WO2015159654A1 - Procédé de traitement d'eaux usées contenant de l'ammoniac - Google Patents

Procédé de traitement d'eaux usées contenant de l'ammoniac Download PDF

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Publication number
WO2015159654A1
WO2015159654A1 PCT/JP2015/058834 JP2015058834W WO2015159654A1 WO 2015159654 A1 WO2015159654 A1 WO 2015159654A1 JP 2015058834 W JP2015058834 W JP 2015058834W WO 2015159654 A1 WO2015159654 A1 WO 2015159654A1
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WO
WIPO (PCT)
Prior art keywords
ammonia
hypobromite
containing wastewater
hypochlorite
hypochlorous acid
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Application number
PCT/JP2015/058834
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English (en)
Japanese (ja)
Inventor
小野　貴史
田中　浩一
水野　誠
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 CN201580019769.0A priority Critical patent/CN106232532B/zh
Publication of WO2015159654A1 publication Critical patent/WO2015159654A1/fr

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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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens

Definitions

  • the present invention relates to a method for treating ammonia-containing wastewater, and more particularly, to a method for treating ammonia-containing wastewater with hypobromite and / or hypobromite.
  • Biological nitrification denitrification is a method of reducing to nitrogen gas by nitrifying bacteria.
  • the reaction in this method is a microbial reaction, there are disadvantages such as being unstable with respect to various fluctuation factors, a large installation area, and requiring treatment of sludge.
  • the stripping method is a method of releasing in the air by contacting with a large amount of air under alkaline conditions.
  • this method requires an alkali cost, and it is necessary to treat the diffused ammonia, so that the treatment cost is high.
  • the chlorine oxidation method is a method in which ammonia is oxidized to nitrogen gas via chloramine, which is a kind of bonded chlorine, by adding chlorine.
  • chloramine which is a kind of bonded chlorine
  • hypochlorous acid and ammonia react under alkaline conditions to produce relatively stable chloramine.
  • chloramine Under alkaline conditions, chloramine is gradually oxidized and decomposed into nitrogen and hydrochloric acid as shown in the above formula (5). However, since chloramine, which is a transit, is relatively stable and is bound chlorine, the residual oxidant concentration increases when the ammonia concentration is high. Further, OCl ⁇ , NH 2 Cl, and NHCl 2 are in a high concentration state, and gas is generated. Moreover, unless chloramine decomposition proceeds, ammonia decomposition does not proceed.
  • Chlorine oxidation method is suitable for decomposing most of ammonia in water, but not suitable for partial decomposition of ammonia.
  • factories that drain ammonia-containing water there are many cases where ammonia drainage standards are set for each factories. For example, there is a need to reduce the ammonium ion concentration to a predetermined concentration or less. In such a case, the treatment by the conventional chlorine oxidation method is not suitable.
  • An object of the present invention is to solve the above-mentioned conventional problems, and to provide a method for treating ammonia-containing water that prevents generation of harmful gases even during the decomposition of ammonia at a high concentration and is suitable for partial decomposition of ammonia.
  • the method for treating ammonia-containing wastewater of the present invention includes a step of oxidizing and decomposing ammonia by adding a chemical solution containing hypobromite and / or hypochlorous acid to the ammonia-containing wastewater.
  • the chemical liquid substantially contains only hypobromite and / or hypobromite as the oxidant component.
  • medical solution contains hypochlorous acid and / or hypobromite, and hypochlorous acid and / or hypochlorite as an oxidizing agent component.
  • Ammonia” in the present invention includes ammonium ions.
  • ammonia is oxidatively decomposed by hypobromite ions according to the reaction of the following formula.
  • bromamine (bromoamine) is produced under alkaline conditions, but it is unstable and immediately decomposes into nitrogen and bromine. Due to the rapid decomposition of bromamine into nitrogen, high concentrations of ammonia do not increase as bromamine. Therefore, the residual oxidant concentration is low and the generation of harmful gases is small. In addition, the decomposition of bromamine is fast and the decomposition of ammonia is easy to proceed.
  • the ammonia concentration decreases linearly with an increase in the amount of hypobromite and / or hypobromite, so the ammonia concentration in the treated water is set to a target concentration or less. It is easy to partially oxidize ammonia by adjusting the amount of bromine acid and / or hypobromite.
  • ammonia-containing wastewater to be treated is exemplified by ammonia-containing wastewater such as ironworks wastewater, plating factory wastewater, electronic industrial wastewater, and oil refinery factory wastewater, but is not limited thereto.
  • the ammonia concentration in such ammonia-containing wastewater is 10 mg / L or more, for example, about 10 to 10,000 mg / L.
  • the pH is about 6 to 10.
  • Ammonia-containing wastewater may contain organic substances such as coal and coke.
  • concentration of the organic substance is usually 1 mg / L or more, for example, about 1 to 1500 mg / L.
  • the pH of the ammonia-containing wastewater when treated by adding hypobromite and / or hypobromite is about 7 to 12, particularly about 8 to 10.
  • the pH is adjusted with NaOH or the like as necessary.
