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WO2025239076A1 - Système et procédé de régénération de résine échangeuse d'ions à l'aide d'acide résiduaire ou d'alcali résiduaire - Google Patents

Système et procédé de régénération de résine échangeuse d'ions à l'aide d'acide résiduaire ou d'alcali résiduaire

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Publication number
WO2025239076A1
WO2025239076A1 PCT/JP2025/014337 JP2025014337W WO2025239076A1 WO 2025239076 A1 WO2025239076 A1 WO 2025239076A1 JP 2025014337 W JP2025014337 W JP 2025014337W WO 2025239076 A1 WO2025239076 A1 WO 2025239076A1
Authority
WO
WIPO (PCT)
Prior art keywords
exchange resin
waste
sulfuric acid
acid
ion exchange
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/014337
Other languages
English (en)
Japanese (ja)
Inventor
浩一郎 橋本
沙耶 伊藤
美和 伊藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Organo Corp
Original Assignee
Organo Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Organo Corp filed Critical Organo Corp
Publication of WO2025239076A1 publication Critical patent/WO2025239076A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/04—Processes using organic exchangers
    • 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
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • 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
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/13—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
    • 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
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
    • B01J49/53—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for cationic exchangers
    • 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
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
    • B01J49/57—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for anionic exchangers

Definitions

  • the present invention relates to a system and method for regenerating ion exchange resins using waste acid or waste alkali.
  • SPM cleaning is a method of cleaning wafers by immersing them in a cleaning solution made from a fixed ratio of sulfuric acid and hydrogen peroxide for a set period of time. After being used in SPM cleaning, the cleaning solution becomes acid (waste acid) containing various impurities from the cleaning process. In recent years, there has been research into reusing the waste acid used in SPM cleaning.
  • Patent Document 1 discloses a method for reusing ion exchange resin regenerated liquid, in which the final one-third of the regenerated liquid passed through the ion exchange resin is mixed into new regenerated liquid as a regenerant blend solution, in order to reduce the running costs of the ion exchange resin regenerated liquid used to regenerate the ion exchange resin.
  • Patent Document 2 also discloses a method for subjecting a mixed solution of waste acid and waste alkali used to regenerate ion exchange resin to electrodialysis, and then recovering the acid and alkali separately.
  • the object of the present invention is to provide a system and method for regenerating ion exchange resin using waste acid or waste alkali, which allows for the production of treated water of stable quality using a simple method.
  • the present invention provides a system for regenerating an ion exchange resin, comprising: a tank for storing the waste acid or waste alkali containing impurities; a measuring means for measuring the concentration of impurities in the waste acid or waste alkali; a determining means for determining whether or not the waste acid or waste alkali can be reused based on the concentration of the impurities; a regeneration means for regenerating an ion exchange resin using the waste acid or waste alkali determined to be reusable by the determination means;
  • the present invention relates to a regeneration system for ion exchange resins, characterized by comprising:
  • the present invention also provides a method for regenerating an ion exchange resin, comprising the steps of: a storage step of storing the impurity-containing waste acid or waste alkali in a tank; a measuring step of measuring the concentration of impurities in the waste acid or waste alkali; a determining step of determining whether the waste acid or waste alkali can be reused based on the concentration of the impurities; a regeneration step of reusing the waste acid or waste alkali determined to be reusable in the determination step for regenerating an ion exchange resin;
  • the method for regenerating an ion exchange resin is characterized by comprising the steps of:
  • the present invention provides a system and method for regenerating ion exchange resins using waste acid or waste alkali, which can produce treated water of stable quality using a simple method.
  • FIG. 1 is a schematic diagram showing a regeneration system for an ion exchange resin according to one embodiment of the present invention.
  • 1 is a schematic diagram showing a regeneration system for an ion exchange resin according to one embodiment of the present invention.
  • an ion exchange resin regeneration system includes a waste liquid tank 1 for storing impurity-containing waste acid or waste alkali, a measuring means (not shown) for measuring the concentration of impurities in the waste acid or waste alkali, and a determining means (not shown) for determining whether the waste acid or waste alkali can be reused based on the measured impurity concentration.
  • the ion exchange resin regeneration system also includes a regeneration means 3 for regenerating the ion exchange resin using the waste acid or waste alkali determined to be reusable by the determining means.
  • the waste acid or waste alkali determined to be reusable by the determining means can be reused to regenerate the cation exchange resin or anion exchange resin in the cation exchange resin tower or anion exchange resin tower serving as the regeneration means 3.
