JPH06201588A - Measuring method of concentration of ammonium ion in water - Google Patents

Measuring method of concentration of ammonium ion in water

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Publication number
JPH06201588A
JPH06201588A JP4359036A JP35903692A JPH06201588A JP H06201588 A JPH06201588 A JP H06201588A JP 4359036 A JP4359036 A JP 4359036A JP 35903692 A JP35903692 A JP 35903692A JP H06201588 A JPH06201588 A JP H06201588A
Authority
JP
Japan
Prior art keywords
nitrite
concentration
amount
ammonia
added
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.)
Granted
Application number
JP4359036A
Other languages
Japanese (ja)
Other versions
JP3287040B2 (en
Inventor
Yasuhiko Takabayashi
泰彦 高林
Nobuhiro Oda
信博 織田
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.)
Kurita Water Industries Ltd
Original Assignee
Kurita Water Industries Ltd
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 Kurita Water Industries Ltd filed Critical Kurita Water Industries Ltd
Priority to JP35903692A priority Critical patent/JP3287040B2/en
Publication of JPH06201588A publication Critical patent/JPH06201588A/en
Application granted granted Critical
Publication of JP3287040B2 publication Critical patent/JP3287040B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

PURPOSE:To measure the concentration of ammonium ions in a test water at real time by a method whereby nitrite of a known amount is added to the test water containing ammonium ions, the added substance is supplied to an ammonia decomposing apparatus filled with a catalyst holding a noble metal while the substance is heated, the absorbance of an ultraviolet part of the obtained effluent is measured and the consuming amount of nitrite is detected. CONSTITUTION:A known amount of nitrite is added to a to-be-tested water containing ammonium ions, which is supplied to an ammonia decomposing apparatus filled with a catalyst holding a noble metal while being heated. The amount of the noble metal is generally 0.1-10wt.% to the carrier. The decomposing condition at the decomposing apparatus is generally 70-300 deg.C of the temperature and 3-60 minutes of the reaction time. 0.5-10hr is set for SV and pH is near to neutral. The ammonia in the to-be-tested water is decomposed according to a formula NH4<+>+NO2<-> N2 +2H2O. The absorbance of an ultraviolet part of the effluent from the apparatus is measured thereby to obtain the consuming amount of nitrite. The concentration of ammonium ions is calculated from the consuming amount.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は水中のアンモニウムイオ
ン濃度の測定方法に関するものである。さらに詳しくい
えば、本発明は、例えば復水脱塩装置の再生排水など、
アンモニア濃度が高く、かつ実質上有機物を含まない排
水に亜硝酸塩を添加し、加熱触媒接触分解するに際し、
該亜硝酸塩の注入量を制御することなどを目的として、
排水中のアンモニウムイオン濃度を特別の試薬を用いる
ことなく、ほぼリアルタイムで効率よく測定する方法に
関するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for measuring ammonium ion concentration in water. More specifically, the present invention relates to, for example, reclaimed drainage of a condensate demineralizer,
When the nitrite is added to the wastewater that has a high ammonia concentration and contains substantially no organic matter, and when catalytically decomposing by heating,
For the purpose of controlling the injection amount of the nitrite,
The present invention relates to a method for efficiently measuring the concentration of ammonium ions in wastewater in almost real time without using a special reagent.

【0002】[0002]

【従来の技術】復水脱塩装置の再生排水などには、アン
モニアが高い濃度で含まれており、通常亜硝酸塩を添加
し、アンモニアを加熱触媒接触分解する処置がとられて
いる。このようなアンモニアの分解方法においては、排
水のアンモニウムイオン濃度の変化に対応して、亜硝酸
塩の注入量を制御することが必要であり、そのためには
該排水中のアンモニウムイオン濃度をリアルタイムで測
定することが必要となる。従来、排水中のアンモニウム
イオン濃度を測定する方法としては、例えば(1)ネス
ラー試薬法やインドフェノール法などの比色法による方
法、(2)イオン電極法、(3)蒸留、中和滴定法など
が知られている。しかしながら、前記(1)の方法にお
いては、特別の発色試薬が必要であり、その試薬の安定
性が悪い上、高濃度域を測定できないなどの欠点があ
る。また(2)の方法は電極の安定性に欠け、かつpH調
整が必要であるなどの欠点を有し、さらに(3)の方法
においては連続測定しにくいなどの問題がある。このよ
うに、従来の排水中のアンモニウムイオン濃度の測定方
法はなんらかの欠点を有し、その排水を処理するのに適
した量の薬品(例えば亜硝酸塩など)を注入制御するこ
とが困難であった。
2. Description of the Related Art Recycled waste water from a condensate demineralizer contains a high concentration of ammonia. Usually, nitrite is added to carry out catalytic decomposition of ammonia with heating. In such a method for decomposing ammonia, it is necessary to control the injection amount of nitrite in response to changes in the ammonium ion concentration in the wastewater, and for that purpose, the ammonium ion concentration in the wastewater is measured in real time. Will be required. Conventionally, as a method for measuring the ammonium ion concentration in wastewater, for example, (1) a colorimetric method such as Nessler reagent method or indophenol method, (2) ion electrode method, (3) distillation, neutralization titration method Are known. However, the method (1) has the drawbacks that a special color-forming reagent is required, the stability of the reagent is poor, and a high concentration range cannot be measured. Further, the method (2) has drawbacks such as lack of electrode stability and pH adjustment, and the method (3) has a problem that continuous measurement is difficult. As described above, the conventional method for measuring the concentration of ammonium ions in wastewater has some drawbacks, and it is difficult to control the injection of a suitable amount of chemicals (such as nitrite) for treating the wastewater. .

