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WO2015076371A1 - Adsorbant polymère hydrophile et procédé de traitement de l'eau utilisant celui-ci - Google Patents

Adsorbant polymère hydrophile et procédé de traitement de l'eau utilisant celui-ci Download PDF

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Publication number
WO2015076371A1
WO2015076371A1 PCT/JP2014/080911 JP2014080911W WO2015076371A1 WO 2015076371 A1 WO2015076371 A1 WO 2015076371A1 JP 2014080911 W JP2014080911 W JP 2014080911W WO 2015076371 A1 WO2015076371 A1 WO 2015076371A1
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Prior art keywords
water
adsorbent
hydrophilic polymer
adsorption
membrane
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Ceased
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PCT/JP2014/080911
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English (en)
Japanese (ja)
Inventor
森川圭介
立花祐貴
涌井孝
藤原直樹
渡辺義公
山村寛
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Kuraray Co Ltd
Chuo University
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Kuraray Co Ltd
Chuo University
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Priority claimed from JP2013243150A external-priority patent/JP2017018842A/ja
Priority claimed from JP2014053176A external-priority patent/JP2017018844A/ja
Priority claimed from JP2014053175A external-priority patent/JP2017018843A/ja
Application filed by Kuraray Co Ltd, Chuo University filed Critical Kuraray Co Ltd
Publication of WO2015076371A1 publication Critical patent/WO2015076371A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3425—Regenerating or reactivating of sorbents or filter aids comprising organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
    • 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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/20—Prevention of biofouling

Definitions

  • the present invention relates to an adsorbent having adsorptivity to organic carbon (particularly a causative substance that causes membrane fouling) contained in raw water obtained from a natural environment or an artificial environment, and a water treatment using the same. Regarding the method.
  • DOC dissolved organic carbon
  • Patent Document 1 DOC is a term encompassing organic carbon, organic colorants, and natural organic substances, and humic acid and fulvic acid, which is a mixture of organic compounds formed by decomposition of plant residues. Such humic substances are also included, and the main compounds and materials constituting the DOC are soluble and cannot be easily separated from water.
  • patent document 1 a. Adding an ion exchange resin to water containing dissolved organic carbon; b. Dispersing the resin in the water to allow adsorption of the dissolved organic carbon onto the resin; and c. It proposes a method for removing dissolved organic carbon from water by separating the resin loaded with the dissolved organic carbon from the water. And d. A process for regenerating a resin loaded with organic carbon has also been proposed.
  • ultrafiltration (UF) membrane microfiltration (MF) membrane, nanofiltration (NF) membrane, reverse osmosis (RO) in the field of water treatment such as water purification, ultrapure water, pharmaceutical water, domestic water purification, wastewater purification, etc.
  • UF ultrafiltration
  • MF microfiltration
  • NF nanofiltration
  • RO reverse osmosis
  • Membranes are becoming popular. Although these membrane filtrations allow high-level water treatment, on the other hand, membranes used for water treatment cause membrane fouling as the operating time elapses.
  • Biofouling which is membrane contamination with organic carbon, is a physically irreversible fouling and is currently a major problem in water treatment by membrane filtration.
  • a water treatment method has been proposed in which an activated carbon treatment, an adsorption treatment with a porous inorganic adsorbent, a coagulation treatment, a treatment using ozone treatment, or the like is provided in the front stage of the filtration membrane.
  • the adsorptivity of organic carbon is insufficient in the activated carbon treatment or the adsorption treatment with the porous inorganic adsorbent.
  • the agglomeration treatment has a drawback that a large amount of an aggregating agent such as ferric chloride needs to be added when the organic carbon concentration increases. Further, there is a problem that aggregation of organic carbon having high hydrophilicity becomes incomplete.
  • Ozone treatment has the problem of disinfection by-products such as bromic acid, and alternative techniques are required.
  • Non-Patent Document 1 the causative substances of physically irreversible membrane fouling are aromatic carbons such as humic acid and fulvic acid among organic carbons. It has been reported that biopolymers such as saccharides and proteins, which are organic carbons having relatively higher hydrophilicity than hydrophobic substances having a family ring, are the main causes. Further, in Non-Patent Document 2, the phenomenon that the RO membrane permeation performance is reduced is caused by biofouling caused by the growth of microorganisms, and the biofouling is greatly contributed by polysaccharides that are nutrients for microorganisms. Has been reported.
  • Patent Document 2 proposes a removal method using a colloidal adsorbent as a technique for adsorbing and removing saccharides.
  • Patent Document 3 exemplifies zeolite and activated carbon, and a regeneration method is also proposed.
  • Patent Document 4 proposes a method of using, as an adsorbent, particles made of a cationic polymer that swells in water and does not substantially dissolve in water.
  • the adsorbent of the invention of Patent Document 1 is mainly an adsorbent having a hydrophobic main skeleton, organic carbon having a high hydrophilicity, especially a causative substance of physically irreversible membrane fouling is used. It cannot be removed efficiently. Further, with the colloidal adsorbent used in the invention of Patent Document 2, it is difficult to regenerate the adsorbent.
  • the invention of Patent Document 3 discloses a method for removing a biopolymer by physical adsorption using surface pores. However, in the case of physical adsorption using pores, physics using surface pores is disclosed.
  • any of the adsorbents illustrated in the first place requires a large amount of adsorbent because the adsorption performance of the highly hydrophilic biopolymer is insufficient.
  • an adsorbent regeneration method is also exemplified.
  • an aqueous medium that is a regeneration medium is formed even inside an adsorbent having a hydrophobic resin as a main skeleton. Since the medium does not penetrate sufficiently, there is a concern that the reproduction efficiency is poor. Also in Patent Document 3, it is considered difficult to efficiently remove and regenerate the biopolymer clogged in the pores.
  • the particles made of the cationic polymer disclosed in Patent Document 4 have a particle size in water of about 10 to 200 times (that is, 1000 to 200000%) with respect to the particle size when not swollen with water. Since it has an extremely large swellability, it is difficult to handle during the adsorption and regeneration treatment, and has a problem that the liquid permeability is lowered due to adhesion between particles, particularly in a closed environment.
  • the object of the present invention is to efficiently adsorb organic carbon (especially biopolymer) having relatively high hydrophilicity, such as saccharides and proteins, which is a membrane contaminant of membrane filtration in view of the above-described circumstances.
  • An object of the present invention is to provide a polymer adsorbent that can be used.
  • Another object of the present invention is to provide a water treatment method that not only enables efficient water treatment using such a polymer adsorbent, but also maintains the water permeability of the membrane over a long period of time. .
  • Still another object of the present invention is to provide organic carbon contained in raw water obtained from a natural environment or an artificial environment, in particular, a causative substance of physically irreversible membrane fouling, and a biopolymer reported to be the main cause thereof. It is to provide a water treatment method capable of efficiently adsorbing and adsorbing the adsorbent after adsorption by a simple method.
  • the inventors of the present invention have intensively studied to achieve the above object, and as a result, have found the following configurations.
  • the degree of swelling in water at 25 ° C. is 20 to 500% (for example, 20 to 400%), has a hydrophilic polymer as a main skeleton, and at least a part of organic carbon in the water to be treated. It is a hydrophilic polymer adsorbent having a functional group capable of forming a bond with a component (hereinafter referred to as a bond forming group).
  • the bond-forming group has an ability to form at least one bond selected from the group consisting of a hydrogen bond, an ionic bond, and a chelate bond with respect to the adsorbed component. It may be. Further, the bond-forming group may be a different type from the hydrophilic group contained in the hydrophilic polymer.
  • the bond-forming group may be a bond-forming group containing at least one element selected from the group consisting of N, S, P and O, for example.
  • the bond-forming group is preferably at least one selected from the group consisting of amino groups, quaternary ammonium groups, and salts thereof.
  • the component adsorbed in the adsorption step may contain a biopolymer.
  • the adsorbed components include components with a retention time of 25 to 38 minutes measured by the method described in Stefan A. Huber et al. Water Research 45 (2011) pp879-885. May be.
  • the removal rate of the biopolymer may be 15% or more.
  • the hydrophilic polymer adsorbent preferably has higher biopolymer adsorbability than humic adsorbent, for example, biopolymer model water at 25 ° C. (sodium alginate concentration: 4.3 mg-C / L sodium alginate) Aqueous solution) and humic model water (sodium humate concentration: 4.3 mg-C / L sodium humate aqueous solution), sodium alginate adsorption rate (A), sodium humate adsorption rate (B), The ratio of (A) / (B) may be 1.0 to 10.
  • the adsorption rate (A) of sodium alginate is 30% or more. There may be.
  • the hydrophilic polymer is polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl acetal (eg, polyvinyl formal, polyvinyl butyral), polyvinyl alkyl alcohol, polyalkylene glycol, polyvinyl alkyl.
  • At least one selected from ether, polyalkylene oxide, poly (meth) acrylamide, cationic polymer, anionic polymer, phenol resin, polyamide, polyvinylpyrrolidone, cellulose derivative, dextrin, chitin, and chitosan Also good.
  • the polymer adsorbent may have a hydrophilic polymer as a main skeleton, and a bond-forming group is introduced into the hydrophilic polymer.
  • the polymer adsorbent may be a polymer alloy including a bond-forming group-containing polymer (A) and a hydrophilic matrix polymer (B).
