JP2006334471A - Water treatment device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water treatment device for efficiently purifying oil and fat-containing water to be treated. <P>SOLUTION: The water treatment device comprises a water to be treated supply port for supplying the water to be treated containing at least oil and fat, a water channel for retaining purification material containing at least ruthenium, and passing the water to be treated supplied from the water to be treated supply port while bringing it into contact with the purification material, and an oxidizing water supply means for supplying oxidizing water to the purification material retained in the water channel to bring the oxidizing water into contact with the purification material. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a water treatment apparatus for oxidatively decomposing and removing organic matter from water to be treated (raw water) containing at least oils and fats.

  A large amount of fats and oils is discharged from the factory cafeteria, various restaurants and general households, especially stores such as yakiniku restaurants and cake shops that use a lot of oils and fats, into the sewage. The discharged oil and fat adheres to the inside of the drain pipe and is slimmed, which causes a reduction in the cross-sectional area of the flowing water and a cause of the pipe clogging. In addition, the discharged fats and oils cannot be sufficiently removed by sewage treatment, which is a major cause of the water quality environment in the surrounding rivers and nearby seas.

  In order to avoid such problems, it is obliged for business to install a grease trap so as not to flow a large amount of oil and fat, and to provide the oil and fat collected in the tank of the grease trap to appropriate disposal as industrial waste. . The business owner bears a lot of expenses for such oil separation and maintenance and maintenance processing. In order to suppress this cost, the most common method of oxidative decomposition by microorganisms is not only to separate oils and fats but also to decompose and remove them.

In addition, oxidative decomposition by microorganisms has problems such as requiring a large reaction tank, taking a long time for the reaction, and many of the oxidatively decomposed microorganisms becoming sludge (microorganisms). It cannot be owned by small businesses such as urban restaurants, yakiniku restaurants and cake shops. On the other hand, methods for chemically oxidizing and decomposing organic substances in treated water have been studied. For example, in order to remove organic substances in the treated water, chemical oxidative decomposition treatment using an oxidizing agent and a catalyst has been proposed (for example, Patent Documents 1 and 2).
Japanese Patent Laid-Open No. 9-201590 JP-A-9-253696

  However, the techniques proposed in Patent Document 1 still have the following problems (1) to (3). (1) Since a high temperature of 100 ° C. or higher, more preferably 150 to 370 ° C. is required, a large amount of energy is required, and the reaction vessel is corroded and deteriorated. (2) In order to maintain the liquid phase at the above-mentioned high temperature, it is necessary to carry out the reaction at a higher pressure, which increases the equipment cost including the reaction vessel and piping. (3) Since the reaction is performed under intense conditions of high temperature and high pressure, the catalyst is easily contaminated and deteriorated.

  Moreover, the technique described in Patent Document 2 divides the reaction into two steps, and the heating conditions using the catalyst are 50 to 150 ° C., which is a lower temperature, so that the influence of catalyst contamination and deterioration can be reduced. . However, the following problems occur: (i); In the first step, which is non-catalyst, a high temperature of 100 to 250 ° C., enormous energy is required. (Ii); In order to maintain the liquid phase at the above temperature, a high pressure resistant container is required. (Iii); Since it is in a temperature range where the reactivity of the organic substance is very high, the compound produced by the decomposition again undergoes polymerization and the like, tar is generated, and the container is contaminated.

  Accordingly, an object of the present invention is to provide an apparatus for oxidatively decomposing and removing oils and fats from treated water at a low temperature, with a simple operation, and efficiently.

The water treatment apparatus according to the present invention is
A treated water supply port for supplying treated water containing at least oil and fat;
Holding a purification material containing at least ruthenium, and a water passage for passing the treated water supplied from the treated water supply port while contacting the purified material;
Oxidized water supply means for supplying oxidized water to the purification material held in the water passage and bringing the oxidized water into contact with the purification material;
It is characterized by comprising.

  Here, “oxidized water” in the present invention is water containing an oxidizing substance, and examples of the “oxidizing substance” include OH radical, ozone, peroxydisulfate ion, hydrogen peroxide, permanganate ion. , Chlorine, nitric acid ion, oxygen, chlorine dioxide, halogen acid, hypohalous acid, hypohalous acid ion, and the like. Examples of the halogen include chloride (Cl), bromide (Br), iodide (I), or any combination thereof.

  In addition, the term “oil” in the present invention refers to vegetable oils such as soybean oil, rapeseed oil, sesame oil, corn oil and palm oil, edible oils such as animal oils such as lard, beef tallow and fish oil, and lubricating oils, It includes synthetic oils and mineral oils such as silicon oils, diester oils and polyol ester oils used for machine oils and insulating oils.

The water treatment apparatus according to the present invention as described above preferably includes water flow control means for controlling a ratio of the water to be treated and the oxidized water in the water flow path.
The oxidized water supply means includes electrolyzed water generation means for generating electrolyzed water by electrolyzing water containing at least one of chlorine and a halogen salt, and supplies the electrolyzed water as the oxidized water. Is preferred.

Moreover, it is preferable that the water treatment apparatus according to the present invention includes a heating unit for heating the water to be treated in the water passage, and the temperature of the water to be treated in the vicinity of the purification material is 50 by the heating unit. It is preferable to heat to below.
Furthermore, it is preferable that the purification material includes a carrier made of a titanium compound or a carbide and has a ruthenium content of 1 to 5% by weight.

