WO2012018038A1 - Method and device for treating acetic acid-containing wastewater - Google Patents

Method and device for treating acetic acid-containing wastewater Download PDF

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Publication number
WO2012018038A1
WO2012018038A1 PCT/JP2011/067746 JP2011067746W WO2012018038A1 WO 2012018038 A1 WO2012018038 A1 WO 2012018038A1 JP 2011067746 W JP2011067746 W JP 2011067746W WO 2012018038 A1 WO2012018038 A1 WO 2012018038A1
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acetic acid
exchange resin
treating
water
containing wastewater
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PCT/JP2011/067746
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French (fr)
Japanese (ja)
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雄壱 小野
祐公 角谷
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栗田工業株式会社
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Priority to CN201180037972.2A priority Critical patent/CN103052599B/en
Publication of WO2012018038A1 publication Critical patent/WO2012018038A1/en

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    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • 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
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/427—Treatment of water, waste water, or sewage by ion-exchange using mixed beds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • 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
    • C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
    • 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
    • C02F2303/02—Odour removal or prevention of malodour
    • 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
    • C02F2303/16—Regeneration of sorbents, filters

Definitions

  • the present invention relates to a method and an apparatus for treating wastewater discharged from a food factory or the like and containing acetic acid and further peracetic acid.
  • chlorinated chemicals have been mainly used as disinfectants or disinfectants used in food factories, but chlorinated chemicals have problems such as safety to the human body and corrosiveness to metals. Therefore, in recent years, a medicine mainly composed of peracetic acid has been used as a bactericide or disinfectant instead of a chlorine-based medicine.
  • This agent is usually used as a peracetic acid-based fungicide (oxonia) comprising peracetic acid, acetic acid, hydrogen peroxide and water having the following composition.
  • water containing peracetic acid is treated by adding a reducing agent (sodium bisulfite, sodium thiosulfate, etc.) to peracetic acid-containing water to reduce peracetic acid to acetic acid, or peracetic acid-containing water.
  • a reducing agent sodium bisulfite, sodium thiosulfate, etc.
  • JP-A-4-22494 a transition metal catalyst
  • the cost of the reducing agent is high, and there is a problem of an increase in ions such as sulfate ions generated by the reduction, which is inappropriate for the recovery and reuse of water.
  • the transition metal in the catalyst such as copper is oxidized by reduction and eluted into the treated water, which may deteriorate the water quality.
  • Japanese Patent No. 3606031 Japanese Patent Laid-Open No. 2001-129564
  • oxonia wastewater is contacted with activated carbon to reduce peracetic acid to acetic acid, then contacted with a cation exchange resin to remove cations, and then contacted with an anion exchange resin to acetic acid.
  • acetic acid can be efficiently adsorbed and removed by subsequent contact treatment with an anion exchange resin.
  • Patent Document 2 The treatment technique of Patent Document 2 is sufficient from the viewpoint of the purity of recovered water, but an anion exchange resin is disposed in the final stage, so that amines that elute in a small amount from the anion exchange resin depending on the recovery conditions. Measures against odor are required. In addition, since the odor becomes strong when the water temperature is a high temperature of 50 ° C. or more like oxonia waste water, a sufficient countermeasure against odor is required.
  • the present invention provides a method and apparatus for treating acetic acid-containing wastewater that can sufficiently remove acetic acid from acetic acid-containing wastewater, and that prevents elution of amines into treated water and prevents odor generation. Objective.
  • the method for treating acetic acid-containing wastewater according to the first aspect is a method for treating acetic acid-containing wastewater discharged from a food or beverage factory, a step of bringing the water to be treated into contact with an anion exchange resin, and a step of bringing it into contact with a cation exchange resin thereafter. It is characterized by having.
  • the method for treating acetic acid-containing wastewater according to the second aspect is a method for treating acetic acid-containing wastewater discharged from a food or beverage factory, wherein the treated water is brought into contact with a mixed bed containing at least an anion exchange resin and a cation exchange resin. It is characterized by having.
  • the method for treating acetic acid-containing wastewater according to the third aspect is the mixing ratio of anion exchange resin and cation exchange resin in the mixed bed containing the anion exchange resin and the cation exchange resin in the method for treating acetic acid-containing wastewater according to the second aspect (
  • a method for treating acetic acid-containing wastewater according to a fourth aspect is the method for treating acetic acid-containing wastewater according to any one of the first to third aspects, wherein the anion exchange resin is a weakly basic anion exchange resin and the cation exchange resin is strongly acidic. It is a cation exchange resin.
  • the method for treating acetic acid-containing wastewater according to the fifth aspect is a method for treating wastewater containing acetic acid and peracetic acid discharged from a food or beverage factory, bringing the wastewater into contact with activated carbon and reducing it to acetic acid,
  • the activated carbon-treated water is treated by the method for treating acetic acid-containing wastewater according to any one of the first to fourth aspects.
  • the method for treating acetic acid-containing wastewater according to the sixth aspect is characterized in that, in the method for treating acetic acid-containing wastewater according to any one of the first to fifth aspects, the wastewater is oxonia wastewater having a water temperature of 40 ° C. or higher.
  • the apparatus for treating acetic acid-containing wastewater according to the seventh aspect is the apparatus for treating acetic acid-containing wastewater discharged from a food or beverage factory, wherein an anion exchange tower into which water to be treated is introduced, and an effluent from the anion exchange tower are introduced. And a cation exchange column.
  • the acetic acid-containing wastewater treatment apparatus is the acetic acid-containing wastewater treatment apparatus according to the seventh aspect, wherein the water flow SV of the anion exchange tower is 5 to 25 hr ⁇ 1 and the water flow SV of the cation exchange tower is 10 to 30 hr ⁇ 1 .
  • a treatment apparatus for acetic acid-containing wastewater according to a ninth aspect is a mixed-bed resin tower including at least an anion exchange resin and a cation exchange resin into which water to be treated is introduced in a treatment apparatus for acetic acid-containing wastewater discharged from a food or beverage factory. It is provided with.
  • the acetic acid-containing wastewater treatment device of the tenth aspect is characterized in that, in the acetic acid-containing wastewater treatment device of the ninth aspect, the water flow SV of the mixed bed resin tower is 10 to 30 hr ⁇ 1 .
  • An acetic acid-containing wastewater treatment apparatus is the treatment apparatus for wastewater containing acetic acid and peracetic acid discharged from a food or beverage factory, wherein the activated carbon tower into which the wastewater is introduced and the effluent from the activated carbon tower And a treatment apparatus for acetic acid-containing wastewater according to any one of the seventh to tenth aspects, which is treated as water to be treated.
  • An acetic acid-containing wastewater treatment apparatus is the acetic acid-containing wastewater treatment apparatus according to the eleventh aspect, wherein the activated carbon tower is a multi-stage fluidized bed activated carbon tower having an upward flow, and its water flow SV is 5 to 5. It is characterized by being 20 hr ⁇ 1 .