  • the hydrophilic polymer or hydrophilic matrix polymer (B) includes polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl acetal, polyvinyl alkyl alcohol, polyalkylene glycol, polyvinyl alkyl ether, polyalkylene oxide, poly ( It may contain at least one selected from the group consisting of (meth) acrylamide, cationic polymer, anionic polymer, phenol resin, polyamide, polyvinylpyrrolidone, cellulose derivative, dextrin, chitin, and chitosan.
  • the second configuration of the present invention is as follows: A water treatment method comprising at least an adsorption step in which water to be treated containing organic carbon is brought into contact with the hydrophilic polymer adsorbent to adsorb at least a part of the organic carbon.
  • the water to be treated may be raw water obtained from a natural environment or an artificial environment, and may be, for example, fresh water or water containing salts.
  • the water treatment method may further include a membrane filtration step in which the adsorption treated water obtained in the adsorption step is subjected to membrane filtration by a membrane filtration treatment.
  • the membrane filtration step is performed using at least one membrane selected from the group consisting of an ultrafiltration (UF) membrane, a microfiltration (MF) membrane, a nanofiltration (NF) membrane, and a reverse osmosis (RO) membrane. Or it may be performed in multiple stages.
  • UF ultrafiltration
  • MF microfiltration
  • NF nanofiltration
  • RO reverse osmosis
  • the water treatment method may further include a regeneration step in which the adsorbent after the adsorption step is brought into contact with an aqueous medium to regenerate the adsorbent.
  • the aqueous medium used in the regeneration step may be water or a metal ion-containing aqueous solution (for example, an alkali metal ion-containing aqueous solution).
  • the temperature of the aqueous medium may be about 40 ° C. to 110 ° C.
  • the present invention is a polymer adsorbent used for water treatment
  • the polymer adsorbent is a hydrophilic polymer adsorbent having a degree of swelling of 20 to 500% in water at 25 ° C.
  • the polymer adsorbent includes a polymer adsorbent that can adsorb at least a part of organic carbon contained in raw water and can be regenerated after the adsorption step. May be.
  • an adsorbent regeneration method in which the polymer adsorbent adsorbing at least part of organic carbon contained in raw water is regenerated by contact with an aqueous medium. It may be included.
  • the first configuration of the present invention by using a specific hydrophilic polymer adsorbent, organic carbon contained in raw water, which has been difficult to remove in the past, particularly physically irreversible membrane fouling is generated.
  • Causative substances especially highly hydrophilic biopolymers such as sugars and proteins
  • the second configuration of the present invention by performing water treatment using the hydrophilic polymer adsorbent, organic carbon in the adsorption treated water (water subjected to the adsorption treatment), particularly the cause of membrane fouling. The amount of substance can be reduced.
  • the adsorbent after the adsorption step can be regenerated by simply desorbing the adsorbent from the adsorbent by contact with an aqueous medium. Furthermore, if necessary, the regenerated adsorbent can be effectively used again for the adsorption treatment.
  • membrane fouling when using the adsorption treated water that has undergone the adsorption treatment, when combined with various membrane filtration steps, membrane fouling, particularly physically, can be achieved by a simple method. It is possible to suppress the occurrence of irreversible membrane fouling and maintain the water permeability of the filtration membrane over a long period of time.
  • the hydrophilic polymer adsorbent can also be packed into a column.
  • a simple method is obtained by combining the organic carbon removal step by using the column and the membrane filtration step.
  • the water permeability can be maintained for a long time.
  • the hydrophilic polymer adsorbent which is the first embodiment of the present invention will be described.
  • the hydrophilic polymer adsorbent according to the first embodiment has a swelling degree of 20 to 500% in water at 25 ° C., and has a functionality capable of forming a bond with at least a part of the organic carbon in the water to be treated. It is a hydrophilic polymer adsorbent having a group (hereinafter referred to as a bond-forming group).
  • the wettability to water is increased, and at least some components of organic carbon, especially the causative substances that cause physically irreversible membrane fouling, are adsorbed by appropriate swelling. It can penetrate into the material.
  • the internal adsorptive functional group can also be used effectively, and clogging with organic carbon is unlikely to occur, so that excellent organic carbon removing ability can be expressed.
  • the infiltrated component is captured by an interaction such as a hydrogen bond, a coordination bond, a chelate bond, or an ionic bond by a group capable of forming a bond with this component (bond-forming group), and the adsorbent Efficiently removes at least some components of organic carbon, especially those that cause physically irreversible membrane fouling (especially biopolymers that are beginning to be considered to be highly hydrophilic and a concern for membrane contamination) It is presumed that it can be adsorbed.
  • the degree of swelling of the hydrophilic polymer adsorbent in water at 25 ° C.
  • the degree of swelling is controlled within a predetermined range, even when a hydrophilic polymer is used as the main skeleton, while suppressing the deterioration of the handleability of the adsorbent due to excessive swelling, It is possible to adsorb organic carbon efficiently.
  • the hydrophilic polymer adsorbent has a controlled degree of swelling, unlike the cationic polymer described in Patent Document 4 that swells in water and does not substantially dissolve in water, the hydrophilic polymer adsorbent is previously swollen in water. You may make it contact with to-be-processed water, without performing a process.
  • swelling property is controlled, even if it is a water-containing state, it is excellent in the distribution
  • the hydrophilic polymer adsorbent is a functional group capable of forming a bond with at least a part of the organic carbon contained in the raw water (especially a causative substance that causes physically irreversible membrane fouling) ( Or a bond-forming group).
  • the bond-forming group can form various bonds (for example, hydrogen bond, coordination bond, chelate bond, ionic bond, etc.) with the adsorbing component. By such various bonds, the component can be adsorbed to the adsorbent.
  • examples of the bond-forming group include a hydrogen bond-forming group, a chelate-forming group, a cationic ion-exchange group, and an anion ion-exchange group.
  • the organic carbon contained in the raw water with respect to the adsorbent particularly physical There is no particular limitation as long as adsorbability to a causative substance that causes irreversible membrane fouling can be imparted.
  • the bond-forming group may be a bond-forming group containing at least one element selected from the group consisting of N, S, P and O, for example.
  • functional groups include amino groups (primary amino groups, secondary amino groups, tertiary amino groups), quaternary ammonium groups, iminium groups, imidazole groups, quaternary imidazolium groups, pyridyl groups.
  • These functional groups may be present in a salt state.
  • These functional groups may be present alone or in combination of two or more.
  • preferred functional groups include amino groups, quaternary ammonium groups, iminium groups, imidazole groups, quaternary imidazolium groups, pyridyl groups, quaternary pyridinium groups, and salts thereof, more preferably amino groups. Quaternary ammonium groups and their salts are mentioned.
  • the hydrophilic polymer adsorbent has a hydrophilic polymer as a main skeleton, and when the hydrophilic polymer is produced, a bond-forming group may be introduced by polymerization or post-modification.
  • the bond-forming group may be introduced by alloying the component having a hydrophilic polymer component.
  • the hydrophilic polymer adsorbent may have a hydrophilic polymer as a main skeleton, and the hydrophilic polymer itself may have a bond-forming group in its structure.
  • the hydrophilic polymer adsorbent can introduce a bond-forming group into the main chain or side chain by homopolymerizing or copolymerizing a monomer (or a derivative thereof) containing the bond-forming group.
  • the copolymerization may be a copolymerization of monomers (or derivatives thereof) containing a bond-forming group, a monomer (or derivative thereof) containing a bond-forming group, and a monomer (not containing a bond-forming group). Or copolymerization thereof).
  • the hydrophilic polymer adsorbent may have a hydrophilic polymer as a main skeleton, and a bond forming group may be introduced into the hydrophilic polymer.
  • a bond-forming group may be introduced by post-modification.
  • the bond-forming group to be introduced may be a different type of functional group from the hydrophilic group of the hydrophilic polymer.
  • the amount of the bond-forming group introduced is 2 to 100 mol%, preferably 3 to 95 mol%, more preferably 5 to 90 mol%, based on the total number of monomer units in the polymer. There may be.
  • the polymer adsorbent may have a hydrophilic polymer as a main skeleton and a bond-forming group is introduced into the hydrophilic polymer.
  • a polymer alloy in which a hydrophilic polymer as a main skeleton constitutes a matrix component may be used.
  • the hydrophilic polymer has a solubility parameter ( ⁇ ) calculated by the following formula using the cohesive energy density (Ecoh) and molar molecular volume (V) calculated by the Fedor's estimation method. A certain polymer may be sufficient.
  • the solubility parameter ( ⁇ ) is preferably 24 or more, and more preferably 25 or more.
  • the upper limit of the solubility parameter is not particularly limited, but may be about 35, for example.
  • hydrophilic polymer examples include a polymer having a hydrophilic group such as a hydroxyl group, an ether group, a cationic group, an anionic group, and an amide group in a repeating unit.
  • hydrophilic polymer examples include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl acetal (eg, polyvinyl formal, polyvinyl butyral), polyvinyl alkyl alcohol, polyalkylene glycol, polyvinyl alkyl ether, polyalkylene oxide, Poly (meth) acrylamide, cationic polymer (eg, polyethyleneimine, polyallylamine, polyvinylamine, polyamidoamine dendrimer, polypyridine, polyvinylpyridine, polyamino acid, polydiallyldimethylammonium halide, polyvinylbenzyltrimethylammonium halide, polydiacryldimethylammonium halide , Polydimethylaminoethyl methacrylate hydrochloride, polynucleotide ), Anionic polymers (for example, polystyrene sulfonic acid, polyvinyl sulfate, poly (methacryl
  • These polymers may have other comonomer units (eg, monomer units having unsaturated carboxylic acid units such as maleic acid, itaconic acid, acrylic acid, silanol groups, aldehyde groups, or sulfonic acid groups). Good.