  In the water treatment apparatus according to the present invention, ruthenium as a purification material disposed in a water passage temporarily holds active oxygen on the surface by contacting with oxidized water. In this state, when the fats and oils in water come into contact with ruthenium, the fats and oils are oxidized and sufficiently reduced in molecular weight or gasified in spite of the water. Therefore, the water treatment apparatus according to the present invention has dramatically improved oxidative decomposability of fats and oils in water and can be decomposed and removed even at a low temperature near room temperature. It is possible to remove oils and fats in water at a relatively low economical cost.

Embodiment 1
Hereinafter, Embodiment 1 of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing the configuration of the water treatment apparatus according to Embodiment 1 of the present invention.
The water treatment apparatus 1 in FIG. 1 holds a purification material 12 and allows water to be treated 13 containing oils and fats to pass through while being in contact with the purification material, and then drains the water from the discharge port 14. 11 to be treated water inflow valve 15 for controlling the inflow of water 13 to be treated, oxidized water supply means 16 for supplying the oxidized water 17, and oxidized water supply valve 18 for controlling the supply of the oxidized water 17 to the purification material 12. , A purification material holder 19 that holds the purification material 12, and a partition plate 20 that constitutes a flow path of the water to be treated 13.

  Water treatment can be performed using the water treatment apparatus 1 as follows. First, with the treated water inflow valve 15 closed, the oxidized water supply valve 18 is opened to supply the oxidized water 17 to the purification material 12. In this state, when the oxidant in the oxidized water 17 and the ruthenium in the purification material 12 come into contact with each other for a predetermined time, active oxygen is generated on the ruthenium surface, and this surface is in a state where it is easy to oxidize fats and oils in water. . Thereafter, the treated water 13 is passed through the water passage 11 by closing the oxidized water supply valve 18 and releasing the treated water inflow valve 15.

  In the present embodiment, the partition plate 20 does not directly contact the water to be contacted 13 with the purification material 12, but purifies the oil and fat floating separately from the water to be treated 13 between the two partition plates. The material 20 is made to contact efficiently. Oils and fats floating between the two partition plates 20 are oxidized by coming into contact with the ruthenium of the purification material 12 to be reduced in molecular weight and further gasified to be removed from the water. Those that cannot be completely gasified are also reduced in molecular weight, improved in water solubility by oxidation, dissolved in water, and discharged from the outlet 14. Therefore, there is no blockage in the water distribution pipe, and further biodegradability is improved, so that decomposition at the sewage treatment plant is easy. In the opening / closing control of the oxidized water supply valve 18 and the treated water inflow valve 15, the above operation is periodically repeated for a predetermined period, and the concentration of the oxidized water 17 is increased around the purification material 12 to activate the surface of the purification material 12. The state is played back.

  When the water to be treated 13 is supplied while flowing the water to be treated 13, active oxygen on the ruthenium surface consumed by the oxidation is additionally supplied, which is particularly preferable for prolonging the oxidation reaction on the ruthenium surface. However, even in that case, since the oxidizing power gradually decreases due to the ruthenium surface becoming dirty, the concentration of oxidized water around the ruthenium can be increased by reducing the flow rate of the treated water 13 every predetermined period. preferable.

  In the present embodiment, the purifying material 12 is disposed between the two partition plates 20, but it is of course possible to dispose the purification material 12 at a location where the treated water 13 directly flows. In this case, since soluble organic substances other than fats and oils, such as starch, are also oxidized, it is preferable to cope by increasing the supply of oxidized water. Moreover, it is possible to increase the number of partition plates, increase the number of oil separations, and arrange the purification material 12 at a plurality of locations.

  Here, as described above, “oxidized water” in the present invention is water containing an oxidizing substance, and examples of the “oxidizing substance” include OH radical, ozone, peroxydisulfate ion, hydrogen peroxide. , Permanganate ions, chlorine, nicrate ions, oxygen, chlorine dioxide, halohalic acid, hypohalous acid, hypohalous acid ions, and the like. Examples of the halogen include chloride (Cl), bromide (Br), iodide (I), or any combination thereof, and chloride or bromide is preferred because of its strong oxidizing power. In particular, hypochlorous acid and hypochlorite ion are particularly preferable because they can be easily obtained as reagents and can be easily prepared by electrolysis of saline solution.

  Oxidized water 17 containing an oxidizing substance is prepared by, for example, dissolving ozone generated by an ozone generator in water, or separately storing hydrogen peroxide (diluted for ease of storage) or liquid chlorine. Oxidized water containing an oxidizing substance can be generated by adding to water. In addition, sodium chlorite, sodium hypochlorite, calcium hypochlorite (including highly bleached powder), potassium permanganate, potassium dichromate, etc. are added to water to ionize the ionic species as oxidizing substances Oxidized water may be generated. Furthermore, hydrochloric acid can be added to sodium chlorite to produce chlorine dioxide, and this chlorine dioxide can be mixed with water to produce oxidized water.

  The oxidation water supply means 16 may be any device that can supply the oxidation water 17 containing an oxidizing substance. The supply of the oxidized water 17 may be automatically performed according to the amount of the oxidized water in the housing unit, or the opening and closing of the oxidized water supply valve 18 may be automated using a timer, or may be performed manually. The oxidized water supply means 16 can be made of a material that is not attacked by oxidized water containing an oxidizing substance, such as a plastic container.