  • the apparatus for treating acetic acid-containing wastewater according to the thirteenth aspect is characterized in that, in the apparatus for treating acetic acid-containing wastewater according to any of the seventh to twelfth aspects, the wastewater is oxonia wastewater having a water temperature of 40 ° C. or higher.
  • acetic acid-containing wastewater is first contacted with an anion exchange resin to remove anionic species, and then contacted with a cation exchange resin to remove the cation species. Trace amounts of amines are eluted from the first contact step with the anion exchange resin, but these amines are removed by the subsequent contact treatment with the cation exchange resin. As a result, treated water in which acetic acid is sufficiently removed and odor generation due to the eluted amines is prevented can be obtained.
  • acetic acid-containing wastewater is brought into contact with a mixed bed containing at least an anion exchange resin and a cation exchange resin.
  • acetic acid is removed by the anion exchange resin, and amines are removed by the cation exchange resin, so that treated water in which odor generation is prevented is obtained.
  • Yet another aspect of the present invention is a method and apparatus for treating peracetic acid-containing wastewater, wherein the peracetic acid-containing wastewater is first contacted with activated carbon to reduce peracetic acid to acetic acid. Thereafter, the treatment is performed in accordance with the method and apparatus for treating acetic acid-containing wastewater of the first or second aspect.
  • treated water in which peracetic acid and acetic acid are sufficiently removed and odor generation is prevented can be obtained.
  • acetic acid exchanged and adsorbed on the anion exchange resin can be desorbed and recovered as CH 3 COONa in the regeneration waste liquid by regenerating the anion exchange resin with sodium hydroxide or the like.
  • 1 is a flow diagram illustrating the method and apparatus of the present invention. 1 is a flow diagram illustrating the method and apparatus of the present invention. It is a flowchart which shows the conventional method and apparatus.
  • FIG. 1 is a system diagram showing a peracetic acid-containing water treatment device (treatment recovery device) according to a first embodiment of the present invention.
  • peracetic acid-containing water (raw water) is passed through the activated carbon tower 1 to reduce peracetic acid to acetic acid.
  • the raw material and shape of the activated carbon charged in the activated carbon tower 1 are not particularly limited in terms of the function of reducing peracetic acid to acetic acid, and coal-based, coconut-based, or other granular or powdery materials may be used. it can.
  • Water passing rate of the activated carbon column 1 has superficial velocity in terms of reduction efficiency (SV) 5 ⁇ 20hr -1, preferably in the particular 8 ⁇ 12hr -1.
  • the activated carbon tower 1 When hydrogen peroxide (H 2 O 2 ) is contained in the raw water, the activated carbon tower 1 also reduces H 2 O 2 to water and removes it.
  • H 2 O 2 hydrogen peroxide
  • the effluent from the activated carbon tower 1 is first passed through the anion exchange tower 2 to adsorb and remove acetic acid produced by reduction of peracetic acid and acetic acid derived from raw water.
  • the anion exchange resin packed in the anion exchange tower 2 is preferably a weakly basic anion exchange resin, and is preferably treated with water flow SV5 to 25 hr ⁇ 1 .
  • the effluent water from the anion exchange column 2 is water from which peracetic acid has been highly removed.
  • the raw water is oxonia wastewater, all of peracetic acid, H 2 O 2 and acetic acid are highly removed.
  • the acetic acid exchanged and adsorbed on the anion exchange resin of the anion exchange column 2 is removed as CH 3 COONa in the regenerated waste liquid by regenerating the acetic acid exchanged / adsorbed anion exchange resin with sodium hydroxide or the like. Can be separated and collected.
  • the regenerated waste liquid may be biologically treated, and CH 3 COONa in the regenerated waste liquid can be easily reused because both the concentration and purity are high.
  • the effluent water from the anion exchange tower 2 is then passed to the cation exchange tower 3.
  • Cation species such as K + and Na + contained in the raw water and amines eluted from the anion exchange tower 2 are removed by the ion exchange treatment in the cation exchange tower 3.
  • the cation exchange resin packed in the cation packed tower 3 is preferably a strongly acidic cation exchange resin, and the water flow SV is preferably about 10 to 30 hr ⁇ 1 .
  • FIG. 2 is a system diagram showing a peracetic acid-containing water treatment device (treatment recovery device) according to a second embodiment of the present invention.
  • peracetic acid-containing water (raw water) is passed through the activated carbon tower 1 to reduce peracetic acid to acetic acid.
  • the configuration and water flow conditions of the activated carbon tower 1 are the same as those in the first embodiment.
  • the effluent from the activated carbon tower 1 is then passed through a mixed bed resin tower 4 containing at least a cation exchange resin and an anion exchange resin. Thereby, both cation and anion are removed, and treated water in which amines eluted from the anion exchange resin are adsorbed and removed by the cation exchange resin is obtained.
  • a combination of a strongly acidic cation exchange resin and a strongly basic anion exchange resin is preferable, and the mixing ratio (weight ratio) of the cation exchange resin and the anion exchange resin is preferred.
  • the water flow SV is preferably about 10 to 30 hr ⁇ 1 .
  • Such a method and apparatus of the present invention is suitable for the treatment of oxonia wastewater containing peracetic acid, acetic acid and H 2 O 2 at a temperature of about 40 ° C. to 50 ° C., particularly from the oxonia cleaning step using pure water.
  • the concentration of peracetic acid and acetic acid generated is about 50 to 300 mg / L in total, and it is suitable for the treatment of relatively low concentration wastewater having a hydrogen peroxide concentration of about 10 to 300 mg / L.
  • the method and apparatus of the present invention are also suitable for the treatment of acid cleaning rinse water in a CIP apparatus.
  • the CIP device is a device that cleans a production line for beverages such as soft drinks, natural waters, juices, ketchups, mayonnaises and the like having various tanks, plates, pipes, and other configurations without disassembling.
  • Example 1 Oxonia wastewater containing peracetic acid and acetic acid in an amount of 176 mg / L in terms of acetic acid and 36 mg / L of hydrogen peroxide was passed through the treatment apparatus shown in FIG. The test water temperature was adjusted to 50 ° C., which is the actual oxonia drainage temperature.
  • each column The specifications of each column are as follows, and the water flow SV was activated carbon tower: 10 hr ⁇ 1 , cation exchange tower: 20 hr ⁇ 1 , and anion exchange tower 10 hr ⁇ 1 .
  • Activated carbon tower A 220 mL column packed with 200 mL of granular activated carbon “Crycol WG” manufactured by Kurita Kogyo Co., Ltd.
  • Cation exchange tower A column with a capacity of 220 mL packed with 100 mL of cation exchange resin “DIAION SK-112L” (deodorized conditioned product) manufactured by Mitsubishi Chemical Corporation.
  • Example 2 In Example 1, a water flow test was conducted under the same conditions as in Example 1 except that the effluent water of the activated carbon tower 1 was passed through the mixed bed resin tower 4 as shown in FIG.
