WO2023053701A1 - Water treatment device - Google Patents

Water treatment device Download PDF

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WO2023053701A1
WO2023053701A1 PCT/JP2022/028980 JP2022028980W WO2023053701A1 WO 2023053701 A1 WO2023053701 A1 WO 2023053701A1 JP 2022028980 W JP2022028980 W JP 2022028980W WO 2023053701 A1 WO2023053701 A1 WO 2023053701A1
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electrode
water
treated
product
current
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PCT/JP2022/028980
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French (fr)
Japanese (ja)
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弘樹 奈良
浩史 藤田
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パナソニックＩｐマネジメント株式会社
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Publication of WO2023053701A1 publication Critical patent/WO2023053701A1/en

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation

Definitions

  • the present disclosure relates to water treatment equipment.
  • the purpose of the present disclosure is to provide a water treatment apparatus that enables efficient removal of humic substances from water to be treated, which has been difficult with conventional coagulation sedimentation techniques.
  • the water treatment apparatus includes an electrolytic cell into which water to be treated containing humic substances flows, a first electrode and a second electrode that are immersed in the water to be treated in the electrolytic cell, and a first electrode and a second electrode.
  • a power source that applies a current between the first electrode and the second electrode
  • at least one of the first electrode and the second electrode is made of a material that elutes iron ions by applying a current from the power source
  • the first electrode and the second electrode is the first product formed by the reaction of humic substances and iron ions on the anode side and the second product formed by the reaction of hydroxide ions and iron ions on the cathode side when a current is applied from a power source.
  • the two products are arranged so that they agglomerate to form flocs.
  • FIG. 1 is a schematic diagram of a water treatment apparatus according to an embodiment of the present disclosure during purification treatment.
  • FIG. 2 is a schematic diagram of electrolysis in the electrolytic cell of the embodiment according to the present disclosure.
  • FIG. 3 is a diagram showing the chromaticity of treated water of the water treatment apparatus according to the embodiment of the present disclosure.
  • FIG. 4 is a diagram showing the chromaticity of treated water of the water treatment apparatus according to the embodiment of the present disclosure.
  • the water treatment apparatus includes an electrolytic cell into which water to be treated containing humic substances flows, a first electrode and a second electrode that are immersed in the water to be treated in the electrolytic cell, and a first electrode and a second electrode.
  • a power source that applies a current between the first electrode and the second electrode
  • at least one of the first electrode and the second electrode is made of a material that elutes iron ions by applying a current from the power source
  • the first electrode and the second electrode is the first product formed by the reaction of humic substances and iron ions on the anode side and the second product formed by the reaction of hydroxide ions and iron ions on the cathode side when a current is applied from a power source.
  • the two products are arranged so that they agglomerate to form flocs.
  • the first product and the second product can be formed, and the aggregation of the first product and the second product causes humin A textured floc can be formed. Therefore, humic substances having a small size can be precipitated as flocs, and humic substances can be efficiently removed from the water to be treated.
  • the distance between the first electrode and the second electrode may be 0.5 mm or more.
  • the concentration of iron ions eluted from at least one of the first electrode and the second electrode is twice or more the concentration of humic substances contained in the water to be treated by the power supply. You may apply a current so that it becomes.
  • the first electrode and the second electrode are both made of a material from which iron ions are eluted by applying a current from a power supply, and when a current is applied, the first electrode and the second electrode.
  • the passivity can be peeled off from the electrode surface where the passivity accumulates and the current cannot be applied sufficiently. Therefore, it is possible to suppress the accumulation of passivation, thereby suppressing the decrease in purification treatment efficiency due to the current not flowing due to the passivity.
  • the water treatment apparatus may further include a separation unit that removes flocs from water to be treated that has undergone electrolytic treatment.
  • the raw water in peat areas contains dissolved organic matter such as humic substances and may have a high degree of color.
  • raw water in the island of Sumatra in Indonesia, raw water has a chromaticity of 100 TCU to 500 TCU (TCU: true color units) and exhibits a color similar to black tea.
  • TCU true color units
  • the humic substance contained in raw water is a product produced by decomposition of plants and the like by microorganisms. Humic substances are roughly divided into fume substances, humic acid, and fulvic acid, and the molecular size decreases in the order of fume substances, humic acid, and fulvic acid.
  • humic substances those that precipitate in an alkaline aqueous solution are called fumes, those that are soluble in an alkaline aqueous solution but precipitate in an acid aqueous solution are called humic acids, and those that are soluble in both an alkaline and acid aqueous solution are called fulvic. called acid.
  • fumes those that precipitate in an alkaline aqueous solution
  • acid aqueous solution those that are soluble in both an alkaline and acid aqueous solution
  • acid fulvic.
  • the present inventor conducted repeated basic studies and found that it is possible to generate a component that aggregates and coarsens humic substances by electrolytic treatment using iron electrodes. Specifically, a direct current is applied between iron electrodes immersed in water containing humic substances. As a result, iron ions are eluted from the anode side, iron ions and humic substances form a chelate complex, and hydroxide ions and iron ions generated on the cathode side form iron hydroxide. They found that the chelate complex and iron hydroxide aggregate with each other to form flocs large enough for precipitation.
  • Flocs can be easily removed by precipitation or a solid-liquid separation method such as MF (Microfiltration) membrane separation with a filtration accuracy of about 0.1 ⁇ m to 1 ⁇ m.
  • the water treatment apparatus of this embodiment is an apparatus capable of removing humic substances from water to be treated using this aggregation action.
  • FIG. 1 is a schematic diagram of a water treatment device 1 according to Embodiment 1 of the present disclosure during purification treatment.
  • the water treatment device 1 of Embodiment 1 is a device for purifying water 21 to be treated, which contains humic substances and has a high degree of chromaticity, for use as colorless and transparent domestic water.
  • the water treatment device 1 includes an inlet 2, a purified water outlet 3, an electrolyzer 4, a power source 5, a separation section 6, an inflow pipe 7, a water pipe 8, and a discharge pipe 9. , a first electrode 10a and a second electrode 10b.
  • the inflow port 2 is an opening for introducing the water to be treated 21 containing humic substances, which is pressure-fed from the outside of the water treatment device 1, into the device.
  • Water to be treated 21 is introduced into the water treatment apparatus 1 from a water source such as a well, a river, or a pond through the inlet 2 .
  • the inflow port 2 is provided in a housing that constitutes the water treatment device 1, and is connected to the electrolytic cell 4 through an inflow pipe 7 inside the device.
  • the purified water outlet 3 is an opening for taking out the treated water 21 treated by the water treatment device 1 as post-treatment water 22 to the outside of the device.
  • the flow rate and purified water discharge port 3 are provided in a housing that constitutes the device, and are connected to a discharge pipe 9 inside the device.
  • the electrolytic cell 4 is a container for fixing the first electrode 10a and the second electrode 10b inside, taking in the water 21 to be treated, and electrolyzing it.
  • the inside of the electrolytic bath 4 is connected to an inflow pipe 7 and a water pipe 8 for communication.
  • the power supply 5 is connected to the first electrode 10a and the second electrode 10b, and applies current between the first electrode 10a and the second electrode 10b. Further, the power supply 5 incorporates a circuit for reversing the polarities of the currents applied to the first electrode 10a and the second electrode 10b.
  • the separation unit 6 separates and removes aggregates generated by electrolysis in the electrolytic bath 4, and aggregates that have taken in humic substances.
  • the separation unit 6 is a filtration membrane with a filtration accuracy of 1 ⁇ m.
  • the separation unit 6 is connected to the water pipe 8 and the discharge pipe 9 for communication.
  • the inflow pipe 7 is connected to the inflow port 2 and the electrolytic cell 4 and delivers the water to be treated 21 taken in from the inflow port 2 to the electrolytic cell 4 .
  • the water pipe 8 is connected to the electrolytic cell 4 and the separation unit 6 and delivers the water to be treated 21 electrolyzed in the electrolytic cell 4 to the separation unit 6 .
  • the discharge pipe 9 is connected and communicated with the separation section 6 and the purified water discharge port 3 .
  • the discharge pipe 9 delivers the water to be treated 21 from which the aggregates have been separated and removed in the separation unit 6 to the purified water discharge port 3 .
  • the water to be treated 21 is continuously taken in from the inflow port 2 and purified by flowing through the inflow pipe 7, the electrolytic bath 4, the water pipe 8, the separation section 6, and the discharge pipe 9.
  • Purified water 21 to be treated is continuously taken out as post-treatment water 22 from the purified water discharge port 3 .
  • the flow rate, the flow rate at which the water 21 to be treated flows into and out of the separation section 6, the flow rate at which the water 21 to be treated flows through the discharge pipe 9, and the flow rate at which the treated water 22 is taken out from the purified water discharge port 3 are all the same.
  • FIG. 2 is a schematic diagram of electrolysis in the electrolytic cell 4 of the water treatment device 1.
  • Both the first electrode 10a and the second electrode 10b are made of iron.
  • the first electrode 10a and the second electrode 10b are installed facing each other, and the distance between the electrodes is 3 mm.
  • it is preferable that the distance between the electrodes is 0.5 mm or more. This is to reduce the possibility that flocs 11h, which will be described later, or passive states formed on the electrodes clog the gap between the electrodes.
  • the frequency of the reaction between the iron ions eluted from the anode and the hydroxide ions generated from the cathode which is a reaction described later, may decrease.
  • the probability of occurrence of the reaction in which the first product 11f generated in the vicinity and the second product 11g generated mainly between the electrodes to form the flocs 11h decreases is increased. That is, by reducing the distance between the electrodes, the formation efficiency of the second product 11g and the flocs 11h is improved. Therefore, it is preferable that the distance between the electrodes is small enough to prevent clogging of the passive state and the flocs 11h.
  • the first electrode 10a and the second electrode 10b are connected to the power source 5.
  • a direct current is applied between the first electrode 10a and the second electrode 10b by the power supply 5, and the water 21 to be treated is electrolyzed.
  • One of the first electrode 10a and the second electrode 10b is on the anode side, and the other is on the cathode side.
  • iron ions 11c are eluted from the anode side electrode, and hydroxide ions 11d are generated from the cathode side.
  • the iron ions 11c and hydroxide ions 11d are both components forming flocs 11h that take in the humic substance 11b.
  • the amount of eluted iron ions 11c can be controlled by the amount of current applied, and the amount of eluted iron ions 11c increases or decreases in proportion to the increase or decrease in the amount of current. Therefore, by setting the amount of electric current to be applied according to the concentration of the humic substances 11b contained in the water 21 to be treated, the elution amount of the iron ions 11c can be controlled according to the water quality, and the water 21 to be treated can be purified. be able to.
  • first electrode 10a and the second electrode 10b are reversed by a circuit built in the power supply 5.
  • Both the first electrode 10a and the second electrode 10b are made of iron. Therefore, since it can act as either an anode or a cathode in the later-described electrolysis reaction, the purification process can be continued even during the polarity reversal.
  • the electrodes that emit the iron ions 11c can be replaced. Therefore, consumption of only one electrode can be suppressed.
  • the reversal of polarity promotes chemical reactions near the electrodes.
  • the polarity reversal can improve the frequency of occurrence of the reaction in the purification process.
  • both the iron ions 11c eluted before the pole reversal and the hydroxide ions 11d generated after the pole reversal are present at relatively high concentrations near the pole that has changed from the anode to the cathode due to the pole reversal. Therefore, the second product 11g is likely to be generated by the polarity reversal.
  • flocs 11h are produced by reacting the produced second product 11g with the first product 11f produced before the polarity reversal.
  • both the hydroxide ions 11d generated before the pole reversal and the iron ions 11c eluted after the pole reversal are present at relatively high concentrations near the pole where the cathode has become the anode due to the pole reversal. Therefore, the second product 11g is likely to be generated by the polarity reversal. Furthermore, the humic substance 11b, which had not reacted before the polarity reversal due to the relatively low concentration of the iron ions 11c, reacts with the eluted iron ions 11c, facilitating the formation of the first product 11f. Then, the first product 11f and the second product 11g react with each other to easily generate flocs 11h.
  • the polarity reversal it is possible to increase the occurrence frequency of the formation reaction of the second product 11g and the floc 11h. While the polarity reversal for removing the passive state is performed, for example, once a week, the polarity reversal for promoting the chemical reaction may be performed about once every 30 minutes.