When producing the oxidized water 17 containing these oxidizing substances, except for using an ozone generator, it is prepared by diluting water containing an oxidizing substance at a high concentration. Some of the oxidizing substances as described above need to be handled as a first-class hazardous material, and these may be handled, for example, by a person who has a license for a hazardous material handler.
Further, the concentration of the oxidizing substance contained in the oxidized water is preferably 50 to 3000 ppm. If it is less than 50 ppm, the oxidizing power is insufficient, and if it exceeds 3000 ppm, the oxidizing power is sufficient, but the corrosion on the purifier retainer 19 and the like also increases, which is not preferable.

  The purification material 12 is configured by supporting ruthenium on the surface of the carrier. This carrier is a titanium carrier such as alumina, silica, silica-alumina or titania, a particulate carrier such as carbide such as zirconia or activated carbon, or a metal porous particulate carrier such as nickel, nickel-chromium, nickel-chromium-iron, etc. it can. However, with the oxidative decomposition of fats and oils, many organic acids are generated and become acidic. Therefore, it is particularly preferred to use a titanium compound or carbide support that is chemically stable even when it becomes strongly acidic.

The supported amount of ruthenium is usually about 0.05 to 25%, preferably 1 to 5% by weight of the carrier weight. This is because if the amount is less than 1% by weight, the oxidizing power is low, and if it exceeds 5% by weight, there is no significant difference in oxidizing power.
As the shape of the purification material 12, various forms such as a spherical shape, a pellet shape, a columnar shape, a fragmented shape, and a powder shape can be used. The size of the purification material 12 is about 1 to 50 mm so that it can be easily held. The filling amount of the catalyst 20 on the purification material holder 19 is filled to such an extent that the surface of the treated water 13 is immersed.

  Of course, the purification material 12 can also add a precious metal other than ruthenium and a base metal below the weight of ruthenium. Examples of the noble metal component include rhodium, palladium, osmium, iridium, platinum, and gold. Examples of the base metal component include iron, copper, cobalt, manganese, nickel, magnesium, and tungsten. If necessary, co-catalyst components such as tellurium, lanthanum, cerium, and selenium are used in combination to increase ruthenium oxidation activity, improve the heat resistance, durability, and mechanical strength of the catalyst body. Can do.

It is preferable that the water passage 11, the partition plate 20, and the purification material holder 19 are made of a material having sufficient durability against corrosion by acid due to oxidative decomposition of the oxidized water 17 and fats and oils. As such a constituent material, for example, the inner surface at least in contact with the oxidized water 17 is coated with a stainless steel such as SUS304 or SUS316, a heat resistant alloy such as Hastelloy or Inconel, or a fluororesin such as PTFE or PFA. It is preferable.
The purifying material holder 19 has holes that are smaller than the size of the purifying material 12 so as not to disturb the oil and fat that floats and separates from the water 13 to be treated, and does not fall. A quality shape can be adopted.

By heating the vicinity of the purification material 12, the oxidation reaction on the ruthenium surface can be accelerated. At this time, examples of the heating means (not shown) include an electric heating means using Joule heat, a combustion means using combustion heat such as gas or petroleum, a heat pump, and an induction heating means. When a contact heating means that heats by electric heating or the like is used as the heating means, such a heating means can be installed on the inner wall of the housing part, or the piping can be coiled like a throwing heater and directly into the water inside the housing part. It is preferable to arrange them in contact. By setting it as such a form, it becomes possible to improve heating efficiency.
The heating temperature is preferably 50 ° C. or less. This is because the higher the value, the faster the oxidation reaction, but the faster the decomposition rate of the oxidizing substance, and the lower the oxidation rate when the temperature exceeds 50 ° C.

Embodiment 2
FIG. 2 is a schematic cross-sectional view showing the configuration of the water treatment device 2 according to Embodiment 2 of the present invention. In FIG. 2, the same components as those in FIG.
The water treatment apparatus 2 of FIG. 2 includes electrolyzed water generating means 21 that electrolyzes water 22 containing an electrolyte to generate electrolyzed water that is anode electrolyzed water 23 and cathode electrolyzed water 24 instead of the oxidized water supply means 16. . The electrolyzed water generating means 21 is composed of an electrolyzer 25, a diaphragm 26 and a pair of electrodes 27, and only electrolyzes water 22 containing an electrolyte such as a halogen salt, so that the electrolyzed water generating means 21 is easily managed. It becomes. Therefore, the water treatment apparatus of the present embodiment can be used not only in industrial applications where a chemical substance management system can be realized, but also in places where management of chemical substances is difficult, such as general households and restaurants.

  Next, water treatment can be performed using the water treatment apparatus 2 in the same manner as in the first embodiment as follows. First, with the treated water inflow valve 15 closed, the oxidized water supply valve 18 is opened, and water 22 containing an electrolyte is introduced into the electrolytic bath 25 and energized between a pair of electrodes to generate electrolyzed water. To do. Anode electrolyzed water 22, which is electrolyzed water on the anode side, is supplied to the purification material 12. The remaining cathode electrolyzed water 24 is mixed with the water to be treated 13 after contacting the purification material 12 and partially functions as neutralization.