  • the mixed bed resin tower 4 a column having a capacity of 220 mL and a mixture of 50 mL of the above cation exchange resin and 100 mL of anion exchange resin (SAT15L manufactured by Mitsubishi Chemical Corporation) is used, and the water flow SV is 10 hr ⁇ 1. It was. Table 1 shows the quality of the treated water.
  • Example 1 In Example 1, the order of the anion exchange tower 2 and the cation exchange tower 3 is reversed, and the effluent water of the activated carbon tower 1 is passed in the order of the cation exchange tower 3 and the anion exchange tower 2 as shown in FIG. The water flow test was conducted under the same conditions as in Example 1. Table 1 shows the measurement results of the electrical conductivity and TOC of the effluent water of the cation exchange tower 3 and the quality of the treated water.
  • Example 2 while maintaining the purity of pure water by contacting activated carbon tower effluent water in the order of anion exchange resin ⁇ cation exchange resin or contacting with mixed bed resin,
  • the amine concentration can be reduced from about 85 ⁇ g / L in Comparative Example 1 to about 2 ⁇ g / L (Example 2) or 1 ⁇ g / L or less (Example 1), and the odor can be improved to an odorless state.

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  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
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Abstract

[Problem] To provide a method and a device for treating acetic acid-containing wastewater, which are capable of adequately removing peracetic acid and acetic acid from wastewater containing acetic acid or peracetic acid, and which prevent the leaching of amines into the treated water and prevent odor generation. [Solution] After peracetic acid-containing wastewater such as oxonia wastewater is passed through an active carbon tower (1) and brought into contact with active carbon, same is passed through an anion exchange tower (2) and brought into contact with an anion exchange resin and is then passed through a cation exchange tower (3) and brought into contact with a cation exchange resin. Alternatively, after the peracetic acid-containing wastewater is passed through the active carbon tower (1), same is passed through a mixed bed resin tower (4) comprising an anion exchange resin and a cation exchange resin.

Description

酢酸含有排水の処理方法及び装置Method and apparatus for treating wastewater containing acetic acid
　本発明は、食品工場等から排出される、酢酸さらには過酢酸を含有する排水を処理する方法及び装置に関する。 The present invention relates to a method and an apparatus for treating wastewater discharged from a food factory or the like and containing acetic acid and further peracetic acid.
　食品工場等で使用される殺菌剤ないし除菌剤としては、従来、塩素系の薬剤が主に使用されていたが、塩素系の薬剤は、人体に対する安全性、金属に対する腐食性等の問題があるため、近年、塩素系の薬剤に代わる殺菌剤ないし除菌剤として、過酢酸を主成分とする薬剤が使用されるようになってきた。この薬剤は、通常、下記組成の過酢酸、酢酸、過酸化水素及び水からなる過酢酸系殺菌剤（オキソニア）として使用されている。 Conventionally, chlorinated chemicals have been mainly used as disinfectants or disinfectants used in food factories, but chlorinated chemicals have problems such as safety to the human body and corrosiveness to metals. Therefore, in recent years, a medicine mainly composed of peracetic acid has been used as a bactericide or disinfectant instead of a chlorine-based medicine. This agent is usually used as a peracetic acid-based fungicide (oxonia) comprising peracetic acid, acetic acid, hydrogen peroxide and water having the following composition.
［過酢酸系殺菌剤（オキソニア）の組成］
　　過酢酸（ＣＨ３ＣＯＯＯＨ）：１０重量％
　　酢酸（ＣＨ３ＣＯＯＨ）　　：２０重量％
　　過酸化水素（Ｈ２Ｏ２）　　：２０重量％
　従って、食品工場等からは、過酢酸、酢酸及び過酸化水素を含有する所謂オキソニア排水（廃水）が排出されるため、これを処理する必要がある。 [Composition of peracetic acid fungicide (oxonia)]
Peracetic acid (CH 3 COOOH): 10% by weight
Acetic acid (CH 3 COOH): 20% by weight
Hydrogen peroxide (H 2 O 2 ): 20% by weight
Therefore, since so-called oxonia wastewater (waste water) containing peracetic acid, acetic acid and hydrogen peroxide is discharged from a food factory or the like, it must be treated.
　従来、過酢酸を含有する水を処理する方法としては、過酢酸含有水に還元剤（重亜硫酸ソーダ、チオ硫酸ソーダ等）を添加して過酢酸を酢酸に還元する方法、或いは過酢酸含有水を遷移金属触媒と接触させて過酢酸を酢酸に還元する方法（特開平４－２２４９４号公報）が提案されている。しかしながら、還元剤による方法では、還元剤のコストが高くつく上に、還元により生成する硫酸イオン等のイオンの増加の問題があり、水の回収、再利用には不適当である。また、遷移金属触媒を用いる方法では、銅などの触媒中の遷移金属が還元により酸化されて処理水中に溶出し、水質を低下させる恐れがある。 Conventionally, water containing peracetic acid is treated by adding a reducing agent (sodium bisulfite, sodium thiosulfate, etc.) to peracetic acid-containing water to reduce peracetic acid to acetic acid, or peracetic acid-containing water. Has been proposed in which peracetic acid is reduced to acetic acid by contacting with a transition metal catalyst (JP-A-4-22494). However, in the method using a reducing agent, the cost of the reducing agent is high, and there is a problem of an increase in ions such as sulfate ions generated by the reduction, which is inappropriate for the recovery and reuse of water. In the method using a transition metal catalyst, the transition metal in the catalyst such as copper is oxidized by reduction and eluted into the treated water, which may deteriorate the water quality.
　特許３６０３７０１（特開２００１－１２９５６４）には、オキソニア排水を活性炭と接触させて過酢酸を酢酸に還元した後、カチオン交換樹脂と接触させてカチオンを除去し、次いでアニオン交換樹脂と接触させて酢酸を吸着除去する方法及び装置が記載されている。この方法によれば、共存カチオンを初めに除去するために、その後のアニオン交換樹脂との接触処理により酢酸を効率よく吸着除去することができる。 In Japanese Patent No. 3606031 (Japanese Patent Laid-Open No. 2001-129564), oxonia wastewater is contacted with activated carbon to reduce peracetic acid to acetic acid, then contacted with a cation exchange resin to remove cations, and then contacted with an anion exchange resin to acetic acid. Is described. According to this method, in order to remove the coexisting cations first, acetic acid can be efficiently adsorbed and removed by subsequent contact treatment with an anion exchange resin.
特許３６０３７０１Patent 3606031 特開平４－２２４９４JP-A-4-22494
　近年、食品、飲料工場において、回収水を含めて使用水の水質面での要求は厳しくなってきており、特に臭気や細菌数を低く抑えることが強く求められている。 In recent years, food and beverage factories have become increasingly demanding in terms of water quality, including recovered water, and there is a strong demand for reducing odors and bacterial counts in particular.