  • the ion exchange resin regeneration system according to the present invention may include a water sampling means 4 (and 5) for passing water to be treated through the regenerated ion exchange resin to obtain treated water.
  • a water sampling means 4 and 5 for passing water to be treated through the regenerated ion exchange resin to obtain treated water.
  • Waste acid or waste alkali containing impurities flows into the waste liquid tank 1 through the flow path L1, where the waste acid or waste alkali is temporarily stored.
  • Any container capable of storing waste acid or waste alkali can be used as the waste liquid tank 1.
  • waste acids include sulfuric acid, hydrochloric acid, and nitric acid waste liquids
  • waste alkalis include sodium hydroxide, potassium hydroxide, calcium hydroxide, and aqueous ammonia waste liquids.
  • the sulfuric acid is preferably sulfuric acid discharged from semiconductor factories. In particular, sulfuric acid used in SPM cleaning in semiconductor manufacturing processes is suitable for use in the present invention.
  • the types of impurities contained in the waste acid are not particularly limited, but include, for example, ammonia. Since it is expected that waste acid used in SPM cleaning will be used, other impurities include metal elements such as sodium and cationic TOC components.
  • the types of impurities contained in the waste alkali are not particularly limited, but include, for example, anions such as chloride ions and sulfate ions, and anionic TOC components.
  • a measuring means for measuring the concentration of impurities in the waste acid or waste alkali may be provided in the waste liquid tank 1.
  • the measuring means may be used to measure the concentration of impurities in a sample solution obtained by extracting a portion of the waste liquid from the waste liquid tank 1.
  • the measuring means is not particularly limited as long as it can measure the concentration of the impurity directly or indirectly.
  • the impurity is ammonia
  • examples of the measuring means include a conductivity meter, a resistivity meter, ion chromatography, and devices required for calculating the concentration of the impurity by the indophenol method, electrophoresis, etc.
  • the determination means is a means for determining whether the waste acid or waste alkali can be reused for regenerating ion exchange resins based on the concentration of impurities measured by the measurement means.
  • the determination means is not limited as long as it can make such a determination. Specifically, it may be a means in which a person makes a determination based on the numerical values obtained after manual analysis, a means in which a person makes a determination using a computer, or a means in which automatic calculations are performed using a sequencer or the like. Specific criteria for determining whether the waste acid can be reused for regenerating cation exchange resins will be described later.
  • the determining means determines that the waste acid stored in waste liquid tank 1 can be reused to regenerate cation exchange resin, the waste acid is stored in reuse chemical tank 2 through flow path L2. Furthermore, if the determining means determines that the waste alkali stored in waste liquid tank 1 can be reused to regenerate anion exchange resin, the waste alkali is stored in reuse chemical tank 2 through flow path L2. Note that if waste acid or waste alkali determined to be reuseable to regenerate ion exchange resin is passed directly to regeneration means 3, the installation of reuse chemical tank 2 can be omitted. On the other hand, if the waste acid or waste alkali stored in waste liquid tank 1 is determined to be unreusable to regenerate ion exchange resin, the waste acid or waste alkali is discharged to the system through flow path L5.
  • the regeneration means 3 is, for example, a cation exchange resin tower or an anion exchange resin tower filled with a cation exchange resin or an anion exchange resin.
  • the waste acid containing impurities stored in the reuse chemical tank 2 is sent through flow path L3 to a cation exchange resin tower 3 filled with a cation exchange resin, and reused for regenerating the cation exchange resin.
  • the speed, flow rate, and time of passing the waste acid through the cation exchange resin tower are not particularly limited, and can be appropriately adjusted so as to achieve regeneration of the cation exchange resin.
  • the waste acid used for regenerating the cation exchange resin may be discharged outside the system through flow path L4 and discarded. Alternatively, if the waste acid can be repeatedly used to regenerate the cation exchange resin, it may be reused as a regenerant.
  • the cation exchange resin is not particularly limited, but an organic polymer-based cation exchange resin with an organic polymer as its base is preferred.
  • the base organic polymer include styrene-based resins and acrylic resins.
  • the base of the cation exchange resin may be either a transparent gel type with small pore diameters, a macrolitercular type (MR type) with large pore diameters, or a macroporous type (also called a porous type or high-porous type).
  • styrene-based resin refers to a resin containing 50% by mass or more of structural units derived from styrene or a styrene derivative, either homopolymerized or copolymerized with styrene or a styrene derivative.
  • styrene derivatives include ⁇ -methylstyrene, vinyltoluene, chlorostyrene, ethylstyrene, i-propylstyrene, dimethylstyrene, and bromostyrene.