  In this state, when left for a predetermined time, an oxidizing agent such as hypochlorous acid in the anode electrolyzed water 23 and the ruthenium of the purification material 12 come into contact with each other, so that active oxygen is generated on the surface of ruthenium, and the oils and fats in the water are easily oxidized. It becomes a state. Thereafter, the treated water 13 is passed through the water passage 11 by closing the oxidized water supply valve 18 and releasing the treated water inflow valve 15. Also in this embodiment, the partition plate 20 does not directly apply the contacted water 13 to the purification material 12 but purifies the oil and fat floating separately from the water to be treated 13 between the two partition plates. The material 20 is made to contact efficiently.

  Oils and fats floating between the two partition plates 20 are oxidized by coming into contact with the ruthenium of the purification material 12 to be reduced in molecular weight and further gasified to be removed from the water. Those that cannot be completely gasified are also reduced in molecular weight, improved in water solubility by oxidation, dissolved in water, and discharged from the outlet 14. Therefore, there is no blockage in the water distribution pipe, and further biodegradability is improved, so that decomposition at the sewage treatment plant is easy.

  The anodic electrolyzed water 23 is particularly preferable for supplying the treated water 13 while flowing, so that active oxygen on the ruthenium surface consumed by the oxidation is additionally supplied, and the oxidation reaction on the ruthenium surface is prolonged. Furthermore, the mixing of the cathode electrolyzed water 24 is particularly preferable because the pH of the water to be treated 13 acidified by the decomposition of fats and oils is neutralized to the neutral side. However, even when electrolytic water is continuously supplied, the oxidizing power gradually decreases due to contamination of the ruthenium surface. Therefore, the flow rate of the water to be treated 13 is reduced by reducing the flow rate of the water to be treated 13 every predetermined period. It is preferable to increase the concentration of the electrolyzed water 23.

The electrolyzed water is generated by electrolyzing (hereinafter also referred to as “electrolysis”) water 22 containing an electrolyte, particularly water containing at least one halogen salt such as chlorine. Of these, the use of a halogen salt as the electrolyte is particularly preferable because it increases the amount of the oxidizing substance in the electrolytic water. When water in which the halogen salt is dissolved is electrolyzed, chlorine and hypohalous acid, which are oxidizing substances, are generated in the vicinity of the anode side according to the following formula (1).
2X ^- → X ₂ + 2e ^-
X ₂ + H ₂ O → HXO + HX
(X = F, Cl, Br) (1)

Halogen salts include chloride, bromide, or fluoride. Sodium chloride, potassium chloride, calcium chloride, sodium bromide, potassium bromide, and calcium bromide have a high degree of dissociation into ions and are easy to handle. It is particularly preferable because it is easy.
The electrolyzed water as described above already contains an oxidizing substance such as hypochlorous acid and hydrogen peroxide. For this reason, since it is not necessary to add an oxidizing substance as a chemical, it is easy to handle and is preferable to the water treatment apparatus 1 described above. Electrolyzed water can also be obtained by electrolyzing tap water with residual chlorine. In order to increase the amount of oxidizing substances, electrolyzed water containing the halogen salt as described above, It is preferable to produce.

Furthermore, in the present invention, the same applies to the first embodiment, but it is preferable that the effect of the oxidizing substance to oxidize the organic substance is as large as possible. Among these, when using hypochlorous acid or chlorous acid, protons dissociate into ions when the pH increases. For example, when hypochlorous acid (HClO), the pH is increased, ClO ^- ends up increasing, oxidizing power of the oxidizing water is reduced. Therefore, when using hypochlorous acid or chlorous acid as an oxidizing substance, the pH of the oxidized water is less than 8 so that they exist in an acid type (charge neutral) state instead of ions. Preferably there is. In the case of hypochlorous acid, the presence of the acid form is 90% or more, so it is particularly preferable that the pH of the oxidized water be 6.5 or less.

  As the electrolyzed water generating means 21, an electrolyzer comprising an electrolyzer 25 and two electrodes 27 (an anode and a cathode) disposed in the electrolyzer via a diaphragm 26 can be used. Since the anode and the cathode are separated by a diaphragm, the electrolyzed water on the anode side and the cathode side can be taken out separately as the anode electrolyzed water 23 and the cathode electrolyzed water 24, particularly the anode. The electrolyzed water 23 contains hypochlorous acid and the like and can be used as oxidized water having strong oxidizing power. In addition, what added alkaline alkaline electrolyzed water 24 to this acidic anodic electrolyzed water 23, adjusted pH, and was made into electrolyzed water can also be used as oxidized water.

  The electrode 27 used for the electrolysis is made of a material usually used for an electrolysis reaction, for example, a material whose surface has ruthenium, iridium, platinum, palladium, rhodium, tin, or an oxide or ferrite thereof. Things. The electrode itself may be made of ruthenium, iridium, platinum, palladium, rhodium, tin, oxides thereof, ferrite, or the like. Alternatively, the surface of the substrate of the electrode may be covered with ruthenium, iridium, platinum, palladium, rhodium, tin, oxides thereof, ferrite, or the like. Ruthenium, iridium, platinum, palladium, rhodium, or tin may be a simple metal or an oxide. Moreover, alloys of these metals are also preferably used. Examples of the alloy include a platinum-iridium alloy, a ruthenium-tin alloy, and a ruthenium-titanium alloy. The above metals are excellent in corrosion resistance and are suitable for use as an anode.