　上記特許文献２の処理技術は、回収水の純度の観点からは充分な処理であるが、最終段にアニオン交換樹脂を配しているため、回収条件によってはアニオン交換樹脂から微量溶出するアミン類に対する臭気対策が必要となる。なお、オキソニア排水のように水温が５０℃以上の高温度であると、臭気が強くなるので、十分な臭気対策が必要となる。 The treatment technique of Patent Document 2 is sufficient from the viewpoint of the purity of recovered water, but an anion exchange resin is disposed in the final stage, so that amines that elute in a small amount from the anion exchange resin depending on the recovery conditions. Measures against odor are required. In addition, since the odor becomes strong when the water temperature is a high temperature of 50 ° C. or more like oxonia waste water, a sufficient countermeasure against odor is required.
　この臭気対策として、
　i)　臭気が問題にならなくなるまで、処理水を排出する。　
　ii)　アニオン交換処理の後に、活性炭処理や再度カチオン交換塔を設置する。
といった方式が考えられるが、いずれも処理水の廃棄量増加、あるいは初期投資費用の増加といった課題がある。 As measures against this odor,
i) Drain the treated water until odor is no longer an issue.
ii) After anion exchange treatment, install activated carbon treatment or cation exchange tower again.
However, there are problems such as increasing the amount of treated water discarded or increasing the initial investment cost.
　本発明は、酢酸含有排水から酢酸を十分に除去することができ、しかも処理水中へのアミン類の溶出が防止され、臭気発生が防止される酢酸含有排水の処理方法及び装置を提供することを目的とする。 The present invention provides a method and apparatus for treating acetic acid-containing wastewater that can sufficiently remove acetic acid from acetic acid-containing wastewater, and that prevents elution of amines into treated water and prevents odor generation. Objective.
　第１態様の酢酸含有排水の処理方法は、食品又は飲料工場から排出される酢酸含有排水の処理方法において、被処理水をアニオン交換樹脂と接触させる工程と、その後カチオン交換樹脂と接触させる工程とを有することを特徴とする。 The method for treating acetic acid-containing wastewater according to the first aspect is a method for treating acetic acid-containing wastewater discharged from a food or beverage factory, a step of bringing the water to be treated into contact with an anion exchange resin, and a step of bringing it into contact with a cation exchange resin thereafter. It is characterized by having.
　第２態様の酢酸含有排水の処理方法は、食品又は飲料工場から排出される酢酸含有排水の処理方法において、被処理水を少なくともアニオン交換樹脂とカチオン交換樹脂とを含む混床と接触させる工程を有することを特徴とする。 The method for treating acetic acid-containing wastewater according to the second aspect is a method for treating acetic acid-containing wastewater discharged from a food or beverage factory, wherein the treated water is brought into contact with a mixed bed containing at least an anion exchange resin and a cation exchange resin. It is characterized by having.
　第３態様の酢酸含有排水の処理方法は、第２態様の酢酸含有排水の処理方法において、前記アニオン交換樹脂とカチオン交換樹脂とを含む混床の、アニオン交換樹脂とカチオン交換樹脂の混合比率（重量比）が、カチオン交換樹脂：アニオン交換樹脂＝１：１．５～１０であることを特徴とする。 The method for treating acetic acid-containing wastewater according to the third aspect is the mixing ratio of anion exchange resin and cation exchange resin in the mixed bed containing the anion exchange resin and the cation exchange resin in the method for treating acetic acid-containing wastewater according to the second aspect ( The weight ratio is cation exchange resin: anion exchange resin = 1: 1.5-10.
　第４態様の酢酸含有排水の処理方法は、第１～３態様のいずれかの酢酸含有排水の処理方法において、前記アニオン交換樹脂が弱塩基性アニオン交換樹脂であり、前記カチオン交換樹脂が強酸性カチオン交換樹脂であることを特徴とする。 A method for treating acetic acid-containing wastewater according to a fourth aspect is the method for treating acetic acid-containing wastewater according to any one of the first to third aspects, wherein the anion exchange resin is a weakly basic anion exchange resin and the cation exchange resin is strongly acidic. It is a cation exchange resin.
　第５態様の酢酸含有排水の処理方法は、食品又は飲料工場から排出される酢酸及び過酢酸を含有する排水の処理方法において、該排水を活性炭と接触させて酢酸に還元する工程と、その後、この活性炭処理水を第１～４態様のいずれかの酢酸含有排水の処理方法によって処理することを特徴とする。 The method for treating acetic acid-containing wastewater according to the fifth aspect is a method for treating wastewater containing acetic acid and peracetic acid discharged from a food or beverage factory, bringing the wastewater into contact with activated carbon and reducing it to acetic acid, The activated carbon-treated water is treated by the method for treating acetic acid-containing wastewater according to any one of the first to fourth aspects.
　第６態様の酢酸含有排水の処理方法は、第１～５態様のいずれかの酢酸含有排水の処理方法において、前記排水が水温４０℃以上のオキソニア排水であることを特徴とする。 The method for treating acetic acid-containing wastewater according to the sixth aspect is characterized in that, in the method for treating acetic acid-containing wastewater according to any one of the first to fifth aspects, the wastewater is oxonia wastewater having a water temperature of 40 ° C. or higher.
　第７態様の酢酸含有排水の処理装置は、食品又は飲料工場から排出される酢酸含有排水の処理装置において、被処理水が導入されるアニオン交換塔と、該アニオン交換塔の流出水が導入されるカチオン交換塔とを備えたことを特徴とする。 The apparatus for treating acetic acid-containing wastewater according to the seventh aspect is the apparatus for treating acetic acid-containing wastewater discharged from a food or beverage factory, wherein an anion exchange tower into which water to be treated is introduced, and an effluent from the anion exchange tower are introduced. And a cation exchange column.
　第８態様の酢酸含有排水の処理装置は、第７態様の酢酸含有排水の処理装置において、前記アニオン交換塔の通水ＳＶが５～２５ｈｒ－１であり、前記カチオン交換塔の通水ＳＶが１０～３０ｈｒ－１であることを特徴とする。 The acetic acid-containing wastewater treatment apparatus according to the eighth aspect is the acetic acid-containing wastewater treatment apparatus according to the seventh aspect, wherein the water flow SV of the anion exchange tower is 5 to 25 hr −1 and the water flow SV of the cation exchange tower is 10 to 30 hr −1 .
　第９態様の酢酸含有排水の処理装置は、食品又は飲料工場から排出される酢酸含有排水の処理装置において、被処理水が導入される少なくともアニオン交換樹脂とカチオン交換樹脂とを含む混床樹脂塔を備えたことを特徴とする。 A treatment apparatus for acetic acid-containing wastewater according to a ninth aspect is a mixed-bed resin tower including at least an anion exchange resin and a cation exchange resin into which water to be treated is introduced in a treatment apparatus for acetic acid-containing wastewater discharged from a food or beverage factory. It is provided with.