【0003】[0003]

【発明が解決しようとする課題】本発明は、このような
事情のもとで、例えば復水脱塩装置の再生排水など、ア
ンモニア濃度が高く、かつ実質上有機物を含まない排水
に亜硝酸塩を添加し、加熱触媒接触分解するに際し、該
亜硝酸塩の注入量を制御するなどを目的として、排水中
のアンモニウムイオン濃度を特別の試薬を用いることな
く、ほぼリアルタイムで効率よく測定する方法を提供す
ることを目的としてなされたものである。
Under the circumstances, the present invention is to provide nitrite in wastewater having a high ammonia concentration and containing substantially no organic matter, such as reclaimed wastewater of a condensate desalination apparatus. Provided is a method for efficiently measuring the ammonium ion concentration in wastewater in near real time, without using a special reagent, for the purpose of controlling the injection amount of the nitrite upon addition by heating and catalytic decomposition. It was made for the purpose.

【0004】[0004]

【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究を重ねた結果、被検体に既知
量の亜硝酸塩を添加し、これを貴金属担持触媒を充填し
たアンモニア分解装置に供給し、得られる流出水の紫外
部吸光度から該亜硝酸塩の消費量を求め、この消費量か
ら該被検体中のアンモニウムイオン濃度を算出すること
により、その目的を達成しうることを見い出し、この知
見に基づいて、本発明を完成するに至った。すなわち、
本発明は、被検体のアンモニウムイオン含有水に、既知
量の亜硝酸塩を添加したのち、これを加熱下に貴金属担
持触媒を充填したアンモニア分解装置に供給し、得られ
る流出水の紫外部吸光度を測定して前記亜硝酸塩の消費
量を求め、この消費量から該被検体中のアンモニウムイ
オン濃度を算出することを特徴とする水中のアンモニウ
ムイオン濃度の測定方法を提供するものである。
Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have added a known amount of nitrite to a test sample, and added it to an ammonia loaded with a noble metal-supported catalyst. By supplying to the decomposition apparatus, the consumption of the nitrite from the ultraviolet absorbance of the resulting effluent is obtained, by calculating the ammonium ion concentration in the analyte from this consumption, it is possible to achieve the purpose. The present invention has been completed, and based on this finding, the present invention has been completed. That is,
The present invention, the ammonium ion-containing water of the analyte, after adding a known amount of nitrite, it is supplied to an ammonia decomposing device filled with a noble metal-supported catalyst under heating, the ultraviolet absorbance of the resulting effluent The present invention provides a method for measuring the concentration of ammonium ions in water, which comprises measuring the consumption of the nitrite and calculating the concentration of ammonium ions in the sample from the consumption.

【0005】以下、本発明を詳細に説明する。本発明方
法においては、まず被検体のアンモニウムイオン含有水
に、既知量の亜硝酸塩を添加し、これを加熱下に貴金属
担持触媒を充填したアンモニア分解装置に供給する。こ
の際、用いられる亜硝酸塩としては、例えば亜硝酸ナト
リウムや亜硝酸カリウムが挙げられる。また、アンモニ
ア分解装置に充填される貴金属担持触媒における貴金属
としては、例えば白金、パラジウムなどの白金族金属が
好ましく用いられる。また、担体としては、例えばα−
アルミナ、γ−アルミナ、チタニア、活性炭、ジルコニ
ア、ゼオライト、ガラス、シリカ、シリカアルミナ、イ
オン交換樹脂などが挙げられる。前記貴金属の担持量
は、担体に対して通常0.1〜10重量%程度である。
The present invention will be described in detail below. In the method of the present invention, first, a known amount of nitrite is added to the ammonium ion-containing water of the analyte, and this is supplied to an ammonia decomposing device filled with a noble metal-supported catalyst while being heated. In this case, examples of the nitrite used include sodium nitrite and potassium nitrite. As the noble metal in the noble metal-supported catalyst packed in the ammonia decomposing device, platinum group metals such as platinum and palladium are preferably used. Further, as the carrier, for example, α-
Alumina, γ-alumina, titania, activated carbon, zirconia, zeolite, glass, silica, silica-alumina, ion exchange resin and the like can be mentioned. The amount of the noble metal supported is usually about 0.1 to 10% by weight with respect to the carrier.

