WO2016199385A1 - Couche favorisant l'agrégation d'une matière métallique, et dispositif de traitement de l'eau l'utilisant - Google Patents

Couche favorisant l'agrégation d'une matière métallique, et dispositif de traitement de l'eau l'utilisant Download PDF

Info

Publication number
WO2016199385A1
WO2016199385A1 PCT/JP2016/002695 JP2016002695W WO2016199385A1 WO 2016199385 A1 WO2016199385 A1 WO 2016199385A1 JP 2016002695 W JP2016002695 W JP 2016002695W WO 2016199385 A1 WO2016199385 A1 WO 2016199385A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
metal
treated
particles
iron
Prior art date
Application number
PCT/JP2016/002695
Other languages
English (en)
Japanese (ja)
Inventor
哲章 平山
真二郎 野間
廣田　達哉
太輔 五百崎
Original Assignee
パナソニックＩｐマネジメント株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by パナソニックＩｐマネジメント株式会社 filed Critical パナソニックＩｐマネジメント株式会社
Priority to JP2017523103A priority Critical patent/JP6519934B2/ja
Priority to CN201680040651.0A priority patent/CN107848848B/zh
Priority to KR1020177030282A priority patent/KR102027103B1/ko
Publication of WO2016199385A1 publication Critical patent/WO2016199385A1/fr

