WO2019208532A1 - Procédé de traitement d'eau et dispositif de traitement d'eau - Google Patents

Procédé de traitement d'eau et dispositif de traitement d'eau Download PDF

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Publication number
WO2019208532A1
WO2019208532A1 PCT/JP2019/017115 JP2019017115W WO2019208532A1 WO 2019208532 A1 WO2019208532 A1 WO 2019208532A1 JP 2019017115 W JP2019017115 W JP 2019017115W WO 2019208532 A1 WO2019208532 A1 WO 2019208532A1
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Prior art keywords
water
cationic polymer
treated
membrane separation
inorganic flocculant
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PCT/JP2019/017115
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English (en)
Japanese (ja)
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貴子 岩見
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栗田工業株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D21/00—Separation of suspended solid particles from liquids by sedimentation
    • B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/58—Multistep processes
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • 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
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a reduced water treatment method and a water treatment apparatus.
  • Patent Document 1 describes a technique for aggregating high-pH or high-alkaliness water to be treated by adding a cationic polymer prior to the addition of an inorganic flocculant.
  • organic substances and SS in the raw water first react with the cationic polymer, the required amount of the cationic polymer is large, leading to an increase in cost.
  • Patent Document 2 discloses a technique in which an inorganic flocculant and a polymer flocculant are added and agglomeration treatment is performed, and then the inorganic flocculant is added again before solid-liquid separation. In this method, the flocculant is added many times, and the apparatus is complicated and the operation becomes complicated.
  • Patent Document 3 discloses a method of using an inorganic flocculant prior to the addition of particles made of a cationic polymer that is substantially insoluble in water.
  • the aggregated flocs containing water-insoluble particles become coarse, causing turbid contamination in the membrane separation apparatus used for solid-liquid separation.
  • dissolve in water settles in a stationary state, it is necessary to always stir the inside of a chemical
  • the present inventor first reacted an organic substance or SS in raw water with an inorganic flocculant, and then added a water-soluble cationic polymer having a specific molecular weight to disperse the inorganic flocculant colloid and fine floc that are dispersed.
  • Cationic polymer can be reacted efficiently, and even if the membrane is separated directly with a membrane separator after addition of the cationic polymer, the membrane separator is not contaminated, and the amount of coagulant used can be reduced. I found out.
  • the gist of the present invention is as follows.
  • a water treatment method in which an inorganic flocculant is added to water to be treated and then agglomerated, and then membrane separation is performed with a membrane separation apparatus, the inorganic flocculant is added to the water to be treated, and then the mass average molecular weight is 100,000 to 8 million.
  • a water treatment method comprising: adding a water-soluble cationic polymer to agglomerate, and subjecting the agglomerated water to membrane separation directly with a membrane separator.
  • the treated water is industrial water, city water, well water, industrial wastewater, or biologically treated water containing any of phosphorus, biological metabolites, organic acids having a chelating effect, and inorganic carbon.
  • the amount of the cationic polymer necessary for neutralizing the charge of the water to be treated is determined as the cation consumption A by titrating the water to be treated with the cationic polymer by the streaming potential method.
  • the cationic polymer addition amount and the inorganic flocculant addition amount are controlled such that the cation consumption amount A and the concentration of the inorganic flocculant and the cationic polymer satisfy the following relational expression (I): [1]
  • First coagulation treatment means for adding an inorganic coagulant to the water to be treated, and water-soluble cations having a mass average molecular weight of 100,000 to 8 million in the aggregation treatment water of the first coagulation treatment means
  • a water treatment apparatus comprising: a second agglomeration treatment unit for adding a functional polymer to agglomerate, and a membrane separation device for directly separating the agglomerated water of the second agglomeration treatment unit.
  • the treated water is industrial water, city water, well water, industrial wastewater, or biologically treated water containing wastewater containing any of phosphorus, biological metabolites, chelating organic acids, and inorganic carbon.
  • the amount of the cationic polymer necessary for neutralizing the charge of the water to be treated is determined as the cation consumption A by titrating the water to be treated with the cationic polymer by the streaming potential method.
  • the inorganic flocculant and the addition concentration of the cationic polymer further have means for controlling the addition amount of the cationic polymer and the addition amount of the inorganic flocculant so that the following relational expression (I) is satisfied: [6] The water treatment device according to any one of [9].
  • the amount of the flocculant used can be reduced while preventing contamination of the membrane separator.