  • the styrene-based resin is primarily composed of a homopolymer or copolymer of styrene or a styrene derivative, it may also be a copolymer with other copolymerizable vinyl monomers.
  • vinyl monomers examples include one or more selected from the group consisting of divinylbenzenes such as o-divinylbenzene, m-divinylbenzene, and p-divinylbenzene; polyfunctional monomers such as alkylene glycol di(meth)acrylates, including ethylene glycol di(meth)acrylate and polyethylene glycol di(meth)acrylate; (meth)acrylonitrile; and methyl (meth)acrylate.
  • divinylbenzenes such as o-divinylbenzene, m-divinylbenzene, and p-divinylbenzene
  • polyfunctional monomers such as alkylene glycol di(meth)acrylates, including ethylene glycol di(meth)acrylate and polyethylene glycol di(meth)acrylate
  • (meth)acrylonitrile examples of such other vinyl monomers
  • divinylbenzene, ethylene glycol di(meth)acrylate, or polyethylene glycol di(meth)acrylate having an ethylene polymerization number of 4 to 16 is preferred, with divinylbenzene or ethylene glycol di(meth)acrylate being more preferred, and divinylbenzene being particularly preferred.
  • acrylic resin means a resin obtained by homopolymerizing or copolymerizing one or more types selected from acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, and containing 50% by mass or more of structural units selected from structural units derived from acrylic acid, structural units derived from methacrylic acid, structural units derived from acrylic acid esters, and structural units derived from methacrylic acid esters.
  • acrylic resins include one or more selected from the group consisting of homopolymers of acrylic acid, homopolymers of methacrylic acid, homopolymers of acrylic esters, homopolymers of methacrylic esters, copolymers of acrylic acid and other monomers (e.g., acrylic esters, methacrylic acid, methacrylic esters, and ⁇ -olefins (e.g., ethylene, divinylbenzene, etc.)), copolymers of methacrylic acid and other monomers (e.g., acrylic acid, acrylic esters, methacrylic esters, and ⁇ -olefins (e.g., ethylene, divinylbenzene, etc.)), copolymers of acrylic esters and other monomers (e.g., acrylic acid, methacrylic acid, methacrylic esters, and ⁇ -olefins (e.g., ethylene, divinylbenzene, etc.)), and copolymers of methacrylic acid
  • the acrylic acid ester is preferably an alkyl acrylate, more preferably a linear or branched alkyl ester of acrylic acid, and even more preferably a linear alkyl ester of acrylic acid.
  • the alkyl group contained in the alkyl ester moiety preferably has 1 to 4 carbon atoms, and it is particularly preferred that the acrylic acid ester be methyl acrylate or ethyl acrylate.
  • the methacrylic acid ester is preferably an alkyl methacrylate, more preferably a linear or branched alkyl ester of methacrylic acid, and even more preferably a linear alkyl ester of methacrylic acid.
  • the alkyl group contained in the alkyl ester moiety preferably has 1 to 4 carbon atoms, and it is particularly preferred that the methacrylic acid alkyl ester be methyl methacrylate or ethyl methacrylate.
  • cation exchange resins include, but are not limited to, the Allite DS series (trade name, manufactured by Organo Corporation), the Amberlite series (trade name, manufactured by DuPont de Nemours), the Amberjet series (trade name, manufactured by DuPont de Nemours), and the Diaion series (trade name, manufactured by Mitsubishi Chemical Corporation).
  • Allite DS series trade name, manufactured by Organo Corporation
  • Amberlite series trade name, manufactured by DuPont de Nemours
  • Amberjet series trade name, manufactured by DuPont de Nemours
  • Diaion series trade name, manufactured by Mitsubishi Chemical Corporation.
  • One type of cation exchange resin may be used alone, or two or more types may be used in combination.
  • the cation exchange resin may be further regenerated using new acid (not recycled acid).
  • new acid is used as the regenerant, but because the resin has already been regenerated using waste acid, the amount of new regenerant used can be significantly reduced.
  • ultrapure water or pure water may be passed through as needed to push out any acid remaining in the cation exchange resin tower.
  • the waste alkali containing impurities stored in the reuse chemical tank 2 is sent through flow path L3 to the anion exchange resin tower 3 filled with anion exchange resin, and reused for regenerating the anion exchange resin.
  • the speed, flow rate, and time of passing the waste alkali through the anion exchange resin tower are not particularly limited, and can be appropriately adjusted so as to achieve regeneration of the anion exchange resin.
  • the waste alkali used for regenerating the anion exchange resin may be discharged outside the system through flow path L4 and discarded. Alternatively, if the waste alkali can be repeatedly used to regenerate the anion exchange resin, it may be reused as a regenerant.