Links

Images

Classifications

    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone

Definitions

  • the present invention relates to a metal material aggregation promoting layer for purifying water to be treated, and a water treatment apparatus using the same.
  • Patent Document 1 The conventional water treatment apparatus as disclosed in Patent Document 1 is generally assumed to be used in an area where it is assumed that water purification is performed in a public water treatment facility.
  • An object of the present invention is to provide a metal material aggregation promoting layer capable of efficiently removing metal-related substances such as metal ions, metal particles, metal oxide particles, and metal hydroxide particles, and It is to provide a used water treatment device.
  • the metal material aggregation promoting layer includes a base material and a porous carrier layer provided on the surface of the base material. Furthermore, the metal material aggregation promoting layer is supported on the porous carrier layer and includes at least one trivalent iron ion compound selected from the group consisting of Fe 2 O 3 , Fe 3 O 4 , Fe (OH) 3 and FeOOH. Has adsorbed particles.
  • treated water containing at least one metal-related substance selected from the group consisting of metal ions, metal particles, metal oxide particles, and metal hydroxide particles flows. It has a to-be-treated water flow path and an oxidant supply unit for supplying an oxidant to the to-be-treated water. Further, the water treatment apparatus has the metal material aggregation promoting layer according to the first aspect, and adsorbs the metal-related substance contained in the water to be treated to the adsorbed particles by the action of the oxidizing agent, thereby aggregating the metal-related substance. It has an aggregation promoting part to promote.
  • FIG. 1 is a mimetic diagram for explaining the whole water treatment equipment composition concerning an embodiment of the present invention.
  • FIG. 2 is a conceptual diagram for explaining the principle of water treatment in the water treatment apparatus according to the embodiment of the present invention.
  • FIG. 3 is a cross-sectional view for explaining the structure of the metal material aggregation promoting layer according to the embodiment of the present invention.
  • FIG. 4 shows that in the aggregation promoting part of the water treatment apparatus according to the embodiment of the present invention, trivalent iron ions are converted into iron oxide or iron hydroxide supported on the porous carrier by the oxidizing action of the oxidizing agent. It is a schematic diagram for demonstrating being adsorbed.
  • FIG. 5 is a mimetic diagram for explaining the whole water treatment apparatus composition of other examples concerning the embodiment of the present invention.
  • FIG. 6 is a schematic diagram for explaining the overall structure of the water treatment apparatus according to Embodiment 1 of the present invention.
  • FIG. 7 is a cross-sectional view for explaining the structures of the oxidant supply unit and the mixing unit of the water treatment apparatus according to Embodiment 1 of the present invention.
  • FIG. 8 is a schematic diagram for explaining the overall structure of the water treatment apparatus according to Embodiment 2 of the present invention, and is a view showing that the water to be treated flows in the forward direction.
  • FIG. 6 is a schematic diagram for explaining the overall structure of the water treatment apparatus according to Embodiment 1 of the present invention.
  • FIG. 7 is a cross-sectional view for explaining the structures of the oxidant supply unit and the mixing unit of the water treatment apparatus according to Embodiment 1 of the present invention.
  • FIG. 8 is a schematic diagram for explaining the overall structure of the water treatment apparatus according
  • FIG. 9 is a schematic diagram for explaining the entire structure of the water treatment apparatus according to Embodiment 2 of the present invention, and is a diagram showing that the water to be treated flows in the reverse direction.
  • FIG. 10 is a schematic diagram for explaining the overall structure of a water treatment device according to Embodiment 3 of the present invention.
  • Drawing 11 is a mimetic diagram for explaining the whole water treatment device composition in an example.
  • FIG. 12 is a graph showing the relationship between the concentration of iron remaining in treated water and the concentration of chlorine introduced into treated water in Example 2.
  • FIG. 13 is a graph showing the relationship between the concentration of free chlorine remaining in the treated water and the concentration of chlorine added to the treated water in Example 2.
  • FIG. 12 is a graph showing the relationship between the concentration of iron remaining in treated water and the concentration of chlorine introduced into treated water in Example 2.
  • FIG. 13 is a graph showing the relationship between the concentration of free chlorine remaining in the treated water and the concentration of chlorine added to the treated water in Example 2.
  • Example 14 relates to Example 3 when the flow rate of the water to be treated is 0.2 L / min, 0.5 L / min, 0.75 L / min, 1 L / min, 1.5 L / min, 2 mL / min. It is a graph which shows the relationship between the density
  • the metal-related substance means one or more substances selected from the group consisting of metal ions M + , metal particles M, metal oxide particles MO, and metal hydroxide particles MOH.
  • the to-be-processed water W shall contain at least any one of the metal ion M ⁇ +> which is a metal related substance, the metal particle M, the metal oxide particle MO, and the metal hydroxide particle MOH.
  • metal ions M + , metal particles M, metal oxide particles MO, and metal hydroxide particles MOH, which are metal-related substances, are all supported on a porous carrier. Adsorbed to at least one of the object particles. Therefore, in this specification, metal oxide particles and metal hydroxide particles having a function of adsorbing metal-related substances are referred to as adsorption particles.
  • the water treatment apparatus 100 of the present embodiment includes treated water flow paths 11, 12, and 13 through which treated water W flows.
  • the mixing unit 1 is connected between the treated water channel 11 and the treated water channel 12.
  • the aggregation promoting unit 2 is connected between the treated water channel 12 and the treated water channel 13.
  • the mixing unit 1 is supplied with the oxidizing agent O from the oxidizing agent supply unit 4.
  • the treated water W that has flowed out from the aggregation promoting unit 2 to the treated water channel 13 is filtered by the filter unit 3 and reaches the faucet or the like as treated water via the supply channel 14.
  • the water to be treated W containing a metal-related substance flows into the mixing unit 1 from the water flow path 11 to be treated. That is, the water to be treated W including the metal ions M + , the metal particles M, the metal oxide particles MO, and the metal hydroxide particles MOH flows into the mixing unit 1 from the water to be treated flow path 11.
  • the metal ions M + are, for example, divalent iron ions (Fe 2+ ) and trivalent iron ions (Fe 3+ ).
  • the metal particles M are, for example, iron (Fe) particles.
  • the metal oxide particles MO are, for example, iron oxide (FeO, Fe 2 O 3 , Fe 3 O 4 ) particles.
  • the metal hydroxide particles MOH are particles of iron hydroxide (Fe (OH) 2 , Fe (OH) 3 , FeO (OH)).
  • the oxidant supply unit 4 supplies the oxidant O to the mixing unit 1.
  • the mixing unit 1 is configured to mix the water to be treated W flowing through the water channel 11 to be treated and the oxidant O supplied from the oxidant supply unit 4.
  • the treated water W flowing out from the mixing unit 1 flows into the aggregation promoting unit 2 via the treated water flow path 12.
  • the oxidizing agent O causes an oxidizing action on the metal-related substance in the water to be treated W.
  • the metal-related substance is a divalent iron ion, it has an action of oxidizing to a trivalent iron ion.
  • Such an oxidizing agent O preferably contains ozone or chlorine. Ozone and chlorine can be easily used because they can be easily added to the water to be treated W and efficiently oxidize metal-related substances.