  • the water treatment method of the present invention is a water treatment method in which an inorganic flocculant is added to the water to be treated, and then the membrane is separated by a membrane separation apparatus. It is characterized in that 100,000 to 8 million water-soluble cationic polymers are added and subjected to agglomeration treatment, and the agglomerated water is directly subjected to membrane separation with a membrane separator.
  • the water treatment apparatus of the present invention includes a first aggregating treatment means for adding an inorganic flocculant to the water to be treated and aggregating treatment water of the first aggregating treatment means, and a mass average molecular weight of 100,000 to 8 million. And a membrane separation device for directly performing membrane separation of the agglomerated water of the second agglomeration treatment means.
  • an inorganic flocculant is first added to the water to be treated to react the organic matter or SS in the water to be treated with the inorganic flocculant, and then the cationic polymer is added. Colloids and fine flocs can be reacted efficiently with cationic polymers. Even if the membrane is separated directly with a membrane separator after the addition of the cationic polymer, the membrane separator is not contaminated. Reduction is also possible.
  • a cationic polymer If a cationic polymer is added before the inorganic flocculant, the cationic polymer reacts with anion components such as SS and organic matter in the raw water and is consumed. This increases the amount of cationic polymer required to react with the dispersed inorganic flocculant colloid as compared to adding the cationic polymer after the inorganic flocculant.
  • the ratio of the addition amount of the cationic polymer / the addition amount of the inorganic flocculant becomes a certain value or more, the aggregated floc is easily adsorbed on the separation membrane and easily contaminates the membrane. Therefore, in the present invention, the cationic polymer is added after the inorganic flocculant is added.
  • the cationic polymer used in the present invention has a relatively large mass average molecular weight of 100,000 or more, the aggregated floc is unlikely to cause membrane clogging, as shown in Examples described later. Since the cationic polymer used in the present invention has a mass average molecular weight of 8 million or less and is water-soluble, aggregated flocs are difficult to deposit in the membrane module. For this reason, it is possible to prevent contamination in the membrane separation apparatus and continue the treatment stably over a long period of time.
  • the amount of the inorganic flocculant added can be reduced by the combined use of the inorganic flocculant and the cationic polymer. At that time, the cationic polymer is added after the inorganic flocculant. The amount added can be reduced, and as a result, the total amount of flocculant used can be reduced.
  • the water to be treated to be treated in the present invention is not particularly limited, but the present invention provides phosphorus, a biological metabolite, an organic acid having a chelating action, which is difficult to obtain a sufficient flocculating effect only with an inorganic flocculant, Alternatively, it is effective for the treatment of biological water such as industrial water, city water, well water, industrial wastewater, and wastewater containing inorganic carbon.
  • organic acids having a chelating action examples include citric acid, formic acid, succinic acid, acetic acid and butyric acid. These organic acids are used, for example, in a plating process in a semiconductor manufacturing process, and act as a complex ion forming agent or a dispersing agent for an inorganic flocculant when the waste water is treated. In such agglomeration of wastewater containing an organic acid, the higher the aggregation pH, the higher the complex ion forming ability of the organic acid, and the agglomerated state deteriorates.
  • the agglomeration pH becomes high is, for example, when the agglomeration is performed for the purpose of treating heavy metals such as Cu and Mn, or when the optimum agglomeration pH in the TOC removal in the raw water is 6 or more, the inorganic flocculant is polychlorinated. This is the case where aluminum is used.
  • the inorganic flocculant added to the water to be treated it is preferable to use an iron-based or aluminum-based inorganic flocculant capable of forming flocs in a wide pH range.
  • the iron-based inorganic flocculant include ferric chloride, ferric sulfate, polyferric chloride, and polyferric sulfate.
  • the aluminum-based inorganic flocculant include polyaluminum chloride and aluminum sulfate.
  • ferric chloride which is an iron-based inorganic flocculant, is preferable from the viewpoints of the aggregation effect and cost.
  • These inorganic flocculants may be used individually by 1 type, and 2 or more types may be mixed and used for them.
  • the amount of the inorganic flocculant added to the water to be treated varies depending on the quality of the water to be treated, the type of inorganic flocculant used, the quality of the water to be treated, etc., but the amount of active ingredient is in the range of 2 to 100 mg / L. It is preferable that
  • the inorganic flocculant has a suitable flocculation treatment pH range depending on the type thereof.
  • the pH is preferably about 5 to 6
  • the pH is preferably about 6 to 7. . Therefore, it is preferable to adjust the pH to a suitable pH range by adding an acid or an alkali as necessary.