  • the anion exchange resin is not particularly limited, but, like the cation exchange resin, an organic polymer-based anion exchange resin with an organic polymer as its base is preferred.
  • the base organic polymer include styrene-based resins and acrylic-based resins.
  • the base of the anion exchange resin may be either a transparent gel type with small pore diameters, a macrolitercular type (MR type) with large pore diameters, or a macroporous type (also called a porous type or high-porous type).
  • anion exchange resins include strongly basic type I anion exchange resins having trimethylammonium groups (R-N + (CH 3 ) 3 OH - : R represents the parent compound of the ion exchange resin) as the quaternary ammonium group, strongly basic type II anion exchange resins having dimethylethanolammonium groups (R-N + (CH 3 ) 2 CH 2 CH 2 OH - ) as the quaternary ammonium group, and weakly basic anion exchange resins having primary, secondary, or tertiary amino groups as functional groups.
  • One type of anion exchange resin may be used alone, or two or more types may be used in combination.
  • anion exchange resins include, but are not limited to, the Allite DS series (trade name, manufactured by Organo Corporation), the Amberlite series (trade name, manufactured by DuPont de Nemours), the Amberjet series (trade name, manufactured by DuPont de Nemours), the Diaion series (trade name, manufactured by Mitsubishi Chemical Corporation), the UltraClean series and NRW series (all trade names, manufactured by Purolite Co., Ltd.), and the Muromac HG series (trade name, manufactured by Muromachi Chemical Co., Ltd.).
  • the anion exchange resin may be further regenerated using new alkali (not recycled alkali).
  • new alkali is used as the regenerant, but because the resin has already been regenerated using waste alkali, the amount of new regenerant used can be significantly reduced.
  • ultrapure water or pure water may be passed through as needed to push out any alkali remaining in the anion exchange resin tower.
  • the ion exchange resin regeneration system may include a water sampling means 4 (and 5).
  • the water sampling means preferably includes a cation exchange resin tower (hereinafter also referred to as “K tower”) 4 packed with a cation exchange resin regenerated using waste acid, and an anion exchange resin tower (hereinafter also referred to as “A tower”) 5 packed with an anion exchange resin.
  • the anion exchange resin is an anion exchange resin other than the anion exchange resin regenerated using waste alkali according to the present invention.
  • the water sampling means preferably includes a K tower 4 packed with a cation exchange resin and an A tower 5 packed with an anion exchange resin regenerated using waste alkali.
  • the cation exchange resin is a cation exchange resin other than the cation exchange resin regenerated using waste acid according to the present invention.
  • the water to be treated is passed through a flow path L6 or L7 through the ion exchange resin regenerated using waste acid or waste alkali to obtain treated water.
  • the water sampling means for obtaining treated water by passing the water to be treated through the cation exchange resin after regeneration treatment using waste acid will be described below.
  • the water sampling means is a means for sequentially passing the water to be treated through a cation exchange resin tower 4 filled with a cation exchange resin regenerated by the regeneration means, and an anion exchange resin tower 5 filled with an anion exchange resin, to obtain treated water.
  • the anion exchange resin used in the anion exchange resin tower may be the same as the anion exchange resin exemplified in the regeneration means.
  • the water to be treated is passed through flow path L6 through the cation exchange resin tower 4 filled with a cation exchange resin regenerated using waste acid.
  • the cation exchange resin tower 4 may be the same as the cation exchange resin tower 3 used as the regeneration means 3, or a different one may be used.
  • the water to be treated may be, but is not limited to, groundwater, tap water, industrial water, or other raw water. A certain amount of NH 4 + ions derived from the waste acid are present in the cation exchange resin after regeneration using waste acid.
  • the water to be treated contains impurities such as Na + ions, Ca2 + ions, Cl- ions, and SO42- ions .
  • K tower 4 which is filled with a regenerated cation exchange resin
  • cations such as Na + ions and Ca2 + ions in the water to be treated are ion-exchanged with H + ions in the regenerated cation exchange resin, resulting in the release of H + ions into the water to be treated.
  • these H + ions are ion-exchanged with NH4 + ions derived from the waste acid in the cation exchange resin, resulting in the release of NH4 + ions into the treated water obtained from the outlet of K tower 4 (K tower outlet treated water).
  • the K tower outlet treated water (A tower inlet treated water) obtained from the outlet of K tower 4 is passed through flow path L7 to A tower 5, which is filled with an anion exchange resin.