  • the first electrode 10a arranged inside the electrolytic cell 4 is made of iron. As shown in chemical formula (1), after the water 21 to be treated flows into the electrolytic cell 4, a current is applied by the power source 5 between the first electrode 10a as the anode and the second electrode 10b as the cathode, and from the anode side Fe 2+ is eluted by electrolysis.
  • y [L/s] be the flow rate at which the water to be treated 21 is taken into the electrolytic cell 4, the concentration of Fe 2+ taken into the water to be treated 21 is 55.85 ⁇ x/(96485 ⁇ 2 ⁇ y ⁇ 10 3 ) [mg/L], ie 2.89 ⁇ (x/y) ⁇ 10 ⁇ 7 [mg/L]. Since the concentration of Fe 2+ is the same as the concentration of iron ions 11c that are Fe 3+ , the concentration of iron ions 11c eluted in the water 21 to be treated is 2.89 ⁇ (x/y) ⁇ 10 ⁇ 7 [mg /L].
  • the iron ion 11c combines with the humic substance 11b to become the first product 11f.
  • the humic substance 11b is contained in the water to be treated 21, and its size is about 10 nm to 100 nm. Therefore, it is difficult to remove them with an MF membrane or the like having a filtration accuracy of about 0.1 ⁇ m to 1 ⁇ m.
  • the first product 11f which is a small chelate complex with a size of about 10 nm to 100 nm, is easily aggregated with various particles. Since the first product 11f is a chelate complex, it easily adsorbs the second product 11g, which will be described later.
  • water molecules 11a are electrolyzed to produce hydrogen 11e and hydroxide ions 11d.
  • the generated hydroxide ions 11d combine with the iron ions 11c to form the second product 11g, which is iron hydroxide particles with a size of about 100 nm to 1 ⁇ m.
  • the first product 11f and the second product 11g have the property of mutually adsorbing and aggregating, and the agglomeration of the first product 11f and the second product 11g causes coarse flocs 11h to be formed. It is formed.
  • the flocs 11h grow inside the electrolytic bath 4 and inside the water pipe 8 . Since the coarse flocs containing the humic substances 11b eventually reach a size of several ⁇ m or more, they can be easily separated by MF membrane filtration (filtration accuracy of about 0.1 ⁇ m to 1 ⁇ m) in the subsequent separation unit 6. .
  • the water from which the flocs 11h have been separated and removed is obtained as post-treatment water 22 from the discharge pipe 9 and the purified water discharge port 3, and is supplied as domestic water.
  • Water to be treated 21 containing humic substances 11 b is introduced into the water treatment apparatus 1 through the inlet 2 and flows into the electrolytic cell 4 .
  • the water 21 to be treated is electrolyzed by the first electrode 10 a and the second electrode 10 b in the electrolytic bath 4 . Due to electrolysis, the reaction of chemical formula (1) occurs at the anode, and the iron ions 11c are eluted.
  • the humic substances 11b in the water 21 to be treated react with the iron ions 11c to produce the first product 11f.
  • the reaction between hydroxide ions 11d generated by the reaction of chemical formula (2) during electrolysis and iron ions 11c produces a second product 11g.
  • the first product 11f which is a chelate complex
  • the second product 11g adsorb to each other and aggregate to form flocs 11h. That is, the humic substances 11b in the water 21 to be treated are taken into the flocs 11h.
  • the water containing the flocs 11 h is sent to the separation section 6 through the water pipe 8 .
  • the separation unit 6 has an MF membrane and separates the flocs 11h by filtering.
  • the water from which the flocs 11h have been separated is sent to the purified water discharge port 3 through the discharge pipe 9, and discharged as the treated water 22 from the purified water discharge port 3.
  • FIG. The post-treatment water 22 can be used as domestic water with reduced chromaticity.
  • FIG. 3 is a diagram showing the chromaticity of the treated water 22 of the water treatment device 1 of the embodiment according to the present disclosure.
  • the chromaticity of the water to be treated used in the experiment and the experimental result of filtering with an MF membrane after coagulation with PSI (Poly Silicate Iron) as a general coagulation sedimentation method are also shown.
  • PSI Poly Silicate Iron
  • the chromaticity of 300 TCU of the water to be treated 21 is mainly due to humic substances 11b, and compared with the chromaticity of 255 TCU after purification by a general coagulation-sedimentation method, the water after purification by the water treatment device 1.
  • the chromaticity of the post-treatment water 22 is reduced to 20 TCU, and the humic substances 11b are well removed.
  • a passive state such as iron hydroxide is gradually formed on the surface of the second electrode 10b, which is the cathode, and is applied between the electrode plates. This may cause problems such as a decrease in the current applied. Since this passivation can be stripped off by switching the polarity of the electrodes, the polarity of the voltage applied between the first electrode 10a and the electrode plate is changed periodically (for example, once a week). It is desirable that the inversion is controlled by a circuit incorporated in the power supply. After the polarity reversal, after waiting until the passivation is peeled off while the current is applied, the polarity may be reversed to return to the original polarity.
  • the first electrode 10a acts as a cathode and the second electrode 10b acts as an anode. Therefore, it is possible to continuously perform the same treatment as the treatment represented by the chemical formulas (1) to (3) while stripping off the passive state.
  • the size of the passive state that peels off is approximately 0.5 mm, by separating the electrode plates by at least 0.5 mm or more, the passive state that has fallen off between the electrodes clogs the space, and current does not flow in the clogged portion. , it is possible to reduce the possibility that the electrolysis shown by the chemical formulas (1) to (3) cannot be performed.
  • the plates are arranged parallel to the direction of water flow in the electrolytic cell in order to facilitate the stripping of the passivation.
  • the concentration of the iron ions 11c eluted from the first electrode 10a or the second electrode 10b is set to form a chelate complex with the humic substances 11b in the water 21 to be treated and to obtain a sufficient amount of iron hydroxide. It is desirable to make it twice or more the density
  • FIG. 4 shows the result of removing humic substances from water 21 to be treated with a concentration of 100 mg/L of humic substances 11b in water treatment apparatus 1 of Embodiment 1 according to the present disclosure, and measuring the chromaticity of treated water 22. is.
  • the chromaticity which is an indicator of the concentration of humic substances, at an iron ion concentration of 200 mg/L or more, which is more than twice the concentration of humic substances of 100 mg/L. 5 TCU and sufficiently lowered post-treatment water 22 can be obtained.
  • the generated iron ions 11c are consumed by the formation of the second product 11g, and the first product 11f becomes the humic substance 11b. becomes difficult to capture.
  • the first product 11f and the second product 11g are produced, they are in small amounts, so that the formation reaction of the flocs 11h is difficult to occur. Therefore, the chromaticity of the water to be treated 21 is increased by the humic substance 11b or the first product 11f or the second product 11g.
  • the elution concentration of iron is more than twice the concentration of humic substances 11b (200 mg/L to 300 mg/L in FIG.
  • iron ions 11c are not only the second product 11g, but also the second product 11g. It is also fully available for the production of one product 11f. Therefore, the first product 11f and the second product 11g are sufficiently present in the water, and the formation reaction of the flocs 11h easily occurs. Therefore, the chromaticity of the water to be treated 21 can be reduced.
  • the concentration of the iron ions 11c eluted from the first electrode 10a or the second electrode 10b should be such that it forms a chelate complex with the humic substances 11b in the water 21 to be treated and a sufficient amount of iron hydroxide is obtained.
  • the current was applied so that the concentration of the humic substances 11b was at least twice that of the humic substances 11b.
  • the concentration of the iron ions 11c eluted from the first electrode 10a or the second electrode 10b which is set to be twice the concentration of the humic substance 11b, is the same as the iron ions 11c and the hydroxide ions 11d that react with the humic substance 11b. This is the concentration containing the reacting iron ions 11c.
  • the water 21 to be treated can be purified by removing humic substances by performing purification treatment with the above-described electrolytic cell 4 .
  • the water treatment apparatus 1 includes an electrolytic bath 4 into which water to be treated 21 containing humic substances 11b flows, a first electrode 10a and a second electrode 10b immersed in the water to be treated 21 in the A power supply 5 that applies a current between the one electrode 10a and the second electrode 10b, and at least one of the first electrode 10a and the second electrode 10b is applied with a current from the power supply 5, whereby iron ions are eluted.
  • the first electrode 10a and the second electrode 10b are formed by the reaction between the humic substances 11b and the iron ions 11c on the anode side when a current is applied from the power supply 5, and the first product 11f and the , the second product 11g formed by the reaction between the hydroxide ions 11d and the iron ions 11c on the cathode side aggregates to form flocs 11h.
  • the first product 11f and the second product 11g can be formed, and the first product 11f and the second product 11g aggregate.
  • flocs 11h incorporating humic substances 11b can be formed. Therefore, the humic substances 11b having a small size can be precipitated as flocs 11h, and the humic substances 11b can be efficiently removed from the water 21 to be treated.
  • the water treatment device 1 is configured such that the distance between the first electrode 10a and the second electrode 10b is 0.5 mm or more.
  • the water treatment apparatus 1 uses the power source 5 to increase the concentration of the iron ions 11c eluted from at least one of the first electrode 10a and the second electrode 10b with respect to the concentration of the humic substances 11b contained in the water to be treated 21.
  • a current is applied so as to double or more.
  • the first electrode 10a and the second electrode 10b are both made of a material from which iron ions 11c are eluted by applying a current from the power supply 5, and when a current is applied, the first electrode 10a and the second electrode 10b The polarity is reversed between the one electrode 10a and the second electrode 10b.
  • the passivity can be peeled off from the electrode surface where the passivity accumulates and the current cannot be applied sufficiently. Therefore, it is possible to suppress the accumulation of passivation, thereby suppressing the decrease in purification treatment efficiency due to the current not flowing due to the passivity. Further, by reversing the anode side and the cathode side by reversing the polarity, the electrodes that emit the iron ions 11c can be replaced. Therefore, it is possible to suppress the decrease of only one electrode.
  • both electrodes are made of a material that elutes iron ions 11c, for example, in the vicinity of the pole that has changed from the anode to the cathode due to pole reversal, the iron ions 11c eluted before pole reversal and the water generated after pole reversal Both oxide ions 11d are present in relatively high concentrations.
  • both the hydroxide ions 11d generated before the pole reversal and the iron ions 11c eluted after the pole reversal are present at relatively high concentrations near the pole where the cathode has become the anode due to the pole reversal. Therefore, by performing the polarity reversal, it is possible to increase the occurrence frequency of the formation reaction of the second product 11g and the floc 11h.
  • the water treatment apparatus 1 further includes a separation unit 6 that removes the flocs 11h from the water 21 to be treated that has undergone the electrolytic treatment.
  • the flocs 11h remaining in the post-treatment water 22 can be removed more reliably. Therefore, the removal efficiency of humic substances from the water 21 to be treated can be improved.
  • a stirring mechanism such as a stirrer or bubbling may be provided inside the electrolytic bath 4 or the water pipe 8 .
  • a stirring mechanism such as a stirrer or bubbling may be provided inside the electrolytic bath 4 or the water pipe 8 .
  • the separation unit 6 is configured to perform MF membrane filtration, but the present invention is not limited to this.
  • filtration using granular filter media can be used in addition to MF membrane filtration.
  • Granular filter media include, for example, sand, anthracite, garnet, ceramics, activated carbon, iron oxyhydroxide, manganese sand, etc., as long as they settle in water and have a hardness that makes them difficult to deform under pressure. may be used by stacking in the vertical direction.
  • a polymer coagulant or an inorganic coagulant may be additionally injected.
  • the growth of the flocs 11h can be realized more quickly and stably.
  • the separation unit 6 is configured to perform MF membrane filtration, but the present invention is not limited to this.
  • the separation section 6 may be a sedimentation tank for sedimenting the flocs 11h.
  • the supernatant liquid is taken out after waiting until the flocs 11h settle at the bottom of the sedimentation tank, so that the treated water with a sufficiently low concentration of the humic substances 11b can be obtained. 22 can be obtained.
  • a valve is provided in the water pipe 8 to prevent continuous inflow of the water to be treated 21 after electrolytic treatment into the separation unit 6. By doing so, the sedimentation time necessary for all the flocs 11h in the sedimentation tank to sediment can be ensured. Further, the electrolytic bath 4 may also function as a sedimentation tank.