　第１０態様の酢酸含有排水の処理装置は、第９態様の酢酸含有排水の処理装置において、前記混床樹脂塔の通水ＳＶが１０～３０ｈｒ－１であることを特徴とする。 The acetic acid-containing wastewater treatment device of the tenth aspect is characterized in that, in the acetic acid-containing wastewater treatment device of the ninth aspect, the water flow SV of the mixed bed resin tower is 10 to 30 hr −1 .
　第１１態様の酢酸含有排水の処理装置は、食品又は飲料工場から排出される酢酸及び過酢酸を含有する排水の処理装置において、該排水が導入される活性炭塔と、該活性炭塔の流出水を被処理水として処理する第７～１０態様のいずれかの酢酸含有排水の処理装置とを備えたことを特徴とする。 An acetic acid-containing wastewater treatment apparatus according to an eleventh aspect is the treatment apparatus for wastewater containing acetic acid and peracetic acid discharged from a food or beverage factory, wherein the activated carbon tower into which the wastewater is introduced and the effluent from the activated carbon tower And a treatment apparatus for acetic acid-containing wastewater according to any one of the seventh to tenth aspects, which is treated as water to be treated.
　第１２態様の酢酸含有排水の処理装置は、第１１態様の酢酸含有排水の処理装置において、前記活性炭塔が上向流の多段式の流動床式活性炭塔であり、その通水ＳＶが５～２０ｈｒ－１であることを特徴とする。 An acetic acid-containing wastewater treatment apparatus according to a twelfth aspect is the acetic acid-containing wastewater treatment apparatus according to the eleventh aspect, wherein the activated carbon tower is a multi-stage fluidized bed activated carbon tower having an upward flow, and its water flow SV is 5 to 5. It is characterized by being 20 hr −1 .
　第１３態様の酢酸含有排水の処理装置は、第７～１２態様のいずれかの酢酸含有排水の処理装置において、排水が水温４０℃以上のオキソニア排水であることを特徴とする。 The apparatus for treating acetic acid-containing wastewater according to the thirteenth aspect is characterized in that, in the apparatus for treating acetic acid-containing wastewater according to any of the seventh to twelfth aspects, the wastewater is oxonia wastewater having a water temperature of 40 ° C. or higher.
　本発明の一態様に係る酢酸含有排水の処理方法及び装置では、酢酸含有排水をまずアニオン交換樹脂と接触させてアニオン種を除去し、次いでカチオン交換樹脂と接触させてカチオン種を除去する。最初のアニオン交換樹脂との接触工程からは微量のアミン類が溶出するが、このアミン類は後段のカチオン交換樹脂との接触処理により除去される。これにより、酢酸が十分に除去され、また溶出アミン類に起因した臭気発生も防止された処理水が得られる。 In the method and apparatus for treating acetic acid-containing wastewater according to one embodiment of the present invention, acetic acid-containing wastewater is first contacted with an anion exchange resin to remove anionic species, and then contacted with a cation exchange resin to remove the cation species. Trace amounts of amines are eluted from the first contact step with the anion exchange resin, but these amines are removed by the subsequent contact treatment with the cation exchange resin. As a result, treated water in which acetic acid is sufficiently removed and odor generation due to the eluted amines is prevented can be obtained.
　本発明の別態様の酢酸含有排水の処理方法及び装置では、酢酸含有排水を少なくともアニオン交換樹脂とカチオン交換樹脂とを含む混床と接触させる。これにより、酢酸がアニオン交換樹脂で除去されると共に、アミン類がカチオン交換樹脂によって除去され、臭気発生も防止された処理水が得られる。 In the method and apparatus for treating acetic acid-containing wastewater according to another aspect of the present invention, acetic acid-containing wastewater is brought into contact with a mixed bed containing at least an anion exchange resin and a cation exchange resin. Thereby, acetic acid is removed by the anion exchange resin, and amines are removed by the cation exchange resin, so that treated water in which odor generation is prevented is obtained.
　本発明のさらに別の態様は、過酢酸含有排水を処理する方法及び装置であって、まず過酢酸含有排水を活性炭と接触させ、過酢酸を酢酸に還元する。その後は、上記第１又は第２態様の酢酸含有排水の処理方法及び装置に従って処理を行う。これにより過酢酸及び酢酸が十分に除去され、臭気発生も防止された処理水が得られる。
　なお、本発明では、アニオン交換樹脂に交換・吸着された酢酸は、このアニオン交換樹脂を水酸化ナトリウム等で再生することにより、再生廃液中にＣＨ３ＣＯＯＮａとして脱離回収することができる。 Yet another aspect of the present invention is a method and apparatus for treating peracetic acid-containing wastewater, wherein the peracetic acid-containing wastewater is first contacted with activated carbon to reduce peracetic acid to acetic acid. Thereafter, the treatment is performed in accordance with the method and apparatus for treating acetic acid-containing wastewater of the first or second aspect. As a result, treated water in which peracetic acid and acetic acid are sufficiently removed and odor generation is prevented can be obtained.
In the present invention, acetic acid exchanged and adsorbed on the anion exchange resin can be desorbed and recovered as CH 3 COONa in the regeneration waste liquid by regenerating the anion exchange resin with sodium hydroxide or the like.
本発明方法及び装置を示すフロー図である。1 is a flow diagram illustrating the method and apparatus of the present invention. 本発明方法及び装置を示すフロー図である。1 is a flow diagram illustrating the method and apparatus of the present invention. 従来方法及び装置を示すフロー図である。It is a flowchart which shows the conventional method and apparatus.
　以下に、図面を参照して本発明の実施の形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
　図１は本発明の第１の実施の形態に係る過酢酸含有水の処理装置（処理回収装置）を示す系統図である。 FIG. 1 is a system diagram showing a peracetic acid-containing water treatment device (treatment recovery device) according to a first embodiment of the present invention.
　図１の実施の形態にあっては、まず過酢酸含有水（原水）を活性炭塔１に通水して過酢酸を酢酸に還元する。この活性炭塔１に充填する活性炭の原料及び形状には、過酢酸を酢酸に還元するという機能上からは特に制限はなく、石炭系、ヤシガラ系、その他の粒状ないし粉状のものを用いることができる。 In the embodiment of FIG. 1, first, peracetic acid-containing water (raw water) is passed through the activated carbon tower 1 to reduce peracetic acid to acetic acid. The raw material and shape of the activated carbon charged in the activated carbon tower 1 are not particularly limited in terms of the function of reducing peracetic acid to acetic acid, and coal-based, coconut-based, or other granular or powdery materials may be used. it can.
