WO2013015128A1 - Procédé de traitement biologique et dispositif de traitement pour des eaux résiduaires à teneur en amine - Google Patents

Procédé de traitement biologique et dispositif de traitement pour des eaux résiduaires à teneur en amine Download PDF

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Publication number
WO2013015128A1
WO2013015128A1 PCT/JP2012/067817 JP2012067817W WO2013015128A1 WO 2013015128 A1 WO2013015128 A1 WO 2013015128A1 JP 2012067817 W JP2012067817 W JP 2012067817W WO 2013015128 A1 WO2013015128 A1 WO 2013015128A1
Authority
WO
WIPO (PCT)
Prior art keywords
biological treatment
amine
treatment tank
tank
waste water
Prior art date
Application number
PCT/JP2012/067817
Other languages
English (en)
Japanese (ja)
Inventor
小野　徳昭
哲朗 深瀬
Original Assignee
栗田工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 栗田工業株式会社 filed Critical 栗田工業株式会社
Priority to KR1020137029320A priority Critical patent/KR20140037837A/ko
Priority to CN201280032844.3A priority patent/CN103648989B/zh
Publication of WO2013015128A1 publication Critical patent/WO2013015128A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/04—Non-contaminated water, e.g. for industrial water supply for obtaining ultra-pure water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the present invention relates to a method and apparatus for biological treatment of amine-containing organic wastewater from an ultrapure water recovery system.
  • ultrapure water recovery system organic wastewater contains various amines such as ethanolamine and alkaline components such as N-methylformamide and tetramethylammonium hydroxide (TMAH).
  • Amine-containing wastewater containing is discharged.
  • the activated sludge method (AS), the membrane separation activated sludge method (MBR), the fluidized bed biological treatment method (FB), and the like are applied.
  • a pH adjustment tank is provided in front of the biological treatment tank to automatically adjust the pH. Adjustment is performed (Patent Document 1).
  • amine is biodegraded, and nitrification occurs by oxidizing the ammonia produced by the biodegradation into nitric acid.
  • the production of this nitric acid lowers the pH in the biological treatment tank.
  • alkali In order to reduce the amount of alkali added to neutralize the pH that has decreased due to this nitrification, a part of the alkali may be recovered by performing a denitrification treatment. This denitrification process is often employed in MBR.
  • the denitrification method a circulation method using amine in wastewater as an organic substance source is usually used.
  • the present invention stabilizes the treatment at the time of fluctuation of conditions in the biological treatment of amine-containing organic wastewater from the ultrapure water recovery system, and can perform stable treatment even at the start of operation, wastewater composition and load fluctuation. It is an object of the present invention to provide a biological treatment method and treatment apparatus for wastewater contained.
  • the present inventors examined the cause of the instability of the treatment at the time of condition change in the biological treatment of amine-containing wastewater that is an ultrapure water recovery organic wastewater, and obtained the following knowledge.
  • the organic wastewater from the ultrapure water recovery system such as semiconductors, liquid crystals, plasma displays, etc. has only a slight amount of organic matter dissolved in the ultrapure water and contains almost no alkalinity.
  • the pH fluctuation is extremely large. For this reason, it is greatly affected by the pH increase due to ammonia generated by the decomposition of amine, and greatly deviates from the pH range necessary for biological reaction.
  • the biological treatment activity is reduced and the treatment becomes unstable. Become. This tendency is promoted when the inflow of wastewater into the biological treatment tank becomes intermittent, and is reduced as it approaches continuously. This tendency is further promoted when the biological treatment tank is a plug flow type, and is reduced when the biological treatment tank is a fully mixed biological treatment tank.
  • the present invention has been achieved on the basis of such knowledge, and the gist thereof is as follows.
  • [3] A biological treatment method for amine-containing wastewater, wherein in [1] or [2], an acid is added to the biological treatment tank so that the pH value is 8.5 or less.
  • a biological treatment apparatus for amine-containing wastewater that is an ultrapure water recovery system organic wastewater
  • a biological treatment tank into which the amine-containing wastewater is introduced a pH meter that measures the pH of the liquid in the biological treatment tank
  • An amine-containing wastewater biological treatment apparatus comprising: an acid addition means for adding an acid to the biological treatment tank based on a measurement value of the pH meter.
  • the biological treatment tank is a biological treatment tank having a structure in which the solution in the tank is completely mixed, and the amine-containing wastewater is continuously introduced into the biological treatment tank.
  • Biological treatment equipment for wastewater containing amine are a biological treatment tank having a structure in which the solution in the tank is completely mixed, and the amine-containing wastewater is continuously introduced into the biological treatment tank.
  • an increase in the pH of the liquid in the biological treatment tank due to ammonia generated by the oxidation of amine is detected and the pH value is determined.
  • the solution in the biological treatment tank can be adjusted to an optimum pH value for biological treatment. A stable and efficient treatment can be performed without reducing the activity of the treatment.