  • rapid stirring is preferably performed for about 2 to 10 minutes in order to sufficiently react the organic matter or SS in the water to be treated with the inorganic flocculant.
  • rapid stirring refers to about 100 to 200 rpm as the rotational speed
  • slow stirring refers to about 20 to 100 rpm as the rotational speed
  • the cationic polymer used in the present invention is a water-soluble one having a mass average molecular weight of 100,000 to 8 million.
  • Water-soluble means that the solubility in water is 1 g or more / 100 g of water (20 ° C.).
  • the “cationic polymer” is one having a positive colloidal equivalent.
  • the colloidal equivalent is preferably 1.0 to 6.0 meq / g.
  • the colloidal equivalent is measured by the streaming potential method after titration with 1 / 400N PVSK (polyvinyl potassium sulfate).
  • the mass average molecular weight of the cationic polymer is a value of a mass average molecular weight measured by a chromatography method (GPC method).
  • the weight average molecular weight of the cationic polymer is less than 100,000, the aggregated flocs that are formed become fine, and membrane clogging is likely to occur.
  • the mass average molecular weight of the cationic polymer exceeds 8 million, the aggregated flocs become too coarse and are easily deposited in the membrane module. Therefore, the weight average molecular weight of the cationic polymer used in the present invention is in the range of 100,000 to 8 million, preferably 200,000 to 1 million.
  • the cationic polymer is not particularly limited as long as it is water-soluble having the above-described mass average molecular weight, but a copolymer of a cationic monomer and a nonionic monomer such as acrylamide can be suitably used. .
  • cationic monomer for example, dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate acid salt or quaternary ammonium salt thereof, dimethylaminopropyl acryamide or dimethylaminopropyl methacrylate acid acid salt or quaternary ammonium salt is preferably used. However, it is not limited to these.
  • quaternary ammonium salt a quaternary ammonium salt such as methyl chloride or ethyl chloride can be used.
  • cationic polymer one kind may be used alone, or two or more kinds may be mixed and used.
  • the amount of the cationic polymer added to the agglomerated treated water with inorganic coagulant depends on the quality of the water to be treated or the inorganic agglomerated treated water and the type of the cationic polymer used.
  • the amount of active ingredient is preferably in the range of 0.1 to 5 mg / L, although it varies depending on the type of active ingredient.
  • agglomerated water obtained by adding a cationic polymer to the inorganic agglomerated water (hereinafter sometimes referred to as “cation agglomerated water”) is directly subjected to membrane separation by a membrane separation device.
  • Direct membrane separation means that water is directly supplied to the membrane separation apparatus without adding a flocculant to the cation flocculation treated water or performing solid-liquid separation using a precipitation tank or the like.
  • the membrane separator used in the present invention is not particularly limited in its membrane material, membrane type and structure.
  • As the membrane separator an MF membrane separator or a UF membrane separator is preferably used.
  • the pore size of the UF membrane and MF membrane is preferably 0.2 ⁇ m or less, for example, about 0.1 to 0.01 ⁇ m.
  • the membrane separation method using the membrane separator there is no particular limitation on the membrane separation method using the membrane separator.
  • the dead end water flow method is used, but a cross flow water flow method may be used.
  • the treated water obtained by membrane separation by the above membrane separator is of high quality from which organic substances, SS, etc. are sufficiently removed, and can be used as industrial water or discharged as it is, but if necessary
  • RO membrane treatment may be performed by a reverse osmosis (RO) membrane separation apparatus.
  • RO reverse osmosis
  • the cation consumption A of the water to be treated is obtained in this way, and the inorganic flocculant and the cationic polymer are added so that the added concentration of the inorganic flocculant and the cationic polymer satisfies the following relational expression (I). It is preferable to control the addition amount.
  • Cation consumption A ⁇ ⁇ Cationic polymer addition concentration (mg / L) + Inorganic flocculant addition concentration (mg / L) ⁇ ⁇ (I)
  • ⁇ is a safety factor taking into account fluctuations in water quality, and is usually about 0.6 to 0.9.
  • ⁇ is a coefficient for converting the cation amount of the inorganic flocculant used to the cation amount of the cationic polymer, and is obtained by titration using a flow ammeter.
  • Control of the addition amount of the cationic polymer and the inorganic flocculant is performed by inputting the cation consumption A of the water to be treated obtained in advance, the conversion coefficient ⁇ of the inorganic flocculant to be used, and the preset safety coefficient ⁇ . It can be performed automatically by means.