  • iron is used as the material of the first electrode 10a and the second electrode 10b, but the material is not limited to this.
  • the material of the electrode is preferably iron, but aluminum, which is cheaper than iron, can be used as a material that chelates the humic substance 11b, hydroxides it, and elutes the ions that aggregate with the chelate complex.
  • iron is used for both electrodes as the material for the first electrode 10a and the second electrode 10b, but the material is not limited to this.
  • iron may be used only for the anode.
  • the circuit for controlling the polarity reversal is built in the power supply 5, but the present invention is not limited to this.
  • the polarity reversal may be controlled by manually switching the circuit connecting the electrodes and the power supply 5 .
  • the flow rate of the water to be treated 21 taken into the inflow port 2 the flow rate of the water to be treated 21 flowing through the inflow pipe 7, and the water to be treated 21 entering the electrolytic cell 4
  • Flow rate of inflow and outflow, flow rate of water to be treated 21 flowing through water pipe 8, flow rate of water to be treated 21 flowing into and out of separation unit 6, flow rate of water to be treated 21 flowing through discharge pipe 9, and treated water 22 is taken out from the purified water discharge port 3 at the same flow rate, that is, the water to be treated 21 flows through each component in the water treatment apparatus 1 at a constant flow rate. do not have.
  • a certain amount of water to be treated 21 may be stored in the electrolytic cell 4 , the stored water to be treated 21 may be electrolyzed, and the electrolyzed water may be sent to the water pipe 8 .
  • the maintenance frequency of the separation unit 6 (for example, the frequency of replacement of the MF membrane) can be reduced.
  • the water treatment apparatus according to the present disclosure is useful for removing humins from water containing humic substances and obtaining domestic water with reduced chromaticity.
  • Water Treatment Device 1 Water Treatment Device 2 Inlet 3 Clean Water Outlet 4 Electrolyzer 5 Power Source 6 Separation Unit 7 Inflow Pipe 8 Water Pipe 9 Discharge Pipe 10a First Electrode 10b Second Electrode 11a Water Molecule 11b Humic Substance 11c Iron Ion 11d Hydroxide Ion 11e hydrogen 11f first product 11g second product 11h floc 21 water to be treated 22 water after treatment

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Abstract

This water treatment device (1) comprises an electrolysis tank (4), a first electrode (10a) and a second electrode (10b), and a power supply (5). At least one of the first electrode (10a) and the second electrode (10b) is configured from a material from which iron ions are eluted due to a current being applied from the power supply (5). The first electrode (10a) and the second electrode (10b) are positioned such that, when a current is applied from the power supply (5), a first product formed through a reaction between a humic substance and iron ions on the positive-electrode side and a second product formed through a reaction between hydroxide ions and iron ions on the negative-electrode side agglomerate and form flocs.

Description

水処理装置water treatment equipment
　本開示は、水処理装置に関する。 The present disclosure relates to water treatment equipment.
　従来から、井戸、河川、又は池などの水源の水を、飲料水や生活用水として利用するために浄化する水浄化方法が知られている。浄化により水から除去する物質は、例えば、濁りの原因である無機懸濁物あるいは色や臭気の原因である溶存有機物である。溶存有機物に関しては、例えば、インドネシアのカリマンタン島及びスマトラ島に代表される泥炭地域の水源の水には、フミン質という溶存有機物が高濃度で含まれることから色度が高く、生活水用途に用いる場合には洗濯物が着色する等問題となる。フミン質の除去方法としては、凝集剤を用いてフミン質を沈殿させて除去する凝集沈殿法（特許文献１参照）などが知られている。 Conventionally, water purification methods for purifying water from water sources such as wells, rivers, or ponds for use as drinking water or domestic water have been known. Substances that are removed from water by purification are, for example, inorganic suspended matter that causes turbidity or dissolved organic matter that causes color and odor. Regarding dissolved organic matter, for example, water from peat regions represented by the islands of Kalimantan and Sumatra in Indonesia contains a high concentration of dissolved organic matter called humic substances, so it has a high degree of color and is used as domestic water. In some cases, it causes problems such as coloration of the laundry. As a method for removing humic substances, there is known a coagulation-sedimentation method (see Patent Document 1) in which humic substances are precipitated and removed using a flocculating agent.
特開平１０－２１６７３８号公報JP-A-10-216738
　フミン質が含まれた色度の高い水から、色度の原因であるフミン質を凝集沈殿法で除去しようとする場合、フミン質の分子が小さいことから凝集させることが難しく、沈殿が容易な大きさのフロック（凝集剤及び、懸濁物或いは溶存物による沈殿物）を形成しづらいという課題があった。 When trying to remove humic substances, which cause chromaticity, from highly colored water containing humic substances by the coagulation-sedimentation method, it is difficult to coagulate them because the molecules of humic substances are small, and precipitation is easy. There is a problem that it is difficult to form large flocs (coagulant and sediment due to suspended matter or dissolved matter).
　本開示は、従来の凝集沈殿技術において困難であった被処理水からのフミン質の効率的な除去を可能とする水処理装置を提供することを目的とする。 The purpose of the present disclosure is to provide a water treatment apparatus that enables efficient removal of humic substances from water to be treated, which has been difficult with conventional coagulation sedimentation techniques.
　本開示に係る水処理装置は、フミン質を含む被処理水が流入する電解槽と、電解槽内において被処理水に浸漬する第一電極及び第二電極と、第一電極と第二電極との間に電流を印加する電源と、を備え、第一電極及び第二電極の少なくとも一方は、電源から電流を印加することで鉄イオンが溶出する材料で構成され、第一電極及び第二電極は、電源から電流を印加した際に、陽極側においてフミン質と鉄イオンとの反応により形成される第一生成物と、陰極側において水酸化物イオンと鉄イオンとの反応により形成される第二生成物とが凝集してフロックを形成するように配置されている。 The water treatment apparatus according to the present disclosure includes an electrolytic cell into which water to be treated containing humic substances flows, a first electrode and a second electrode that are immersed in the water to be treated in the electrolytic cell, and a first electrode and a second electrode. a power source that applies a current between the first electrode and the second electrode, at least one of the first electrode and the second electrode is made of a material that elutes iron ions by applying a current from the power source, the first electrode and the second electrode is the first product formed by the reaction of humic substances and iron ions on the anode side and the second product formed by the reaction of hydroxide ions and iron ions on the cathode side when a current is applied from a power source. The two products are arranged so that they agglomerate to form flocs.
　本開示によれば、被処理水からフミン質を効率的に除去することが可能な水処理装置を提供することができる。 According to the present disclosure, it is possible to provide a water treatment apparatus capable of efficiently removing humic substances from water to be treated.
図１は、本開示に係る実施の形態の水処理装置の浄化処理時における模式図である。FIG. 1 is a schematic diagram of a water treatment apparatus according to an embodiment of the present disclosure during purification treatment. 図２は、本開示に係る実施の形態の電解槽の電気分解における模式図である。FIG. 2 is a schematic diagram of electrolysis in the electrolytic cell of the embodiment according to the present disclosure. 図３は、本開示に係る実施の形態の水処理装置の処理後水の色度を示した図である。FIG. 3 is a diagram showing the chromaticity of treated water of the water treatment apparatus according to the embodiment of the present disclosure. 図４は、本開示に係る実施の形態の水処理装置の処理後水の色度を示した図である。FIG. 4 is a diagram showing the chromaticity of treated water of the water treatment apparatus according to the embodiment of the present disclosure.
　本開示に係る水処理装置は、フミン質を含む被処理水が流入する電解槽と、電解槽内において被処理水に浸漬する第一電極及び第二電極と、第一電極と第二電極との間に電流を印加する電源と、を備え、第一電極及び第二電極の少なくとも一方は、電源から電流を印加することで鉄イオンが溶出する材料で構成され、第一電極及び第二電極は、電源から電流を印加した際に、陽極側においてフミン質と鉄イオンとの反応により形成される第一生成物と、陰極側において水酸化物イオンと鉄イオンとの反応により形成される第二生成物とが凝集してフロックを形成するように配置されている。 The water treatment apparatus according to the present disclosure includes an electrolytic cell into which water to be treated containing humic substances flows, a first electrode and a second electrode that are immersed in the water to be treated in the electrolytic cell, and a first electrode and a second electrode. a power source that applies a current between the first electrode and the second electrode, at least one of the first electrode and the second electrode is made of a material that elutes iron ions by applying a current from the power source, the first electrode and the second electrode is the first product formed by the reaction of humic substances and iron ions on the anode side and the second product formed by the reaction of hydroxide ions and iron ions on the cathode side when a current is applied from a power source. The two products are arranged so that they agglomerate to form flocs.
　こうした構成によれば、水処理装置に電流を印加することにより、第一生成物及び第二生成物を形成させることができ、第一生成物と第二生成物とが凝集することにより、フミン質を取り込んだフロックを形成することができる。したがって、サイズの小さなフミン質をフロックとして沈殿させることができ、被処理水からフミン質を効率的に除去することが可能となる。 According to such a configuration, by applying an electric current to the water treatment device, the first product and the second product can be formed, and the aggregation of the first product and the second product causes humin A textured floc can be formed. Therefore, humic substances having a small size can be precipitated as flocs, and humic substances can be efficiently removed from the water to be treated.
　また、本開示に係る水処理装置では、第一電極と第二電極との間の距離は、０．５ｍｍ以上であってもよい。 Further, in the water treatment device according to the present disclosure, the distance between the first electrode and the second electrode may be 0.5 mm or more.
　このような構成とすることにより、電極から剥がれ落ちる不働態が電極間に詰まることを低減できる。したがって、不働態が詰まった部分に電流が流れなくなることにより、第一生成物と第二生成物の生成、及びフロックの形成が、阻害される可能性を低減できる。 With such a configuration, it is possible to reduce the clogging between the electrodes of the passive state peeled off from the electrodes. Therefore, it is possible to reduce the possibility that the generation of the first product and the second product and the formation of flocs will be inhibited by the current not flowing through the passive state-filled portion.
　また、本開示に係る水処理装置は、電源により、被処理水に含まれるフミン質の濃度に対して、第一電極及び第二電極の少なくとも一方から溶出する鉄イオンの濃度が２倍以上となるように電流を印加してもよい。 Further, in the water treatment apparatus according to the present disclosure, the concentration of iron ions eluted from at least one of the first electrode and the second electrode is twice or more the concentration of humic substances contained in the water to be treated by the power supply. You may apply a current so that it becomes.
　このような構成とすることにより、第一生成物の生成及び第二生成物の生成に十分な鉄イオンが溶出する。したがって、第一生成物及び第二生成物の凝集物であるフロックを効率的に形成でき、被処理水中のフミン質を効率よく除去することが可能となる。 With such a configuration, sufficient iron ions are eluted for the production of the first product and the production of the second product. Therefore, flocs, which are aggregates of the first product and the second product, can be efficiently formed, and humic substances in the water to be treated can be efficiently removed.
　また、本開示に係る水処理装置は、第一電極及び第二電極が、いずれも電源から電流を印加することで鉄イオンが溶出する材料で構成され、電流を印加した際に、第一電極と第二電極との間で極性を反転させてもよい。 Further, in the water treatment device according to the present disclosure, the first electrode and the second electrode are both made of a material from which iron ions are eluted by applying a current from a power supply, and when a current is applied, the first electrode and the second electrode.
　このような構成とすることにより、不働態が蓄積して電流を十分に印加できなくなった電極表面から不働態を剥がし落とすことができる。したがって、不働態の蓄積を抑制でき、不働態により電流が流れなくなり、浄化処理効率が低減することを抑制可能となる。 With such a configuration, the passivity can be peeled off from the electrode surface where the passivity accumulates and the current cannot be applied sufficiently. Therefore, it is possible to suppress the accumulation of passivation, thereby suppressing the decrease in purification treatment efficiency due to the current not flowing due to the passivity.
　また、本開示に係る水処理装置は、電解処理を行った被処理水からフロックを除去する分離部をさらに備えてもよい。 In addition, the water treatment apparatus according to the present disclosure may further include a separation unit that removes flocs from water to be treated that has undergone electrolytic treatment.