　過酢酸の還元では、酸素と少量の炭酸ガス気泡が発生することから、この気泡を速やかに除去するために活性炭塔１としては、上向流の多段式の流動床式活性炭塔が好適である。この活性炭塔１の通水速度は、還元効率の面から空塔速度（ＳＶ）５～２０ｈｒ－１、特に８～１２ｈｒ－１とするのが好ましい。 In the reduction of peracetic acid, oxygen and a small amount of carbon dioxide gas bubbles are generated. Therefore, as the activated carbon tower 1, an upward-flow multistage fluidized bed activated carbon tower is suitable for quickly removing the bubbles. . Water passing rate of the activated carbon column 1 has superficial velocity in terms of reduction efficiency (SV) 5 ~ 20hr -1, preferably in the particular 8 ~ 12hr -1.
　なお、原水に過酸化水素（Ｈ２Ｏ２）が含まれる場合には、活性炭塔１でＨ２Ｏ２も水に還元されて除去される。 When hydrogen peroxide (H 2 O 2 ) is contained in the raw water, the activated carbon tower 1 also reduces H 2 O 2 to water and removes it.
　活性炭搭１の流出水はまずアニオン交換塔２に通水して過酢酸の還元で生じた酢酸及び原水由来の酢酸を吸着除去する。このアニオン交換塔２に充填するアニオン交換樹脂としては、弱塩基性アニオン交換樹脂が好ましく、通水ＳＶ５～２５ｈｒ－１で処理するのが好ましい。 The effluent from the activated carbon tower 1 is first passed through the anion exchange tower 2 to adsorb and remove acetic acid produced by reduction of peracetic acid and acetic acid derived from raw water. The anion exchange resin packed in the anion exchange tower 2 is preferably a weakly basic anion exchange resin, and is preferably treated with water flow SV5 to 25 hr −1 .
　アニオン交換塔２の流出水は、過酢酸が高度に除去された水であり、特に原水がオキソニア廃水である場合には、過酢酸、Ｈ２Ｏ２及び酢酸がいずれも高度に除去される。 The effluent water from the anion exchange column 2 is water from which peracetic acid has been highly removed. In particular, when the raw water is oxonia wastewater, all of peracetic acid, H 2 O 2 and acetic acid are highly removed.
　なお、このアニオン交換塔２のアニオン交換樹脂に交換・吸着された酢酸は、この酢酸を交換・吸着したアニオン交換樹脂を水酸化ナトリウム等で再生することにより、再生廃液中にＣＨ３ＣＯＯＮａとして脱離・回収することができる。再生廃液は、生物処理してもよく、また、この再生廃液中のＣＨ３ＣＯＯＮａは濃度、純度が共に高いため、容易に再利用することもできる。 The acetic acid exchanged and adsorbed on the anion exchange resin of the anion exchange column 2 is removed as CH 3 COONa in the regenerated waste liquid by regenerating the acetic acid exchanged / adsorbed anion exchange resin with sodium hydroxide or the like. Can be separated and collected. The regenerated waste liquid may be biologically treated, and CH 3 COONa in the regenerated waste liquid can be easily reused because both the concentration and purity are high.
　アニオン交換塔２の流出水は次いでカチオン交換搭３に通水する。原水に含まれるＫ＋，Ｎａ＋等のカチオン種や、アニオン交換塔２から溶出したアミン類がこのカチオン交換搭３でのイオン交換処理により除去される。このカチオン充填塔３に充填するカチオン交換樹脂としては、強酸性カチオン交換樹脂が好ましく、その通水ＳＶは１０～３０ｈｒ－１程度とするのが好ましい。 The effluent water from the anion exchange tower 2 is then passed to the cation exchange tower 3. Cation species such as K + and Na + contained in the raw water and amines eluted from the anion exchange tower 2 are removed by the ion exchange treatment in the cation exchange tower 3. The cation exchange resin packed in the cation packed tower 3 is preferably a strongly acidic cation exchange resin, and the water flow SV is preferably about 10 to 30 hr −1 .
　なお、原水が過酢酸を含有しない酢酸含有排水である場合には、活性炭塔１を経由せずに原水をアニオン交換塔２に導入すればよい。 In addition, what is necessary is just to introduce | transduce raw | natural water into the anion exchange tower 2 without going through the activated carbon tower 1, when raw | natural water is acetic acid containing waste water which does not contain peracetic acid.
　図２は本発明の第２の実施の形態に係る過酢酸含有水の処理装置（処理回収装置）を示す系統図である。 FIG. 2 is a system diagram showing a peracetic acid-containing water treatment device (treatment recovery device) according to a second embodiment of the present invention.
　この図２の実施の形態にあっては、まず過酢酸含有水（原水）を活性炭塔１に通水して過酢酸を酢酸に還元する。この活性炭塔１の構成及び通水条件は上記第１の実施の形態と同様である。 In the embodiment of FIG. 2, first, peracetic acid-containing water (raw water) is passed through the activated carbon tower 1 to reduce peracetic acid to acetic acid. The configuration and water flow conditions of the activated carbon tower 1 are the same as those in the first embodiment.
　活性炭塔１の流出水は次いで少なくともカチオン交換樹脂とアニオン交換樹脂とを含む混床樹脂塔４に通水する。これにより、カチオン及びアニオンの双方が除去されると共に、アニオン交換樹脂から溶出したアミン類がカチオン交換樹脂によって吸着除去された処理水が得られる。 The effluent from the activated carbon tower 1 is then passed through a mixed bed resin tower 4 containing at least a cation exchange resin and an anion exchange resin. Thereby, both cation and anion are removed, and treated water in which amines eluted from the anion exchange resin are adsorbed and removed by the cation exchange resin is obtained.
　混床樹脂塔４に充填するカチオン交換樹脂及びアニオン交換樹脂としては、強酸性カチオン交換樹脂及び強塩基性アニオン交換樹脂の組み合わせが好ましく、そのカチオン交換樹脂とアニオン交換樹脂との混合比率（重量比）は、排水原水水質にもよるが、１：１．５～１０程度が好適である。通水ＳＶは１０～３０ｈｒ－１程度とするのが好ましい。 As the cation exchange resin and anion exchange resin packed in the mixed bed resin tower 4, a combination of a strongly acidic cation exchange resin and a strongly basic anion exchange resin is preferable, and the mixing ratio (weight ratio) of the cation exchange resin and the anion exchange resin is preferred. ) Is preferably about 1: 1.5 to 10 although it depends on the quality of the wastewater. The water flow SV is preferably about 10 to 30 hr −1 .
　なお、原水が過酢酸を含有しない酢酸含有排水である場合には、活性炭塔１を経由せずに原水を混床樹脂塔４に導入すればよい。 In addition, what is necessary is just to introduce | transduce raw | natural water into the mixed bed resin tower 4 without going through the activated carbon tower 1, when raw | natural water is acetic acid containing waste water which does not contain peracetic acid.