  • inorganic flocculants and cationic polymers used in the following examples and comparative examples are as follows.
  • Inorganic flocculant ferric chloride
  • Cationic polymer dimethylaminoethyl acrylate / methyl chloride quaternary salt / acrylamide copolymer having a mass average molecular weight of 50,000, 100,000, 200,000, 700,000, 1 million, 8 million or 10 million Combined (colloid equivalent 2.5-3.0 meq / g)
  • an external pressure type mini-module test apparatus shown in FIGS. 1A and 1B (external pressure type hollow fiber UF membrane, pore diameter: 0.02 ⁇ m, membrane length: 7.5 cm, membrane area: 10.6 cm) 2 , film material polyvinylidene fluoride) was used.
  • 1 is a hollow fiber membrane
  • 2 is a potting agent
  • 3 is a raw water inlet
  • 4 is a drain.
  • Reference numeral 5 denotes a module housing in which the hollow fiber membrane 1 is loaded. The raw water is introduced into the housing 5 from the inlet 3, and the permeated water that has permeated through the hollow fiber membrane 1 is taken out from the inside of the hollow fiber membrane 1 to the outside of the housing 5.
  • V 2 During wastewater, while stopping the pump P, and valve V 1, V 2 opens, the valve V 3 is closed, the air air into the pipe 11 from the pipe 11A, the discharge of water of the pipe 12 from the module 10 Let Air from the pipes 11A and 13A was supplied at 0.15 MPa.
  • the valve V 2 At the time of water filling, the valve V 2 is opened, the valves V 1 and V 3 are closed, the pump P is operated, and the water in the water supply tank 6 is introduced into the module 10.
  • PI is a pressure gauge.
  • the obtained agglomerated water was passed through an external pressure mini-module test apparatus shown in FIGS. 1 (a) and 1 (b) for 48 hours. Measured with a pressure gauge Pl provided on the pipe 11 after passing through water and backwashing every 30 minutes with a flux of 4 m 3 / m 2 / d (30 seconds), then draining (30 seconds), and then watering (30 seconds). The rate of increase in transmembrane pressure was investigated.
  • the SS concentration of the feed water (flocculated treated water subjected to membrane separation treatment) and the amount of SS in the wastewater obtained by passing water for 48 hours were measured, and the SS residual ratio in the module was calculated by the following formula. .
  • the feed water SS concentration and the amount of SS in the wastewater were measured as the dry weight of the filtered material obtained when these waters were filtered through glass filter paper having a diameter of 47 mm and a pore diameter of 1 ⁇ m. The results are shown in Table 1.
  • Table 1 shows the following.
  • the flocs became fine, so that the membrane was likely to be clogged and the rate of increase in the differential pressure tended to increase (Comparative Example 1).
  • the molecular weight of the cationic polymer is increased, flocs are coarsened, so that they are easily deposited in the module, and the SS residual ratio is increased (Comparative Example 2). From these results, it is understood that the proper mass average molecular weight of the cationic polymer is 100,000 to 8 million, and desirably 200,000 to 1 million from the viewpoint of membrane contamination.
  • Example I Using the following inorganic flocculant and cationic polymer, an experiment was conducted to examine the effect of the addition order of the inorganic flocculant and the cationic polymer.
  • Inorganic flocculant Ferric chloride
  • Cationic polymer Polydiallyldimethylammonium chloride having a mass average molecular weight of 200,000 (colloid equivalent 5.9 meq / g, intrinsic viscosity 0.75 dg / L)
  • Test water Model water to which phosphoric acid (phosphoric acid was added for the purpose of dispersing the inorganic flocculant) was added to domestic industrial water so as to be 6 mg / L asP was used.
  • the test method is as follows.
  • inorganic flocculant (ferric chloride) as a 38% aqueous solution and 0.6 mg / L of cationic polymer (as pure component) are added to the test water, and the pH is adjusted to 5 using a pH adjuster (sodium hydroxide).
  • No. 5 was subjected to flocculation treatment, and the obtained flocculation water was designated After filtration through 5A filter paper, the filtrate was filtered under reduced pressure at ⁇ 500 mmHg using a cellulose acetate membrane filter having a diameter of 25 mm and a pore diameter of 0.45 ⁇ m.
  • the time required to filter the first 150 mL is T1 (seconds)
  • the time required to filter the next 150 mL is T2 (seconds)
  • the aggregation treatment procedure using the inorganic flocculant and the cationic polymer was as follows for each example.