  • the ORP of the ammonia-containing waste water after adding hypobromite and / or hypobromite is preferably 420 mV or more, for example, 420 to 800 mV, particularly about 420 to 650 mV.
  • a chemical solution containing hypobromite and / or hypobromite is added to such ammonia-containing wastewater to decompose ammonia.
  • the chemical solution substantially contains only hypobromite and / or hypobromite as an oxidant component.
  • medical solution contains hypochlorous acid and / or hypobromite, and hypochlorous acid and / or hypochlorite as an oxidizing agent component.
  • Examples of the salt include sodium salt and potassium salt, and sodium salt is particularly preferable.
  • Hypobromite or hypobromite is preferably produced by reacting hypochlorous acid or a salt thereof (preferably sodium hypochlorite) with bromine and / or bromide, preferably sodium bromide. Hypochlorous acid and sodium bromide react in equimolar amounts according to the following formula to form hypobromous acid.
  • hypochlorous acid or a salt thereof preferably sodium hypochlorite
  • bromine and / or bromide preferably sodium bromide
  • sodium hypochlorite and sodium bromide react in equimolar amounts according to the following formula to form sodium hypobromite.
  • Hypochlorous acid to be reacted with bromine and / or bromide may be chlorine-dissolved water in which chlorine is dissolved in water to produce hypochlorous acid.
  • the amount of hypobromite and / or hypobromite or a liquid (chemical solution) containing hypochlorous acid and / or hypochlorite to the ammonia-containing wastewater depends on the ammonia concentration in the raw water. You only have to set it.
  • 1.0 to 10.0 times the amount of ammonia to be treated (molar amount), especially 1.2 to 3.0 times (molar amount) of oxidizing agent (next) Bromine acid and / or hypobromite or further hypochlorous acid and / or hypochlorite) is preferably added to the ammonia-containing waste water. It is also possible to obtain an oxidant addition amount that is equal to or lower than the target ammonia concentration in the treated water by preliminary experiments and add the chemical solution so that this addition amount is obtained.
  • the concentration of hypobromite and / or hypobromite and hypochlorous acid and / or hypochlorite When adding hypobromite and / or hypobromite and hypochlorous acid and / or hypochlorite to ammonia-containing wastewater, the concentration of hypobromite and / or hypobromite The added molar amount is preferably 0.1 to 1.0 times, more preferably 0.3 to 0.5 times the added molar amount of hypochlorous acid and / or hypochlorite.
  • the treatment of the ammonia-containing wastewater may be carried out batchwise in the tank, and the ammonia-containing wastewater is continuously flowed into and out of the reaction tank, and the ammonia decomposition reaction is carried out in the reaction tank.
  • ammonia-containing waste water may be flowed through a pipe, and a chlorine source, a bromine source, and an alkali may be added to the pipe as needed to perform line treatment.
  • the temperature of the ammonia-containing waste water may be 40 ° C. or higher, for example, 40 to 80 ° C., particularly about 50 to 70 ° C., thereby increasing the ammonia decomposition reaction rate.
  • the water temperature is preferably 80 ° C. or lower, particularly 70 ° C. or lower.
  • ammonium ion concentration analysis was measured according to JIS K 0102.
  • the total residual chlorine concentration and the free residual chlorine concentration were measured with a residual chlorine meter manufactured byhack using a DPD reagent.
  • the combined chlorine concentration was determined by subtracting the free residual chlorine concentration from the total residual chlorine concentration.
  • the presence / absence of chlorine gas generation was determined by a chlorine gas monitor manufactured by Riken Keiki Co., Ltd. (alarm generation at 0.5 ppm or more).
  • generated sodium hypobromite was used.
  • Test water 1000 mL was placed in a glass container, the water temperature was kept at 50 ° C., and the pH was adjusted to 9.6 with NaOH, and then the above sodium hypobromite aqueous solution was added. The reaction time was 5 min.
  • Table 1 shows the amount of sodium hypobromite added and the residual chlorine concentration, ORP, ammonium ion concentration and ammonium ion decomposition rate after the reaction time.
  • the NH 4 + concentration linearly decreases in proportion to the amount of sodium hypobromite added.
  • sodium hypochlorite it can be seen that the NH 4 + concentration rapidly decreases when the amount added is greater than about 20 mmol / L. Therefore, when ammonia decomposition is performed with sodium hypobromite added, the residual ammonia concentration decreases linearly in proportion to the amount added, so the dosage is controlled to achieve the target ammonia concentration. It was found to be easy to do.
  • sodium hypobromite and sodium hypochlorite-containing liquid As the sodium hypobromite and sodium hypochlorite-containing liquid, a sodium bromide solution having a concentration of 40 wt% and a sodium hypochlorite aqueous solution having a concentration of 12 wt% were mixed at a weight ratio shown in Table 2 to prepare hypobromine. The liquid in which sodium acid was produced was used.
  • Test water 1000 mL was placed in a glass container, the water temperature was kept at 50 ° C., and the pH was adjusted to 9.6 with NaOH, and then an aqueous sodium hypobromite solution was added. The reaction time was 5 min.
  • Table 2 shows the chemical addition amount (however, converted to NaBr and NaOCl addition rates with respect to the test water), the residual chlorine concentration, the ammonium ion concentration, and the ammonium ion decomposition rate after the above reaction time.