In particular, the anode for generating chlorine is required to have further insolubility, safety of electrolytic water quality, and durability during reverse voltage cleaning. As such an electrode, an electrode mainly composed of palladium, ruthenium, an alloy of platinum and iridium, or the like is preferable.
Since the cathode is not required to be particularly insoluble, a cathode made of nickel alloy such as stainless steel, carbon steel, titanium or titanium alloy, Hastelloy, or Inconel can be used.

The electrolysis is preferably carried out, for example, under conditions of a voltage of 5 to 50 V and a current of 0.5 to 600 A / m ² per electrode surface area. When the current density is higher than 600 A / m ² , the surface of the anode is peeled off or the anode itself is easily eluted. When the current density is smaller than 0.5 A / m ^2, it is necessary to increase the area of the anode, and it is difficult to reduce the size of the electrolyzed water generating means.

For the diaphragm 26, ceramic, resin, glass fiber, or the like can be used. For example, the diaphragm may be made hydrophilic by attaching a resin film having pores with a pore diameter of 0.2 to 200 μm to a nonwoven fabric such as polyester or glass fiber.
As the electrolytic cell 25, for example, a material made of a resin such as vinyl chloride resin, polypropylene, or polyethylene can be used. Moreover, a hard polyvinyl chloride pipe | tube etc. can be used for piping for supplying electrolyzed water.

  The electrolyzed water generating means 21 may be any device that can generate electrolyzed water containing the oxidizing substance. For example, as the electrolyzed water generating means 21, an electrolytic means comprising an electrolytic cell and an anode and a cathode arranged in the electrolytic cell without a diaphragm can be used. Since this apparatus does not have a diaphragm, the electrolyzed water generated near the anode and the electrolyzed water generated near the cathode are naturally mixed. Weakly acidic electrolyzed water obtained by the mixing can also be used as oxidized water.

  As described above, the electrolyzed water includes acidic anode water generated at the anode by electrolysis, alkaline cathode water generated at the cathode by electrolysis, anode water generated at the anode and cathode water generated at the cathode. There is weakly acidic electrolyzed water. By changing the diaphragm used in the above apparatus and the type of the electrolyzed liquid, acidic water, slightly acidic water, electrolytic hyponitrous acid, alkaline water, and the like can be formed.

  When water containing chlorine or chloride salt is electrolyzed, the electrolyzed water contains hypochlorous acid, hypochlorite ions, chlorine and the like. At this time, it is preferable that the effective chlorine concentration containing hypochlorous acid, hypochlorite ion, and chlorine contained in electrolyzed water is adjusted to 50 to 3000 ppm. When the effective chlorine concentration of electrolyzed water is less than 50 ppm, the oxidizing power is insufficient. When the effective chlorine concentration exceeds 3000 ppm, the oxidizing power is sufficient, but the portion in contact with the electrolyzed water such as the housing portion is corroded. The same applies to the following embodiments.

Embodiment 3
FIG. 3 is a schematic cross-sectional view showing the configuration of the water treatment device 3 according to Embodiment 3 of the present invention. In FIG. 3, the same components as those in FIGS. 1 and 2 are given the same reference numerals.
The water treatment apparatus 3 in FIG. 3 includes an anodic electrolyzed water 23 in the same place as the water to be treated 13 and the oxidation water supply valve 18 and the water to be treated inflow valve 15 in order to periodically activate the purification material 12. A water flow control means 30 for controlling the inflow of the anodic electrolyzed water 23 and the treated water 13 by performing release control is provided. In this case, since the anode electrolyzed water 23 is sufficiently mixed, the oil and fat is oxidized and decomposed by the purification material 12 more efficiently.

  Moreover, since the structure which lets the purification material 22 flow is taken, in order to promote the floating decomposition of fats and oils, the purification material 12 is arrange | positioned in two places. However, in order to avoid a reduction in oxidizing power due to the purification material 12, the inflow of the water to be treated 13 is periodically throttled by the water flow control means 30. Moreover, in this embodiment, since all the to-be-processed water 13 passes the purification | cleaning material 12, the organic substance disperse | distributed or solubilized in water other than fats and oils can also be removed by oxidative decomposition.

  Next, the water treatment can be performed using the water treatment apparatus 3 in the following manner basically in the same manner as in the first and second embodiments. First, the to-be-processed water inflow valve | bulb 15 is made into the state which narrowed down or the state closed completely. Next, the oxidized water supply valve 18 is opened, and water 22 containing an electrolyte is introduced into the electrolytic bath 25 and energized between a pair of electrodes to generate electrolyzed water. Anode electrolyzed water 22, which is electrolyzed water on the anode side, is supplied to the entrance of the water channel 11. The remaining cathode electrolyzed water 24 is mixed with the water to be treated 13 after contacting the purification material 12 and partially functions as neutralization. The supplied anode electrolyzed water 22 reaches the purification material 22 through the purification material holder 19 along the partition plate 20.