  • the content of the comonomer unit is preferably 10 mol% or less, more preferably 5% mol or less in all monomer units.
  • the weight average molecular weight of the hydrophilic polymer can be appropriately set in accordance with the type of the polymer.
  • the weight average molecular weight of the hydrophilic polymer is at least 5000 or more (for example, from 5000 to 100,000), preferably 10,000 or more.
  • a weight average molecular weight can be calculated
  • Particularly preferred hydrophilic polymers include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl acetal (polyvinyl formal, polyvinyl butyral), and polyamide (for example, polyamide 6, polyamide 10, polyamide 6,6, polyamide 11, polyamide). 12, polyamide 6,12, polyamide 6,10, polyamide 6 / 6,6 copolymer, polyamide 6,6 / 6,10 copolymer, polyamide 6,11, polyamide 6,6 / 6,10 / 6
  • An ethylene-vinyl alcohol copolymer is particularly preferable from the viewpoint of not only water resistance but also excellent organic carbon (particularly biopolymer) adsorption performance, moldability and hydrophilicity.
  • the content of ethylene units is preferably 20 to 60 mol%, more preferably 25 to 55 mol% (for example, 25 to 50 mol%) in all monomer units. Good. If the ethylene content is too small, the durability may deteriorate. On the other hand, when there is too much ethylene content, there exists a possibility that hydrophilicity may fall.
  • the polyvinyl alcohol may be defined by the viscosity average degree of polymerization, and the viscosity average degree of polymerization obtained from the viscosity of the 30 ° C. aqueous solution can be selected from a wide range of about 100 to 15000, for example. From the viewpoint of improving durability, those having a high degree of polymerization are preferably used. In this case, for example, the viscosity average degree of polymerization is preferably about 800 to 13000, and more preferably about 1000 to 10,000.
  • the degree of saponification of polyvinyl alcohol can be appropriately selected according to the purpose and is not particularly limited. For example, it may be 88 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more. Good. In particular, from the viewpoint of improving durability, those having a saponification degree of 98 mol% or more are preferred.
  • the polymer adsorbent of the present invention uses the above hydrophilic polymer as a matrix component and is alloyed with a component having a bond-forming functional group (bond-forming group) to convert the bond-forming group into a hydrophilic polymer. It may be introduced. From the viewpoint of ease of introduction, the polymer adsorbent is preferably a polymer alloy of a bond-forming group-containing polymer (A) and a hydrophilic polymer matrix (B).
  • the bond-forming group-containing polymer (or chemisorbable functional group-containing polymer) (A) is polystyrene sulfonic acid (PSS), polyvinyl sulfate (PVS), polyacrylic acid (PAA), polymethacrylic acid (PMA).
  • Anionic polymers such as polymaleic acid and polyamic acid; polyethyleneimine, polyallylamine, polyvinylamine, polyamidoamine dendrimer, polypyridine, polyvinylpyridine, polyamino acid, polydiallyldimethylammonium halide, polyvinylbenzyltrimethylammonium halide
  • Cationic polymers such as polydiacryldimethylammonium halide, polydimethylaminoethyl methacrylate hydrochloride, and polynucleotide may be used. Such polymers may be used alone or in combination of two or more.
  • adsorbing organic carbon contained in raw water particularly causative substances (particularly biopolymers) that cause physically irreversible membrane fouling, in combination with a hydrophilic matrix polymer.
  • a polymer having a high cation density for example, polyethyleneimine, polyallylamine, etc. is preferable.
  • the hydrophilic matrix polymer (B) may be the predetermined hydrophilic polymer described above.
  • the bond-forming group-containing polymer (A) and the hydrophilic matrix polymer (B) in the alloy of the bond-forming group-containing polymer (A) and the hydrophilic polymer matrix (B). ) Is not particularly limited as long as the polymer (A) is dispersed within a predetermined range.
  • the polymer (A) / polymer (B) is approximately 1/99 to 70/30 in mass ratio. It may be about 5/95 to 65/45, more preferably about 8/92 to 60/40.
  • the polymer (A) is preferably dispersed in the hydrophilic matrix polymer (B).
  • the hydrophilic polymer adsorbent having organic carbon adsorptivity contains other polymer polymers as a resin component or a forming component within a range not impairing the effects of the present invention. Also good.
  • the hydrophilic polymer adsorbent of the present invention is, for example, a cross-linking agent, an antioxidant, a stabilizer, a lubricant, a processing aid, an antistatic agent, a colorant, an antifoaming agent, a dispersing agent, etc. if necessary. These various additives may be included.
  • the degree of swelling at 25 ° C. is 20 to 500% (for example, 20 to 400) in terms of mass% from the viewpoint of enabling the adsorption of biopolymers and improving the handling properties. %), Preferably 30 to 450%, more preferably 40 to 400%.
  • the swelling degree of the hydrophilic polymer adsorbent may be more preferably about 40 to 300% (for example, 40 to 200%), and still more preferably about 50 to 200% (for example, 50 to 160%). It may be.
  • the swelling degree of a hydrophilic polymer adsorbent shows the value measured by the method described in the Example mentioned later.
  • the swelling property of the hydrophilic polymer adsorbent may be controlled by crosslinking with a crosslinking agent and / or low swelling property or non-swelling property with respect to the bond-forming group-containing polymer (A). It may be controlled as an alloy material combining a hydrophilic matrix polymer (for example, ethylene-vinyl alcohol copolymer and polyamide).
  • a hydrophilic matrix polymer for example, ethylene-vinyl alcohol copolymer and polyamide
  • the hydrophilic polymer adsorbent of the present invention is preferably crosslinked with a crosslinking agent from the viewpoint of controlling durability and swelling property.
  • the crosslinking agent can be appropriately determined according to the type of the crosslinking reactive group of the hydrophilic polymer. For example, an epoxy group, a carboxyl group, a halogen group, an acid anhydride group, an acid halide group, a formyl group, N -A compound containing at least two functional groups of at least one or two or more selected from chloroformyl group, chloroformate group, amidinyl group, isocyanate group, vinyl group, aldehyde group, azetidine group, carbodiimide group, etc. It is done.
  • zirconyl crosslinking agents zirconyl nitrate, ammonium zirconium carbonate, zirconyl chloride, zirconyl acetate, zirconyl sulfate
  • titanium crosslinking agents titanium crosslinking agent, titanium lactate, titanium diisopropoxybis (triethanolamate)
  • Such a cross-linking agent can use various commercially available cross-linking agents, and is not particularly limited, but is selected from epoxy groups, halogen groups, isocyanate groups, vinyl groups, aldehyde groups, azetidine groups, carbodiimide groups, and the like.
  • a compound containing at least two functional groups of at least one kind or two or more kinds is preferred.
  • the crosslinking structure may be introduced with a crosslinking agent by using a copolymer component such as a divinyl monomer during the synthesis of the hydrophilic polymer adsorbent.
  • a copolymer component such as a divinyl monomer
  • melt kneading method in which the components of the hydrophilic polymer adsorbent, the crosslinking agent, and if necessary, optional components are melt kneaded using a biaxial kneader or the like can be mentioned. According to the melt kneading method, there is an advantage that it is easy to obtain an adsorbent in which each component is uniformly dispersed.
  • the hydrophilic polymer adsorbent material is molded by melt molding, solution molding, etc. to form molded bodies of various shapes
  • the molded body is immersed in a solution containing a crosslinking agent to introduce a crosslinked structure.
  • melt molding for example, a hydrophilic polymer adsorbent material excluding at least a crosslinking agent is melt-kneaded using a biaxial kneader or the like, and the melt-kneaded material is formed into various shapes by extrusion molding, injection molding, or the like.
  • the molded body may be subjected to crosslinking treatment by dipping in a solution containing a crosslinking agent.
  • a mixed solution is prepared using an appropriate solvent, and using this mixed solution, cast film formation or dry spinning, After obtaining a film-like or fibrous shaped body by wet spinning or the like, the shaped body may be dipped in a solution containing a crosslinking agent and subjected to a crosslinking treatment.
  • Such a polymer adsorbent is particularly excellent in absorbability of biopolymer, and biopolymer model water at 25 ° C. (sodium alginate concentration: 4.3 mg-C / L sodium alginate aqueous solution) and humic model water (
  • sodium alginate concentration: 4.3 mg-C / L sodium alginate aqueous solution) and humic model water
  • sodium alginate is used as the biopolymer model
  • sodium humate is used as the humic model.
  • each adsorption rate shows the value measured by the method described in the Example mentioned later.
  • the polymer adsorbent used in the present invention has an adsorption rate (A) of sodium alginate in biopolymer model water (sodium alginate concentration: 4.3 mg-C / L sodium alginate aqueous solution) at 25 ° C., for example. , 30% or more, preferably 35% or more, and more preferably 45% or more.
  • A adsorption rate of sodium alginate in biopolymer model water (sodium alginate concentration: 4.3 mg-C / L sodium alginate aqueous solution) at 25 ° C., for example. , 30% or more, preferably 35% or more, and more preferably 45% or more.
  • A adsorption rate
  • the hydrophilic polymer adsorbent can have various shapes as long as it can be used for adsorption treatment of at least a part of the organic carbon in the water to be treated (for example, biopolymer). It may be a shape, a fiber shape, various three-dimensional shapes or the like. From the viewpoint of improving the adsorption efficiency, the hydrophilic polymer adsorbent is preferably in the form of particles or fibers.