  • a chlorine-based chemical is preferable, and one in which hypochlorous acid is generated inside the water to be treated W is particularly preferable.
  • the oxidizing agent O at least one selected from the group consisting of sodium hypochlorite, calcium hypochlorite and chlorinated isocyanuric acid can be used.
  • calcium hypochlorite at least one of bleached powder (effective chlorine 30%) and highly bleached powder (effective chlorine 70%) can be used.
  • the chlorinated isocyanuric acid at least one selected from the group consisting of sodium trichloroisocyanurate, potassium trichloroisocyanurate, sodium dichloroisocyanurate, and potassium dichloroisocyanurate can be used.
  • sodium hypochlorite is a liquid and can be particularly preferably used because it can be quantitatively added to the water to be treated W by using an injection method using a metering pump. Moreover, since the inorganic advanced bleaching powder has very high solubility in the water to be treated W, it can exhibit a high oxidizing action.
  • the aggregation promoting unit 2 includes a metal material aggregation promoting layer 200, and the metal material aggregation promoting layer 200 is treated water W to which an oxidant O is added via the treated water channel 12. Flows in.
  • the metal material aggregation promoting layer 200 includes a base material 201 and a porous carrier layer 202 provided inside the base material 201.
  • the base material 201 holds the porous carrier layer 202 so that the water W to be treated flowing from the water channel 12 to be treated permeates the porous carrier layer 202 and flows out from the water channel 13 to be treated.
  • a cylinder or a box having a space capable of holding the porous carrier layer 202 can be used.
  • a frame that can hold the porous carrier layer 202 on the surface can be used.
  • the treated water flow path 12 is connected to the upper surface of the base material 201 in the metal material aggregation promoting layer 200, and the treated water flow path 13 is connected to the lower surface of the base material 201.
  • network 203 is provided so that the porous support
  • the porous carrier layer 202 includes a porous carrier C carrying adsorbed particles A on the surface.
  • a porous carrier C carrying adsorbed particles A on the surface.
  • the porous carrier C at least one selected from the group consisting of activated carbon, silica, ceramics, and zeolite can be used.
  • the porous carrier C has an opening ratio that maintains the flow rate of the water to be treated W containing the oxidizing agent O at a certain level or higher. Further, the porous carrier C has a surface area and adsorbability sufficient to support the adsorbed particles A necessary for removing the metal-related substances M + , M, MO, and MOH.
  • the adsorbed particles A include at least one of metal oxide particles and metal hydroxide particles. Specifically, the adsorbed particles A contain at least one trivalent iron ion compound selected from the group consisting of Fe 2 O 3 , Fe 3 O 4 , Fe (OH) 3 and FeOOH.
  • the aggregation promoting unit 2 receives the water to be treated W containing the oxidant O from the water channel to be treated 12.
  • the aggregation promoting unit 2 adsorbs the metal-related substance contained in the water to be treated W to the adsorbed particles A by the action of the oxidizing agent O.
  • the aggregation promoting part 2 promotes the aggregation of the mixed particles composed of the metal oxide particles MO and the metal hydroxide particles MOH derived from the metal-related substance on the surface of the porous carrier C.
  • the metal-related substances contained in the water to be treated W are iron ions, iron particles, iron oxide, and iron hydroxide
  • iron is oxidized by the oxidizing action of the oxidizing agent O.
  • the ions are oxidized to trivalent iron ions (Fe 3+ ).
  • the trivalent iron ions, iron particles, iron oxide, and iron hydroxide are adsorbed on the surface of the adsorbed particles A with the trivalent iron ion compound contained in the adsorbed particles A serving as a nucleus.
  • the metal-related substance grows into an aggregate MDA composed of iron oxide particles having a diameter ⁇ of 1 ⁇ m or more, iron hydroxide, and the like.
  • divalent iron ions (Fe 2+ ) contained in the water to be treated W are adsorbed on the surface of the activated carbon constituting the porous carrier C, Grows into aggregate MDA.
  • the metal constituting the adsorbed particles A and the metal constituting the metal-related substance contained in the water to be treated W are the same element.
  • the adsorbed particles A are considered to have a high metal-related substance adsorption effect.
  • the adsorbed particles A only need to be able to adsorb metal-related substances in the water to be treated W. Therefore, the metal constituting the adsorbed particles A and the metal constituting the metal-related substance may not be the same element.
  • the aggregate MDA aggregated on the surface of the porous carrier C becomes larger than a certain size, it is detached from the surface of the porous carrier C by the water flow of the water to be treated W as shown in FIG. And flows downstream. That is, the to-be-treated water W containing the aggregate MDA flows into the filter unit 3 from the aggregation promoting unit 2 via the to-be-treated water flow path 13.
  • the filter unit 3 is provided downstream of the aggregation promoting unit 2 and captures the aggregate MDA that has flowed from the aggregation promoting unit 2 together with the water to be treated W.
  • the filter part 3 is a sand filtration part. According to the filter unit 3, the aggregate MDA can be removed from the water to be treated W. As a result, in the downstream of the filter unit 3, treated water from which the aggregate MDA of the metal ions M + , the metal particles M, the metal oxide particles MO, and the metal hydroxide particles MOH has been removed is generated. This treated water is supplied to the faucet via the supply channel 14.
  • the water treatment device of the comparative example is an oxygen (O 2), containing no oxidizing agent O.
  • O 2 oxygen
  • the activated carbon has a property of easily adsorbing divalent iron ions (Fe 2+ ).
  • a divalent iron ion is oxidized in water to become a trivalent iron ion (Fe 3+ )
  • the trivalent iron ion instantaneously binds to oxygen and changes to fine-particle iron oxide.
  • activated carbon is less likely to adsorb iron oxide particles than iron ions, and as a result, trivalent iron ions often pass through the activated carbon without being adsorbed.
  • the divalent iron ions are adsorbed on the porous carrier C
  • the trivalent iron ions are combined with oxygen to form iron oxide particles of several nm level, so that they pass through the porous carrier C. End up.
  • a reverse osmosis membrane (RO membrane) or the like In order to remove such iron oxide particles of several nm level, a reverse osmosis membrane (RO membrane) or the like must be used, which greatly increases the cost.
  • RO membrane reverse osmosis membrane
  • the iron oxide particles of several nm level can be coarsened using a flocculant, it is necessary to leave for a long time for coarsening, so that the removal efficiency is greatly reduced.
  • the oxidizing agent O when supplied into the water to be treated W, the divalent iron ions are converted into trivalent iron ions. Oxidized.
  • the trivalent iron ions are adsorbed by the adsorbed particles A present in the aggregation promoting part 2. That is, the adsorbed particles A contain at least one trivalent iron ion compound selected from the group consisting of Fe 2 O 3 , Fe 3 O 4 , Fe (OH) 3 and FeOOH.
  • the trivalent iron ions in the water to be treated W have high affinity with the trivalent iron ion compound in the adsorbed particles A, the trivalent iron ion compound serves as a nucleus and is adsorbed on the surface of the adsorbed particles A. .
  • iron ions in the water W to be treated aggregate on the surface of the adsorbed particles A, and iron oxide or iron hydroxide aggregate MDA is generated.
  • the divalent iron ions not oxidized by the oxidant O are adsorbed on the porous carrier C, and adsorbed particles A and aggregate MDA existing on the surface of the porous carrier C are generated.