  In this state, when left for a predetermined time, an oxidizing agent such as hypochlorous acid in the anode electrolyzed water 23 and the ruthenium of the purification material 12 come into contact with each other, so that active oxygen is generated on the surface of ruthenium, and the oils and fats in the water are easily oxidized. It becomes a state. Thereafter, the treated water inflow valve 15 is released to allow the treated water 13 to pass through the water passage 11 and to contact the purification material 12 for purification treatment. In the present embodiment, it is preferable not to completely stop the supply of the anodic electrolyzed water 23 but to gradually supply the anode electrolyzed water 23 so as not to reduce the oxidizing power of the purification material 12.

  Oils and fats in water are oxidized by coming into contact with ruthenium in the purification material 12, and are reduced in molecular weight and further gasified to be removed from the water. Those that cannot be completely gasified are also reduced in molecular weight, improved in water solubility by oxidation, dissolved in water, and discharged from the outlet 14. Therefore, there is no blockage in the water distribution pipe, and further biodegradability is improved, so that decomposition at the sewage treatment plant is easy.

  The anodic electrolyzed water 23 is particularly preferable for supplying the treated water 13 while flowing, so that active oxygen on the ruthenium surface consumed by the oxidation is additionally supplied, and the oxidation reaction on the ruthenium surface is prolonged. Furthermore, the pH of the water 13 to be treated, which has been acidified by the decomposition of fats and oils, is neutralized to the neutral side by mixing the cathode electrolyzed water 24, which is particularly preferable. However, even when electrolytic water is continuously supplied, the oxidizing power gradually decreases due to contamination of the ruthenium surface. Therefore, the flow rate of the water to be treated 13 is reduced by reducing the flow rate of the water to be treated 13 every predetermined period. It is preferable to increase the concentration of the electrolyzed water 23.

Although the heating means has been described in the first embodiment, it can be added in the second and third embodiments as necessary.
The water treatment apparatus of the present invention can be used as an alternative to a conventional grease trap. In addition to the treatment of wastewater containing a large amount of oil and fat from restaurants, etc., not only when waste garbage and excreta are treated with microorganisms in the septic tank, but also when wastewater after treatment by sewerage treatment equipment is further purified. Useful.

In Embodiments 1 to 3, the number of partition plates is not limited, and the number of floatation separations of oil and fat can be further increased, and the purification material 12 can also be disposed at a plurality of locations.
Here, the Example of the water treatment apparatus of this invention is described below. The following examples are for explaining one embodiment of the present invention, and do not limit the present invention.

Example 1
Using the water treatment device 2 shown in FIG. 2, water treatment was performed on kitchen wastewater containing fats and oils. As kitchen wastewater containing fats and oils, soybean oil suspended in water was used as simulated kitchen wastewater.
As the water treatment device 2, a water treatment device made of stainless steel such as SUS316 and having a volume of about 5 L was used. Further, a punching metal made of SUS316 having an opening diameter of 2 mm was used for the purifying material holder 19. About 200 g of pellet-shaped purification material 12 having a particle diameter of about 5 mm and supporting 5 wt% ruthenium using alumina as a carrier was filled in the upper portion of the purification material holder 19.

  First, with the treated water inflow valve 15 closed, the oxidized water supply valve 18 is opened, and water 22 containing an electrolyte is introduced into the electrolytic bath 25 and energized between a pair of electrodes to generate electrolyzed water. To do. Electrolyzed water was 0.1% by weight saline and electrolyzed under the condition of about 20 V to produce anodic electrolyzed water 22 having a pH of 3 and an effective chlorine concentration of 1800 ppm. The anode electrolyzed water 22 is supplied to the purification material 12.

  When left in this state for 1 hour, an oxidizing agent such as hypochlorous acid in the anode electrolyzed water 23 and the ruthenium of the purification material 12 come into contact with each other, so that active oxygen is generated on the ruthenium surface, and the oils and fats in the water are easily oxidized. It becomes a state. Thereafter, the treated water 13 is passed through the water passage 11 by closing the oxidized water supply valve 18 and releasing the treated water inflow valve 15. In this example, suspended wastewater containing soybean oil prepared to TOC 250 ppm was passed as water to be treated at 10 L / min.

  Due to the partition plate 20, the water to be contacted 13 is not directly applied to the purification material 12, but the purification material 20 is efficiently used against the soybean oil that floats separately from the water to be treated 13 between the two partition plates. I was in contact. The soybean oil floating between the two partition plates 20 is oxidized by contacting with the ruthenium of the purification material 12 to be reduced in molecular weight and further gasified to be removed from the water. Those that cannot be completely gasified are also reduced in molecular weight, improved in water solubility by oxidation, dissolved in water, and discharged from the outlet 14. When the TOC of the water to be treated discharged from the drain port 14 was measured, it was about 10 ppm, and no turbidity of the liquid was observed.

  Therefore, there is no blockage in the water distribution pipe, and further biodegradability is improved, so that decomposition at the sewage treatment plant is easy. In addition, when the TOC was measured by sampling the water to be treated in the vicinity of the purification material, it was 50 ppm, which was a higher concentration than the drain outlet, but it was considerably reduced. Although it was operated for one month in this state, there was almost no accumulation of dirt oil or the like in the vicinity of the purification material and in the water treatment device 2, and there was no need for maintenance.

  As described above, according to this embodiment, by applying the water treatment device of the present invention to wastewater containing oil, the oil is oxidized and decomposed to purify the wastewater, and there is no oil accumulation and maintenance is performed. Easy wastewater treatment.