  • the particle diameter is not particularly limited, and can be selected from a wide range of 0.5 ⁇ m to 20 mm.
  • the particle diameter may be 1 ⁇ m or more, 10 ⁇ m or more, or 100 ⁇ m or more.
  • the particle diameter may be 10 mm or less, 5 mm or less, 4 mm or less, or 3 mm or less.
  • the particle size is preferably 1 ⁇ m to 5000 ⁇ m, more preferably 10 ⁇ m to 4000 ⁇ m, and most preferably 20 ⁇ m to 3000 ⁇ m.
  • a particle diameter shows the value classified by sieving.
  • the average particle diameter of the polymer adsorbent in a swollen state in 25 ° C. water may be, for example, 1 ⁇ m or more depending on the purpose, and may be 5 ⁇ m or more, 50 ⁇ m or more, more than 100 ⁇ m (for example, 110 ⁇ m or more). It may be 150 ⁇ m or more, or 200 ⁇ m or more.
  • the average particle diameter of the polymer adsorbent in a swollen state in 25 ° C. water may be 10 mm or less, 4.5 mm or less, 3.5 mm or less, or 3 mm. It may be the following. In addition, an average particle diameter shows the value measured by the method described in the Example mentioned later.
  • the average fiber diameter is not particularly limited, but can be selected from a wide range of 0.1 to 1000 ⁇ m, for example, 1 to 500 ⁇ m, preferably 2 It may be up to 200 ⁇ m.
  • the average fiber diameter can be calculated as an average fiber diameter by measuring the fiber diameter at 10 locations of fibers in a standard state defined by JIS L 0105 with a micrometer.
  • a continuous fiber may be sufficient and a short fiber may be sufficient.
  • the fiber length may be, for example, about 0.1 to 100 mm (for example, 1 to 100 mm), preferably about 0.5 to 80 mm (for example, 5 to 80 mm), more preferably 10 It may be about 50 mm.
  • Water treatment method 2nd Embodiment of this invention is equipped with the to-be-processed water containing organic carbon, and a specific hydrophilic polymer adsorbent, and is provided with the adsorption
  • Water treatment method may include a filtration step of performing membrane filtration on the adsorption-treated water subjected to the adsorption treatment.
  • the water to be treated can use various raw waters obtained in natural and artificial environments as water to be treated, it contains organic carbon, especially the causative substances that cause physically irreversible membrane fouling.
  • organic carbon especially the causative substances that cause physically irreversible membrane fouling.
  • as raw water in general river water, lake water, seawater (salt content 2 to 4% by mass), brackish water (salt content 0.5 to 2% by mass), oil fields and gas fields
  • Examples include associated water generated, soil elution water, irrigation water, biologically treated water, biologically treated water in sewage treatment and human waste treatment facilities, highly treated water such as tertiary treatment, and various factory effluents.
  • the raw water that is the treated water may contain organic carbon, particularly a causative substance that causes physically irreversible membrane fouling, and water that contains 0.5% by mass or more of salt,
  • organic carbon particularly a causative substance that causes physically irreversible membrane fouling
  • water that contains 0.5% by mass or more of salt For example, water containing various salts obtained from raw water in the natural environment, such as water with higher salt concentration, obtained by treating the raw water such as seawater, is used as raw water that is to be treated. Can do.
  • the water to be treated may have a salt concentration of 0.5% by mass or more (for example, about 0.5 to 30% by mass), 1% by mass or more, or 2% by mass or more.
  • Examples of the salt in the water to be treated include alkali metal salts such as sodium chloride and potassium chloride; alkaline earth metal salts such as magnesium chloride, magnesium sulfate, calcium chloride, and calcium sulfate. Can be calculated as the concentration of the total amount of these salts.
  • the salt may be a salt that makes the aqueous solution neutral.
  • the organic carbon contained in the raw water usually means an organic compound constituting the total organic carbon (TOC) contained in the raw water described above.
  • the organic carbon includes dissolved organic carbon (Dissolved Organic carbon) and particulate organic carbon (POC).
  • the causative substance that causes physically irreversible membrane fouling is a kind of organic carbon, and it is difficult to remove substances that are difficult to remove by means such as physical backwashing when performing membrane filtration. I mean.
  • specific causative substances are still under study, when the treated water that has undergone the adsorption process of the present invention is supplied to the membrane treatment process, the treated water is supplied to the membrane treatment process without going through the adsorption process. Thus, the lifetime of the film in the film processing step can be improved. Therefore, even if the causative substance is not specifically identified, it is possible to confirm that the amount of causative substance that causes physically irreversible membrane fouling can be reduced by the adsorption process.
  • the causative substances adsorbed in the adsorption process belong to organic substances having a particle diameter of 0.45 ⁇ m or less that are considered difficult to desorb when physically adsorbed. It may be a substance.
  • organic substances having a particle size of 0.45 ⁇ m or less include aromatic-containing organic substances such as humic acid and fulvic acid, synthetic chemical substances such as surfactants, biopolymers, etc.
  • the adsorbed component is a hydrophilic compound having 100,000 daltons or more, and the retention time during which a humic signal peak appears in LC-OCD in which a wet total organic carbon measuring instrument is connected to high performance liquid chromatography. It may be a substance that exhibits a signal peak in a shorter holding time.
  • the adsorption step it is preferable to adsorb at least the biopolymer as a component of at least a part of the causative substance by the polymer adsorbent.
  • Biopolymers are compounds (for example, polysaccharides and proteins) having hydrophilic high molecular weight (for example, 100,000 daltons or more). More specifically, the A fraction measured by the method described in Stefan A. Huber et al. Water Research 45 (2011) pp879-885, for example, the retention time by LC-OCD is 25 to 38 minutes. There may be. In the examples, a component having a holding time of 25 minutes or more and 38 minutes or less is measured as a biopolymer in the analysis of LC-OCD (manufactured by DOC-Labor) based on the above-described method. Further, the humic substance may be a B fraction in the measurement under the same conditions, for example, a component exceeding the holding time of 38 minutes and not more than 50 minutes.
  • Biopolymers are mainly composed of organic substances with few hydrophobic structures such as benzene rings and mainly high hydrophilicity.
  • biopolymers are composed of organic substances exhibiting an SUVA value of 1.0 [L / (m ⁇ mg)] or less. May be.
  • the humic substance contains not only a UV-absorbing structure because it contains a benzene ring, but also has a high hydrophobicity, for example, an SUVA value of 2.0 [L / (m ⁇ mg)] or more It may be composed of an organic material showing.
  • SUVA (L / mg-C ⁇ m) UV (m ⁇ 1 ) / DOC (mg-C / L)
  • each parameter for calculating the SUVA value was measured by the method described in Stefan A. Huber et al. Water Research 45 (2011) pp879-885, and "area value" The area value obtained by LC-OCD is expressed, “UV” indicates the absorbance at a wavelength of 254 nm, and “DOC” indicates the DOC concentration (mg-C / L) in the test sample.
  • DOC of biopolymer DOC of the entire test sample x area value of biopolymer in the spectrum (holding time t b : 25 minutes ⁇ t b ⁇ 38 minutes) / area value of the entire spectrum
  • Humic DOC DOC of the entire test sample x area value of humic substance in the spectrum (holding time t h : 38 minutes ⁇ t h ⁇ 50 minutes) / area value of the entire spectrum
  • the ion-exchange resins and chelate resins mainly composed of hydrophobic polymers such as styrene that are currently on the market have organic carbon contained in raw water, especially physically irreversible membrane fouling.
  • the resulting causative substance cannot be adsorbed efficiently.
  • a specific hydrophilic polymer adsorbent for example, even hydrophilic organic carbon can be adsorbed efficiently.
  • the adsorption step it is not particularly limited as long as the water to be treated and the hydrophilic polymer adsorbent can be brought into contact.
  • the adsorbent is added to the water to be treated, and known as necessary.
  • the adsorption treatment may be carried out by stirring by a method; or the adsorption treatment may be carried out by passing water to be treated through a column filled with a hydrophilic polymer adsorbent as a continuous type.
  • the adsorption step may be a single step or a multi-step.
  • the solid-liquid separation step may be performed by a known method as necessary, and the adsorbent after the adsorption treatment may be removed from the adsorption treatment liquid by the solid-liquid separation step. .
  • the temperature of the water to be treated in the adsorption step can be selected as long as the causative substance can be adsorbed.
  • the temperature of the water to be treated is, for example, 0 to 40 ° C. from the viewpoint of adsorptivity. It may be 5 to 35 ° C, more preferably 10 to 33 ° C.
  • the temperature of the water to be treated may be, for example, 10 to 40 ° C., preferably 15 to 35 ° C., more preferably 18 to 33 ° C. from the viewpoint of adsorptivity. May be.
  • the amount of adsorbent used for the water to be treated can be appropriately selected according to the type of water to be treated, the form of the adsorbent, etc.
  • the amount of adsorbent is It can be selected from a wide range of 0.05 to 50 g per liter of treated water, and may be, for example, about 0.05 to 30 g, preferably about 0.1 to 10 g.
  • the amount of the adsorbent may be about 0.1 to 50 g, preferably about 0.5 to 30 g, per liter of water to be treated. *
  • the adsorbent when the adsorbent is immersed in the water to be treated and stirred, the adsorbent may be stirred by mechanical stirring or bubble stirring.