  • the aggregate MDA desorbs from the surface of the adsorbed particles A after the particle diameter of the aggregate MDA reaches a level of several ⁇ m. That is, iron ions in the water to be treated W aggregate on the surface of the adsorbed particles A as iron oxide or iron hydroxide aggregate MDA.
  • the aggregate MDA becomes several ⁇ m or more, the aggregate MDA is detached from the surface of the adsorbed particles A by the water flow of the water to be treated W and reaches the filter unit 3.
  • the aggregate MDA is several ⁇ m or more, it can be easily removed by, for example, sand filtration without using a reverse osmosis membrane.
  • the adsorbed particles A preferably include at least one trivalent iron ion compound selected from the group consisting of Fe 2 O 3 , Fe 3 O 4 , Fe (OH) 3 and FeOOH.
  • the adsorbed particles A contain at least one of Fe (OH) 3 and FeOOH.
  • Fe (OH) 3 and FeOOH have a particularly high affinity with trivalent iron ions, so it becomes easy to produce aggregate MDA and metal-related substances can be efficiently removed from the water to be treated W. It becomes.
  • the to-be-treated water W contains particles of iron hydroxide (Fe (OH) 3 ), iron oxide (Fe 2 O 3 ), and iron (Fe), iron hydroxide Iron oxide and iron particles pass through the porous carrier C.
  • the adsorbed particles A can also adsorb iron hydroxide, iron oxide and iron particles, it can be removed as an aggregate MDA.
  • the treated water W may contain arsenic, manganese, silica, alumina, etc. in addition to iron as a metal-related substance.
  • Silica and alumina deteriorate water quality as a suspended component.
  • these metal-related substances can be aggregated on the surface of the adsorbed particles A in a form of being engulfed by iron ions, it becomes possible to form and remove the aggregate MDA together with iron.
  • the water to be treated W containing iron ions together with the oxidizing agent is passed through the porous carrier layer 202 where the adsorbed particles containing the trivalent iron ion compound are present at high density.
  • divalent iron ions are adsorbed on the surface of the porous carrier C.
  • trivalent iron ions are adsorbed on iron oxide particles or iron hydroxide particles as adsorbed particles A attached to the surface of the porous carrier C.
  • aggregation of the metal-related substance is promoted on the surface of the porous carrier C. According to this, iron ions can be removed to the required level regardless of the valence of the iron ions contained in the water to be treated W.
  • the oxidizing agent O contains chlorine.
  • the oxidizing agent O containing chlorine can promote the aggregation of the metal-related substances and can sterilize the water W to be treated.
  • the iron fiber material is installed in the mixing unit 1. Thereby, in the mixing unit 1, iron ions and iron particles are supplied to the water to be treated W. The iron particles may be changed into iron ions, iron oxide particles, and iron hydroxide particles in the water to be treated W.
  • raw water to be treated water W is metal ions M + , metal particles M, metal oxide particles MO, and metal hydroxide particles MOH as metal-related substances.
  • the raw water contains at least one of iron ions, iron particles, iron oxide particles, and iron hydroxide particles.
  • trivalent iron ions, iron particles, iron oxide particles, and iron hydroxide particles are separated from the raw water by the chlorine oxidizing action and the metal material aggregation promoting layer 200 as described above. Particles can be removed.
  • the divalent iron ions are removed from the raw water by the adsorption action of the porous carrier C.
  • the raw water to be treated water W may not contain any of iron ions, iron particles, iron oxide particles, and iron hydroxide particles.
  • metal-related substances other than iron such as arsenic, manganese, silica, and alumina, are aggregated and removed on the surface of the adsorbed particles A in a form of being involved in iron ions, so that the raw water does not contain iron. May be difficult to remove these metal-related substances. Therefore, it is preferable to intentionally add iron to the water to be treated W to easily remove these metal-related substances.
  • a fiber material for supplying iron to the treated water W is provided in the mixing unit 1.
  • the divalent iron ions and the trivalent iron ions dissolve into the water W to be treated by the reaction between the iron fiber material and chlorine. Further, in the water to be treated W, trivalent iron ions, iron particles, iron oxide particles, and iron hydroxide particles are adsorbed by the adsorbed particles A in the metal material aggregation promoting layer 200. Also in this case, the adsorbed particles A contain at least one trivalent iron ion compound selected from the group consisting of Fe 2 O 3 , Fe 3 O 4 , Fe (OH) 3 and FeOOH.
  • the water treatment apparatus 100 actively applies iron ions, iron particles, iron oxide particles, and iron hydroxide particles from the iron fiber material to the water W to be treated. It is added. Thereby, the aggregation of iron oxide particles and iron hydroxide particles is intentionally promoted on the surface of the adsorbed particles A, and metal-related substances other than iron such as arsenic, manganese, silica, and alumina can be removed. It becomes possible.
  • metal-related substances are removed from the water to be treated W to the required level without providing a large storage tank due to the oxidizing action of chlorine. can do. Therefore, according to the water treatment apparatus 100, the space efficiency of the removal of metal-related substances can be improved. Further, the fine particles can be removed from the water to be treated W by utilizing the fact that the iron fiber material dissolves into the water to be treated W as iron ions.
  • Embodiment 1 The water treatment apparatus 100 of Embodiment 1 is demonstrated using FIG.6 and FIG.7.
  • the aggregation promoting unit 2 and the filter unit 3 are provided in one storage tank 10.
  • the to-be-processed water flow path 13 is provided in the storage tank 10, and is a boundary part of the aggregation promotion part 2 and the filter part 3 in the storage tank 10.
  • the pump P1 is provided in the to-be-treated water flow path 11.
  • the pump P1 sends the water to be treated W from the well or the like to the mixing unit 1.
  • the water to be treated W that has flowed out of the mixing unit 1 flows into the storage tank 10 from the upper part of the storage tank 10 via the water to be treated flow path 12.
  • the to-be-processed water W flows down from the upper side to the lower side.
  • the to-be-treated water W flowing down passes through the aggregation promoting unit 2 and the filter unit 3.
  • the treated water flows out from the lower part of the storage tank 10 and is supplied to the faucet via the supply channel 14.
  • the mixing unit 1 and the oxidant supply unit 4 are integrated.
  • the mixing unit 1 includes a mixed oxidation tank 23 having a lid 22.
  • the oxidizing agent supply unit 4 is a tablet-like chlorine-based chemical 24 itself as the oxidizing agent O installed in the mixing unit 1.
  • a fibrous iron 25 that supplies iron ions and iron particles to the water to be treated W is installed together with the tablet-like chlorine-based chemical 24.
  • the water to be treated W is blown from the water flow path 11 to the space 21 in the mixed oxidation tank 23. Thereafter, the water to be treated W comes into contact with the tablet-like chlorinated chemical 24 and the fibrous iron 25 installed at the lower part of the mixed oxidation tank 23. Thereby, the tablet-like chlorinated medicine 24 and the fibrous iron 25 supply the oxidant O, iron ions, and iron particles to the water to be treated W.
  • chlorinated isocyanuric acid is preferably used, for example, sodium dichloroisocyanurate or sodium trichloroisocyanurate is more preferably used, and sodium trichloroisocyanurate is particularly preferably used. Since sodium trichloroisocyanurate has low solubility in water, when used as a tablet-like chlorinated drug 24, a small amount of drug can be continuously added over a long period of time.