　このような本発明の方法及び装置は、過酢酸、酢酸及びＨ２Ｏ２を含む温度４０℃～５０℃程度のオキソニア廃水の処理に好適であり、特に、純水を用いたオキソニア洗浄工程から発生する、過酢酸及び酢酸の濃度が合計で５０～３００ｍｇ／Ｌ程度であり、過酸化水素濃度が１０～３００ｍｇ／Ｌ程度の比較的低濃度の廃水の処理に好適である。なお、本発明の方法及び装置は、ＣＩＰ装置の酸洗浄すすぎ水の処理にも好適である。ＣＩＰ装置は、各種タンク、プレート、配管、その他の構成からなる清涼飲料水、天然水、ジュース、ケチャップ、マヨネーズ等の飲料等の製造ラインを分解することなく洗浄する装置である。 Such a method and apparatus of the present invention is suitable for the treatment of oxonia wastewater containing peracetic acid, acetic acid and H 2 O 2 at a temperature of about 40 ° C. to 50 ° C., particularly from the oxonia cleaning step using pure water. The concentration of peracetic acid and acetic acid generated is about 50 to 300 mg / L in total, and it is suitable for the treatment of relatively low concentration wastewater having a hydrogen peroxide concentration of about 10 to 300 mg / L. The method and apparatus of the present invention are also suitable for the treatment of acid cleaning rinse water in a CIP apparatus. The CIP device is a device that cleans a production line for beverages such as soft drinks, natural waters, juices, ketchups, mayonnaises and the like having various tanks, plates, pipes, and other configurations without disassembling.
　以下に実施例及び比較例を挙げて本発明をより具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.
［実施例１］
　図１に示す処理装置に、過酢酸及び酢酸を酢酸換算で１７６ｍｇ／Ｌ含有すると共に、過酸化水素３６ｍｇ／Ｌを含有するオキソニア排水を通水した。試験水温は、実機のオキソニア排水温度である５０℃に調整した。アニオン交換塔２の出口水及び処理水について、電気伝導率（純水純度の指標）、ＴＯＣ（全有機炭素濃度：酢酸や共存する有機物の除去効果の指標）、臭気（官能試験：処理水の臭気の指標）及びアミン類（トリメチルアミン、ジメチルアミン、モノメチルアミン及び合計の全アミン濃度：臭気に影響を与える物質がどの程度溶出しているかの指標）を測定し、結果を表１に示した。 [Example 1]
Oxonia wastewater containing peracetic acid and acetic acid in an amount of 176 mg / L in terms of acetic acid and 36 mg / L of hydrogen peroxide was passed through the treatment apparatus shown in FIG. The test water temperature was adjusted to 50 ° C., which is the actual oxonia drainage temperature. About the outlet water and treated water of the anion exchange tower 2, electrical conductivity (index of pure water purity), TOC (total organic carbon concentration: index of removal effect of acetic acid and coexisting organic substances), odor (sensory test: treated water) Odor index) and amines (trimethylamine, dimethylamine, monomethylamine and total total amine concentration: an index of how much the substances affecting odor are eluted) were measured, and the results are shown in Table 1.
　なお、各塔の仕様は下記の通りであり、通水ＳＶは各々、活性炭塔：１０ｈｒ－１，カチオン交換搭：２０ｈｒ－１，アニオン交換塔１０ｈｒ－１とした。 The specifications of each column are as follows, and the water flow SV was activated carbon tower: 10 hr −1 , cation exchange tower: 20 hr −1 , and anion exchange tower 10 hr −1 .
　活性炭塔　：　容量２２０ｍＬのカラムに栗田工業（株）製粒状活性炭「クリコールＷＧ」を２００ｍＬ充填したもの
　アニオン交換搭：　容量２２０ｍＬのカラムにランクセス（株）製アニオン交換樹脂「ＵＰ１２３１ＭＤ」（脱臭コンディショニング品）を２００ｍＬ充填したもの
　カチオン交換搭：　容量２２０ｍＬのカラムに三菱化学（株）製カチオン交換樹脂「ＤＩＡＩＯＮ　ＳＫ－１１２Ｌ」（脱臭コンディショニング品）を１００ｍＬ充填したもの Activated carbon tower: A 220 mL column packed with 200 mL of granular activated carbon “Crycol WG” manufactured by Kurita Kogyo Co., Ltd. Cation exchange tower: A column with a capacity of 220 mL packed with 100 mL of cation exchange resin “DIAION SK-112L” (deodorized conditioned product) manufactured by Mitsubishi Chemical Corporation.
［実施例２］
　実施例１において、活性炭塔１の流出水を図２のように混床樹脂塔４に通水するようにした他は実施例１と同一条件にて通水試験を行った。なお、混床樹脂塔４としては、容量２２０ｍＬのカラムに上記カチオン交換樹脂５０ｍＬとアニオン交換樹脂（三菱化学（株）製ＳＡＴ１５Ｌ）１００ｍＬとを混合充填したものを用い、通水ＳＶは１０ｈｒ－１とした。処理水の水質を表１に示す。 [Example 2]
In Example 1, a water flow test was conducted under the same conditions as in Example 1 except that the effluent water of the activated carbon tower 1 was passed through the mixed bed resin tower 4 as shown in FIG. As the mixed bed resin tower 4, a column having a capacity of 220 mL and a mixture of 50 mL of the above cation exchange resin and 100 mL of anion exchange resin (SAT15L manufactured by Mitsubishi Chemical Corporation) is used, and the water flow SV is 10 hr −1. It was. Table 1 shows the quality of the treated water.
［比較例１］
　実施例１において、アニオン交換塔２とカチオン交換塔３との順番を逆にし、図３の通り、活性炭塔１の流出水をカチオン交換塔３、アニオン交換塔２の順番に通水するようにした他は実施例１と同一条件にて通水試験を行った。カチオン交換塔３の流出水の電気伝導率及びＴＯＣと、処理水の水質の測定結果を表１に示す。 [Comparative Example 1]
In Example 1, the order of the anion exchange tower 2 and the cation exchange tower 3 is reversed, and the effluent water of the activated carbon tower 1 is passed in the order of the cation exchange tower 3 and the anion exchange tower 2 as shown in FIG. The water flow test was conducted under the same conditions as in Example 1. Table 1 shows the measurement results of the electrical conductivity and TOC of the effluent water of the cation exchange tower 3 and the quality of the treated water.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１の通り、実施例１及び実施例２によると、活性炭塔流出水をアニオン交換樹脂→カチオン交換樹脂の順に接触させるか又は混床樹脂と接触させることにより、純水純度を維持しながら、アミン類濃度を比較例１の８５μｇ／Ｌ程度から２μｇ／Ｌ（実施例２）又は１μｇ／Ｌ以下（実施例１）程度にまで低減し、臭気を無臭状態まで改善することができる。 As shown in Table 1, according to Example 1 and Example 2, while maintaining the purity of pure water by contacting activated carbon tower effluent water in the order of anion exchange resin → cation exchange resin or contacting with mixed bed resin, The amine concentration can be reduced from about 85 μg / L in Comparative Example 1 to about 2 μg / L (Example 2) or 1 μg / L or less (Example 1), and the odor can be improved to an odorless state.