  • the peripheral speed When performing mechanical stirring, the peripheral speed may be about 0.1 to 20 m / s, or about 0.3 to 15 m / s.
  • the flow rate of the water to be treated to the column is, for example, the superficial velocity that is a value obtained by dividing the treated water flow rate by the adsorbent volume. It may be about 0.5 ⁇ 500h -1 (for example, about 0.5 ⁇ 200h -1), preferably about 1 ⁇ 300h -1 (for example, about 1 ⁇ 150h -1).
  • the removal rate (or adsorption rate) of the biopolymer from the water to be treated may be, for example, 15% or more, preferably 20% or more, more preferably 30% or more.
  • a removal rate shows the value measured by the method described in the Example mentioned later. If the removal rate is too low, the effect of suppressing membrane contamination in the subsequent membrane filtration step may not be sufficient.
  • the adsorption-treated water (or supply water) subjected to the adsorption treatment may be subjected to membrane filtration in the membrane filtration step, if necessary.
  • membrane filtration By combining such membrane filtration, it is possible to purify water according to the application.
  • the membrane filtration step may be a single step or multiple steps. About the kind of film
  • the membrane filtration step is performed appropriately using a microfiltration membrane (MF membrane), an ultrafiltration membrane (UF membrane), a nanofiltration membrane (NF membrane), a reverse osmosis (RO) membrane, etc., depending on the purpose of water treatment. be able to.
  • MF membrane microfiltration membrane
  • UF membrane ultrafiltration membrane
  • NF membrane nanofiltration membrane
  • RO reverse osmosis
  • the adsorption process can reduce the amount of organic carbon contained in the raw water, particularly the causative substance that causes physically irreversible membrane fouling. It is possible to efficiently suppress the occurrence of membrane fouling.
  • these membranes may be used alone or in one or more stages for membrane filtration, or a plurality of types of membranes may be combined, and each one or more stages may be used for membrane filtration.
  • the membrane water may be further filtered with an NF membrane or a reverse osmosis (RO) membrane after membrane filtration treatment of the treated water supplied with the MF membrane or UF membrane.
  • RO reverse osmosis
  • the membrane material of the filtration membrane in the membrane filtration step is not particularly limited, and any known material can be applied.
  • the film material for the UF film and the MF film include cellulose acetate, polyacrylonitrile, polyethylene, polyethersulfone, polysulfone, polypropylene, polyvinylidene fluoride, and ceramic.
  • the film material of the NF film include polyamide-based, polypiperazine amide-based, polyester amide-based, or water-soluble vinyl polymer crosslinked.
  • Examples of the membrane material for the RO membrane include cellulose acetate and polyamide.
  • the membrane form is not particularly limited, and may be any shape such as a flat membrane, a tubular membrane, and a hollow fiber membrane.
  • the film thickness may be in the range of 10 ⁇ m to 1 mm, and in the case of a hollow fiber membrane, the inner diameter may be about 0.2 to 2 mm and the outer diameter may be about 0.4 to 5 mm.
  • the filtration membrane may have a fine porous structure such as a network structure, a honeycomb structure, or a fine gap structure.
  • filtration membranes may be modularized. For example, in the case of a flat membrane, a spiral type, a pleat type, a plate-and-frame type, or a disc type in which discs are stacked may be used. It may be a hollow fiber membrane type bundled in an I shape and stored in a container.
  • the filtration flow rate can be appropriately set according to the type of water supplied to the membrane, the type of filtration membrane, and the like. For example, when filtration is performed by the cross flow method, the filtration flow rate is from flux 0.5 to
  • the liquid may be passed through the filtration membrane at 5.0 (m 3 / m 2 / day), and may preferably be from Flux 1.0 to 4.0 (m 3 / m 2 / day).
  • organic carbon that is a causative substance of membrane fouling is caused from water supplied to the filtration membrane. Substances can be reduced. As a result, it is possible to suppress the occurrence of membrane fouling (particularly physically irreversible membrane fouling) in the filtration membrane, and it is possible to suppress the reduction of water permeability of the filtration membrane due to clogging of the filtration membrane. . Furthermore, since the amount of the causative substance in the supply water can be reduced, membrane fouling can be suppressed, the frequency of cleaning, the amount of cleaning chemical used can be reduced, and the life of the membrane can be extended.
  • the water treatment method of the present invention may be combined with an existing water treatment method as necessary within a range not impairing the effects of the invention.
  • the existing water treatment method include sand filtration treatment, coarse filtration treatment, coagulation sedimentation treatment, ozone treatment, adsorption treatment using an existing adsorbent or activated carbon, biological treatment, and the like. These treatments may be performed singly or in combination of two or more. Further, these water treatments may be appropriately performed before and / or after the adsorption treatment.
  • water from which particles having a particle diameter of 5 ⁇ m or more, preferably particles of 1 ⁇ m or more, more preferably particles larger than 0.45 ⁇ m are excluded by pretreatment for adsorption is used as water to be treated in the adsorption step.
  • particles having a particle diameter of 5 ⁇ m or more, preferably particles of 1 ⁇ m or more, more preferably particles larger than 0.45 ⁇ m are excluded by pretreatment for adsorption is used as water to be treated in the adsorption step. preferable.
  • the adsorbent that has adsorbed at least a part of the organic carbon in the adsorption step is separated by a known filtering means as necessary and is supplied to the regeneration step.
  • the adsorption-treated water that has been subjected to solid-liquid separation by filtering the adsorbent may be used in a membrane filtration step as needed, and membrane filtered in the filtration step.
  • the adsorbent may be regenerated by bringing an adsorbent that has adsorbed at least a part of the organic carbon into contact with an aqueous medium.
  • the aqueous medium is a medium composed of a liquid containing water as a main component (for example, 50% by mass or more), and may be, for example, water or an aqueous solution containing metal ions. Further, the contact with the aqueous medium in the regeneration step may be one stage or multiple stages, and in the case of multiple stages, a plurality of types of aqueous media may be used separately.
  • the metal ion used in the metal ion-containing aqueous solution is not particularly limited as long as the causative substance can be eliminated, but typically includes an alkali metal ion, specifically, an aqueous sodium chloride solution, Examples include potassium chloride aqueous solution, lithium chloride aqueous solution, sodium carbonate, potassium carbonate, lithium carbonate and the like.
  • the aqueous medium may be a metal ion-containing aqueous solution containing the same type of metal ions as the salts present in the water to be treated.
  • the concentration of the metal ion-containing aqueous solution can be selected from a wide range of, for example, about 0.1 to 50% by mass as a solute ratio with respect to water, and a low concentration (for example, about 0.1 to 10% by mass, preferably 0.3 to 8% by mass, more preferably about 0.5 to 8% by mass), and high concentration (for example, about 10 to 50% by mass, preferably 15 to 45% by mass, more preferably 20 to 40% by mass).
  • the temperature of the aqueous medium used in the regeneration step may be equal to or higher than the temperature of the liquid to be treated in the adsorption step, and preferably set to be higher than the temperature of the liquid to be treated in the adsorption step. Good.
  • the regeneration step is not particularly limited as long as the aqueous medium and the hydrophilic polymer regeneration material can be brought into contact with each other.
  • an adsorbent is added to the aqueous medium, and if necessary, a known method is used.
  • the regeneration treatment may be carried out by stirring; or as a continuous type, the regeneration treatment may be carried out by passing an aqueous medium through a column filled with a polymer adsorbent. Further, the regeneration step may be a single step or multiple steps.
  • an appropriate temperature can be selected as long as the causative substance can be eliminated, but the temperature of the aqueous medium is, for example, 40 to 110 ° C. from the viewpoint of elimination.
  • the temperature may be 45 to 100 ° C, more preferably 50 to 90 ° C.
  • the amount of the aqueous medium used for the adsorbent can be appropriately selected according to the type of the aqueous medium, the form of the adsorbent, the type of regeneration process (batch type or continuous type), and the like.
  • the adsorbent may be stirred by mechanical stirring, bubble stirring, or the like.
  • the peripheral speed may be about 0.1 to 20 m / s, or about 0.3 to 18 m / s. *
  • the adsorbent regenerated by the regeneration step may be separated by a known filtering means as necessary and may be provided again to the adsorption step.
  • the adsorbent in the regeneration process, can be efficiently regenerated by contact with the aqueous medium.
  • the adsorption rate of the adsorbent before and after the regeneration treatment can be evaluated as regeneration efficiency.
  • the regeneration efficiency may be 30% or more, preferably 50% or more, more preferably May be 80% or more, particularly preferably 90% or more. Note that the regeneration efficiency is a value measured by a method described in Examples described later.
  • an adsorption step in which raw water containing organic carbon is brought into contact with a polymer adsorbent, and at least a part of the organic carbon is adsorbed by the polymer adsorbent;
  • a water treatment method comprising at least a regeneration step of bringing the adsorbent adsorbing the components into contact with an aqueous medium and regenerating the adsorbent,
  • the polymer adsorbent may include a water treatment method that is a hydrophilic polymer adsorbent having a hydrophilic polymer as a main skeleton and having a specific functional group.
  • wettability to water is increased by using a hydrophilic polymer as a main skeleton, and at least a part of organic carbon, particularly a causative substance that causes physically irreversible membrane fouling is adsorbed.
  • the infiltrated component is, for example, an adsorbent having a group capable of forming a bond with this component (bond-forming group) such as a hydrogen bond, a coordinate bond, an ionic bond, or a chelate bond.