  • the chlorine-based chemical 24 and the fibrous iron 25 are arranged close to the mixed oxidation tank 23. Therefore, iron ions, iron, iron oxides, and iron hydroxides are easily eluted from the iron 25 due to the effect of the chlorine-based chemical 24, and the oxidizing agent O for the water to be treated W, as well as iron ions, iron, iron oxides. In addition, iron hydroxide can be efficiently added.
  • the water treatment apparatus 100 according to the first embodiment is used even when the raw water to be treated water W contains almost no iron ions, iron, iron oxide, and iron hydroxide. Thus, iron can be intentionally added to the water to be treated W. As a result, metal-related substances other than iron such as arsenic, manganese, silica, and alumina can be removed.
  • the water treatment apparatus 100 of Embodiment 2 is demonstrated using FIG.8 and FIG.9.
  • the water treatment apparatus 100 further includes a flow path switching valve 50 and a drain port 17.
  • the flow path switching valve 50 is connected to the treated water flow path 12 and the supply flow path 14.
  • the mixing part 1 and the flow path switching valve 50 are connected by the to-be-processed water flow path 12a.
  • the flow path switching valve 50 and the storage tank 10 are connected by the to-be-processed water flow path 12b.
  • the storage tank 10 and the flow path switching valve 50 are connected by a supply flow path 14a.
  • the flow path switching valve 50 and the faucet 16 are connected by a supply flow path 14b.
  • the flow path switching valve 50 is also connected to the drain port 17.
  • the flow path switching valve 50 is a so-called five-way valve.
  • the water to be treated W shown in FIG. 8 flows in the forward direction X from the aggregation promoting unit 2 to the filter unit 3, and the water to be treated W shown in FIG.
  • the state which flows in the reverse direction Y toward the promotion part 2 is switched.
  • the water to be treated W is mixed with the mixing unit 1, the channel switching valve 50, the aggregation promoting unit 2, the filter unit 3, the channel switching valve 50, and the faucet. 16 flows in this order.
  • the water to be treated W is mixed with the mixing unit 1, the channel switching valve 50, the filter unit 3, the aggregation promoting unit 2, the channel switching valve 50, and the drainage. It flows through the mouth 17 in this order.
  • the drain port 17 is positioned downstream of the aggregation promoting unit 2 in a state where the treated water W flows in the reverse direction Y, and discharges the treated water W to the outside. Therefore, according to the water treatment apparatus 100, the filter unit 3 can be backwashed. Further, when the filter unit 3 is back-washed, the adsorbed particles A adhering to the filter unit 3 are adsorbed by the adsorbed particles A adsorbed to the aggregation promoting unit 2. As a result, the ability of the adsorbed particles A of the aggregation promoting unit 2 can be recovered.
  • the aggregation promoting unit 2 has a porous carrier C including, for example, a group of particles
  • the filter unit 3 includes a sand filtering unit including, for example, a group of sand particles.
  • the density of the group of granules in the aggregation promoting unit 2 is smaller than the density of the group of sand particles in the filter unit 3. Therefore, in the water in the storage tank 10, the group of particles in the aggregation promoting unit 2 is positioned above the group of sand particles in the filter unit 3.
  • the group of granular bodies constituting the aggregation promoting part 2 and the group of sand grains constituting the filter part 3 are deposited so as to be aligned in the vertical direction.
  • the water treatment apparatus 100 can be reduced in size.
  • the group of granulates constituting the aggregation promoting unit 2 and the group of sand particles constituting the filter unit 3 naturally maintain their mutual arrangement due to gravity.
  • the group of sand grains constituting the filter unit 3 is, for example, manganese sand.
  • the density of manganese sand is 2.57 to 2.67 g / cm 3 .
  • the manganese adhesion amount of manganese sand is 0.3 mg / g or more.
  • the filter part 3 may be formed with general filter sand (2.5 g / cm 3 ).
  • the density of the porous carrier C including a group of particles constituting the aggregation promoting portion 2 is, for example, 0.5 g / cm 3 in the case of activated carbon and 0.9 to 1.1 / cm 3 in the case of zeolite. In the case of silica, it is 2.2 g / cm 3 , and in the case of ceramics, it is 0.7 g / cm 3 .
  • the water treatment apparatus 100 of Embodiment 3 is demonstrated using FIG.
  • the water treatment apparatus 100 further includes a reducing agent adsorbing unit 18 that is provided in the to-be-treated water channel 11 upstream of the mixing unit 1 and adsorbs ammonia as a reducing agent contained in the to-be-treated water W. Therefore, it can suppress that the oxidizing agent O in the mixing part 1 is consumed for the oxidation of the ammonia in the to-be-treated water W.
  • the reducing agent adsorption unit 18 is a zeolite that contains sodium ions and adsorbs ammonia in the water W to be treated by substituting the sodium ions and ammonium ions in the water W to be treated.
  • the water treatment apparatus 100 includes a regenerating liquid supply unit 19 that regenerates the ammonia adsorption effect of zeolite.
  • the regenerating liquid supply unit 19 causes the reducing agent adsorbing unit 18 to adsorb new sodium ions by supplying a regenerating liquid containing sodium chloride to the zeolite. Thereby, the adsorption effect of ammonia by the reducing agent adsorption unit 18 can be maintained.
  • Example 1 First, an iron compound as adsorbed particles was supported on activated carbon as a porous carrier as follows. First, 300 mL of activated carbon was placed in a cylindrical processing tank having an inner diameter of ⁇ 50 mm and a capacity of 1 L. Note that activated carbon having a particle diameter ⁇ of 0.5 mm to 2.3 mm was used. Next, water containing 0.7 ppm of divalent iron ions and sodium hypochlorite solution are continuously passed through the activated carbon inside the cylindrical treatment tank, and the activated carbon, water and hypochlorous acid are treated in the treatment tank. The sodium solution was in good contact.
  • the water flow rate was 6 L / min, and the amount of sodium hypochlorite solution injected was quantitatively controlled so that the free chlorine concentration in the treatment tank was maintained at 5 ppm.
  • the water and the sodium hypochlorite solution were injected for 10 hours, and the iron compound was supported on the activated carbon.
  • a water treatment apparatus shown in FIG. 11 was produced using activated carbon carrying an iron compound obtained as described above. And in order to confirm the iron removal performance of a metal material aggregation promotion layer, it compared with the prior art. Compared with conventional high-speed filtration, which promotes agglomeration of iron with an oxidizer and grows grains, and then filters with filtration sand.
  • the comparative experiment was performed using the water treatment apparatus shown in FIG.
  • a cylindrical container having an inner diameter ⁇ of 50 mm and a capacity of 1 L was used for the aggregation promoting part and the sand filtration tank.
  • 100 mL of filtration gravel ( ⁇ 2 to 4 mm) and 300 mL of activated carbon carrying an iron compound were placed inside the container, and an aggregation promoting part including a metal material aggregation promoting layer was produced.
  • the filter gravel used had a particle diameter ⁇ of 2 mm to 4 mm.
  • 100 mL of filtration gravel and 300 mL of manganese sand ( ⁇ 0.35 mm) were placed inside the container to prepare a sand filtration tank.
  • the filter gravel used had a particle diameter ⁇ of 2 mm to 4 mm, and the manganese sand used had a particle diameter ⁇ of 0.35 mm.
  • the aggregation promoting part is arranged on the upstream side of the sand filtration tank, and on the upstream side of the aggregation promoting part, raw water supply pump as the to-be-processed water, and oxidation
  • the oxidizing agent a sodium hypochlorite solution having a chlorine concentration of 10,000 ppm was used.
  • the bypass line (BL) was provided between the injection