　このような構成とすることにより、処理後水に残留するフロックをより確実に除去することができる。したがって、被処理水からのフミン質の除去効率を向上することができる。 With such a configuration, it is possible to more reliably remove flocs remaining in the treated water. Therefore, the removal efficiency of humic substances from the water to be treated can be improved.
　以下、本開示の実施の形態について図面を参照しながら説明する。なお、以下の実施の形態は、本開示を具体化した一例であって、本開示の技術的範囲を限定するものではない。また、実施形態において説明する各図は、模式的な図であり、各図中の各構成要素の大きさ及び厚さそれぞれの比が、必ずしも実際の寸法比を反映しているとは限らない。 Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. It should be noted that the following embodiments are examples that embody the present disclosure, and do not limit the technical scope of the present disclosure. In addition, each drawing described in the embodiment is a schematic drawing, and the ratio of the size and thickness of each component in each drawing does not necessarily reflect the actual dimensional ratio. .
　本開示の実施の形態を具体的に説明する前に、従来技術の課題を改めて説明するとともに、実施の形態の概要を説明する。 Before specifically describing the embodiments of the present disclosure, the problems of the conventional technology will be described again, and the outline of the embodiments will be described.
　上述のように、泥炭地域の原水には、フミン質のような溶存有機物が含まれており、色度が高い場合がある。例えば、インドネシアのスマトラ島では、原水の色度が１００ＴＣＵ～５００ＴＣＵ（ＴＣＵ：ｔｒｕｅ　ｃｏｌｏｒ　ｕｎｉｔｓ）であり、あたかも紅茶の様な色を呈している。原水に含まれるフミン質は、植物などが微生物による分解を経て生成された生成物である。フミン質は、大きく分けてヒュームス質、フミン酸、及びフルボ酸から構成されており、分子の大きさは、ヒュームス質、フミン酸、及びフルボ酸の順に小さくなる。フミン質において、アルカリ水溶液で沈殿するものをヒュームス質といい、アルカリ水溶液に可溶であるが酸水溶液で沈殿するものをフミン酸といい、アルカリ水溶液にも酸水溶液にも可溶なものをフルボ酸という。フミン質のような元々サイズが極めて小さい溶存物に凝集沈殿法を適用しても、除去対象物を沈殿に十分な大きさのフロックにまで凝集させることは難しく、十分な浄化性能は得られない。 As mentioned above, the raw water in peat areas contains dissolved organic matter such as humic substances and may have a high degree of color. For example, in the island of Sumatra in Indonesia, raw water has a chromaticity of 100 TCU to 500 TCU (TCU: true color units) and exhibits a color similar to black tea. The humic substance contained in raw water is a product produced by decomposition of plants and the like by microorganisms. Humic substances are roughly divided into fume substances, humic acid, and fulvic acid, and the molecular size decreases in the order of fume substances, humic acid, and fulvic acid. Among humic substances, those that precipitate in an alkaline aqueous solution are called fumes, those that are soluble in an alkaline aqueous solution but precipitate in an acid aqueous solution are called humic acids, and those that are soluble in both an alkaline and acid aqueous solution are called fulvic. called acid. Even if the coagulation-sedimentation method is applied to dissolved substances such as humic substances, which are originally extremely small in size, it is difficult to coagulate the substances to be removed into flocs large enough for precipitation, and sufficient purification performance cannot be obtained. .
　そこで本発明者は基礎検討を重ね、フミン質をも凝集させ粗大化させる成分を、鉄電極を用いた電解処理によって生成可能であることを見出した。具体的には、フミン質を含む水中に浸漬した鉄の電極間に直流電流を印加する。これにより、陽極側からは鉄イオンが溶出し、鉄イオンとフミン質とがキレート錯体を形成し、陰極側で生成された水酸化物イオンと鉄イオンとが水酸化鉄を形成する。そして、キレート錯体と水酸化鉄とが互いに凝集し、沈殿に十分な大きさのフロックを形成することを発見した。フロックは、沈殿、或いは、ろ過精度０．１μｍ～１μｍ程度のＭＦ（Ｍｉｃｒｏｆｉｌｔｒａｔｉｏｎ）膜分離等の固液分離法で容易に除去可能である。本実施形態の水処理装置は、この凝集作用を用いて被処理水からフミン質を除去することが可能な装置である。 Therefore, the present inventor conducted repeated basic studies and found that it is possible to generate a component that aggregates and coarsens humic substances by electrolytic treatment using iron electrodes. Specifically, a direct current is applied between iron electrodes immersed in water containing humic substances. As a result, iron ions are eluted from the anode side, iron ions and humic substances form a chelate complex, and hydroxide ions and iron ions generated on the cathode side form iron hydroxide. They found that the chelate complex and iron hydroxide aggregate with each other to form flocs large enough for precipitation. Flocs can be easily removed by precipitation or a solid-liquid separation method such as MF (Microfiltration) membrane separation with a filtration accuracy of about 0.1 μm to 1 μm. The water treatment apparatus of this embodiment is an apparatus capable of removing humic substances from water to be treated using this aggregation action.
　（実施の形態１）
　図１を参照して、本実施の形態１に係る水処理装置１について説明する。図１は、本開示に係る実施の形態１の水処理装置１の浄化処理時における模式図である。 (Embodiment 1)
A water treatment apparatus 1 according to Embodiment 1 will be described with reference to FIG. FIG. 1 is a schematic diagram of a water treatment device 1 according to Embodiment 1 of the present disclosure during purification treatment.
　本実施の形態１の水処理装置１は、図１に示すように、フミン質を含み色度の高い被処理水２１を浄化して無色透明の生活用水として使用するための装置である。具体的には、水処理装置１は、流入口２と、浄水排出口３と、電解槽４と、電源５と、分離部６と、流入管７と、送水管８と、排出管９と、第一電極１０ａと、第二電極１０ｂとを有して構成される。 As shown in FIG. 1, the water treatment device 1 of Embodiment 1 is a device for purifying water 21 to be treated, which contains humic substances and has a high degree of chromaticity, for use as colorless and transparent domestic water. Specifically, the water treatment device 1 includes an inlet 2, a purified water outlet 3, an electrolyzer 4, a power source 5, a separation section 6, an inflow pipe 7, a water pipe 8, and a discharge pipe 9. , a first electrode 10a and a second electrode 10b.
　流入口２は、フミン質を含む被処理水２１であり、水処理装置１の外部から圧送されてきた被処理水２１を、装置内に導入するための開口である。流入口２により、井戸、河川、又は池などの水源から、被処理水２１が水処理装置１内に導入される。流入口２は、水処理装置１を構成する筐体に設けられており、装置内の流入管７によって電解槽４と連通接続されている。 The inflow port 2 is an opening for introducing the water to be treated 21 containing humic substances, which is pressure-fed from the outside of the water treatment device 1, into the device. Water to be treated 21 is introduced into the water treatment apparatus 1 from a water source such as a well, a river, or a pond through the inlet 2 . The inflow port 2 is provided in a housing that constitutes the water treatment device 1, and is connected to the electrolytic cell 4 through an inflow pipe 7 inside the device.
　浄水排出口３は、水処理装置１で処理された被処理水２１を処理後水２２として装置外部に取り出すための開口である。流量と浄水排出口３は装置を構成する筐体に設けられており、装置内の排出管９と連通接続されている。 The purified water outlet 3 is an opening for taking out the treated water 21 treated by the water treatment device 1 as post-treatment water 22 to the outside of the device. The flow rate and purified water discharge port 3 are provided in a housing that constitutes the device, and are connected to a discharge pipe 9 inside the device.
　電解槽４は、第一電極１０ａと第二電極１０ｂを内部に固定し、被処理水２１を内部に取り込み、電気分解を行うための容器である。電解槽４の内部は、流入管７及び送水管８と連通接続されている。 The electrolytic cell 4 is a container for fixing the first electrode 10a and the second electrode 10b inside, taking in the water 21 to be treated, and electrolyzing it. The inside of the electrolytic bath 4 is connected to an inflow pipe 7 and a water pipe 8 for communication.
　電源５は、第一電極１０ａ及び第二電極１０ｂに接続されており、第一電極１０ａと第二電極１０ｂの間に電流を印加する。また、電源５は、第一電極１０ａと第二電極１０ｂに印加される電流の極性を反転させる転極を行う回路を内蔵している。 The power supply 5 is connected to the first electrode 10a and the second electrode 10b, and applies current between the first electrode 10a and the second electrode 10b. Further, the power supply 5 incorporates a circuit for reversing the polarities of the currents applied to the first electrode 10a and the second electrode 10b.
　分離部６は、電解槽４内における電気分解で発生する凝集物であり、フミン質を取り込んだ凝集物を分離除去する。分離部６は、ろ過精度１μｍのろ過膜である。分離部６に用いるろ過膜としては、例えばＭＦ（Ｍｉｃｒｏ　Ｆｉｌｔｒａｔｉｏｎ）ろ過膜を用いることができる。分離部６は、送水管８と排出管９に連通接続されている。 The separation unit 6 separates and removes aggregates generated by electrolysis in the electrolytic bath 4, and aggregates that have taken in humic substances. The separation unit 6 is a filtration membrane with a filtration accuracy of 1 μm. As the filtration membrane used in the separation unit 6, for example, an MF (Micro Filtration) filtration membrane can be used. The separation unit 6 is connected to the water pipe 8 and the discharge pipe 9 for communication.
　流入管７は、流入口２及び電解槽４と連通接続されており、流入口２から取り込まれた被処理水２１を電解槽４に届ける。 The inflow pipe 7 is connected to the inflow port 2 and the electrolytic cell 4 and delivers the water to be treated 21 taken in from the inflow port 2 to the electrolytic cell 4 .
　送水管８は、電解槽４及び分離部６と連通接続されており、電解槽４で電気分解により処理された被処理水２１を分離部６に届ける。 The water pipe 8 is connected to the electrolytic cell 4 and the separation unit 6 and delivers the water to be treated 21 electrolyzed in the electrolytic cell 4 to the separation unit 6 .
　排出管９は、分離部６及び浄水排出口３と連通接続されている。排出管９は、分離部６で凝集物が分離除去された被処理水２１を浄水排出口３に届ける。 The discharge pipe 9 is connected and communicated with the separation section 6 and the purified water discharge port 3 . The discharge pipe 9 delivers the water to be treated 21 from which the aggregates have been separated and removed in the separation unit 6 to the purified water discharge port 3 .
　被処理水２１は、流入口２から連続的に取り込まれ、流入管７、電解槽４、送水管８、分離部６、排出管９を流れることにより、浄化処理される。浄化処理された被処理水２１は、処理後水２２として浄水排出口３から連続的に取り出される。被処理水２１が流入口２に取り込まれる流量と、被処理水２１が流入管７を流れる流量、被処理水２１が電解槽４に流入・流出する流量、被処理水２１が送水管８を流れる流量、被処理水２１が分離部６に流入・流出する流量、被処理水２１が排出管９を流れる流量、処理後水２２が浄水排出口３から取り出される流量はそれぞれ同じである。 The water to be treated 21 is continuously taken in from the inflow port 2 and purified by flowing through the inflow pipe 7, the electrolytic bath 4, the water pipe 8, the separation section 6, and the discharge pipe 9. Purified water 21 to be treated is continuously taken out as post-treatment water 22 from the purified water discharge port 3 . The flow rate of the water to be treated 21 taken into the inflow port 2, the flow rate of the water to be treated 21 flowing through the inflow pipe 7, the flow rate of the water to be treated 21 flowing into and out of the electrolytic cell 4, the water to be treated 21 flowing through the water pipe 8 The flow rate, the flow rate at which the water 21 to be treated flows into and out of the separation section 6, the flow rate at which the water 21 to be treated flows through the discharge pipe 9, and the flow rate at which the treated water 22 is taken out from the purified water discharge port 3 are all the same.