  • the amine-containing wastewater to be treated in the present invention is organic wastewater from ultrapure water recovery systems such as semiconductors, liquid crystals, plasma displays, and such ultrapure water recovery system organic wastewater is usually as follows.
  • the amine-containing organic waste water from the ultrapure water recovery system when introduced into the biological treatment tank for biological treatment, the pH of the liquid in the biological treatment tank is measured, and the biological treatment is performed based on the measured value. Add acid to the bath.
  • the organic waste water from the ultrapure water recovery system is usually alkaline with a pH of about 8-11. Since the wastewater does not contain nutrients necessary for biological treatment, it is preferable to add the necessary nutrients for biological treatment.
  • a normal aeration tank can be used.
  • the biological treatment tank a tank in which the liquid in the tank can be completely mixed, specifically, the following (1) and / or Alternatively, it is preferable to use the one as in (2), and it is preferable to use a single tank structure without providing a plurality of biological treatment regions in series.
  • the acid is added to the biological treatment tank so that the pH value of the liquid in the biological treatment tank becomes pH 7 to 8.5 suitable for biological treatment. Therefore, when the pH value of the liquid in the biological treatment tank exceeds 8.5, an acid such as sulfuric acid or hydrochloric acid is added to adjust the pH so that the liquid in the biological treatment tank has a pH of 8.5 or less. It is preferable. When the pH of the liquid in the biological treatment tank is below 7, it is preferable to add an alkali such as sodium hydroxide or potassium hydroxide.
  • the addition of acid or alkali based on the pH value of the liquid in the biological treatment tank can be automatically performed by a chemical injection means linked to a pH meter provided in the biological treatment tank.
  • the biological treatment tank may be filled with a carrier for holding sludge.
  • the carrier may be either a fluidized bed or a fixed bed, but a fluidized bed type carrier is preferred for mixing the liquid in the tank, and the filling rate is preferably about 10 to 50% with respect to the tank volume.
  • sulfuric acid was added to water of pH 9.5 to which nutrient salts were added as follows, to the amine-containing organic waste water from the ultrapure water recovery system of the following water quality liquid crystal factory. Then, the water adjusted to pH 7.5 was treated as raw water.
  • Example 1 The raw water was biologically treated using a biological treatment apparatus in which three 3L aeration tanks were connected in series, and each aeration tank was filled with 20% by volume of a 10 mm square polyurethane sponge carrier.
  • a pH meter is installed in the first aeration tank (first stage aeration tank) and the third aeration tank (third stage aeration tank), and when the measured value of the pH meter decreases to 7.0, 1N NaOH aqueous solution is added. To be added.
  • the residence time in the aeration tank was 3 hours each, for a total of 9 hours.
  • the TOC (soluble TOC) of the treated water (outflow water of the third aeration tank) on the second day of treatment was 50 mg / L, and the treated water TOC was 42 mg / L on the third day of treatment.
  • the pH was measured the treated water had a pH of 9.0, and the liquid in the second aeration tank (second stage aeration tank) rose to pH 8.8.
  • the TOC of the treated water was 39 mg / L, pH 8.8 to 9.0. Thereafter, the treatment was continued for 2 weeks, but the treated water TOC did not become 20 mg / L or less.
  • the nitrate nitrogen of the treated water was hardly detected on the next day after the increase in load, and ammonia nitrogen was detected at about 45 mg / L instead.
  • the TOC exceeded 20 mg / L, and the treated water TOC of 20 to 25 mg / L was continued for 3 days.
  • the pH of the treated water was 8.8 to 9.1.
  • the treatment gradually deteriorated, and after one week, the treated water TOC exceeded 30 mg / L. Since the process did not recover, the load was reduced and restored. However, after that, the treatment hardly recovered for more than one week, and the treated water TOC did not become 10 mg / L or less.
  • Comparative Example 1 is set such that a pH meter is provided in each of the first aeration tank and the third aeration tank, and a 1N H 2 SO 4 aqueous solution is automatically added to each aeration tank when the measured value of the pH meter exceeds 8. The process was continued. As a result, the TOC of the treated water became 5 mg / L or less after 3 days, and the ammoniacal nitrogen concentration of the treated water became 1 mg / L or less after one week. Therefore, the load was tripled. As a result, after 5 days from the increase in load, the treated water TOC was stabilized at 5 mg / L or less and the treated water ammonia nitrogen concentration was 1 mg / L or less, and then the treatment did not deteriorate.
  • Example 2 A pH meter and a 1N NaOH aqueous solution or a 1N H 2 SO 4 aqueous solution are added to a 9 L aeration tank (one tank) so that the measured value of the pH meter is 7.0 to 8.5 in conjunction with the pH meter.
  • a 9 L aeration tank one tank
  • the same load of raw water of the same quality as in Example 1 load increase
  • the water was passed at the later load.
  • the treated water TOC became 3 to 5 mg / L after one week.
  • nitrification was completed after 2 weeks, and the ammoniacal nitrogen concentration of the treated water was about 1 mg / L.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Microbiology (AREA)
  • Activated Sludge Processes (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
  • Physical Water Treatments (AREA)

