants.

5 shows a pilot scale wastewater treatment apparatus actually manufactured.

The apparatus is composed of a front end 300 is filled with a fixed peroxidase and the rear end 400 occurs the oxidation reaction by the hypochlorite and the electrolytic decomposition. The front end 300 has five pairs of anodes 310 and a cathode 320, and the rear end 400 is configured to have five pairs of anodes 410 and a cathode 420.

In the above apparatus, titanium plates plated with a thickness of 0.3 μm are used as the anodes 310 and 410, and stainless plates are used as the cathodes 320 and 420.

The anodes 310 and 410 and the cathodes 320 and 420 each have an effective area of 800 cm ² (20 cm and 40 cm). In addition, the spacing of each electrode is fixed at 2 cm.

192 circular holes 360 and 460 having a diameter of 2 mm are formed on the left side of the anodes 310 and 410, and 192 circular holes having a diameter of 2 mm are formed on the right side of the reducing electrodes 320 and 420. 370 and 470 are formed to form a zigzag flow path.

In order to supply oxygen necessary for generating hydrogen peroxide to the front end 300, an aeration device 330 is installed between the electrodes to inject 50 ml / min of air.

The rear end 400 is to be injected at a rate of 0 ~ 12 ml / min 1M sodium chloride solution through the sodium chloride solution inlet 430.

The celite support 340 fixed with the peroxidase is filled between the electrodes of the front end portion 300. The peroxidase immobilized on the celite carrier 340 causes decomposition of the aromatic organic material.

A peristaltic pump (not shown) is installed in the inflow passage (not shown) to introduce wastewater at a rate of 1 L / min, and the wastewater after the reaction is completed is also installed with a peristaltic pump (not shown) in the discharge passage (not shown). Outflow at min speed.

Figure 6 shows the change in the relative activity and protein content for the initial activity according to the applied voltage when the citrate carrier fixed with the peroxidase fixed 340 in the wastewater treatment apparatus.

Since the activity of peroxidase directly affects the degradation efficiency of pollutants, it is essential to determine and operate the voltage conditions under which peroxidase activity is maintained to maintain the efficiency and long-term stability of the entire system.

Peroxidase activity was measured by ABTS (2,2'-Azino-bis (3-ethylbenzthiazoline-6-sulfonic acid) mixed solution (5% ABTS 0.32 ml + 0.5 wt% H ₂ O ₂ 0.16 ml + 0.05 M acetate buffer solution) pH 5.0) 2.42 ml + HRP sample 0.1 ml) was measured in the absorbance-time mode and calculated through the initial slope value of the graph, the protein content is calculated using the BCA (Bicinchoninic aicd) method.

Figure 7 shows the amount of hydrogen peroxide generated according to the voltage applied in the pilot scale electrochemical reactor.

6 and 7, at a supply voltage condition of 3.0 V or less, the relative activity of the initial activity was 0.85 or more and 3.6 mg or more of protein per gram of the celite-fixed cation-fixed carrier. In the relative activity and protein content can be seen that the sharp decrease. In addition to hydrogen peroxide needed for activation under voltage conditions of 3.5 V or more, the electrode reaction produces powerful oxidants such as ozone (Ozone, O ₃ ) and hydroxyl radicals (OH *), which are peroxide enzymes and porous structures. It is believed that the relative activity and protein content decrease because they break the covalent bonds between them.

 In the apparatus of FIG. 5, the front end 300 and the rear end 400 are separately connected to two power supplies (not shown). The front end 300 is applied with a voltage of 2.8 V suitable for the production of hydrogen peroxide, the rear end 400 is applied to a voltage of 8 V for the generation of hypochlorite and calculates the power consumption by recording the current value coming out through the monitor. .

The wastewater discharged from the petrochemical complex whose main products are phenol, bisphenol-A, and alphamethylstyrene was used to treat the actual wastewater using the above apparatus. The properties are shown in Table 1.

Item shame pH (-) 11.28 Conductivity (mS / cm) 19.32 BOD (mg / L) 110.0 COD (mg / L) 537.9 TN (mg / L) 30.94 SS (mg / L) 0.155 Cation (mg / L) Sodium Magnesium Potassium Others (Calcium, Iron, etc.)  16.54 0.91 0.58 0.66 Anion (mg / L) Chlorine Nitrate Others (Nitrite, Sulfate, etc.)  6.24 1.18 1.27

The pilot scale wastewater treatment device was used to remove COD of wastewater discharged from the petrochemical complex having the above characteristics, and the optimum condition was determined by comparing the COD removal rate and power consumption according to the conditions.