  • adsorbents are beginning to be considered at least some components of organic carbon, especially causative agents that cause physically irreversible membrane fouling (especially highly hydrophilic and a concern for membrane contamination) (Iii) Furthermore, the adsorbent after the adsorption treatment can be efficiently regenerated because the bond is broken by contacting with an aqueous medium. It is estimated.
  • Average particle size The average particle size of the adsorbents used in Examples and Comparative Examples was measured with a laser diffraction / scattering particle size distribution analyzer (manufactured by Horiba, Ltd.) after being immersed in water at 25 ° C. for 12 hours.
  • Average fiber diameter As for the average fiber diameter described in the examples, the fiber diameter was measured at 10 points of the obtained fiber with a micrometer, and the average value was defined as the average fiber diameter.
  • Biopolymer removal rate (Biopolymer concentration before adsorption step ⁇ Biopolymer concentration after adsorption step) / (Biopolymer concentration before adsorption step) ⁇ 100 (%)
  • Removal rate of humic substance (humic substance concentration before adsorption process ⁇ humic substance concentration after adsorption process) / (humic substance concentration before adsorption process) ⁇ 100 (%)
  • Example 1-1 Polyvinyl alcohol (“PVA-117” manufactured by Kuraray Co., Ltd.) 88 parts by mass and polyallylamine (“PAA-15C” manufactured by Nitto Bo Medical Co., Ltd.) 12 parts by mass are used, and these resins are dissolved in water. I let you. The solution was wet-spun into a saturated sodium sulfate bath at 40 ° C. from a nozzle having a diameter of 0.08 mm and a pore number of 1000, and taken up at a speed of 15 m / min. The formed yarn was further wet-drawn 2 times, dried at 130 ° C., and subjected to dry heat drawing 5 times at 230 ° C.
  • PVA-117 manufactured by Kuraray Co., Ltd.
  • PAA-15C polyallylamine
  • This fiber was further immersed in a 40 ° C. solution of 1% glutaraldehyde and 2% maleic acid to perform a crosslinking treatment to obtain a target adsorbent (fiber diameter 10 ⁇ m, fiber length 3 cm).
  • the degree of swelling of the obtained adsorbent at 25 ° C. was 65%.
  • the insoluble matter was removed by filtering with a mesh cartridge filter (TMP-2, manufactured by Advantech), and 5 g of the obtained hydrophilic polymer adsorbent was added to 1 L of the filtered water at 25 ° C. for 4 hours.
  • Laboplast mill contains 60 parts by mass of an ethylene-vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd., “F-101B”) and 40 parts by mass of polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., “Epomin SP-200”). After being melt-kneaded at 210 ° C., pulverization was performed to obtain a composite having a particle size of 0.6 to 1.2 mm. Further, this composite was subjected to a crosslinking treatment with a 2% solution of an epoxy compound (Denacol EX-810 (trade name) manufactured by Nagase ChemteX Corp.) at 25 ° C.
  • an epoxy compound (Denacol EX-810 (trade name) manufactured by Nagase ChemteX Corp.) at 25 ° C.
  • a target adsorbent particle diameter of 0.6 to 1). 0.2 mm.
  • the degree of swelling of the obtained adsorbent in 25 ° C. water was 125%.
  • the insoluble matter was removed by filtering with a stainless mesh cartridge filter (TMP-2, manufactured by Advantech), and 5 g of the obtained hydrophilic polymer adsorbent was added to 1 L of the filtered water at 4 ° C. Shaking time.
  • Example 1-3 75 parts of ethylene-vinyl alcohol copolymer (“E-105B” manufactured by Kuraray Co., Ltd.) and 25 parts of polyethyleneimine (“Epomin SP-200” manufactured by Nippon Shokubai Co., Ltd.) were tested at 210 After melt-kneading at 0 ° C., a pulverization treatment was performed to obtain a composite having a particle size of 0.1 to 0.2 mm.
  • This composite was subjected to a crosslinking treatment with a 25% solution of an epoxy compound (Denacol EX-810 (trade name) manufactured by Nagase ChemteX Corp.) at 2% to obtain a target adsorbent (particle diameter of 0.1 to 0.2 mm). )
  • the degree of swelling of the obtained adsorbent in 25 ° C. water was 82%.
  • the water to be treated was adsorbed and filtered in the same manner as in Example 1-2.
  • the long-term water permeability was A. The results are shown in Table 1.
  • Table 1 When the molecular weight distribution of the organic substance contained in the water to be used used in Example 1-3 was measured by LC-OCD, a spectrum as shown in FIG. 1 was obtained.
  • Example 1-4 A vinyl alcohol polymer having a mercapto group at the end was synthesized by the method described in JP-A-59-187005. The content (degree of saponification) of the vinyl alcohol unit determined by 1H-NMR measurement was 98.5 mol%, and the viscosity average degree of polymerization measured according to JIS K6726 was 1500. Next, 563 g of water and 110 g of the above-mentioned terminal mercapto group-containing polyvinyl alcohol were charged, and the mixture was heated to 95 ° C. with stirring in a nitrogen atmosphere to dissolve the polyvinyl alcohol, and then cooled to room temperature.
  • the content of the polymerizable unsaturated monomer in the copolymer, that is, in the polymer was measured.
  • the ratio of the number of vinylbenzyltrimethylammonium chloride monomer units to the total number of monomer units was 10 mol%.
  • 50 g of an aqueous solution of the polymer was added, and ion exchange water was added to prepare a solid concentration of 15%.
  • This aqueous solution was cast on a polyethylene terephthalate film using an applicator and dried at 80 ° C. for 30 minutes. The film thus obtained was heat treated at 170 ° C. for 30 minutes to cause physical crosslinking.
  • the membrane was immersed in 1 L of an aqueous solution in which 350 g of sodium sulfate was dissolved, concentrated sulfuric acid was added to the aqueous solution so that the pH was 1, and the membrane was further immersed as a 3% aqueous solution of glutaraldehyde.
  • Crosslinking treatment was carried out at 3 ° C. for 3 hours.
  • the membrane was washed with ion exchange water and dried to obtain a membrane having a thickness of 70 ⁇ m. This film was cut into 2 mm squares to form adsorbents.
  • the degree of swelling of the obtained adsorbent in water at 25 ° C. was 30%.
  • the water to be treated was adsorbed and filtered in the same manner as in Example 1-2.
  • the long-term water permeability was B. The results are shown in Table 1.
  • Example 1-2 As an adsorbent, water treatment was performed in the same manner as in Example 1-2 except that a commercially available granular activated carbon (Charcoal activated, manufactured by Wako Pure Chemical Industries, Ltd.) having a swelling degree in water at 25 ° C. of 58% was used. As a result of evaluating the water permeability of the manufactured MF membrane (Asahi Kasei Co., Ltd., pore size: 0.1 ⁇ m), the long-term water permeability was C. The results are shown in Table 1.
  • PVDF MF was prepared by performing water treatment in the same manner as in Example 1-2 except that a commercially available anion adsorbent (Amberlite IR A400, manufactured by Sigma-Aldrich) having a degree of swelling of 98% in water at 25 ° C. was used.
  • a commercially available anion adsorbent Amberlite IR A400, manufactured by Sigma-Aldrich
  • the long-term water permeability was C. The results are shown in Table 1.
  • Example 1-5 As a result of evaluating the water permeability of a polyacrylonitrile (PAN) UF membrane (Asahi Kasei Co., Ltd., molecular weight cut off 100 kDa) using treated water adsorbed with the adsorbent used in Example 1-3, long-term water permeability The sex was A. The results are shown in Table 2.
  • PAN polyacrylonitrile
  • Comparative Example 1-1 long-term water permeability cannot be obtained unless a process for removing organic carbon is provided. Further, as seen in Comparative Examples 1-2 and 1-3, when an adsorbent mainly composed of a hydrophobic structure such as commercially available activated carbon or ion exchange resin is used, part of organic carbon can be removed. However, since the removal ability of biopolymer is low, sufficient long-term water permeability cannot be obtained.
  • the crosslinked polymer having quaternary ammonium as in Comparative Example 1-4 has a problem that the degree of swelling is too high.
  • Examples 2-1 to 2-10 Comparative Examples 2-1 to 2-5, Examples 3-1 to 3-5, and Comparative Examples 3-1 to 3-3, the adsorption characteristics and regeneration characteristics of the adsorbents are shown. evaluated. The evaluation of the degree of swelling, the average particle diameter of the adsorbent, and the average fiber diameter were evaluated by the methods performed for Examples 1-1 to 1-5.
  • Adsorption rate of biopolymer Adsorption rate of biopolymer
  • Adsorption evaluation of sodium alginate was carried out as a biopolymer model substance.
  • 1 L of model river water 1 concentration of sodium alginate was obtained from 5.0 g of the adsorbent obtained in each Example and Comparative Example (the mass in the state dried in a vacuum dryer for 12 hours, the same in the following description).
  • the supernatant before and after shaking was analyzed by LC-OCD, and the adsorption rate of sodium humate as humic substance by the adsorbent was evaluated as follows.
  • Humic acid adsorption rate (sodium humate concentration before adsorption evaluation ⁇ sodium humate concentration after adsorption evaluation) / sodium humate concentration before adsorption evaluation ⁇ 100 (%)
  • Ratio of adsorption rate of biopolymer and humic substance adsorption rate of biopolymer / adsorption rate of humic substance
  • polyethyleneimine manufactured by Nippon Shokubai Co., Ltd., “Epomin SP”
  • this particle was subjected to a crosslinking treatment with a 25% solution of 2% of an epoxy compound (manufactured by Nagase ChemteX Corp., “Denacol EX-810”) for 1 hour, filtered and stirred with a large amount of hot water at 80 ° C.