Abstract

Dans un traitement biologique d'eaux résiduaires à teneur en amine, qui sont des eaux résiduaires organiques dans un système de récupération d'eau ultra-pure, le traitement pendant des conditions fluctuantes est stabilisé et un traitement stable est effectué au début de l'opération, et pendant une fluctuation de la charge et une fluctuation de la composition d'eaux résiduaires. L'invention concerne un procédé d'introduction des eaux résiduaires à teneur en amine, qui sont des eaux résiduaires organiques dans un système de récupération d'eau ultra-pure, dans une cuve de traitement biologique pour effectuer un traitement biologique, un acide étant ajouté dans la cuve de traitement biologique sur la base de la valeur de pH du liquide dans la cuve de traitement biologique. Lorsque des résiduaires à teneur en amine, qui sont des eaux résiduaires organiques dans un système de récupération d'eau ultra-pure, doivent être soumises à un traitement biologique, une augmentation est détectée dans le pH du liquide dans la cuve de traitement biologique provoquée par l'ammoniaque générée par une oxydation d'amine, et un acide est ajouté dans la cuve de traitement biologique conformément à la valeur de pH, ce par quoi le liquide dans la cuve de traitement biologique peut être ajusté à une valeur de pH optimale. Par conséquent, un traitement stable et efficace peut être effectué sans la réduction de l'activité du traitement biologique, même pendant le démarrage de l'opération ou pendant une fluctuation de la composition des eaux résiduaires ou d'une fluctuation de la charge des eaux résiduaires.
PCT/JP2012/067817 2011-07-22 2012-07-12 Procédé de traitement biologique et dispositif de traitement pour des eaux résiduaires à teneur en amine WO2013015128A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020137029320A KR20140037837A (ko) 2011-07-22 2012-07-12 아민 함유 배수의 생물 처리법 및 처리 장치
CN201280032844.3A CN103648989B (zh) 2011-07-22 2012-07-12 含胺排水的生物处理方法和处理装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-161104 2011-07-22
JP2011161104A JP5799633B2 (ja) 2011-07-22 2011-07-22 アミン含有排水の生物処理法及び処理装置

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WO2013015128A1 true WO2013015128A1 (fr) 2013-01-31

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JP (1) JP5799633B2 (fr)
KR (1) KR20140037837A (fr)
CN (1) CN103648989B (fr)
TW (1) TW201318980A (fr)
WO (1) WO2013015128A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017176967A (ja) * 2016-03-29 2017-10-05 栗田工業株式会社 生物処理方法及び生物処理装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5929987B2 (ja) * 2014-09-16 2016-06-08 栗田工業株式会社 生物処理方法及び生物処理装置

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Publication number Priority date Publication date Assignee Title
JPS63291692A (ja) * 1987-05-22 1988-11-29 Japan Organo Co Ltd 高濃度ｔｍａｈ含有廃水の処理方法
JPH08150400A (ja) * 1994-11-29 1996-06-11 Japan Organo Co Ltd 有機物含有酸性排水処理装置
JPH09187785A (ja) * 1996-01-09 1997-07-22 Kurita Water Ind Ltd 排水の回収、浄化装置
JP2001038390A (ja) * 1999-07-29 2001-02-13 Kurita Water Ind Ltd 超純水の製造方法
JP2006167574A (ja) * 2004-12-15 2006-06-29 Japan Organo Co Ltd 廃水処理装置及び廃水の生物処理方法
JP2006320844A (ja) * 2005-05-19 2006-11-30 Japan Organo Co Ltd 排水処理方法および装置
JP2007160233A (ja) * 2005-12-14 2007-06-28 Kurita Water Ind Ltd 有機物含有排水の処理装置及び処理方法
JP2010005560A (ja) * 2008-06-27 2010-01-14 Kurita Water Ind Ltd 有機アルカリ排水の処理方法及び処理装置
JP2010253352A (ja) * 2009-04-22 2010-11-11 Kurita Water Ind Ltd 脱窒方法
JP2010274207A (ja) * 2009-05-29 2010-12-09 Japan Organo Co Ltd 嫌気性生物処理方法及び嫌気性生物処理装置

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017176967A (ja) * 2016-03-29 2017-10-05 栗田工業株式会社 生物処理方法及び生物処理装置
WO2017168787A1 (fr) * 2016-03-29 2017-10-05 栗田工業株式会社 Procédé de traitement biologique et appareil de traitement biologique

Also Published As

Publication number Publication date
TW201318980A (zh) 2013-05-16
CN103648989A (zh) 2014-03-19
JP5799633B2 (ja) 2015-10-28
KR20140037837A (ko) 2014-03-27
JP2013022536A (ja) 2013-02-04
CN103648989B (zh) 2016-04-06

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