  • Experimental Example I-1 Additional cationic flocculant after addition of inorganic flocculant: Inorganic flocculant was added while rapidly stirring the test water at 150 rpm, then adjusted to pH 5.5 using a pH adjuster, and further for 5 minutes While stirring rapidly, the cationic polymer was added with rapid stirring and reacted for 5 minutes, and then the mixture was gently stirred at 50 rpm for another 5 minutes for aggregation treatment.
  • Example II Using the same inorganic flocculant and cationic polymer as those used in Experimental Example I, an experiment was conducted to examine the effect of the cationic polymer on wastewater containing an organic acid having a chelating effect.
  • the wastewater from the plating process of a domestic semiconductor factory dissolved organic matter concentration including organic acid 10 to 20 mg / L, copper concentration 6 mg / L was used.
  • the test method is as follows.
  • Aggregation treatment was performed for the purpose of removing copper in the test water.
  • 500 mg / L of an inorganic flocculant (ferric chloride) as a 38% aqueous solution was added while rapidly stirring the test water at 150 rpm, and then adjusted to pH 9 using a pH adjuster (sodium hydroxide).
  • 0-5 mg / L of a cationic polymer (addition amount shown in Table 2 as a pure content) was added with rapid stirring and reacted for 5 minutes. Thereafter, the flocs were grown by gently stirring at 50 rpm for another 5 minutes.
  • the obtained agglomerated treated water was No.
  • the copper ion concentration in the filtrate was measured. It means that the lower the copper ion concentration, the more effectively the aggregation treatment is performed and the better the aggregation state.
  • the results are shown in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Water Supply & Treatment (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Polymers & Plastics (AREA)
  • Environmental & Geological Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Un procédé de traitement d'eau dans lequel un floculant inorganique est ajouté à l'eau d'intérêt pour effectuer un traitement de floculation d'eau puis l'eau est soumise à une séparation par membrane à l'aide d'un appareil de séparation par membrane, le floculant inorganique étant ajouté à l'eau, puis le traitement de floculation est effectué en ajoutant un polymère cationique soluble dans l'eau ayant un poids moléculaire moyen en masse de 100000 à 8000000 à l'eau, puis l'eau qui a subi le traitement de floculation est directement soumise à une séparation par membrane à l'aide d'un appareil de séparation à membrane.
PCT/JP2019/017115 2018-04-25 2019-04-23 Procédé de traitement d'eau et dispositif de traitement d'eau WO2019208532A1 (fr)

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Publication number Priority date Publication date Assignee Title
JP7403387B2 (ja) * 2020-05-29 2023-12-22 水ｉｎｇ株式会社 凝集膜ろ過システムおよび凝集膜ろ過方法
JP7074156B2 (ja) * 2020-06-01 2022-05-24 栗田工業株式会社 水処理方法及び水処理装置

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10180008A (ja) * 1996-12-26 1998-07-07 Kurita Water Ind Ltd 膜分離装置
US6416668B1 (en) * 1999-09-01 2002-07-09 Riad A. Al-Samadi Water treatment process for membranes
WO2009020157A1 (fr) * 2007-08-07 2009-02-12 Kurita Water Industries Ltd. Procédé de séparation par membrane et dispositif de séparation par membrane
WO2014103860A1 (fr) * 2012-12-25 2014-07-03 東レ株式会社 Procédé de traitement d'eau
WO2015045093A1 (fr) * 2013-09-27 2015-04-02 栗田工業株式会社 Méthode de traitement des eaux
WO2017130456A1 (fr) * 2016-01-29 2017-08-03 栗田工業株式会社 Procédé et dispositif de clarification d'eau industrielle

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10180008A (ja) * 1996-12-26 1998-07-07 Kurita Water Ind Ltd 膜分離装置
US6416668B1 (en) * 1999-09-01 2002-07-09 Riad A. Al-Samadi Water treatment process for membranes
WO2009020157A1 (fr) * 2007-08-07 2009-02-12 Kurita Water Industries Ltd. Procédé de séparation par membrane et dispositif de séparation par membrane
WO2014103860A1 (fr) * 2012-12-25 2014-07-03 東レ株式会社 Procédé de traitement d'eau
WO2015045093A1 (fr) * 2013-09-27 2015-04-02 栗田工業株式会社 Méthode de traitement des eaux
WO2017130456A1 (fr) * 2016-01-29 2017-08-03 栗田工業株式会社 Procédé et dispositif de clarification d'eau industrielle

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