  • the target adsorbent 2-1 was obtained as shown in Table 3.
  • the obtained adsorbent had a degree of swelling in 25 ° C. water of 105% and an average particle size of 0.7 mm.
  • the obtained adsorbent 2-1 was immersed and shaken in each of model river water 1 and model river water 2, and an adsorption test for sodium alginate and sodium humate was performed.
  • the adsorbent was filtered off, immersed in a 0.25% NaCl aqueous solution adjusted to 60 ° C., and shaken for 24 hours to regenerate the adsorbent. Thereafter, the regenerated adsorbent was collected by filtration.
  • the regenerated adsorbent collected by filtration was immersed and infiltrated in the model river water 1, and the sodium alginate adsorption test was performed again.
  • Table 4 shows the adsorption rate of sodium alginate and sodium humate of the obtained adsorbent and the adsorption rate of sodium alginate of the regenerated adsorbent.
  • this particle was subjected to a crosslinking treatment with a 25% solution of 2% of an epoxy compound (manufactured by Nagase ChemteX Corp., “Denacol EX-810”) for 1 hour, filtered and stirred with a large amount of hot water at 80 ° C.
  • the target adsorbent 2-2 was obtained as shown in Table 3.
  • the obtained adsorbent had a degree of swelling in 25 ° C. water of 88% and an average particle size of 0.6 mm.
  • the obtained adsorbent 2-2 was immersed and shaken in each of model river water 1 and model river water 2, and an adsorption test for sodium alginate and sodium humate was performed.
  • the adsorbent was filtered, immersed in water adjusted to 80 ° C., shaken for 1 hour, and the adsorbent was regenerated. Thereafter, the regenerated adsorbent that had been regenerated was collected by filtration.
  • the regenerated adsorbent collected by filtration was immersed in the model river water 1 and shaken, and an adsorption test for sodium alginate was performed again.
  • Table 4 shows evaluation results of adsorption and regeneration of the obtained adsorbent.
  • Example 2-3 As shown in Table 4, the adsorption and regeneration were evaluated in the same manner as in Example 2-2, except that the sample was immersed in a 0.25% NaCl aqueous solution adjusted to 25 ° C. and shaken for 24 hours. It was. The evaluation results are shown in Table 4.
  • Example 2-4 Adsorption and regeneration were evaluated in the same manner as in Example 2-2, except that the sample was immersed in water adjusted to 70 ° C. and shaken for 1 hour. The evaluation results are shown in Table 4.
  • this particle was subjected to a crosslinking treatment with a 25% solution of an epoxy compound (manufactured by Nagase ChemteX Corp., “Denacol EX-810”) at 25 ° C. for 1 hour, filtered, and then immersed in a large amount of hot water at 80 ° C.
  • an epoxy compound manufactured by Nagase ChemteX Corp., “Denacol EX-810”
  • the target adsorbent 2-3 was obtained as shown in Table 3.
  • the resulting adsorbent had a degree of swelling in 25 ° C. water of 46% and an average particle size of 0.5 mm.
  • the obtained adsorbent 2-3 was immersed and stirred in each of model river water 1 and model river water 2, and an adsorption test for sodium alginate and sodium humate was performed.
  • the adsorbent is filtered off, immersed in a 2.5% Na 2 CO 3 aqueous solution adjusted to 60 ° C. and shaken for 24 hours to regenerate the adsorbent. went. Thereafter, the regenerated adsorbent that had been regenerated was collected by filtration.
  • the regenerated adsorbent collected by filtration was immersed in the model river water 1 and shaken, and an adsorption test for sodium alginate was performed again.
  • Table 4 shows evaluation results of adsorption and regeneration of the obtained adsorbent.
  • Example 2-6 In Example 2-1, Example 2 was performed except that the adsorbent after the crosslinking treatment was washed with a large amount of 3.5% NaCl 80 ° C. hot water and Model Seawater 1 and Model Seawater 2 were used. The adsorption test was conducted in the same manner as -1. After the adsorption process of sodium alginate from the model seawater 1, the adsorbent was filtered off, immersed in water adjusted to 90 ° C., shaken for 1 hour, and the adsorbent was regenerated. Thereafter, the regenerated adsorbent that had been regenerated was collected by filtration. The regenerated adsorbent was immersed in the model seawater 1 and shaken, and an adsorption test for sodium alginate was performed again. Table 4 shows evaluation results of adsorption and regeneration of the obtained adsorbent.
  • Examples 2-1 to 2-5 can adsorb both sodium alginate and sodium humate from the model river water, and are particularly excellent in sodium alginate adsorbability. .
  • the ratio (A) / (B) of the adsorption rate (A) of sodium alginate and the adsorption rate (B) of sodium humate is 1.5 times or more. Therefore, the adsorbent of the present invention suggests that the biopolymer can be adsorbed efficiently even when, for example, more humic substances are present than the biopolymer.
  • sodium alginate can be adsorbed at a high adsorption rate even from model seawater 1.
  • Examples 2-1 to 2-6 when the regeneration treatment is performed on the adsorbent on which sodium alginate is adsorbed, the adsorbent after the regeneration treatment again adsorbs sodium alginate with a high adsorption rate.
  • the regeneration efficiency is 70% or more in Examples 2-1 to 2-2 and 2-4 to 2-6, and in particular, Examples 2-1 to 2-2 and 2-5 to In 2-6, it is 95% or more.
  • the temperature of the aqueous medium used in the regeneration treatment is 50 ° C. or higher, the regeneration efficiency tends to be high.
  • TMP-2 stainless mesh cartridge filter
  • Example 2-8 The adsorbent 2-2 after contact with the raw water in Example 2-7 was recovered by filtration, and the NaCl 2 . After regenerating for 24 hours using a 5% aqueous solution, it was again contacted with raw water in the same manner as in Example 2-7 to obtain treated water.
  • the long-term water permeability was A. The results are shown in Table 6.
  • TMP-2 stainless mesh cartridge filter with an exclusion diameter of 2 ⁇ m.
  • Example 2-10 The adsorbent 2-2 that had been brought into contact with the raw water in Example 2-9 was collected by filtration, regenerated for 1 hour using water at 80 ° C., and then again with the raw water as in Example 2-7. It was made to contact and the treated water was obtained.
  • PAN polyacrylonitrile
  • UF membrane As a result of evaluating the water permeability of a polyacrylonitrile (PAN) UF membrane (Asahi Kasei Co., Ltd., molecular weight cut-off 100 kDa), the long-term water permeability was A. The results are shown in Table 6.
  • Example 2-5 Evaluation was performed in the same manner as in Example 2-7, except that a commercially available granular activated carbon (manufactured by Kuraray Chemical Co., Ltd., “Kuraray Coal GW20 / 40”) was used as the adsorbent.
  • the long-term water permeability was B. The results are shown in Table 5.
  • the particles were subjected to a crosslinking treatment with a solution of 2% of an epoxy compound (manufactured by Nagase ChemteX Corp., “Denacol EX-810”) at 25 ° C. for 1 hour, and after filtration, a large amount of NaCl 3.5 ° C. at 80 ° C.
  • the intended adsorbent 3-1 was obtained by immersing in a 100% aqueous solution and washing with stirring.
  • the degree of swelling of the obtained adsorbent in 25 ° C. water was 97% and the average particle size was 0.7 mm.
  • the obtained adsorbent 3-1 was immersed and shaken in each of model seawater 1 and model 2, and the adsorption rate of sodium alginate and sodium humate was determined.
  • the evaluation results are shown in Table 8.
  • the particles were subjected to a crosslinking treatment with a solution of 2% of an epoxy compound (manufactured by Nagase ChemteX Corp., “Denacol EX-810”) at 25 ° C. for 1 hour, and after filtration, a large amount of NaCl 3.5 ° C. at 80 ° C.
  • the intended adsorbent 3-2 was obtained by immersing in a 100% aqueous solution and washing with stirring.
  • the obtained adsorbent had a degree of swelling in 25 ° C. water of 88% and an average particle size of 0.6 mm.
  • the obtained adsorbent 3-2 was immersed and shaken in each of model seawater 1 and model seawater 2, and the adsorption rate of sodium alginate and sodium humate was determined.
  • the evaluation results are shown in Table 8.
  • the particles were subjected to a crosslinking treatment with a solution of 2% of an epoxy compound (manufactured by Nagase ChemteX Corp., “Denacol EX-810”) at 25 ° C. for 1 hour, and after filtration, a large amount of NaCl 3.5 ° C. at 80 ° C.
  • the intended adsorbent 3-3 was obtained by immersion in an aqueous solution of 100% and washing with stirring.
  • the obtained adsorbent had a degree of swelling in 25 ° C. water of 110% and an average particle diameter of 0.8 mm.
  • the obtained adsorbent 3-3 was immersed and shaken in each of model brackish water 1 and model brackish water 2, and the adsorption rate of sodium alginate and sodium humate was determined.
  • the evaluation results are shown in Table 8.
  • the resin composition was such that these resins were dissolved in water.
  • the solution was wet-spun into a saturated sodium sulfate bath at 40 ° C. from a nozzle having a diameter of 0.08 mm and a pore number of 1000, and taken up at a speed of 15 m / min.