  • anions such as Cl ⁇ ions and SO 4 2 ⁇ ions in the treated water are adsorbed onto the anion exchange resin, and A-tower outlet treated water containing NH 4 + ions flows out from the outlet of A-tower 5 through flow path L8.
  • the regeneration system according to the present invention includes a water sampling means, in addition to the impurity concentration in the waste acid or waste alkali measured by the measuring means, the conductivity of the water to be treated at the K tower inlet (K tower inlet treated water) and the conductivity of the treated water obtained from the A tower outlet, i.e., the A tower outlet treated water obtained by sequentially passing the water to be treated through the K tower and the A tower, can be calculated and used as the criteria for the determination means.
  • the conductivity of the K tower inlet treated water can be calculated, for example, from the concentration of impurities (metal ions such as Na + and anions such as Cl- ) contained in the treated water.
  • the conductivity of the A tower outlet treated water can be calculated, for example, from the ammonia concentration in the A tower outlet treated water, i.e., the ammonia concentration in the K tower outlet treated water (because the ammonium concentration in the (treated) water remains unchanged before and after treatment in the A tower).
  • the means for measuring the ammonia concentration in the treated water can be the same as those described above as measuring means. Specific criteria for determination will be described later.
  • the water sampling means for obtaining treated water by passing the water to be treated through the anion exchange resin after regeneration treatment using waste alkali is a means for obtaining treated water by passing the water to be treated sequentially through a cation exchange resin tower 4 filled with a cation exchange resin, and an anion exchange resin tower 5 filled with anion exchange resin that has been regenerated by the regeneration means.
  • the cation exchange resin used in the cation exchange resin tower can be the same as the cation exchange resin exemplified in the regeneration means above.
  • the ion exchange resin regeneration system when the ion exchange resin regeneration system according to the present invention has a water sampling means, it is possible to determine whether the waste acid or waste alkali can be reused based on either or both of the impurity concentration in the waste acid or waste alkali measured by the above-mentioned measuring means and the impurity concentration (conductivity) in the K tower inlet water to be treated and the A tower outlet treated water measured by the water sampling means.
  • the water quality of the treated water (A tower outlet treated water) can be predicted and determined from the impurity concentration in the waste acid or waste alkali and the conductivity of the raw water (treated water) for the water purification system.
  • the lower limit of the ammonia concentration is not particularly limited, but taking into account the presence of ammonia as an impurity and the measurement limit, it is, for example, 0.01 ppm or more per 5% by mass of the waste sulfuric acid. Therefore, in the regeneration system shown in FIG. 1 , when the concentration of ammonia in the waste acid is 5,000 ppm or less per 5% by mass of the waste sulfuric acid, the waste acid in the waste liquid tank 1 is transferred to the reuse chemical tank 2 and then passed through flow path L3 to the cation exchange resin tower 3 filled with the cation exchange resin to be regenerated.
  • the waste acid in the waste liquid tank 1 is discharged to the outside of the system through flow path L5.
  • the ammonia concentration in the waste sulfuric acid is preferably 1000 ppm or less per 5% by mass of waste sulfuric acid, and more preferably 100 ppm or less.
  • the treated water referred to here means the treated water at the outlet of tower A obtained by passing the water to be treated through the cation exchange resin tower 4 and the anion exchange resin tower 5 sequentially.
  • the ion exchange resin is a cation exchange resin and the regeneration system further comprises a water sampling means for sequentially passing the water to be treated through a cation exchange resin tower packed with the cation exchange resin after regeneration using waste sulfuric acid containing ammonia as an impurity, and an anion exchange resin tower packed with an anion exchange resin, to obtain treated water
  • the waste sulfuric acid can be reused to regenerate the cation exchange resin when the following formula (1) is satisfied: A ⁇ (B 2 ) ⁇ 3.5 (1).
  • A represents the ammonia concentration [ppm] per 5% by mass of the waste sulfuric acid in the waste sulfuric acid
  • B represents the conductivity [mS/cm] of the water to be treated (water to be treated at the K tower inlet) passed through the cation exchange resin tower.
  • the method for measuring the ammonia concentration A is not particularly limited, and it can be measured using a conductivity meter, a resistivity meter, ion chromatography, or any device necessary to calculate the concentration of impurities using the indophenol method or electrophoresis. Note that conductivity is expressed as 1/resistivity.
  • the conductivity B of the water to be treated at the K tower inlet can be measured using a device such as a conductivity meter or a resistivity meter, just like the ammonia concentration A.
  • a device such as a conductivity meter or a resistivity meter, just like the ammonia concentration A.