Example 2
Using the water treatment apparatus 1 shown in FIG. 1, water treatment was performed on kitchen wastewater containing fats and oils. As kitchen wastewater containing fats and oils, triolein, which is a neutral fat, was suspended and mixed in water and used as simulated kitchen wastewater.
The water treatment apparatus 1 used was made of stainless steel such as SUS316 and had a volume of about 5 L. Further, a punching metal made of SUS316 having an opening diameter of 2 mm was used for the purifying material holder 19. About 200 g of pellet-shaped purification material 12 having a particle diameter of about 5 mm and supporting 5 wt% ruthenium using alumina as a carrier was filled in the upper portion of the purification material holder 19.

  First, with the treated water inflow valve 15 closed, the oxidized water 17 was injected through the oxidized water supply valve 18. In this example, the purification material 12 was supplied using a hypochlorous acid aqueous solution having a pH of 5 and an effective chlorine concentration of 2000 ppm. When left in this state for 1 hour, the oxidant and hypochlorous acid of the oxidized water 17 and the ruthenium of the purification material 12 come into contact with each other, so that active oxygen is generated on the ruthenium surface, and the oils and fats in the water are easily oxidized. . Thereafter, the treated water 13 is passed through the water passage 11 by closing the oxidized water supply valve 18 and releasing the treated water inflow valve 15.

  In this example, suspended wastewater containing triolein prepared at TOC 200 ppm was treated at 10 L / min. Due to the partition plate 20, the water to be contacted 13 is not directly applied to the purification material 12, but the purification material 20 is efficiently used against the soybean oil that floats separately from the water to be treated 13 between the two partition plates. I was in contact. The soybean oil floating between the two partition plates 20 is oxidized by contacting with the ruthenium of the purification material 12 to be reduced in molecular weight and further gasified to be removed from the water. Those that cannot be completely gasified are also reduced in molecular weight, improved in water solubility by oxidation, dissolved in water, and discharged from the outlet 14. When the TOC of the water to be treated discharged from the drain port 14 was measured, it was about 32.4 ppm and almost no turbidity was observed in the liquid.

  Therefore, there is no blockage in the water distribution pipe, and further biodegradability is improved, so that decomposition at the sewage treatment plant is easy. Moreover, when the TOC was measured by sampling the water to be treated in the vicinity of the purification material, it was 75 ppm, which was higher than the drain outlet, but it was considerably reduced. Although it was operated for one month in this state, there was almost no accumulation of dirt oil or the like in the vicinity of the purification material and in the water treatment device 2, and there was no need for maintenance.

  As described above, according to this embodiment, by applying the water treatment device of the present invention to wastewater containing oil, the oil is oxidized and decomposed to purify the wastewater, and there is no oil accumulation and maintenance is performed. Easy wastewater treatment.

<< Examples 3 to 6 >>
Water treatment was performed in the same manner as in Example 1 except that the target drainage was changed as follows. In Example 3, a glucose aqueous solution prepared to 200 ppm, in Example 4, an alanine (amino acid) aqueous solution prepared to 200 ppm, in Example 5, a lactic acid aqueous solution prepared to 200 ppm, and in Example 6, a urea aqueous solution prepared to 200 ppm. The water treatment was performed on each of them.

  As shown in Table 1, it can be seen that even though substances other than oil cannot be expected to be as clean as oil, they are oxidatively decomposed and purified. For this reason, in the treatment of wastewater containing a mixture including oil, not only the oil but also components other than the oil are purified, so that there is no blockage in the water distribution pipe, and biodegradability is further improved. Disassembly at the sewage treatment plant is also easy.

Example 7
Using the water treatment device 3 shown in FIG. 3, water treatment was performed on kitchen wastewater containing fats and oils. As kitchen wastewater containing fats and oils, corn oil, which is a kind of salad oil, suspended and mixed in water was used as simulated kitchen wastewater.
As the water treatment device 3, one having a volume of about 5 L made of stainless steel such as SUS316 was used. Further, a punching metal made of SUS316 having an opening diameter of 2 mm was used for the purifying material holder 19. About 200 g of pellet-shaped purification material 12 having a particle diameter of about 5 mm and supporting 5 wt% ruthenium using alumina as a carrier was filled in the upper portion of the purification material holder 19. Further, in this example, the oxidation reaction on the ruthenium surface was accelerated by heating the vicinity of the purification material 12. The heating means (not shown) was disposed by bringing the throwing heater into direct contact with the water in the purifying material container.

  First, with the treated water inflow valve 15 closed, the oxidized water supply valve 18 is opened, and water 22 containing an electrolyte is introduced into the electrolytic bath 25 and energized between a pair of electrodes to generate electrolyzed water. To do. The electrolyzed water was 0.1% by weight saline, and the anode electrolyzed water 22 adjusted to pH 5 and effective chlorine concentration 2000 ppm was generated by controlling the water flow control means 30 and electrolysis. The anode electrolyzed water 22 is supplied to the purification material 12.