Figure 8 shows the COD removal rate of the wastewater discharged from the petrochemical complex and the power consumed at this time by using the system filled with a celite fixed to the peroxide enzyme as an example. The COD removal rate of the wastewater treated only by electrochemical decomposition by the hypochlorite of the rear end 400 without filling the front end 300 with the peroxide-enzyme-fixed celite carrier is 40% or less. In contrast, the front end portion 300 is filled with a celite carrier 340 to cause electroenzymatic decomposition, and the rear end portion 400 has a COD removal rate of wastewater treated using a system in which electrochemical decomposition is linked by hypochlorite. Keeps 90% constant.

In addition, the power consumed is about 10 watts lower than that of the electrochemical digestion system in which the electroenzyme and electrochemical digestion systems are linked.

On the other hand, the decomposition conditions of the front end 300 is the same and the COD removal rate of the petrochemical discharge wastewater according to the injection rate of 1M sodium chloride solution of the rear end 400 is shown in Table 2.

Injection rate (mL / min) 0 3 6 9 12 COD removal rate (%) 47.1 90.46 92.43 90.17 91.24

In general, peroxidase is inhibited by chlorine ions, reducing the efficiency of the system. Therefore, the sodium chloride solution is careful not to be injected into the front end portion 300 in which the celite-fixed celite carrier 340 is filled, and the sodium chloride solution is injected only into the rear end portion 400. When the applied voltage to the rear end 400 is 8 V, when the sodium chloride solution is not injected, it shows a 47.1% COD removal rate, but when the sodium chloride solution is injected, a strong chlorine salt is formed by the electrode reaction. It can be seen that it works effectively to remove COD. According to the result of Table 2, the injection amount of the sodium chloride solution in the pilot scale wastewater treatment apparatus is the optimum condition of 3 mL / min of the lowest injection amount.

9 is a high-performance liquid chromatography (HPLC) of the wastewater discharged from the petrochemical complex before and after decomposition using the pilot scale wastewater treatment apparatus and by measuring the ATR mode spectrum of the FT-IR to compare the by-products And the decomposition route is presented.

As shown in FIGS. 9 (a) and 9 (b), the wastewater treated by the pilot scale wastewater treatment apparatus in which electroenzyme digestion by peroxidase and electrochemical decomposition by hypochlorite are associated with time. Complex aromatic organic compounds are reduced and only phenol and benzoic acid (C ₇ H ₆ O ₂ ) remain. As the reaction proceeds further, even the phenol and benzene acids disappear. As a result, as shown in FIG. 9 (c), petrochemical wastewater containing various types of aromatic organic substances is effectively decomposed.

Figure 10 confirms the by-products generated through the GC-MS diagram of the petrochemical wastewater discharged after the reaction with the initial petrochemical wastewater. Table 3 shows the GC-MS results of the wastewater in which the pilot scale was introduced into the wastewater treatment system, and the wastewater from which the electroenzymatic degradation by peroxidase and the electrochemical reaction were completed. Various types of aromatic organic substances are effectively decomposed through the pilot scale wastewater treatment apparatus.

Influent Runoff  Detection time (minutes) Chemical formula  Detection time (minutes) Chemical formula 4.850 C ₉ H ₁₂ (methylethyl benzene) 8.942 C ₁₂ H ₂₄ (dodecene) 5.717 C ₉ H ₁₀ (alphamethyl styrene) 11.908 14.588 C ₁₆ H ₃₂ (hexadecene) 7.092 C ₈ H ₈ O (acetophenone) 16.942 C ₁₇ H ₃₂ O (heptadecanal) 7.517 C ₉ H ₁₂ O ₂ (benzaldehyde dimethyl acetal) 18.875 C ₁₂ H ₂₂ O ₄ (dibutyl phthalate) 10.010 C ₁₀ H ₁₄ (tert-butyl benzene) 19.092 21.058 C ₁₈ H ₃₆ (Octadecene) 17.542 C ₁₈ H ₂₂ (dimethyl diphenylbutane) 24.383 C ₂₄ H ₃₈ O ₄ (benzenedicarboxylic acid)

11 shows the results of long-term operation of the wastewater discharged from the petrochemical complex using the reactor for 18 days as COD removal rate and power consumption. The COD removal rate of the wastewater discharged from the petrochemical complex during operation is maintained at 85% to 95%, indicating that about 75 watts of power are consumed.