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  • 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)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

L'invention concerne un procédé de traitement d'eau contenant de l'ammoniac, dans lequel la génération de gaz dangereux est évitée, même au moment de la décomposition de concentrations élevées d'ammoniac, et qui est également approprié pour décomposer partiellement l'ammoniac. Ce procédé de traitement d'eaux usées contenant de l'ammoniac comprend une étape pour oxyder et décomposer l'ammoniac par ajout d'une solution chimique comprenant de l'acide hypobromeux et/ou de l'acide hypochloreux aux eaux usées contenant de l'ammoniac. Une solution, dans laquelle l'acide hypobromeux et/ou un hypobromite a été produit par mélange d'une solution aqueuse de bromure et d'une solution aqueuse d'hypochlorite, est ajoutée aux eaux usées contenant de l'ammoniac. Une solution aqueuse de bromure de sodium et une solution aqueuse d'hypochlorite de sodium sont mélangées et ajoutées à un rapport équimoléculaire, ou de telle sorte que l'hypochlorite de sodium est en excès.
PCT/JP2015/058834 2014-04-16 2015-03-24 Procédé de traitement d'eaux usées contenant de l'ammoniac WO2015159654A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201580019769.0A CN106232532B (zh) 2014-04-16 2015-03-24 含有氨的废水的处理方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014084694A JP2015202483A (ja) 2014-04-16 2014-04-16 アンモニア含有排水の処理方法
JP2014-084694 2014-04-16

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WO2015159654A1 true WO2015159654A1 (fr) 2015-10-22

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JP (1) JP2015202483A (fr)
CN (1) CN106232532B (fr)
TW (1) TWI664151B (fr)
WO (1) WO2015159654A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI690496B (zh) * 2019-02-01 2020-04-11 兆聯實業股份有限公司 水處理系統

Citations (11)