  • the capacity of BL is 1L, and the total capacity is the same regardless of whether the flow path of BL or the aggregation promoting part is passed.
  • the test items were a total of four types consisting of a combination of presence / absence of an aggregation promoting part and presence / absence of chlorine supply.
  • the conventional high-speed filtration corresponds to the case where there is no aggregation promoting part and chlorine as an oxidizing agent is present.
  • the filtration using the aggregation promoting unit according to the present embodiment corresponds to the case where the aggregation promoting unit is present and chlorine is present.
  • raw water water having an iron concentration of 0.72 ppm was used, and the raw water flow rate was 1 L / min. When supplying chlorine, the amount of input was controlled to be 30 ppm.
  • Table 1 shows the iron concentration contained in each treated water.
  • the iron concentration was 0.47 ppm. This is because some iron is grain-grown by the effect of chlorine and filtered by the sand filtration part, but the grain growth time, that is, the capacity of the previous stage of the sand filtration tank is insufficient to perform sufficient iron removal. it is conceivable that.
  • the iron concentration was 0.16 ppm, and it was confirmed that the iron removal performance was improved. This is considered to be a result of the aggregation promoting part accelerating iron aggregation and increasing the amount of iron to be filtered, and the effect of the aggregation promoting part on the iron removal treatment was confirmed. Further, even when only the aggregation promoting part was used (with the aggregation promoting part, without chlorine), the iron concentration was slightly reduced, and the effect of accelerating the grain growth of the aggregation promoting part alone was also confirmed.
  • Example 2 As described in Example 1, it has been confirmed that in the iron removal treatment using the aggregation promoting part, the grain growth of iron is further accelerated by using an oxidizing agent (chlorine). Next, in order to investigate the required amount of chlorine, the input chlorine concentration was changed to 10 ppm, 20 ppm, 30 ppm, and 40 ppm using the water treatment apparatus of Example 1, and the evaluation of the iron concentration and free chlorine concentration in the obtained treated water was performed. went. As in Example 1, the amount of activated carbon carrying an iron compound was 300 mL, and the flow rate of water to be treated was 1 L / min.
  • chlorine oxidizing agent
  • decomposition of ammonia and organic substances contained in the water to be treated can be considered. It is known that the raw water used in this example contains an ammonia component, and it is considered that most of the input chlorine was consumed for the oxidation of the ammonia component.
  • the quality of raw water treated by the water treatment apparatus of the present embodiment is assumed to be different for each case such as the place where it is installed, and the content of organic matter and the like is not constant. Therefore, the amount of input chlorine must be adjusted each time according to the quality of raw water to be treated.
  • Example 3 In Example 3, the influence of the flow rate of water to be treated and the amount of activated carbon supporting an iron compound on the performance of the aggregation promoting portion was examined.
  • the aggregation promotion part whose activated carbon amounts which carry
  • the iron removal performance was examined.
  • FIG. 14 shows the relationship between the concentration of iron remaining in the treated water and the amount of activated carbon carrying an iron compound at each flow rate. Note that the concentration of chlorine added to the water to be treated was 40 ppm.
  • the iron concentration in the treated water can be reduced even if the flow rate of the water to be treated is changed in all the activated carbon amounts of 50 mL, 100 mL, 200 mL, and 300 mL.
  • the amount of activated carbon was 50 mL and 100 mL, good iron removal results were obtained at each flow rate.
  • the best iron removal performance was shown when the amount of activated carbon was 0.75 L / min at 100 mL.
  • the difference in iron removal performance shown in FIG. 14 is considered to be the result of consumption of the input chlorine by activated carbon, and the flow rate of the water to be treated and the amount of activated carbon are within the range where the above-mentioned free chlorine concentration can be maintained. It is considered preferable to adjust.
  • the metal material aggregation promoting layer 200 includes a base material 201 and a porous carrier layer 202 provided on the base material 201. Further, the metal material aggregation promoting layer 200 is supported on the porous carrier layer 202 and is at least one trivalent iron ion compound selected from the group consisting of Fe 2 O 3 , Fe 3 O 4 , Fe (OH) 3 and FeOOH. Adsorbed particles. According to such a configuration, the metal-related substances M + , M, MO, and MOH contained in the water to be treated W can be adsorbed and aggregated on the surface of the adsorbed particles. As a result, since the particle diameter of the metal-related substance aggregate MDA is on the order of several micrometers, it is possible to easily separate from the treated water W and reduce the concentration of the metal-related substance contained in the treated water W. Become.
  • the adsorbed particles contain at least one of Fe (OH) 3 and FeOOH. Since Fe (OH) 3 and FeOOH have a high affinity with a metal-related substance and can be easily adsorbed, an aggregate MDA of the metal-related substance can be efficiently generated.
  • the porous carrier layer 202 contains activated carbon. Since activated carbon has a high specific surface area, the adsorbed particles can be supported at a high concentration. Moreover, since activated carbon adsorbs divalent iron ions, divalent iron ions in the water to be treated can be easily removed.
  • the water treatment apparatus 100 includes treated water flow paths 11, 12, 13, an oxidant supply unit 4, and an aggregation promoting unit 2.
  • the to-be-treated water channels 11, 12, and 13 contain at least one metal-related substance selected from the group consisting of metal ions M + , metal particles M, metal oxide particles MO, and metal hydroxide particles MOH.
  • Water W flows.
  • the oxidant supply unit 4 supplies the oxidant O to the treated water W.
  • the aggregation promoting unit 2 has a metal material aggregation promoting layer 200 and promotes the aggregation of the metal-related substances by causing the adsorbed particles A to adsorb the metal-related substances contained in the water to be treated W by the action of the oxidizing agent O. .
  • the water to be treated W including the metal oxide particle agglomerates MDA adsorbing the metal-related substances flows out from the aggregation promoting unit 2. Therefore, if the aggregate MDA is captured by the filter unit 3 provided downstream of the aggregation promoting unit 2, more metal-related substances can be removed from the water to be treated W. Therefore, the space efficiency of the removal of the metal-related substance from the treated water W can be improved.
  • the oxidizing agent O may contain ozone or chlorine. According to this, both sterilization of the to-be-processed water W and acceleration
  • the water treatment apparatus 100 further includes a filter unit 3 that is provided downstream of the aggregation promoting unit 2 and that filters the metal-related substance aggregate MDA flowing from the aggregation promoting unit 2 together with the water to be treated W. It is preferable. According to this, the filter part 3 can remove the metal-related substance aggregate MDA from the water to be treated W. As a result, water from which the aggregate MDA of the metal-related substance is removed can be generated.
  • the space efficiency of removing one or more metal-related substances selected from the group consisting of metal ions, metal particles, metal oxide particles, and metal hydroxide particles can be improved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Water Treatment By Sorption (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Filtration Of Liquid (AREA)