　図２は、水処理装置１が有する電解槽４の電気分解における模式図である。第一電極１０ａ及び第二電極１０ｂは、いずれも鉄で構成されている。第一電極１０ａと第二電極１０ｂとは対面で設置されており、電極の間の距離は３ｍｍである。なお、電極間の距離は、０．５ｍｍ以上であることが好ましい。これは、後述するフロック１１ｈあるいは電極上に形成される不働態が電極間に詰まる可能性を低減するためである。また、電極間の距離を大きくするにしたがい、後述する反応である、陽極から溶出する鉄イオンと陰極から発生する水酸化物イオンとの反応の発生頻度が低下する可能性、及び、主に陽極付近で生成する第一生成物１１ｆと主に極間で生成する第二生成物１１ｇとがフロック１１ｈを形成する反応の発生頻度が低下する可能性が高まる。つまり、電極間の距離を小さくすることにより、第二生成物１１ｇ及びフロック１１ｈの形成効率が向上する。したがって、電極間の距離は、不働態及びフロック１１ｈが詰まらない程度に小さくすることが好ましく、水処理装置１では、電極間の距離を３ｍｍとした。 FIG. 2 is a schematic diagram of electrolysis in the electrolytic cell 4 of the water treatment device 1. FIG. Both the first electrode 10a and the second electrode 10b are made of iron. The first electrode 10a and the second electrode 10b are installed facing each other, and the distance between the electrodes is 3 mm. In addition, it is preferable that the distance between the electrodes is 0.5 mm or more. This is to reduce the possibility that flocs 11h, which will be described later, or passive states formed on the electrodes clog the gap between the electrodes. In addition, as the distance between the electrodes increases, the frequency of the reaction between the iron ions eluted from the anode and the hydroxide ions generated from the cathode, which is a reaction described later, may decrease. The probability of occurrence of the reaction in which the first product 11f generated in the vicinity and the second product 11g generated mainly between the electrodes to form the flocs 11h decreases is increased. That is, by reducing the distance between the electrodes, the formation efficiency of the second product 11g and the flocs 11h is improved. Therefore, it is preferable that the distance between the electrodes is small enough to prevent clogging of the passive state and the flocs 11h.
　第一電極１０ａ及び第二電極１０ｂは、電源５と接続されている。電源５により、第一電極１０ａと第二電極１０ｂの間に直流電流が印加され、被処理水２１の電気分解が行われる。第一電極１０ａ及び第二電極１０ｂは、いずれか片方が陽極側になり、もう一方が陰極側となる。電気分解により、陽極側の電極からは鉄イオン１１ｃが溶出し、陰極側からは水酸化物イオン１１ｄが発生する。鉄イオン１１ｃ及び水酸化物イオン１１ｄは、いずれもフミン質１１ｂを取り込むフロック１１ｈを形成する成分となる。鉄イオン１１ｃの溶出量は、印加する電流量により制御可能であり、電流量の増減に比例して鉄イオン１１ｃの溶出量も増減する。したがって、被処理水２１に含まれるフミン質１１ｂの濃度に応じて印加する電流量を設定することで、水質に応じて鉄イオン１１ｃの溶出量を制御でき、被処理水２１の浄化処理を行うことができる。 The first electrode 10a and the second electrode 10b are connected to the power source 5. A direct current is applied between the first electrode 10a and the second electrode 10b by the power supply 5, and the water 21 to be treated is electrolyzed. One of the first electrode 10a and the second electrode 10b is on the anode side, and the other is on the cathode side. By electrolysis, iron ions 11c are eluted from the anode side electrode, and hydroxide ions 11d are generated from the cathode side. The iron ions 11c and hydroxide ions 11d are both components forming flocs 11h that take in the humic substance 11b. The amount of eluted iron ions 11c can be controlled by the amount of current applied, and the amount of eluted iron ions 11c increases or decreases in proportion to the increase or decrease in the amount of current. Therefore, by setting the amount of electric current to be applied according to the concentration of the humic substances 11b contained in the water 21 to be treated, the elution amount of the iron ions 11c can be controlled according to the water quality, and the water 21 to be treated can be purified. be able to.
　また、第一電極１０ａ及び第二電極１０ｂは、電源５に内蔵された回路によって転極される。第一電極１０ａ及び第二電極１０ｂは、両極とも鉄で構成されている。したがって、後述する電気分解反応における陽極及び陰極のどちらの極としても作用することができるため、転極中においても、浄化処理を継続することができる。 In addition, the first electrode 10a and the second electrode 10b are reversed by a circuit built in the power supply 5. Both the first electrode 10a and the second electrode 10b are made of iron. Therefore, since it can act as either an anode or a cathode in the later-described electrolysis reaction, the purification process can be continued even during the polarity reversal.
　さらに、転極によって、陽極側と陰極側とを反転させることにより、鉄イオン１１ｃを放出する電極を入れ替えることができる。したがって、一方の電極のみが消費されることを抑制できる。 Furthermore, by reversing the anode side and the cathode side by reversing the polarity, the electrodes that emit the iron ions 11c can be replaced. Therefore, consumption of only one electrode can be suppressed.
　加えて、転極により、電極付近での化学反応が促進される。つまり、転極によって、浄化処理の反応の発生頻度を向上させることができる。例えば、転極によって陽極から陰極となった極付近では、転極前に溶出した鉄イオン１１ｃと、転極後に発生した水酸化物イオン１１ｄとの両方が比較的高濃度で存在している。そのため、転極により第二生成物１１ｇが生成しやすくなる。さらに、生成した第二生成物１１ｇと、転極前に生成した第一生成物１１ｆとが反応することにより、フロック１１ｈが生成する。また、転極によって陰極から陽極となった極付近では、転極前に発生した水酸化物イオン１１ｄと、転極後に溶出した鉄イオン１１ｃとの両方が比較的高濃度で存在している。そのため、転極により第二生成物１１ｇが生成しやすくなる。さらに、転極前には鉄イオン１１ｃの濃度が比較的低いために反応していなかったフミン質１１ｂが、溶出してきた鉄イオン１１ｃと反応し、第一生成物１１ｆが生成しやすくなる。そして、第一生成物１１ｆと第二生成物１１ｇとが反応し、フロック１１ｈが生成しやすくなる。したがって、転極を行うことにより、第二生成物１１ｇ及びフロック１１ｈの形成反応の発生頻度を上昇させることができる。なお、不働態の除去を行うための転極は、例えば１週間に一度行うのに対し、化学反応を促進するために行う転極は、３０分に一回程度行うようにしてもよい。 In addition, the reversal of polarity promotes chemical reactions near the electrodes. In other words, the polarity reversal can improve the frequency of occurrence of the reaction in the purification process. For example, both the iron ions 11c eluted before the pole reversal and the hydroxide ions 11d generated after the pole reversal are present at relatively high concentrations near the pole that has changed from the anode to the cathode due to the pole reversal. Therefore, the second product 11g is likely to be generated by the polarity reversal. Furthermore, flocs 11h are produced by reacting the produced second product 11g with the first product 11f produced before the polarity reversal. Moreover, both the hydroxide ions 11d generated before the pole reversal and the iron ions 11c eluted after the pole reversal are present at relatively high concentrations near the pole where the cathode has become the anode due to the pole reversal. Therefore, the second product 11g is likely to be generated by the polarity reversal. Furthermore, the humic substance 11b, which had not reacted before the polarity reversal due to the relatively low concentration of the iron ions 11c, reacts with the eluted iron ions 11c, facilitating the formation of the first product 11f. Then, the first product 11f and the second product 11g react with each other to easily generate flocs 11h. Therefore, by performing the polarity reversal, it is possible to increase the occurrence frequency of the formation reaction of the second product 11g and the floc 11h. While the polarity reversal for removing the passive state is performed, for example, once a week, the polarity reversal for promoting the chemical reaction may be performed about once every 30 minutes.
　ここで、図２を参照して、電解槽４における電気分解について詳細に説明する。 Here, the electrolysis in the electrolytic bath 4 will be described in detail with reference to FIG.
　電解槽４の内部に配置された第一電極１０ａは、鉄で構成されている。化学式（１）に示すように、被処理水２１が電解槽４に流入後、電源５により陽極である第一電極１０ａと陰極である第二電極１０ｂの間に電流が印加され、陽極側からは電気分解によりＦｅ２＋が溶出する。 The first electrode 10a arranged inside the electrolytic cell 4 is made of iron. As shown in chemical formula (1), after the water 21 to be treated flows into the electrolytic cell 4, a current is applied by the power source 5 between the first electrode 10a as the anode and the second electrode 10b as the cathode, and from the anode side Fe 2+ is eluted by electrolysis.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　溶出したＦｅ２＋は、その殆どが速やかにＦｅ３＋（鉄イオン１１ｃ）に酸化される。鉄イオン１１ｃの濃度制御方法について説明する。電源５により、第一電極１０ａと第二電極１０ｂとの間に印加する電流値をｘ［Ａ］とすると、式（１）とファラデーの電気分解の法則により、１秒あたりに生成するＦｅ２＋ののモル量はｘ／（９６４８５×２）［ｍｏｌ］であり、Ｆｅ２＋の重量は５５．８５×ｘ／（９６４８５×２×１０３）［ｍｇ］である。被処理水２１が電解槽４に取り込まれる流量をｙ［Ｌ／ｓ］とすると、被処理水２１に取り込まれたＦｅ２＋の濃度は、５５．８５×ｘ／（９６４８５×２×ｙ×１０３）［ｍｇ／Ｌ］、すなわち、２．８９×（ｘ／ｙ）×１０－７　［ｍｇ／Ｌ］である。Ｆｅ２＋の濃度は、Ｆｅ３＋である鉄イオン１１ｃの濃度と同じであるため、被処理水２１に溶出する鉄イオン１１ｃの濃度は、２．８９×（ｘ／ｙ）×１０－７　［ｍｇ／Ｌ］で制御可能である。 Most of the eluted Fe 2+ is rapidly oxidized to Fe 3+ (iron ions 11c). A method for controlling the concentration of iron ions 11c will be described. When the current value applied between the first electrode 10a and the second electrode 10b by the power supply 5 is x [A], Fe 2+ generated per second according to the formula (1) and Faraday's law of electrolysis The molar amount of is x/(96485×2) [mol] and the weight of Fe 2+ is 55.85×x/(96485×2×10 3 ) [mg]. Let y [L/s] be the flow rate at which the water to be treated 21 is taken into the electrolytic cell 4, the concentration of Fe 2+ taken into the water to be treated 21 is 55.85×x/(96485×2×y×10 3 ) [mg/L], ie 2.89×(x/y)×10 −7 [mg/L]. Since the concentration of Fe 2+ is the same as the concentration of iron ions 11c that are Fe 3+ , the concentration of iron ions 11c eluted in the water 21 to be treated is 2.89×(x/y)×10 −7 [mg /L].
　鉄イオン１１ｃは、フミン質１１ｂと結合し、第一生成物１１ｆとなる。フミン質１１ｂは、被処理水２１に含まれ、その大きさは１０ｎｍ～１００ｎｍ程度である。したがって、ろ過精度０．１μｍ～１μｍ程度のＭＦ膜等では除去することが難しい。しかし、鉄イオン１１ｃとフミン質１１ｂとが結合することにより、大きさ１０ｎｍ～１００ｎｍ程度と小さいものの、様々な粒子と凝集しやすいキレート錯体である第一生成物１１ｆとなる。第一生成物１１ｆは、キレート錯体であるため、後述する第二生成物１１ｇと吸着しやすい。 The iron ion 11c combines with the humic substance 11b to become the first product 11f. The humic substance 11b is contained in the water to be treated 21, and its size is about 10 nm to 100 nm. Therefore, it is difficult to remove them with an MF membrane or the like having a filtration accuracy of about 0.1 μm to 1 μm. However, when the iron ions 11c and the humic substance 11b are combined, the first product 11f, which is a small chelate complex with a size of about 10 nm to 100 nm, is easily aggregated with various particles. Since the first product 11f is a chelate complex, it easily adsorbs the second product 11g, which will be described later.