* Cited by examiner, † Cited by third party
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JPS60129182A (ja) * 1983-12-17 1985-07-10 Hakutou Kagaku Kk 用排水系の生物障害防止方法
JPS6415200A (en) * 1987-07-10 1989-01-19 Nippon Silica Ind Slime controlling agent
JPH06269785A (ja) * 1993-03-19 1994-09-27 Nitto Kikai Kk 次亜臭素酸アルカリを使用して還元性窒素を分解する水処理方法。
JPH06335688A (ja) * 1993-05-27 1994-12-06 Mitsubishi Kakoki Kaisha Ltd アンモニア含有水の処理方法
JPH07195087A (ja) * 1993-12-29 1995-08-01 Japan Organo Co Ltd アンモニア性窒素含有排水の処理方法及び処理装置
JPH07328663A (ja) * 1994-06-01 1995-12-19 Japan Organo Co Ltd アンモニア性窒素含有排水処理装置
JPH08155463A (ja) * 1994-12-02 1996-06-18 Permelec Electrode Ltd アンモニア性窒素、硝酸性窒素及び／又は亜硝酸窒素の分解方法及び装置
WO2002094719A1 (fr) * 2001-05-21 2002-11-28 Mitsubishi Denki Kabushiki Kaisha Processus et appareil de traitement d'eau contenant de l'azote
US20030234224A1 (en) * 2002-04-19 2003-12-25 Hydro-Trace, Inc. Process for remediating ground water containing one or more nitrogen compounds
JP2005296863A (ja) * 2004-04-14 2005-10-27 Ebara Kogyo Senjo Kk チオ尿素含有廃液の処理方法及び装置
JP2006334508A (ja) * 2005-06-02 2006-12-14 Nippon Parkerizing Co Ltd シアン・アンモニア含有廃液の同時連続処理方法および同時連続処理装置

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JPS5549191A (en) * 1978-10-03 1980-04-09 Hitachi Plant Eng & Constr Co Ltd Purifying treatment method of waste water
JPH1028982A (ja) * 1996-07-15 1998-02-03 Mitsubishi Heavy Ind Ltd アンモニア態窒素を含有する廃液の処理方法
JPH1085764A (ja) * 1996-09-12 1998-04-07 Japan Organo Co Ltd 活性炭による臭素酸含有水の処理方法
JP2004525910A (ja) * 2001-03-02 2004-08-26 ミルブリッジ・インベストメンツ・プロプライエタリー・リミテッド 次亜臭素酸の安定化された溶液
JP2003145178A (ja) * 2001-11-07 2003-05-20 Nippon Parkerizing Co Ltd アンモニア含有廃液の処理方法
JP4862876B2 (ja) * 2008-10-21 2012-01-25 住友金属鉱山株式会社 アンモニア態窒素の分解除去方法及びその装置

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60129182A (ja) * 1983-12-17 1985-07-10 Hakutou Kagaku Kk 用排水系の生物障害防止方法
JPS6415200A (en) * 1987-07-10 1989-01-19 Nippon Silica Ind Slime controlling agent
JPH06269785A (ja) * 1993-03-19 1994-09-27 Nitto Kikai Kk 次亜臭素酸アルカリを使用して還元性窒素を分解する水処理方法。
JPH06335688A (ja) * 1993-05-27 1994-12-06 Mitsubishi Kakoki Kaisha Ltd アンモニア含有水の処理方法
JPH07195087A (ja) * 1993-12-29 1995-08-01 Japan Organo Co Ltd アンモニア性窒素含有排水の処理方法及び処理装置
JPH07328663A (ja) * 1994-06-01 1995-12-19 Japan Organo Co Ltd アンモニア性窒素含有排水処理装置
JPH08155463A (ja) * 1994-12-02 1996-06-18 Permelec Electrode Ltd アンモニア性窒素、硝酸性窒素及び／又は亜硝酸窒素の分解方法及び装置
WO2002094719A1 (fr) * 2001-05-21 2002-11-28 Mitsubishi Denki Kabushiki Kaisha Processus et appareil de traitement d'eau contenant de l'azote
US20030234224A1 (en) * 2002-04-19 2003-12-25 Hydro-Trace, Inc. Process for remediating ground water containing one or more nitrogen compounds
JP2005296863A (ja) * 2004-04-14 2005-10-27 Ebara Kogyo Senjo Kk チオ尿素含有廃液の処理方法及び装置
JP2006334508A (ja) * 2005-06-02 2006-12-14 Nippon Parkerizing Co Ltd シアン・アンモニア含有廃液の同時連続処理方法および同時連続処理装置

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TWI664151B (zh) 2019-07-01
CN106232532A (zh) 2016-12-14
TW201605744A (zh) 2016-02-16
JP2015202483A (ja) 2015-11-16
CN106232532B (zh) 2019-12-31

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