Abstract

L'invention concerne une couche (202) favorisant l'agrégation d'une matière métallique, qui a un substrat (201), une couche de support poreuse (202) disposée sur le substrat, et des particules adsorbantes retenues sur la couche de support poreuse et contenant au moins un type de composé à ion ferreux trivalent choisi dans le groupe consistant en Fe2O3, Fe3O4, Fe(OH)3 et FeOOH. Le dispositif (100) de traitement de l'eau comprend : des canaux (11, 12, 13) d'écoulement d'eau de traitement à travers lesquels circule de l'eau de traitement (W) contenant au moins une substance métallique choisie dans le groupe consistant en ions métalliques, particules métalliques, particules d'oxyde métallique et particules d'hydroxyde métallique ; une unité (4) d'alimentation en oxydant pour acheminer un oxydant (O) dans l'eau de traitement ; et une unité (2) favorisant l'agrégation qui a une couche favorisant l'agrégation d'une matière métallique et qui favorise l'agrégation de substances métalliques en amenant les substances métalliques contenues dans l'eau de traitement à être adsorbées sur les particules d'adsorption par l'effet de l'oxydant.
PCT/JP2016/002695 2015-06-09 2016-06-03 Couche favorisant l'agrégation d'une matière métallique, et dispositif de traitement de l'eau l'utilisant WO2016199385A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2017523103A JP6519934B2 (ja) 2015-06-09 2016-06-03 金属材料凝集促進層、及びそれを用いた水処理装置
CN201680040651.0A CN107848848B (zh) 2015-06-09 2016-06-03 金属材料絮凝促进层和使用其的水处理装置
KR1020177030282A KR102027103B1 (ko) 2015-06-09 2016-06-03 금속 재료 응집 촉진층, 및 그것을 이용한 물처리 장치

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015-116729 2015-06-09
JP2015116729 2015-06-09
JP2015176427 2015-09-08
JP2015-176427 2015-09-08

Publications (1)

Publication Number Publication Date
WO2016199385A1 true WO2016199385A1 (fr) 2016-12-15

Family

ID=57503214

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/002695 WO2016199385A1 (fr) 2015-06-09 2016-06-03 Couche favorisant l'agrégation d'une matière métallique, et dispositif de traitement de l'eau l'utilisant

Country Status (4)

Country Link
JP (1) JP6519934B2 (fr)
KR (1) KR102027103B1 (fr)
CN (1) CN107848848B (fr)
WO (1) WO2016199385A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018132479A (ja) * 2017-02-17 2018-08-23 パナソニックＩｐマネジメント株式会社 配管部材、水質検査方法及び水処理装置
WO2018155120A1 (fr) * 2017-02-24 2018-08-30 パナソニックＩｐマネジメント株式会社 Procédé de fabrication de charbon actif supportant du fer pour dispositif de traitement d'eau
WO2019159917A1 (fr) * 2018-02-14 2019-08-22 パナソニックＩｐマネジメント株式会社 Appareil de traitement de l'eau
WO2020202808A1 (fr) * 2019-03-29 2020-10-08 パナソニックＩｐマネジメント株式会社 Appareil de traitement de l'eau