  • the metal ion concentration in the water to be treated at the K tower inlet can be calculated using a known method, and the conductivity B can be calculated from that value.
  • a method for regenerating an ion exchange resin according to one embodiment of the present invention includes a storage step, a measurement step, a determination step, a regeneration step, and optionally a water sampling step.
  • the storage step is a step of temporarily storing the waste acid or waste alkali containing impurities that has flowed in through the flow path L1 in the waste liquid tank 1.
  • the measuring step is a step of using the measuring means to measure the concentration of impurities in the waste acid or waste alkali in the waste liquid tank 1. This step corresponds to the measuring means.
  • the determination step is a step of determining whether the waste acid or waste alkali can be reused for regenerating an ion exchange resin based on the concentration of impurities measured in the measurement step.
  • the criteria for determining whether the waste acid can be reused for regenerating a cation exchange resin are as described above. This step corresponds to the determination means.
  • the regeneration step is a step of reusing the waste acid or waste alkali determined to be reusable in the determination step for regenerating the ion exchange resin in the cation exchange resin tower or anion exchange resin tower 3 as regeneration means, and corresponds to the regeneration means described above.
  • the regeneration method according to the present invention may include a second storage step after the determination step, in which the waste acid or waste alkali determined to be reusable in the determination step is temporarily stored in the reuse chemical tank 2 until the regeneration step.
  • the regeneration step can be carried out after recovering the amount of waste acid or waste alkali required to regenerate the ion exchange resin in the second storage step.
  • the ion exchange resin may be further regenerated using new acid or alkali (not recycled acid or alkali).
  • new acid or alkali is used as the regenerant, but because the resin has already been regenerated using waste acid or waste alkali, the amount of new regenerant used can be significantly reduced.
  • the regeneration step may include a step of passing ultrapure water or pure water through the ion exchange resin tower as needed after the ion exchange resin regeneration treatment using the above-mentioned waste acid or waste alkali to push out any acid remaining in the ion exchange resin tower.
  • the water sampling process is a process in which the water to be treated is passed through flow path L6 through the ion exchange resin after the regeneration process to obtain treated water.
  • This process corresponds to the water sampling means.
  • this process is, for example, a process in which the water to be treated is passed through K tower 4 packed with a cation exchange resin after the regeneration process using waste sulfuric acid, to obtain K tower outlet treated water, and then the K tower outlet treated water is passed as the water to be treated through A tower 5 packed with an anion exchange resin to obtain A tower outlet treated water.
  • the waste sulfuric acid can be reused to regenerate the cation exchange resin when the ammonia concentration A [ppm] per 5 mass% of the waste sulfuric acid in the waste sulfuric acid and the conductivity B [mS/cm] satisfy the above formula (1).
  • Waste sulfuric acid having ammonia concentrations of 10 ppm, 100 ppm, 1000 ppm, and 5000 ppm per 5 mass % of waste sulfuric acid was prepared in the waste liquid tank 1, respectively.
  • the waste sulfuric acid in the waste liquid tank 1 was passed through a cation exchange resin tower (K tower) 3 packed with a strongly acidic cation exchange resin (trade name: AMBERLITE HPR1200 H, manufactured by DuPont de Nemours) at a space velocity (SV): 4 and a regeneration level: 3 eq/L-R to regenerate the cation exchange resin.
  • Ultrapure water was then passed through at 2.5 BV and SV: 10 to push out the acid.
  • the proportion of ammonium ions in the cation exchange resin after regeneration was measured by the indophenol method using a spectrophotometer (trade name: U-5100, manufactured by Hitachi High-Tech Corporation). In the table, post-regeneration R-NH 4 (%) indicates the proportion relative to the total exchange capacity (eq/L-R) of the cation exchange resin, which is 100%.
  • NaCl-containing water NaCl concentrations of the K tower inlet treated water were 0 ppm, 32.1 ppm, and 80.1 ppm, respectively
  • K tower outlet treated water NaCl concentrations of the K tower inlet treated water were 0 ppm, 32.1 ppm, and 80.1 ppm, respectively
  • the ammonia concentration in the K tower outlet treated water was measured by the indophenol method using the spectrophotometer.
  • the electrical conductivities shown in Table 1 are all theoretical values (calculated values) determined by known methods, and the electrical conductivities of waste sulfuric acid are values calculated from the ammonia concentration per 5% by mass of the waste sulfuric acid in the waste sulfuric acid.
  • the electrical conductivities of the K tower inlet water to be treated are values calculated from the NaCl concentration in the K tower inlet water to be treated that was passed through the K tower inlet.