  • the formed yarn was further wet-drawn 2 times, dried at 130 ° C., and subjected to dry heat drawing 5 times at 230 ° C.
  • This fiber was further immersed in a 40 ° C. solution of 1% glutaraldehyde and 2% maleic acid for crosslinking treatment, then washed with water, then washed with an aqueous NaOH solution, and further immersed in an aqueous 3.5% NaCl solution.
  • the target adsorbent 3-4 (average fiber diameter 10 ⁇ m, fiber length 3 cm) was obtained by washing with stirring. The degree of swelling of the obtained adsorbent in 25 ° C. water was 65%.
  • the obtained adsorbent 3-4 was immersed and shaken in each of model seawater 1 and model seawater 2, and the adsorption rate of sodium alginate and sodium humate was determined.
  • the evaluation results are shown in Table 8.
  • Example 3-5 A vinyl alcohol polymer having a mercapto group at the end was synthesized by the method described in JP-A-59-187005.
  • the vinyl alcohol unit content (degree of saponification) determined by 1 H-NMR measurement was 98.5 mol%, and the viscosity average degree of polymerization measured according to JIS K6726 was 1500.
  • 563 g of water and 110 g of the above-mentioned terminal mercapto group-containing polyvinyl alcohol were charged, and the mixture was heated to 95 ° C. with stirring in a nitrogen atmosphere to dissolve the polyvinyl alcohol, and then cooled to room temperature.
  • the content of the polymerizable unsaturated monomer in the copolymer that is, in the polymer
  • the ratio of the number of vinylbenzyltrimethylammonium chloride monomer units to the total number of monomer units was 10 mol%.
  • 50 g of an aqueous solution of the polymer was added, and ion exchange water was added to prepare a solid concentration of 15%.
  • This aqueous solution was cast on a polyethylene terephthalate film using an applicator and dried at 80 ° C. for 30 minutes. The film thus obtained was heat treated at 170 ° C. for 30 minutes to cause physical crosslinking.
  • the membrane was immersed in 1 L of an aqueous solution in which 350 g of sodium sulfate was dissolved, concentrated sulfuric acid was added to the aqueous solution so that the pH was 1, and the membrane was further immersed as a 3% aqueous solution of glutaraldehyde.
  • Crosslinking treatment was carried out at 3 ° C. for 3 hours.
  • the membrane was washed with ion-exchanged water and a 3.5% aqueous solution of NaCl and dried to obtain a membrane having a thickness of 70 ⁇ m.
  • This membrane was cut into 2 mm squares to obtain the intended adsorbent 3-5 as shown in Table 7.
  • the degree of swelling of the obtained adsorbent in water at 25 ° C. was 30%.
  • the obtained adsorbent 3-5 was immersed and shaken in each of model seawater 1 and model seawater 2, and the adsorption rate of sodium alginate and sodium humate was determined.
  • the evaluation results are shown in Table 8.
  • [Comparative Example 3-2] Commercially available synthetic zeolite with a degree of swelling in water at 25 ° C. of 27% (manufactured by Tosoh Corporation, “synthetic zeolite F-9”, average particle size: 0.9 mm) in a large amount of 80 ° C. NaCl 3.5% aqueous solution. After soaking, stirring and washing, an adsorbent 3-7 was obtained. The obtained adsorbent 3-7 was immersed and shaken in each of model seawater 1 and model seawater 2, and the adsorption rate of sodium alginate and sodium humate was determined. The evaluation results are shown in Table 8, and the adsorbent 3-7 had little adsorption performance for sodium alginate.
  • both sodium alginate and sodium humate can be adsorbed from the model water containing sodium chloride.
  • the ratio (A) / (B) of the adsorption rate (A) of sodium alginate and the adsorption rate (B) of sodium humate is 1.5 times or more. Therefore, the adsorbent of the present invention suggests that the biopolymer can be adsorbed efficiently even when, for example, more humic substances are present than the biopolymer.
  • Examples 3-1 to 3-3 it is possible to adsorb sodium alginate with a high adsorption rate because an ethylene-vinyl alcohol copolymer is used as the main skeleton as the hydrophilic polymer. . Further, as shown in Example 3-4, sodium alginate can be adsorbed at a high adsorption rate even in a fibrous form.
  • Example 3-6 According to Example 3-1, after adsorbing sodium alginate on the adsorbent 3-1, using model water 1, the adsorbent was filtered off. Next, the adsorbent separated by filtration was immersed in pure water adjusted to 80 ° C. and shaken for 1 hour to perform a regeneration treatment. Thereafter, the regenerated adsorbent was collected by filtration, and the adsorption rate of sodium alginate was obtained again using model water 1 in the same manner as in Example 3-1. Table 9 shows the evaluation results.
  • Example 3-7 In accordance with Example 3-2, model water 1 was used to adsorb sodium alginate on the adsorbent 3-2, and then the adsorbent was filtered off. Next, the adsorbent separated by filtration was immersed in pure water adjusted to 90 ° C. and shaken for 1 hour to perform a regeneration treatment. Thereafter, the regenerated adsorbent was collected by filtration, and the adsorption rate of sodium alginate was obtained again using model water 1 in the same manner as in Example 3-1. Table 9 shows the evaluation results.
  • Example 3-8 According to Example 3-3, model a brackish water 1 was used to adsorb sodium alginate on the adsorbent 3-3, and then the adsorbent was filtered off. Subsequently, the adsorbent separated by filtration was immersed in a 0.25% NaCl aqueous solution adjusted to 60 ° C. and shaken for 24 hours to perform a regeneration treatment. Thereafter, the regenerated adsorbent was collected by filtration, and the adsorption rate of sodium alginate was determined again using model brackish water 1 in the same manner as in Example 3-1. Table 9 shows the evaluation results.
  • a hydrophilic polymer adsorbent capable of adsorbing organic carbon, and in particular, capable of efficiently adsorbing biopolymers that have been difficult to adsorb conventionally.
  • Such a composition can be effectively used as an organic carbon adsorbent (particularly, a biopolymer adsorbent) when various raw waters are treated with water.

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Abstract

L'invention concerne un adsorbant qui a une capacité d'adsorption pour le carbone organique (en particulier, des substances causant l'encrassement de membrane) contenu dans de l'eau brute provenant d'environnements naturels et d'environnements artificiels, et un procédé de traitement de l'eau dans lequel l'adsorbant est utilisé. L'adsorbant est un adsorbant polymère hydrophile, qui a un degré de gonflement dans de l'eau à 25 °C de 20 à 500 %, et a un groupe fonctionnel capable de former une liaison avec au moins certains composants du carbone organique contenu dans l'eau à traiter (appelé ci-après groupe de formation de liaison). Le procédé de traitement de l'eau comprend au moins une étape d'adsorption dans laquelle de l'eau contenant du carbone organique à traiter est mise en contact avec l'adsorbant polymère hydrophile pour adsorber le carbone organique sur celui-ci.
PCT/JP2014/080911 2013-11-25 2014-11-21 Adsorbant polymère hydrophile et procédé de traitement de l'eau utilisant celui-ci Ceased WO2015076371A1 (fr)

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CN105727898A (zh) * 2016-04-07 2016-07-06 昆明理工大学 一种再生纤维素共混腐植酸钠大孔径吸附凝胶的制备方法
CN108822813A (zh) * 2018-08-08 2018-11-16 天津渤海中联石油科技有限公司 一种有机褐煤提纯方法
JP2019515785A (ja) * 2016-04-22 2019-06-13 ポール・コーポレーションＰａｌｌ Ｃｏｒｐｏｒａｔｉｏｎ 水処理装置
CN110115988A (zh) * 2019-06-03 2019-08-13 湖南泰谷生态工程有限公司 一种重金属离子型工业废水的处理方法
CN111282556A (zh) * 2020-03-27 2020-06-16 神华神东煤炭集团有限责任公司 一种除氟复合纤维膜、其制备方法及用途
CN112209567A (zh) * 2020-09-29 2021-01-12 江苏盐城环保科技城土壤污染修复研发中心 一种畜禽废水的吸附净化方法

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CN105727898A (zh) * 2016-04-07 2016-07-06 昆明理工大学 一种再生纤维素共混腐植酸钠大孔径吸附凝胶的制备方法
JP2019515785A (ja) * 2016-04-22 2019-06-13 ポール・コーポレーションＰａｌｌ Ｃｏｒｐｏｒａｔｉｏｎ 水処理装置
JP7052178B2 (ja) 2016-04-22 2022-04-12 ポール・コーポレーション 水処理装置
CN108822813A (zh) * 2018-08-08 2018-11-16 天津渤海中联石油科技有限公司 一种有机褐煤提纯方法
CN110115988A (zh) * 2019-06-03 2019-08-13 湖南泰谷生态工程有限公司 一种重金属离子型工业废水的处理方法
CN110115988B (zh) * 2019-06-03 2022-01-21 湖南泰谷生态工程有限公司 一种重金属离子型工业废水的处理方法
CN111282556A (zh) * 2020-03-27 2020-06-16 神华神东煤炭集团有限责任公司 一种除氟复合纤维膜、其制备方法及用途
CN111282556B (zh) * 2020-03-27 2023-03-28 神华神东煤炭集团有限责任公司 一种除氟复合纤维膜、其制备方法及用途
CN112209567A (zh) * 2020-09-29 2021-01-12 江苏盐城环保科技城土壤污染修复研发中心 一种畜禽废水的吸附净化方法

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