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112121753A (zh) * 2020-08-03 2020-12-25 江苏理工学院 一种磁性吸附材料的制备方法与应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57207519A (en) * 1981-04-28 1982-12-20 Amf Inc Filter
JPH07100496A (ja) * 1993-10-01 1995-04-18 Takashi Mae 受水型井戸水水質改善装置
JP2004521728A (ja) * 2000-11-07 2004-07-22 オーテーヴェー エスア マンガンを含有する水の処理方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52107154A (en) * 1976-03-05 1977-09-08 Ebara Infilco Co Ltd Removing system for iron and manganese from water
CN86102044A (zh) * 1986-03-25 1987-10-14 哈尔滨建筑工程学院 用地下水中铁质做混凝剂
US7429551B2 (en) * 2001-08-27 2008-09-30 Calgon Carbon Corporation Adsorbents for removing heavy metals
FR2839507B1 (fr) * 2002-05-07 2004-07-23 Omnium Traitement Valorisa Procede de traitement des eaux contenant du fer, du manganese et de l'arsenic
JP4043412B2 (ja) * 2003-06-30 2008-02-06 東西化学産業株式会社 水処理方法
WO2005058482A1 (fr) * 2003-12-16 2005-06-30 Calgon Carbon Corporation Adsorbants destines a eliminer des metaux lourds, et procedes de production et d'utilisation des adsorbants
JP2007099612A (ja) * 2005-09-06 2007-04-19 National Institute Of Advanced Industrial & Technology 均一な粒子径を有するメソ多孔性炭素ビーズ、その製造方法および製造装置、ならびに該メソ多孔性炭素ビーズを担体とする水処理用触媒、該触媒の性能評価装置と、該触媒を用いた実廃水処理装置
US7378372B2 (en) * 2005-10-11 2008-05-27 Layne Christensen Company Filter and sorbent for removal of contaminants from a fluid
JP2010155196A (ja) * 2008-12-26 2010-07-15 Kawamoto Pump Mfg Co Ltd 濾過装置
JP4707752B2 (ja) * 2009-05-27 2011-06-22 壽昭 落合 水処理方法及び水処理システム
JP5693992B2 (ja) * 2011-02-14 2015-04-01 新日鐵住金株式会社 多種金属イオン含有排水からの溶存鉄の回収方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57207519A (en) * 1981-04-28 1982-12-20 Amf Inc Filter
JPH07100496A (ja) * 1993-10-01 1995-04-18 Takashi Mae 受水型井戸水水質改善装置
JP2004521728A (ja) * 2000-11-07 2004-07-22 オーテーヴェー エスア マンガンを含有する水の処理方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018132479A (ja) * 2017-02-17 2018-08-23 パナソニックＩｐマネジメント株式会社 配管部材、水質検査方法及び水処理装置
WO2018155120A1 (fr) * 2017-02-24 2018-08-30 パナソニックＩｐマネジメント株式会社 Procédé de fabrication de charbon actif supportant du fer pour dispositif de traitement d'eau
JPWO2018155120A1 (ja) * 2017-02-24 2020-01-09 パナソニックＩｐマネジメント株式会社 水処理装置用鉄担持活性炭の製造方法
WO2019159917A1 (fr) * 2018-02-14 2019-08-22 パナソニックＩｐマネジメント株式会社 Appareil de traitement de l'eau
WO2020202808A1 (fr) * 2019-03-29 2020-10-08 パナソニックＩｐマネジメント株式会社 Appareil de traitement de l'eau

Also Published As

Publication number Publication date
JPWO2016199385A1 (ja) 2018-02-22
CN107848848B (zh) 2020-10-20
JP6519934B2 (ja) 2019-05-29
KR20170130505A (ko) 2017-11-28
CN107848848A (zh) 2018-03-27
KR102027103B1 (ko) 2019-11-04

Similar Documents

Publication Publication Date Title
WO2016199385A1 (fr) Couche favorisant l'agrégation d'une matière métallique, et dispositif de traitement de l'eau l'utilisant
KR101426925B1 (ko) 수처리 방법 및 수처리 시스템
JP6846656B2 (ja) 水処理装置
US20100230332A1 (en) Adsorption apparatus for wastewater
US11905187B2 (en) System and method for removal of recalcitrant organic compounds from water
JP5524299B2 (ja) 膜ろ過処理システム
JP5085634B2 (ja) 膜ろ過処理システム
JP6359257B2 (ja) マンガン含有水の処理方法および処理装置
Alsohaimi et al. Highly efficient ultrafiltration membrane performance of PES@ microcrystalline cellulose extracted from waste fruits for the removal of BrO3− from drinking water samples
JP6865399B2 (ja) 水処理装置用鉄担持活性炭の製造方法
WO2021149581A1 (fr) Dispositif de purification d'eau et procédé de purification d'eau
JP4821170B2 (ja) 超純水製造装置
WO2004063097A1 (fr) Procede d'adjonction de charbon actif pour la purification de l'eau, et procede de purification de l'eau
JPH105743A (ja) 浄水フィルタ
WO2020202808A1 (fr) Appareil de traitement de l'eau
JP5808945B2 (ja) 放射性汚染物質の除去装置
JP2016522411A (ja) 水からの放射性核種の除去方法及びその除去システム
JP3063863U (ja) 水浄化還元装置
WO2019159917A1 (fr) Appareil de traitement de l'eau
KN et al. Green synthesis of granular activated carbon/zinc ferro nanocomposites-based bioleached laterite iron (BLaFe) for the removal of Rhodamine B in water using adsorption–Fenton's oxidation process
JP2011152493A (ja) 浄水装置
Antony et al. Application of encapsulated and immobilized nano zero-valent iron for iron removal from roof-harvested rainwater
KR100250510B1 (ko) 세라믹 특수활성체와 미약전류의 인가공을 조합시킨 수처리장치
KR20210063161A (ko) 수처리용 산화 반응 촉매의 제조 방법 및 그의 응용
JP2005246238A (ja) 河川水等の浄化装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16807095

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017523103

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20177030282

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16807095

Country of ref document: EP

Kind code of ref document: A1