　一方、陰極では、化学式（２）に示すように、水分子１１ａが電気分解され、水素１１ｅ及び水酸化物イオン１１ｄが生成する。 On the other hand, at the cathode, as shown in chemical formula (2), water molecules 11a are electrolyzed to produce hydrogen 11e and hydroxide ions 11d.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　化学式（３）に示すように、生成した水酸化物イオン１１ｄは、鉄イオン１１ｃと結合し、大きさ１００ｎｍ～１μｍ程度の水酸化鉄粒子である第二生成物１１ｇとなる。 As shown in chemical formula (3), the generated hydroxide ions 11d combine with the iron ions 11c to form the second product 11g, which is iron hydroxide particles with a size of about 100 nm to 1 μm.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　第一生成物１１ｆと第二生成物１１ｇとは、互いに吸着して凝集する性質を有しており、第一生成物１１ｆと第二生成物１１ｇとが凝集することにより、粗大なフロック１１ｈが形成される。フロック１１ｈは電解槽４の内部や送水管８の内部で成長する。このフミン質１１ｂを含んだ粗大なフロックは、最終的にサイズが数μｍ以上に達することから、後段の分離部６でのＭＦ膜ろ過（ろ過精度０．１μｍ～１μｍ程度）によって容易に分離できる。フロック１１ｈが分離除去された水は、排出管９及び浄水排出口３から処理後水２２として得られ、生活用水として供給される。 The first product 11f and the second product 11g have the property of mutually adsorbing and aggregating, and the agglomeration of the first product 11f and the second product 11g causes coarse flocs 11h to be formed. It is formed. The flocs 11h grow inside the electrolytic bath 4 and inside the water pipe 8 . Since the coarse flocs containing the humic substances 11b eventually reach a size of several μm or more, they can be easily separated by MF membrane filtration (filtration accuracy of about 0.1 μm to 1 μm) in the subsequent separation unit 6. . The water from which the flocs 11h have been separated and removed is obtained as post-treatment water 22 from the discharge pipe 9 and the purified water discharge port 3, and is supplied as domestic water.
　改めて、水処理装置１における被処理水２１の浄化処理について説明する。フミン質１１ｂを含む被処理水２１は、流入口２によって水処理装置１内に導入され、電解槽４に流入する。被処理水２１は、電解槽４内の第一電極１０ａ及び第二電極１０ｂにより電気分解される。電気分解により、陽極では化学式（１）の反応が起こり、鉄イオン１１ｃが溶出する。被処理水２１中のフミン質１１ｂは、鉄イオン１１ｃと反応し、第一生成物１１ｆが生じる。また、化学式（３）に示すように、電気分解の際に化学式（２）の反応により生成する水酸化物イオン１１ｄと、鉄イオン１１ｃとが反応することにより、第二生成物１１ｇが生じる。キレート錯体である第一生成物１１ｆは、第二生成物１１ｇと互いに吸着して凝集することにより、フロック１１ｈを形成する。つまり、被処理水２１中のフミン質１１ｂが、フロック１１ｈ中に取り込まれる。フロック１１ｈを含む水は、送水管８により、分離部６へと送水される。分離部６は、ＭＦ膜を有し、ろ過を行うことにより、フロック１１ｈを分離する。フロック１１ｈが分離された水は、排出管９により浄水排出口３へと送水され、浄水排出口３から処理後水２２として排出される。処理後水２２は、色度が低減された生活用水として用いることができる。 The purification process of the water to be treated 21 in the water treatment device 1 will be explained again. Water to be treated 21 containing humic substances 11 b is introduced into the water treatment apparatus 1 through the inlet 2 and flows into the electrolytic cell 4 . The water 21 to be treated is electrolyzed by the first electrode 10 a and the second electrode 10 b in the electrolytic bath 4 . Due to electrolysis, the reaction of chemical formula (1) occurs at the anode, and the iron ions 11c are eluted. The humic substances 11b in the water 21 to be treated react with the iron ions 11c to produce the first product 11f. Further, as shown in chemical formula (3), the reaction between hydroxide ions 11d generated by the reaction of chemical formula (2) during electrolysis and iron ions 11c produces a second product 11g. The first product 11f, which is a chelate complex, and the second product 11g adsorb to each other and aggregate to form flocs 11h. That is, the humic substances 11b in the water 21 to be treated are taken into the flocs 11h. The water containing the flocs 11 h is sent to the separation section 6 through the water pipe 8 . The separation unit 6 has an MF membrane and separates the flocs 11h by filtering. The water from which the flocs 11h have been separated is sent to the purified water discharge port 3 through the discharge pipe 9, and discharged as the treated water 22 from the purified water discharge port 3. FIG. The post-treatment water 22 can be used as domestic water with reduced chromaticity.
　ここで図３を参照して、水処理装置１によるフミン質の浄化試験の実験結果を示す。図３は、本開示に係る実施の形態の水処理装置１の処理後水２２の色度を示した図である。比較のために、実験で用いた被処理水の色度と、一般的な凝集沈殿法として、ＰＳＩ（Ｐｏｌｙ　Ｓｉｌｉｃａｔｅ　Ｉｒｏｎ）で凝集した後にＭＦ膜でろ過した実験結果についても併記した。 Here, with reference to FIG. 3, the experimental results of the humic substance purification test by the water treatment device 1 are shown. FIG. 3 is a diagram showing the chromaticity of the treated water 22 of the water treatment device 1 of the embodiment according to the present disclosure. For comparison, the chromaticity of the water to be treated used in the experiment and the experimental result of filtering with an MF membrane after coagulation with PSI (Poly Silicate Iron) as a general coagulation sedimentation method are also shown.
　被処理水２１の色度３００ＴＣＵは、主にフミン質１１ｂによるものであり、一般的な凝集沈殿法での浄化後の色度２５５ＴＣＵと比較して、水処理装置１で浄化後の水である処理後水２２の色度は、２０ＴＣＵに低下しており、フミン質１１ｂがよく除去されている。 The chromaticity of 300 TCU of the water to be treated 21 is mainly due to humic substances 11b, and compared with the chromaticity of 255 TCU after purification by a general coagulation-sedimentation method, the water after purification by the water treatment device 1. The chromaticity of the post-treatment water 22 is reduced to 20 TCU, and the humic substances 11b are well removed.
　なお、ここまで述べた電気分解を長時間（例えば、５日間）行った場合、陰極である第二電極１０ｂの表面には徐々に水酸化鉄等の不働態が形成され、極板間に印加される電流が低下するなどの不具合の原因となる。この不働態は、電極の極性を入れ替えることにより剥がし落とすことができるため、第一電極１０ａと電極板の極板間に印加される電圧の極性は、定期的（例えば、１週間に１回）に電源に内蔵された回路により反転制御されることが望ましい。転極後、電流を印加したまま不働態が剥がれ落ちるまで待機した後、再度転極を行い元の極性に戻しても良い。また、水処理装置１では、第一電極１０ａだけでなく、第二電極１０ｂも鉄で構成しているため、転極後には第一電極１０ａが陰極、第二電極１０ｂが陽極として作用する。したがって、不働態を剥がし落としながらそのまま連続的に化学式（１）～化学式（３）で示した処理と同等の処理を行うことが可能となる。また、剥がれ落ちる不働態のサイズは概ね０．５ｍｍであるため、極板間は少なくとも０．５ｍｍ以上離すことで、電極の間に剥がれ落ちた不働態が詰まり、詰まった部分に電流が流れず、化学式（１）～化学式（３）で示した電気分解を行うことができなくなる可能性を低減できる。さらには、不働態の剥がれ落ちを促進するために、極板は電解槽内の水流の方向に並行に配置されることが望ましい。また、第一電極１０ａ或いは第二電極１０ｂから溶出させる鉄イオン１１ｃの濃度は、被処理水２１中のフミン質１１ｂとキレート錯体を形成し、また十分な量の水酸化鉄を得るために、フミン質１１ｂの濃度の２倍以上とすることが望ましい。 In addition, when the electrolysis described so far is performed for a long time (for example, 5 days), a passive state such as iron hydroxide is gradually formed on the surface of the second electrode 10b, which is the cathode, and is applied between the electrode plates. This may cause problems such as a decrease in the current applied. Since this passivation can be stripped off by switching the polarity of the electrodes, the polarity of the voltage applied between the first electrode 10a and the electrode plate is changed periodically (for example, once a week). It is desirable that the inversion is controlled by a circuit incorporated in the power supply. After the polarity reversal, after waiting until the passivation is peeled off while the current is applied, the polarity may be reversed to return to the original polarity. In the water treatment device 1, not only the first electrode 10a but also the second electrode 10b are made of iron. Therefore, after the polarity reversal, the first electrode 10a acts as a cathode and the second electrode 10b acts as an anode. Therefore, it is possible to continuously perform the same treatment as the treatment represented by the chemical formulas (1) to (3) while stripping off the passive state. In addition, since the size of the passive state that peels off is approximately 0.5 mm, by separating the electrode plates by at least 0.5 mm or more, the passive state that has fallen off between the electrodes clogs the space, and current does not flow in the clogged portion. , it is possible to reduce the possibility that the electrolysis shown by the chemical formulas (1) to (3) cannot be performed. Furthermore, it is desirable that the plates are arranged parallel to the direction of water flow in the electrolytic cell in order to facilitate the stripping of the passivation. In addition, the concentration of the iron ions 11c eluted from the first electrode 10a or the second electrode 10b is set to form a chelate complex with the humic substances 11b in the water 21 to be treated and to obtain a sufficient amount of iron hydroxide. It is desirable to make it twice or more the density|concentration of the humic substance 11b.
　ここで図４を参照して、鉄イオンの溶出濃度とフミン質の除去効率の関係について詳細に説明する。図４は、本開示に係る実施の形態１の水処理装置１でフミン質１１ｂの濃度１００ｍｇ／Ｌの被処理水２１中のフミン質を除去し、処理後水２２の色度を測定した結果である。鉄の溶出濃度を１０ｍｇ／Ｌ～３００ｍｇ／Ｌで変化させた場合、フミン質の濃度１００ｍｇ／Ｌの２倍以上となる鉄イオン濃度２００ｍｇ／Ｌ以上でフミン質濃度の指標である色度２．５ＴＣＵと十分下がった処理後水２２を得ることができる。 Here, with reference to FIG. 4, the relationship between the elution concentration of iron ions and the removal efficiency of humic substances will be described in detail. FIG. 4 shows the result of removing humic substances from water 21 to be treated with a concentration of 100 mg/L of humic substances 11b in water treatment apparatus 1 of Embodiment 1 according to the present disclosure, and measuring the chromaticity of treated water 22. is. When the elution concentration of iron is changed from 10 mg/L to 300 mg/L, the chromaticity, which is an indicator of the concentration of humic substances, at an iron ion concentration of 200 mg/L or more, which is more than twice the concentration of humic substances of 100 mg/L. 5 TCU and sufficiently lowered post-treatment water 22 can be obtained.
　鉄の溶出濃度が低い場合（図４での１０ｍｇ／Ｌ～１５０ｍｇ／Ｌ）、生じた鉄イオン１１ｃは、第二生成物１１ｇの生成によって消費されてしまい、第一生成物１１ｆにフミン質１１ｂが取り込まれづらくなる。或いは、第一生成物１１ｆ及び第二生成物１１ｇは生成するものの、少量であるため、フロック１１ｈの形成反応が生じづらくなる。そのため、フミン質１１ｂ或いは第一生成物１１ｆ或いは第二生成物１１ｇにより、被処理水２１の色度が上昇する。一方、鉄の溶出濃度をフミン質１１ｂの濃度の２倍以上とした場合（図４での２００ｍｇ／Ｌ～３００ｍｇ／Ｌ）には、鉄イオン１１ｃは、第二生成物１１ｇだけでなく、第一生成物１１ｆの生成にも十分に供される。したがって、水中に第一生成物１１ｆ及び第二生成物１１ｇが十分に存在し、フロック１１ｈの形成反応が発生しやすくなる。したがって、被処理水２１の色度を低減することができる。 When the elution concentration of iron is low (10 mg/L to 150 mg/L in FIG. 4), the generated iron ions 11c are consumed by the formation of the second product 11g, and the first product 11f becomes the humic substance 11b. becomes difficult to capture. Alternatively, although the first product 11f and the second product 11g are produced, they are in small amounts, so that the formation reaction of the flocs 11h is difficult to occur. Therefore, the chromaticity of the water to be treated 21 is increased by the humic substance 11b or the first product 11f or the second product 11g. On the other hand, when the elution concentration of iron is more than twice the concentration of humic substances 11b (200 mg/L to 300 mg/L in FIG. 4), iron ions 11c are not only the second product 11g, but also the second product 11g. It is also fully available for the production of one product 11f. Therefore, the first product 11f and the second product 11g are sufficiently present in the water, and the formation reaction of the flocs 11h easily occurs. Therefore, the chromaticity of the water to be treated 21 can be reduced.