　本発明を特定の態様を用いて詳細に説明したが、本発明の意図と範囲を離れることなく様々な変更が可能であることは当業者に明らかである。
　なお、本出願は、２０１０年８月６日付で出願された日本特許出願（特願２０１０－１７７７１７）に基づいており、その全体が引用により援用される。 Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2010-177717) filed on Aug. 6, 2010, which is incorporated by reference in its entirety.
　１　活性炭塔
　２　アニオン交換塔
　３　カチオン交換搭
　４　混床樹脂塔 1 Activated carbon tower 2 Anion exchange tower 3 Cation exchange tower 4 Mixed bed resin tower

Claims (13)

  1. 　食品又は飲料工場から排出される酢酸含有排水の処理方法において、被処理水をアニオン交換樹脂と接触させる工程と、その後カチオン交換樹脂と接触させる工程とを有することを特徴とする酢酸含有排水の処理方法。 A method for treating acetic acid-containing wastewater discharged from a food or beverage factory, comprising: a step of bringing treated water into contact with an anion exchange resin; and a step of bringing the water into contact with a cation exchange resin thereafter. Method.
  2. 　食品又は飲料工場から排出される酢酸含有排水の処理方法において、被処理水を少なくともアニオン交換樹脂とカチオン交換樹脂とを含む混床と接触させる工程を有することを特徴とする酢酸含有排水の処理方法。 A method for treating acetic acid-containing wastewater discharged from a food or beverage factory, comprising a step of bringing treated water into contact with a mixed bed containing at least an anion exchange resin and a cation exchange resin. .
  3. 　請求項２において、前記アニオン交換樹脂とカチオン交換樹脂とを含む混床の、アニオン交換樹脂とカチオン交換樹脂の混合比率（重量比）が、カチオン交換樹脂：アニオン交換樹脂＝１：１．５～１０であることを特徴とする酢酸含有排水の処理方法。 3. The mixing ratio (weight ratio) of the anion exchange resin and the cation exchange resin in the mixed bed containing the anion exchange resin and the cation exchange resin is cation exchange resin: anion exchange resin = 1: 1.5 to 10. A method for treating acetic acid-containing wastewater,
  4. 　請求項１ないし３のいずれか１項において、前記アニオン交換樹脂が弱塩基性アニオン交換樹脂であり、前記カチオン交換樹脂が強酸性カチオン交換樹脂であることを特徴とする酢酸含有排水の処理方法。 The method for treating acetic acid-containing wastewater according to any one of claims 1 to 3, wherein the anion exchange resin is a weakly basic anion exchange resin, and the cation exchange resin is a strongly acidic cation exchange resin.
  5. 　食品又は飲料工場から排出される酢酸及び過酢酸を含有する排水の処理方法において、該排水を活性炭と接触させて酢酸に還元する工程と、その後、この活性炭処理水を請求項１ないし４のいずれか１項の酢酸含有排水の処理方法によって処理することを特徴とする酢酸含有排水の処理方法。 A method for treating wastewater containing acetic acid and peracetic acid discharged from a food or beverage factory, contacting the wastewater with activated carbon to reduce it to acetic acid, and then treating the activated carbon treated water with any one of claims 1 to 4. A method for treating acetic acid-containing wastewater, which is treated by the method for treating acetic acid-containing wastewater according to claim 1.
  6. 　請求項１ないし５のいずれか１項において、前記排水が水温４０℃以上のオキソニア排水であることを特徴とする酢酸含有排水の処理方法。 The method for treating acetic acid-containing wastewater according to any one of claims 1 to 5, wherein the wastewater is oxonia wastewater having a water temperature of 40 ° C or higher.
  7. 　食品又は飲料工場から排出される酢酸含有排水の処理装置において、
    　被処理水が導入されるアニオン交換塔と、該アニオン交換塔の流出水が導入されるカチオン交換塔とを備えたことを特徴とする酢酸含有排水の処理装置。     In the treatment equipment for acetic acid-containing wastewater discharged from food or beverage factories,
    An apparatus for treating acetic acid-containing wastewater, comprising: an anion exchange tower into which water to be treated is introduced; and a cation exchange tower into which effluent water from the anion exchange tower is introduced.
  8. 　請求項７において、前記アニオン交換塔の通水ＳＶが５～２５ｈｒ－１であり、前記カチオン交換塔の通水ＳＶが１０～３０ｈｒ－１であることを特徴とする酢酸含有排水の処理装置。 The apparatus for treating acetic acid-containing wastewater according to claim 7, wherein the water flow SV of the anion exchange column is 5 to 25 hr -1 and the water flow SV of the cation exchange column is 10 to 30 hr -1 .
  9. 　食品又は飲料工場から排出される酢酸含有排水の処理装置において、
    　被処理水が導入される少なくともアニオン交換樹脂とカチオン交換樹脂とを含む混床樹脂塔を備えたことを特徴とする酢酸含有排水の処理装置。     In the treatment equipment for acetic acid-containing wastewater discharged from food or beverage factories,
    An apparatus for treating acetic acid-containing wastewater, comprising a mixed bed resin tower containing at least an anion exchange resin and a cation exchange resin into which water to be treated is introduced.
  10. 　請求項９において、前記混床樹脂塔の通水ＳＶが１０～３０ｈｒ－１であることを特徴とする酢酸含有排水の処理装置。 The apparatus for treating acetic acid-containing wastewater according to claim 9, wherein the water passing SV of the mixed bed resin tower is 10 to 30 hr -1 .
  11. 　食品又は飲料工場から排出される酢酸及び過酢酸を含有する排水の処理装置において、該排水が導入される活性炭塔と、該活性炭塔の流出水を被処理水として処理する請求項７ないし１０のいずれか１項の酢酸含有排水の処理装置とを備えたことを特徴とする酢酸含有排水の処理装置。 The apparatus for treating wastewater containing acetic acid and peracetic acid discharged from a food or beverage factory, and treating the activated carbon tower into which the waste water is introduced and the effluent of the activated carbon tower as treated water. An apparatus for treating acetic acid-containing wastewater, comprising the apparatus for treating acetic acid-containing wastewater according to any one of the items.
  12. 　請求項１１において、前記活性炭塔が上向流の多段式の流動床式活性炭塔であり、その通水ＳＶが５～２０ｈｒ－１であることを特徴とする酢酸含有排水の処理装置。 The apparatus for treating acetic acid-containing wastewater according to claim 11, wherein the activated carbon tower is a multi-stage fluidized bed activated carbon tower having an upward flow, and its water flow SV is 5 to 20 hr -1 .
  13. 　請求項７ないし１２のいずれか１項において、排水が水温４０℃以上のオキソニア排水であることを特徴とする酢酸含有排水の処理装置。 The apparatus for treating acetic acid-containing wastewater according to any one of claims 7 to 12, wherein the wastewater is oxonia wastewater having a water temperature of 40 ° C or higher.
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