1A is a perspective view of a wastewater treatment apparatus according to an embodiment of the present invention.

FIG. 1B is an exploded view for explaining in detail the wastewater treatment apparatus shown in FIG. 1A.

Figure 2 shows the mechanism by which the peroxidase is fixed to the celite support which is a porous structure.

Figure 3 shows the FT-IR spectrum of the celite carrier, a multi-step structure in which peroxidase is immobilized by silanization, crosslinking, and immobilization.

4 is a view showing another modified example of the wastewater treatment apparatus shown in FIG.

5 shows a wastewater treatment apparatus of pilot scale.

Figure 6 shows the change in relative activity and protein content for the initial activity according to the applied voltage of the peroxide enzyme immobilized on the celite carrier.

7 shows the amount of hydrogen peroxide generated in the pilot scale wastewater treatment system according to the applied voltage.

8 shows the COD removal rate and power consumption of the actual wastewater discharged from the petrochemical complex using the pilot scale wastewater treatment apparatus.

Figure 9 (a) is a high performance liquid chromatography (HPLC) of petrochemical discharge wastewater before and after the reaction using a pilot scale wastewater treatment apparatus, (b) is attenuated transition reflection of FT-IR ) Spectrum, and (c) shows the decomposition path through it.

10 shows a GC-MS diagram of petrochemical discharge wastewater before and after decomposition using a wastewater treatment apparatus.

FIG. 11 shows the results of long-term operation of the wastewater discharged from the petrochemical complex using the apparatus shown in FIG. 5 as a COD removal rate.

<Explanation of symbols for the main parts of the drawings>

100: electrochemical reactor with electroenzymatic decomposition

110, 210, 310, 410: anode 120, 220, 320, 420: cathode

130: aeration device

140: porous structure fixed with peroxidase

160, 170, 260, 270, 360, 370, 460, 470: hole

200: electrochemical reactor causing oxidation by hypochlorite

230: sodium chloride solution inlet

Claims (10)

A first anode having a plurality of treated water passage holes; A reduction electrode facing the first anode and having a plurality of treated water passage holes; A second oxidation electrode facing the reduction electrode and having a plurality of treated water passage holes; A porous structure disposed between the first anode and the reduction electrode and containing peroxidase; An aeration device for supplying oxygen to the reduction electrode; And And a sodium chloride inlet for supplying sodium chloride to the space between the cathode and the second anode. The method of claim 1, The porous structure is a wastewater treatment apparatus, characterized in that the celite carrier. The method of claim 1, The peroxidase is activated by the hydrogen peroxide generated by the cathode when the activity is lost by decomposition of the aromatic organic material waste water treatment apparatus characterized in that to continuously decompose the aromatic organic material. The method of claim 1, Fixing the peroxidase to the porous structure may include a silanization process for introducing an amine group; Crosslinking process for introducing carbonyl group; And Wastewater treatment device, characterized in that made through the fixing process of peroxidase. The method of claim 1, The anodes are platinum plated titanium, and the cathode is a stainless steel wastewater treatment apparatus. delete delete A first anode having a plurality of treated water through holes, a cathode electrode facing the first anode and having a plurality of treated water through holes, a second electrode facing the reduced electrode and having a plurality of treated water through holes 2 is disposed between the anode, the first anode and the reduction electrode, a porous structure containing peroxidase, an aeration device for supplying oxygen to the reduction electrode and in the space between the reduction electrode and the second anode Providing a wastewater treatment apparatus including a sodium chloride inlet for supplying sodium chloride; Introducing the treated water through the treated water through holes provided in the first anode; Firstly decomposing the treated water by an electroenzyme using the porous structure; Passing the first decomposed treated water through the treated water passing holes provided in the cathode; Injecting sodium chloride into the sodium chloride inlet; Electrochemically decomposing the sodium chloride to generate hypochlorous acid; And Reacting the hypochlorous acid and the passed primary decomposed treated water to secondary decomposition. The method of claim 1, And the first anode, the cathode and the second anode are disposed such that the treatment water passage holes of each other have a zigzag shape. The method of claim 8, After the first step of decomposing the treated water, Injecting oxygen into the aeration device; Reacting the hydrogen ions generated at the first anode with the oxygen to generate hydrogen peroxide; And Wastewater treatment method further comprising the step of activating the porous structure using the hydrogen peroxide.

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