　一方で、鉄の溶出濃度を過剰に大きくすると、過剰な水酸化鉄を生成することになるため、フミン質１１ｂが取り込まれるよりも過剰に鉄イオン１１ｃを溶出させるのは好ましくない。 On the other hand, if the iron elution concentration is excessively increased, excessive iron hydroxide will be generated, so it is not preferable to elute iron ions 11c in excess of the humic substance 11b being taken in.
　したがって、第一電極１０ａ或いは第二電極１０ｂから溶出させる鉄イオン１１ｃの濃度は、被処理水２１中のフミン質１１ｂとキレート錯体を形成し、また十分な量の水酸化鉄を得られる量とすればよく、水処理装置１では、フミン質１１ｂの濃度の２倍以上となるように電流を印加した。なお、ここでフミン質１１ｂの濃度の２倍と設定した第一電極１０ａ或いは第二電極１０ｂから溶出させる鉄イオン１１ｃの濃度は、フミン質１１ｂと反応する鉄イオン１１ｃ及び水酸化物イオン１１ｄと反応する鉄イオン１１ｃを含む濃度である。 Therefore, the concentration of the iron ions 11c eluted from the first electrode 10a or the second electrode 10b should be such that it forms a chelate complex with the humic substances 11b in the water 21 to be treated and a sufficient amount of iron hydroxide is obtained. In the water treatment device 1, the current was applied so that the concentration of the humic substances 11b was at least twice that of the humic substances 11b. Note that the concentration of the iron ions 11c eluted from the first electrode 10a or the second electrode 10b, which is set to be twice the concentration of the humic substance 11b, is the same as the iron ions 11c and the hydroxide ions 11d that react with the humic substance 11b. This is the concentration containing the reacting iron ions 11c.
　以上のように、水処理装置１では、上述した電解槽４により、浄化処理を行うことでフミン質を除去し、被処理水２１の浄化を行うことができる。 As described above, in the water treatment apparatus 1 , the water 21 to be treated can be purified by removing humic substances by performing purification treatment with the above-described electrolytic cell 4 .
　以上、本実施の形態１に係る水処理装置１によれば、以下の効果を享受することができる。 As described above, according to the water treatment device 1 according to Embodiment 1, the following effects can be enjoyed.
　（１）水処理装置１は、フミン質１１ｂを含む被処理水２１が流入する電解槽４と、電解槽４内において被処理水２１に浸漬する第一電極１０ａ及び第二電極１０ｂと、第一電極１０ａと第二電極１０ｂとの間に電流を印加する電源５と、を備え、第一電極１０ａ及び第二電極１０ｂの少なくとも一方は、電源５から電流を印加することで鉄イオンが溶出する材料で構成され、第一電極１０ａ及び第二電極１０ｂは、電源５から電流を印加した際に、陽極側においてフミン質１１ｂと鉄イオン１１ｃとの反応により形成される第一生成物１１ｆと、陰極側において水酸化物イオン１１ｄと鉄イオン１１ｃとの反応により形成される第二生成物１１ｇとが凝集してフロック１１ｈを形成するように配置されている。 (1) The water treatment apparatus 1 includes an electrolytic bath 4 into which water to be treated 21 containing humic substances 11b flows, a first electrode 10a and a second electrode 10b immersed in the water to be treated 21 in the A power supply 5 that applies a current between the one electrode 10a and the second electrode 10b, and at least one of the first electrode 10a and the second electrode 10b is applied with a current from the power supply 5, whereby iron ions are eluted. The first electrode 10a and the second electrode 10b are formed by the reaction between the humic substances 11b and the iron ions 11c on the anode side when a current is applied from the power supply 5, and the first product 11f and the , the second product 11g formed by the reaction between the hydroxide ions 11d and the iron ions 11c on the cathode side aggregates to form flocs 11h.
　こうした構成によれば、水処理装置１に電流を印加することにより、第一生成物１１ｆ及び第二生成物１１ｇを形成させることができ、第一生成物１１ｆと第二生成物１１ｇとが凝集することにより、フミン質１１ｂを取り込んだフロック１１ｈを形成することができる。したがって、サイズの小さなフミン質１１ｂをフロック１１ｈとして沈殿させることができ、被処理水２１からフミン質１１ｂを効率的に除去することが可能となる。 According to such a configuration, by applying an electric current to the water treatment device 1, the first product 11f and the second product 11g can be formed, and the first product 11f and the second product 11g aggregate. By doing so, flocs 11h incorporating humic substances 11b can be formed. Therefore, the humic substances 11b having a small size can be precipitated as flocs 11h, and the humic substances 11b can be efficiently removed from the water 21 to be treated.
　（２）水処理装置１は、第一電極１０ａと第二電極１０ｂとの間の距離は、０．５ｍｍ以上となるように構成されている。 (2) The water treatment device 1 is configured such that the distance between the first electrode 10a and the second electrode 10b is 0.5 mm or more.
　このような構成とすることにより、電極から剥がれ落ちる不働態が電極間に詰まることを低減できる。したがって、不働態が詰まった部分に電流が流れなくなることにより、第一生成物１１ｆと第二生成物１１ｇの生成、及びフロック１１ｈの形成が、阻害される可能性を低減できる。 With such a configuration, it is possible to reduce the clogging between the electrodes of the passive state peeled off from the electrodes. Therefore, it is possible to reduce the possibility that the generation of the first product 11f and the second product 11g and the formation of the flocs 11h will be inhibited by the current not flowing through the passivated portion.
　（３）水処理装置１は、電源５により、被処理水２１に含まれるフミン質１１ｂの濃度に対して、第一電極１０ａ及び第二電極１０ｂの少なくとも一方から溶出する鉄イオン１１ｃの濃度が２倍以上となるように電流を印加される。 (3) The water treatment apparatus 1 uses the power source 5 to increase the concentration of the iron ions 11c eluted from at least one of the first electrode 10a and the second electrode 10b with respect to the concentration of the humic substances 11b contained in the water to be treated 21. A current is applied so as to double or more.
　このような構成とすることで、第一生成物１１ｆの生成及び第二生成物１１ｇの生成に十分な鉄イオン１１ｃが溶出する。したがって、第一生成物１１ｆ及び第二生成物１１ｇの凝集物であるフロック１１ｈを効率的に形成でき、被処理水２１中のフミン質１１ｂを効率よく除去することが可能となる。 With such a configuration, enough iron ions 11c to generate the first product 11f and the second product 11g are eluted. Therefore, flocs 11h, which are aggregates of the first product 11f and the second product 11g, can be efficiently formed, and the humic substances 11b in the water 21 to be treated can be efficiently removed.
　（４）水処理装置１は、第一電極１０ａ及び第二電極１０ｂが、いずれも電源５から電流を印加することで鉄イオン１１ｃが溶出する材料で構成され、電流を印加した際に、第一電極１０ａと第二電極１０ｂとの間で極性を反転させる。 (4) In the water treatment device 1, the first electrode 10a and the second electrode 10b are both made of a material from which iron ions 11c are eluted by applying a current from the power supply 5, and when a current is applied, the first electrode 10a and the second electrode 10b The polarity is reversed between the one electrode 10a and the second electrode 10b.
　このような構成とすることで、不働態が蓄積して電流を十分に印加できなくなった電極表面から不働態を剥がし落とすことができる。したがって、不働態の蓄積を抑制でき、不働態により電流が流れなくなり、浄化処理効率が低減することを抑制可能となる。また、転極によって、陽極側と陰極側とを反転させることにより、鉄イオン１１ｃを放出する電極を入れ替えることができる。したがって、一方の電極のみが減っていくことを抑制できる。 With such a configuration, the passivity can be peeled off from the electrode surface where the passivity accumulates and the current cannot be applied sufficiently. Therefore, it is possible to suppress the accumulation of passivation, thereby suppressing the decrease in purification treatment efficiency due to the current not flowing due to the passivity. Further, by reversing the anode side and the cathode side by reversing the polarity, the electrodes that emit the iron ions 11c can be replaced. Therefore, it is possible to suppress the decrease of only one electrode.
　また、両極とも鉄イオン１１ｃを溶出する材料で構成されていることから、例えば転極によって陽極から陰極となった極付近では、転極前に溶出した鉄イオン１１ｃと、転極後に発生した水酸化物イオン１１ｄとの両方が比較的高濃度で存在している。また、転極によって陰極から陽極となった極付近では、転極前に発生した水酸化物イオン１１ｄと、転極後に溶出した鉄イオン１１ｃとの両方が比較的高濃度で存在している。したがって、転極を行うことにより、第二生成物１１ｇ及びフロック１１ｈの形成反応の発生頻度を上昇させることができる。 In addition, since both electrodes are made of a material that elutes iron ions 11c, for example, in the vicinity of the pole that has changed from the anode to the cathode due to pole reversal, the iron ions 11c eluted before pole reversal and the water generated after pole reversal Both oxide ions 11d are present in relatively high concentrations. Moreover, both the hydroxide ions 11d generated before the pole reversal and the iron ions 11c eluted after the pole reversal are present at relatively high concentrations near the pole where the cathode has become the anode due to the pole reversal. Therefore, by performing the polarity reversal, it is possible to increase the occurrence frequency of the formation reaction of the second product 11g and the floc 11h.
　（５）水処理装置１は、電解処理を行った被処理水２１からフロック１１ｈを除去する分離部６をさらに備える。 (5) The water treatment apparatus 1 further includes a separation unit 6 that removes the flocs 11h from the water 21 to be treated that has undergone the electrolytic treatment.
　このような構成とすることにより、処理後水２２に残留するフロック１１ｈをより確実に除去することができる。したがって、被処理水２１からのフミン質の除去効率を向上することができる。 With such a configuration, the flocs 11h remaining in the post-treatment water 22 can be removed more reliably. Therefore, the removal efficiency of humic substances from the water 21 to be treated can be improved.
　以上、本開示に関して実施の形態をもとに説明した。これらの実施の形態は例示であり、それらの各構成要素あるいは各処理プロセスの組み合わせにいろいろな変形例が可能なこと、またそうした変形例も本開示の範囲にあることは当業者に理解されているところである。 The present disclosure has been described above based on the embodiment. Those skilled in the art will understand that these embodiments are illustrative, and that various modifications can be made to combinations of each component or each treatment process, and such modifications are also within the scope of the present disclosure. I am where I am.
　本実施の形態１に係る水処理装置１において、例えば、電解槽４や送水管８の内部に攪拌機或いはバブリング等の攪拌機構を設けていても良い。これにより、陽極から溶出する鉄イオンと陰極から発生する水酸化物イオンとの反応の発生頻度、及び、主に陽極付近で生成する第一生成物１１ｆと主に極間で生成する第二生成物１１ｇとがフロック１１ｈを形成する反応の発生頻度が向上する。したがって、フロック１１ｈの形成及び成長をより早く安定に実現することができ、被処理水２１の浄化処理を速やかに行うことが可能となる。 In the water treatment device 1 according to Embodiment 1, for example, a stirring mechanism such as a stirrer or bubbling may be provided inside the electrolytic bath 4 or the water pipe 8 . As a result, the frequency of the reaction between the iron ions eluted from the anode and the hydroxide ions generated from the cathode, and the first product 11f mainly generated near the anode and the second product 11f mainly generated between the electrodes The occurrence frequency of the reaction that forms the floc 11h with the substance 11g is improved. Therefore, the flocs 11h can be formed and grown more quickly and stably, and the water 21 to be treated can be quickly purified.
　また、本実施の形態１に係る水処理装置１では、分離部６ではＭＦ膜ろ過を行うように構成したが、これに限られない。例えば、分離部６では、ＭＦ膜ろ過以外にも、粒状のろ材を用いたろ過を用いることができる。粒状のろ材としては、例えば、砂、アンスラサイト、ガーネット、セラミックス、活性炭、オキシ水酸化鉄、マンガン砂など、水中で沈降し、圧力で変形しにくい硬度をもつものであればよく、これらの材料を上下方向に積層したものを用いてもよい。 Also, in the water treatment device 1 according to Embodiment 1, the separation unit 6 is configured to perform MF membrane filtration, but the present invention is not limited to this. For example, in the separation unit 6, filtration using granular filter media can be used in addition to MF membrane filtration. Granular filter media include, for example, sand, anthracite, garnet, ceramics, activated carbon, iron oxyhydroxide, manganese sand, etc., as long as they settle in water and have a hardness that makes them difficult to deform under pressure. may be used by stacking in the vertical direction.