  • the electrical conductivities of the A tower outlet treated water are values calculated from the NH 4 + concentration in the K tower outlet treated water.
  • the intralayer HCl concentration of the K tower inlet water to be treated is a value (maximum value) calculated from the amount of ammonium ions present in the cation exchange resin after regeneration (post-regeneration R-NH 4 ). Since the cations other than ammonium ions present in the cation exchange resin after the regeneration process are hydrogen ions, when an NaCl aqueous solution is passed through the cation exchange resin after the regeneration process, the hydrogen ions exchanged for sodium ions flow into the treated water as hydrochloric acid (HCl). This maximum value means the maximum concentration of HCl that flows out.
  • the waste sulfuric acid can be reused to regenerate the cation exchange resin.
  • the ammonia concentration in the waste sulfuric acid is 100 ppm or less per 5% by mass of the waste sulfuric acid, the conductivity of the treated water at the outlet of Tower A shows better results.
  • the horizontal axis was the conductivity [ ⁇ S/cm] of the water to be treated at the K tower inlet and the vertical axis was the conductivity [ ⁇ S/cm] of the water to be treated at the A tower outlet, and a graph was created by connecting the points.
  • the present invention includes the following configurations.
  • [Configuration 1] A system for regenerating an ion exchange resin, comprising: a tank for storing the waste acid or waste alkali containing impurities; a measuring means for measuring the concentration of impurities in the waste acid or waste alkali; a determining means for determining whether or not the waste acid or waste alkali can be reused based on the concentration of the impurities; a regeneration means for regenerating an ion exchange resin using the waste acid or waste alkali determined to be reusable by the determination means;
  • a system for regenerating an ion exchange resin comprising: [Configuration 2] 2. The system for regenerating an ion exchange resin according to claim 1, wherein the waste acid is waste sulfuric acid.
  • the ion exchange resin is a cation exchange resin
  • the regeneration system further includes a water sampling means for sequentially passing the water to be treated through a cation exchange resin tower filled with a cation exchange resin that has been regenerated using waste sulfuric acid containing ammonia as the impurity, and an anion exchange resin tower filled with an anion exchange resin, to obtain treated water;
  • the regeneration system for an ion exchange resin according to any one of configurations 2 to 5, wherein the determination means determines that the waste sulfuric acid can be reused for regenerating a cation exchange resin when A and B satisfy the following formula (1), where A is the concentration of the ammonia per 5 mass % of the waste sulfuric acid in the waste sulfuric acid [ppm] and B is the conductivity of the water to be treated passed through the cation exchange resin tower [mS/cm]: A ⁇ (B 2 ) ⁇ 3.5 (1).
  • a method for regenerating an ion exchange resin comprising: a storage step of storing the impurity-containing waste acid or waste alkali in a tank; a measuring step of measuring the concentration of impurities in the waste acid or waste alkali; a determining step of determining whether the waste acid or waste alkali can be reused based on the concentration of the impurities; a regeneration step of reusing the waste acid or waste alkali determined to be reusable in the determination step for regenerating an ion exchange resin;
  • a method for regenerating an ion exchange resin comprising: [Configuration 8] 8. The method for regenerating an ion exchange resin according to claim 7, wherein the waste acid is waste sulfuric acid. [Configuration 9] 9.
  • the waste sulfuric acid is waste sulfuric acid discharged from a semiconductor factory.
  • the ion exchange resin is a cation exchange resin
  • the impurities include ammonia
  • the method for regenerating an ion exchange resin according to claim 10, wherein, in the determination step, if the concentration of the ammonia in the waste sulfuric acid is 100 ppm or less per 5 mass% of the waste sulfuric acid, the waste sulfuric acid is determined to be reusable for regenerating a cation exchange resin.
  • the ion exchange resin is a cation exchange resin
  • the regeneration method further includes a water sampling step of sequentially passing the water to be treated through a cation exchange resin tower filled with a cation exchange resin after regenerating the water using waste sulfuric acid containing ammonia as the impurity, and an anion exchange resin tower filled with an anion exchange resin, to obtain treated water; 12.