  In this state, it is allowed to stand at room temperature of about 25 ° C. for 1 hour. When the oxidant and hypochlorous acid of the oxidized water 17 and the ruthenium of the purification material 12 come into contact with each other, active oxygen is generated on the ruthenium surface, It becomes easy to oxidize. Thereafter, the treated water 13 is passed through the water passage 11 by closing the oxidized water supply valve 18 and releasing the treated water inflow valve 15. In this example, suspended wastewater containing corn oil prepared at TOC 200 ppm was treated as water to be treated at a rate of 10 L / min.

  The partition plate 20 does not directly apply the contacted water 13 to the purification material 12, but the purification material 20 is efficiently used for the corn oil that is separated and floated from the treated water 13 between the two partition plates. I was in contact. The corn oil floating between the two partition plates 20 is oxidized by coming into contact with the ruthenium of the purification material 12 to be reduced in molecular weight and further gasified to be removed from the water. Those that cannot be completely gasified are also reduced in molecular weight, improved in water solubility by oxidation, dissolved in water, and discharged from the outlet 14. When the TOC of the water to be treated discharged from the drain port 14 was measured, it was about 36 ppm, and almost no liquid turbidity was observed.

  Therefore, there is no blockage in the water distribution pipe, and further biodegradability is improved, so that decomposition at the sewage treatment plant is easy. Moreover, when the TOC was measured by sampling the water to be treated in the vicinity of the purification material, it was 30 ppm, which was a higher concentration than the drain outlet, but it was considerably reduced. Although it was operated for one month in this state, there was almost no accumulation of dirt oil or the like in the vicinity of the purification material and in the water treatment device 2, and there was no need for maintenance.

<< Examples 8 to 14 >>
Next, water treatment was performed in the same manner as in Example 7 except that the pH of the anode electrolyzed water 22 supplied to the purification material 12 and the temperature of the water containing the purification material were changed as follows. Example 8 is pH 2.5 at 25 ° C., Example 9 is pH 6.5 at 25 ° C., Example 10 is pH 8 at 25 ° C., Example 11 is pH 9 at 25 ° C., Example 12 is 40 The treatment was carried out at 5 ° C., pH 5 at Example 13, pH 5 at 50 ° C., and Example 14 at pH 5 at 60 ° C.
Next, the TOC of the waste water from the outlet in the water treatment of Examples 8 to 14 was measured. The results are shown in Table 2.

  As shown in Table 2, the pH is preferably less than 8. Furthermore, it is more preferable that the pH is 6 or less. This is because, when hypochlorous acid or chlorous acid is used as an oxidizing substance, the pH of the oxidized water is 8 so that they exist in an acid type (charge neutral) state instead of ions. This is because, in the case of hypochlorous acid, the presence of the acid form is 90% or more, and therefore the pH of the oxidized water is particularly preferably 6.5 or less.

  Regarding the temperature, the purification ability is high from around room temperature to 50 ° C., but the purification ability decreases at a temperature higher than 50 ° C. The heating temperature is preferably 50 ° C. or less. This is because the higher the value, the faster the oxidation reaction, but the faster the decomposition rate of the oxidizing substance, and the lower the oxidation rate when the temperature exceeds 50 ° C. Further, at a high temperature, steam is generated, odor becomes strong, energy is required, and therefore, it is preferably 50 ° C. or lower.

  As described above, by applying the water treatment device of the present invention to wastewater containing oil, the oil is oxidized and decomposed to purify the wastewater, and the wastewater treatment is easy without maintenance of oil accumulation. Can do.

  The water treatment apparatus of the present invention enables purification treatment of water containing fats and oils.

It is a schematic sectional drawing which shows the structure of the water treatment apparatus 1 which concerns on Embodiment 1 of this invention. It is a schematic sectional drawing which shows the structure of the water treatment apparatus 2 which concerns on Embodiment 2 of this invention. It is a schematic sectional drawing which shows the structure of the water treatment apparatus 3 which concerns on Embodiment 3 of this invention.

Explanation of symbols

1, 2, 3 Water treatment device 11 Water passage 12 Purifying material 13 Water to be treated 14 Drainage port 15 Water to be treated inflow valve 16 Oxidized water supply means 17 Oxidized water 18 Oxidized water supply valve 19 Purifying material holder 20 Partition plate 21 Electrolysis Water generating means 22 Water containing electrolyte 23 Anode electrolyzed water 24 Cathode electrolyzed water 25 Electrolyzer 26 Separator 27 Electrode 30 Water flow control means

Claims (5)

A treated water supply port for supplying treated water containing at least oil and fat;
Holding a purification material containing at least ruthenium, and a water passage for passing the treated water supplied from the treated water supply port while contacting the purified material;
Oxidized water supply means for supplying oxidized water to the purification material held in the water passage and bringing the oxidized water into contact with the purification material;
A water treatment apparatus comprising:   The water treatment device according to claim 1, further comprising a water flow control means for controlling a ratio of the treated water and the oxidized water in the water flow path.   The said oxidized water supply means is equipped with the electrolyzed water production | generation means which electrolyzes the water containing at least one of chlorine and a halogen salt, and produces | generates electrolyzed water, The said electrolyzed water is supplied as said oxidized water. The water treatment apparatus as described in.   The water treatment apparatus according to claim 1, further comprising a heating unit for heating the water to be treated in the water passage. 3. The water treatment apparatus according to claim 1, wherein the purification material includes a support made of a titanium compound or a carbide, and the content of ruthenium is 1 to 5 wt%.

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