　また、本実施の形態１に係る水処理装置１において、電解槽４での電気分解処理後に、高分子凝集剤や無機系凝集剤を追加で注入してもよい。このようにすることで、フロック１１ｈの成長をより早く安定に実現することができる。 Further, in the water treatment device 1 according to Embodiment 1, after the electrolysis treatment in the electrolytic bath 4, a polymer coagulant or an inorganic coagulant may be additionally injected. By doing so, the growth of the flocs 11h can be realized more quickly and stably.
　また、本実施の形態１に係る水処理装置１では、分離部６ではＭＦ膜ろ過を行うように構成したが、これに限られない。例えば、分離部６は、フロック１１ｈを沈殿させる沈殿池としても良い。これにより、電解処理後の被処理水２１が沈殿池に流入後、フロック１１ｈが沈殿池の底部に沈殿するまで待機した後に上澄み液を取り出すことで、フミン質１１ｂの濃度の十分低い処理後水２２を得ることができる。沈殿池とする場合において、フロックを沈殿させる時間をより確実に制御するためには、送水管８にバルブを設けて分離部６への電解処理後の被処理水２１の連続的な流入を阻止することで、沈殿池内の全てのフロック１１ｈが沈殿するために必要な沈殿時間を確保することができる。また、電解槽４が沈殿池の機能を兼ねていても良い。 Also, in the water treatment device 1 according to Embodiment 1, the separation unit 6 is configured to perform MF membrane filtration, but the present invention is not limited to this. For example, the separation section 6 may be a sedimentation tank for sedimenting the flocs 11h. As a result, after the water to be treated 21 after electrolysis flows into the sedimentation tank, the supernatant liquid is taken out after waiting until the flocs 11h settle at the bottom of the sedimentation tank, so that the treated water with a sufficiently low concentration of the humic substances 11b can be obtained. 22 can be obtained. In the case of a sedimentation tank, in order to more reliably control the floc sedimentation time, a valve is provided in the water pipe 8 to prevent continuous inflow of the water to be treated 21 after electrolytic treatment into the separation unit 6. By doing so, the sedimentation time necessary for all the flocs 11h in the sedimentation tank to sediment can be ensured. Further, the electrolytic bath 4 may also function as a sedimentation tank.
　また、本実施の形態１に係る水処理装置１では、第一電極１０ａ及び第二電極１０ｂの素材として、鉄を用いたが、これに限られない。例えば、電極の素材は鉄であることが望ましいが、鉄以外にも、フミン質１１ｂをキレートし、水酸化物化してキレート錯体と凝集するイオンを溶出する素材として、より安価なアルミを用いることもできる。 Also, in the water treatment device 1 according to Embodiment 1, iron is used as the material of the first electrode 10a and the second electrode 10b, but the material is not limited to this. For example, the material of the electrode is preferably iron, but aluminum, which is cheaper than iron, can be used as a material that chelates the humic substance 11b, hydroxides it, and elutes the ions that aggregate with the chelate complex. can also
　また、本実施の形態１に係る水処理装置１では、第一電極１０ａ及び第二電極１０ｂの素材として、両極ともに鉄を用いたが、これに限られない。例えば、陽極のみに鉄を用いるようにしてもよい。 Further, in the water treatment device 1 according to Embodiment 1, iron is used for both electrodes as the material for the first electrode 10a and the second electrode 10b, but the material is not limited to this. For example, iron may be used only for the anode.
　また、本実施の形態１に係る水処理装置１では、転極を制御する回路を電源５内に内蔵したが、これに限らない。転極の制御は、電極と電源５を接続する回路を手動で繋ぎ替えることで行っても良い。 Also, in the water treatment device 1 according to Embodiment 1, the circuit for controlling the polarity reversal is built in the power supply 5, but the present invention is not limited to this. The polarity reversal may be controlled by manually switching the circuit connecting the electrodes and the power supply 5 .
　また、本実施の形態１に係る水処理装置１では、被処理水２１が流入口２に取り込まれる流量と、被処理水２１が流入管７を流れる流量、被処理水２１が電解槽４に流入及び流出する流量、被処理水２１が送水管８を流れる流量、被処理水２１が分離部６に流入及び流出する流量、被処理水２１が排出管９を流れる流量、及び処理後水２２が浄水排出口３から取り出される流量はそれぞれ同じである、つまり、被処理水２１は、水処理装置１内の各構成要素内をそれぞれ一定流量で流通しているとしたが、これに限られない。例えば、電解槽４に被処理水２１を一定量貯留し、貯留した被処理水２１の電気分解を行い、送水管８に送水するようにしてもよい。これにより、フロック１１ｈの一部が電解槽４内に沈殿するため、分離部６に送出されるフロック１１ｈの量が減少する。したがって、分離部６のメンテンナンス頻度（例えば、ＭＦ膜の交換頻度）を低減することができる。 Further, in the water treatment apparatus 1 according to Embodiment 1, the flow rate of the water to be treated 21 taken into the inflow port 2, the flow rate of the water to be treated 21 flowing through the inflow pipe 7, and the water to be treated 21 entering the electrolytic cell 4 Flow rate of inflow and outflow, flow rate of water to be treated 21 flowing through water pipe 8, flow rate of water to be treated 21 flowing into and out of separation unit 6, flow rate of water to be treated 21 flowing through discharge pipe 9, and treated water 22 is taken out from the purified water discharge port 3 at the same flow rate, that is, the water to be treated 21 flows through each component in the water treatment apparatus 1 at a constant flow rate. do not have. For example, a certain amount of water to be treated 21 may be stored in the electrolytic cell 4 , the stored water to be treated 21 may be electrolyzed, and the electrolyzed water may be sent to the water pipe 8 . As a result, part of the flocs 11h are precipitated in the electrolytic bath 4, so that the amount of the flocs 11h delivered to the separation section 6 is reduced. Therefore, the maintenance frequency of the separation unit 6 (for example, the frequency of replacement of the MF membrane) can be reduced.
　本開示に係る水処理装置は、フミン質を含んだ水源の水からフミンを除去し、色度を低減した生活用水を得る上で有用である。 The water treatment apparatus according to the present disclosure is useful for removing humins from water containing humic substances and obtaining domestic water with reduced chromaticity.
　１　　水処理装置
　２　　流入口
　３　　浄水排出口
　４　　電解槽
　５　　電源
　６　　分離部
　７　　流入管
　８　　送水管
　９　　排出管
　１０ａ　　第一電極
　１０ｂ　　第二電極
　１１ａ　　水分子
　１１ｂ　　フミン質
　１１ｃ　　鉄イオン
　１１ｄ　　水酸化物イオン
　１１ｅ　　水素
　１１ｆ　　第一生成物
　１１ｇ　　第二生成物
　１１ｈ　　フロック
　２１　　被処理水
　２２　　処理後水 1 Water Treatment Device 2 Inlet 3 Clean Water Outlet 4 Electrolyzer 5 Power Source 6 Separation Unit 7 Inflow Pipe 8 Water Pipe 9 Discharge Pipe 10a First Electrode 10b Second Electrode 11a Water Molecule 11b Humic Substance 11c Iron Ion 11d Hydroxide Ion 11e hydrogen 11f first product 11g second product 11h floc 21 water to be treated 22 water after treatment

Claims (5)

  1. 　フミン質を含む被処理水が流入する電解槽と、
    　前記電解槽内において前記被処理水に浸漬する第一電極及び第二電極と、
    　前記第一電極と前記第二電極との間に電流を印加する電源と、を備え、
    　前記第一電極及び前記第二電極の少なくとも一方は、前記電源から電流を印加することで鉄イオンが溶出する材料で構成され、
    　前記第一電極及び前記第二電極は、前記電源から電流を印加した際に、陽極側において前記フミン質と前記鉄イオンとの反応により形成される第一生成物と、陰極側において水酸化物イオンと前記鉄イオンとの反応により形成される第二生成物とが凝集してフロックを形成するように配置されている、
    　水処理装置。     an electrolytic cell into which water to be treated containing humic substances flows;
    a first electrode and a second electrode that are immersed in the water to be treated in the electrolytic bath;
    a power supply that applies a current between the first electrode and the second electrode,
    At least one of the first electrode and the second electrode is made of a material from which iron ions are eluted by applying a current from the power supply,
    When a current is applied from the power source, the first electrode and the second electrode are connected to the first product formed by the reaction between the humic substance and the iron ion on the anode side, and the hydroxide on the cathode side. arranged such that the ions and a second product formed by the reaction of the iron ions aggregate to form flocs;
    Water treatment equipment.
  2. 　前記第一電極と前記第二電極との間の距離は、０．５ｍｍ以上である、
    　請求項１に記載の水処理装置。     The distance between the first electrode and the second electrode is 0.5 mm or more,
    The water treatment device according to claim 1.
  3. 　前記電源は、前記被処理水に含まれる前記フミン質の濃度に対して、前記第一電極及び前記第二電極の前記少なくとも一方から溶出する前記鉄イオンの濃度が２倍以上となるように電流を印加する、
    　請求項１または２に記載の水処理装置。     The power source supplies current so that the concentration of the iron ions eluted from at least one of the first electrode and the second electrode is at least twice the concentration of the humic substances contained in the water to be treated. to apply
    The water treatment device according to claim 1 or 2.
  4. 　前記第一電極及び前記第二電極は、いずれも前記電源から電流を印加することで鉄イオンが溶出する材料で構成され、電流を印加した際に、前記第一電極と前記第二電極との間で極性を反転させる、
    　請求項１～３のいずれか一項に記載の水処理装置。     Both the first electrode and the second electrode are made of a material from which iron ions are eluted by applying a current from the power supply, and when the current is applied, the first electrode and the second electrode are separated. to reverse the polarity between
    A water treatment device according to any one of claims 1 to 3.
  5. 　前記被処理水から前記フロックを除去する分離部をさらに備える、
    　請求項１～４のいずれか一項に記載の水処理装置。     Further comprising a separation unit that removes the flocs from the water to be treated,
    The water treatment device according to any one of claims 1-4.
PCT/JP2022/028980 2021-09-30 2022-07-27 Water treatment device WO2023053701A1 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5817883A (en) * 1981-07-23 1983-02-02 Ebara Infilco Co Ltd Treating method of water containing chromaticity component
JPS59375A (en) * 1982-06-25 1984-01-05 Hitachi Plant Eng & Constr Co Ltd Treatment of water containing difficultly biodegradative substance
JPH09299957A (en) * 1996-05-16 1997-11-25 Matsushita Electric Ind Co Ltd Water cleaning device
JP2002346581A (en) * 2001-05-28 2002-12-03 Yoshikimi Watanabe Treatment apparatus and treatment method for organic wastewater
US20060000784A1 (en) * 2004-06-30 2006-01-05 Khudenko Boris M Water treatment
US20060249465A1 (en) * 2003-09-15 2006-11-09 Yan Jin Removal of microorganisms and disinfection byproduct precursors using elemental iron or aluminum
JP2013198830A (en) * 2012-03-23 2013-10-03 Panasonic Corp Recovering and removing method and recovering and removing apparatus for object to be removed in wastewater

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5817883A (en) * 1981-07-23 1983-02-02 Ebara Infilco Co Ltd Treating method of water containing chromaticity component
JPS59375A (en) * 1982-06-25 1984-01-05 Hitachi Plant Eng & Constr Co Ltd Treatment of water containing difficultly biodegradative substance
JPH09299957A (en) * 1996-05-16 1997-11-25 Matsushita Electric Ind Co Ltd Water cleaning device
JP2002346581A (en) * 2001-05-28 2002-12-03 Yoshikimi Watanabe Treatment apparatus and treatment method for organic wastewater
US20060249465A1 (en) * 2003-09-15 2006-11-09 Yan Jin Removal of microorganisms and disinfection byproduct precursors using elemental iron or aluminum
US20060000784A1 (en) * 2004-06-30 2006-01-05 Khudenko Boris M Water treatment
JP2013198830A (en) * 2012-03-23 2013-10-03 Panasonic Corp Recovering and removing method and recovering and removing apparatus for object to be removed in wastewater

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