  • Waste liquid tank 2 Reusable chemical tank 3: Regeneration means 4: Water sampling means (cation exchange resin tower) 5: Water sampling means (anion exchange resin tower) L1 to L8: flow paths

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatment Of Water By Ion Exchange (AREA)

Abstract

Est proposé un système de régénération d'une résine échangeuse d'ions à l'aide d'acide résiduaire ou d'alcali résiduaire, le système permettant d'obtenir de l'eau traitée de qualité stable par un procédé simple. Ce système de régénération d'une résine échangeuse d'ions est caractérisé en ce qu'il comprend : un réservoir (1) pour stocker un acide résiduaire ou un alcali résiduaire contenant des impuretés ; un moyen de mesure pour mesurer la concentration des impuretés dans l'acide résiduaire ou l'alcali résiduaire ; un moyen d'évaluation pour déterminer, sur la base de la concentration des impuretés, si l'acide résiduaire ou l'alcali résiduaire peut être réutilisé ; et un moyen de régénération 3 pour régénérer la résine échangeuse d'ions à l'aide de l'acide résiduaire ou de l'alcali résiduaire déterminé par le moyen de détermination comme étant réutilisable.
PCT/JP2025/014337 2024-05-13 2025-04-10 Système et procédé de régénération de résine échangeuse d'ions à l'aide d'acide résiduaire ou d'alcali résiduaire Pending WO2025239076A1 (fr)

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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5615844A (en) * 1979-07-17 1981-02-16 Ebara Infilco Co Ltd Regeneration of desalter for condensed water
US4379855A (en) * 1981-07-01 1983-04-12 Ecodyne Corporation Method of ion exchange regeneration
JPS59206054A (ja) * 1983-04-13 1984-11-21 Ebara Infilco Co Ltd イオン交換樹脂の除鉄回生方法
JPS60122043A (ja) * 1983-12-02 1985-06-29 Hitachi Ltd イオン交換樹脂再生廃液処理装置
JPS6180096A (ja) * 1984-09-28 1986-04-23 株式会社荏原製作所 放射性廃棄物を低減する方法
JPH026893A (ja) * 1988-02-25 1990-01-11 Japan Organo Co Ltd 復水脱塩装置
JPH05317729A (ja) * 1992-05-21 1993-12-03 Japan Organo Co Ltd イオン交換樹脂の再生法及び再生設備
JPH11566A (ja) * 1997-06-11 1999-01-06 Kubota Corp イオン交換樹脂再生廃液の処理方法および処理装置
JP2008183526A (ja) * 2007-01-31 2008-08-14 Jfe Steel Kk 酸性廃液およびアルカリ性廃液の処理方法
WO2020013070A1 (fr) * 2018-07-11 2020-01-16 伸栄化学産業株式会社 Dispositif de régénération de liquide acide et procédé de régénération
WO2021201021A1 (fr) * 2020-04-03 2021-10-07 パナソニックＩｐマネジメント株式会社 Dispositif d'adoucissement d'eau et procédé de récupération de dispositif d'adoucissement d'eau
WO2022102263A1 (fr) * 2020-11-10 2022-05-19 オルガノ株式会社 Procédé et appareil de purification de liquide à traiter contenant des ions tétraalkylammonium

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5615844A (en) * 1979-07-17 1981-02-16 Ebara Infilco Co Ltd Regeneration of desalter for condensed water
US4379855A (en) * 1981-07-01 1983-04-12 Ecodyne Corporation Method of ion exchange regeneration
JPS59206054A (ja) * 1983-04-13 1984-11-21 Ebara Infilco Co Ltd イオン交換樹脂の除鉄回生方法
JPS60122043A (ja) * 1983-12-02 1985-06-29 Hitachi Ltd イオン交換樹脂再生廃液処理装置
JPS6180096A (ja) * 1984-09-28 1986-04-23 株式会社荏原製作所 放射性廃棄物を低減する方法
JPH026893A (ja) * 1988-02-25 1990-01-11 Japan Organo Co Ltd 復水脱塩装置
JPH05317729A (ja) * 1992-05-21 1993-12-03 Japan Organo Co Ltd イオン交換樹脂の再生法及び再生設備
JPH11566A (ja) * 1997-06-11 1999-01-06 Kubota Corp イオン交換樹脂再生廃液の処理方法および処理装置
JP2008183526A (ja) * 2007-01-31 2008-08-14 Jfe Steel Kk 酸性廃液およびアルカリ性廃液の処理方法
WO2020013070A1 (fr) * 2018-07-11 2020-01-16 伸栄化学産業株式会社 Dispositif de régénération de liquide acide et procédé de régénération
WO2021201021A1 (fr) * 2020-04-03 2021-10-07 パナソニックＩｐマネジメント株式会社 Dispositif d'adoucissement d'eau et procédé de récupération de dispositif d'adoucissement d'eau
WO2022102263A1 (fr) * 2020-11-10 2022-05-19 オルガノ株式会社 Procédé et appareil de purification de liquide à traiter contenant des ions tétraalkylammonium

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