【0006】このアンモニア分解装置におけるアンモニ
アの分解条件については、温度は通常70〜300℃、
好ましくは80〜250℃の範囲で選ばれ、反応時間は
通常3〜60分間、好ましくは3〜15分間程度であ
る。SVとしては0.5〜10hr-1、好ましくは2〜5h
r-1の範囲が有利である。また、反応時のpHは中性付近
が好ましいが、若干酸性側又はアルカリ性側にあっても
差し支えない。このアンモニア分解装置により、被検体
中のアンモニアは、次に示す反応式に従って分解する。
Regarding the conditions for decomposing ammonia in this ammonia decomposing apparatus, the temperature is usually 70 to 300 ° C.
It is preferably selected in the range of 80 to 250 ° C., and the reaction time is usually 3 to 60 minutes, preferably about 3 to 15 minutes. SV is 0.5-10 hr -1 , preferably 2-5 h
A range of r -1 is preferred. The pH during the reaction is preferably around neutral, but it may be slightly acidic or alkaline. With this ammonia decomposing device, the ammonia in the sample is decomposed according to the following reaction formula.

【0007】 NH4 ++NO2 - → N2↑+2H2O …[1] 次に、前記のアンモニア分解装置からの流出水の紫外部
吸光度を測定し、該亜硝酸塩の消費量を求める。亜硝酸
イオンは紫外部吸収があり、かつ該亜硝酸イオン濃度と
吸光度との間に検量関係がある。被検体中に妨害物質又
は妨害イオンがある場合には、予め被検体をろ過する
か、又は被検体自体(亜硝酸塩を添加する前)の紫外部
吸光度を測定しておき、アンモニア分解後の紫外部吸光
度の測定値を補正するのが好ましい。このようにして求
められた亜硝酸塩の消費量から、被検体中のアンモニウ
ムイオン濃度を算出することができる。
NH 4 + + NO 2 → N 2 ↑ + 2H 2 O ... [1] Next, the ultraviolet absorption of the effluent of the ammonia decomposing device is measured to determine the consumption amount of the nitrite. Nitrite ion has ultraviolet absorption, and there is a calibration relationship between the nitrite ion concentration and the absorbance. If there are any interfering substances or ions in the sample, either filter the sample in advance or measure the UV absorbance of the sample itself (before adding nitrite) to measure the purpleness after ammonia decomposition. It is preferable to correct the external absorbance measurement. From the consumption amount of the nitrite thus obtained, the ammonium ion concentration in the subject can be calculated.

【0008】なお、アンモニウムイオン濃度の測定に際
しては、1つの被検体を10倍、50倍、100倍程度
に希釈したものそれぞれについて、並行に測定するのが
好ましい。本発明方法における被検体のアンモニウムイ
オン含有水としては、有機物が実質上含まれていないも
のが好ましい。該有機物は紫外部吸収を有し、かつ添加
した亜硝酸塩と反応するため、好ましくない。このよう
な被検体としては、例えば復水脱塩装置の再生排水など
が好適である。
[0008] When measuring the ammonium ion concentration, it is preferable to measure in parallel for each one specimen diluted 10 times, 50 times, 100 times. As the ammonium ion-containing water of the test object in the method of the present invention, it is preferable to use water that does not substantially contain organic substances. This organic substance is not preferable because it has ultraviolet absorption and reacts with the added nitrite. As such an object, for example, reclaimed waste water from a condensate demineralizer is suitable.

【0009】本発明方法が適用できる分野としては、例
えば前記の復水脱塩装置の再生排水などのアンモニア濃
度が高く、実質上有機物を含まない排水に亜硝酸塩を添
加し、加熱触媒接触分解するに際し、該亜硝酸塩の注入
量を制御する分野が挙げられる。この場合、本発明方法
により求められた必要量の1〜3倍モル程度の亜硝酸塩
を注入するのが有利である。なお、アンモニアの加熱分
解処理条件は、本発明のアンモニウムイオン濃度測定法
と同じに設定するのが望ましい。さらに、本発明方法
は、生物脱窒処理における水素供与体(メタノールな
ど)の添加量制御や、塩素によるアンモニア分解時にお
ける塩素の添加量制御などに有効に適用できる。
As a field to which the method of the present invention can be applied, for example, nitrite is added to wastewater having a high ammonia concentration such as reclaimed wastewater of the above-mentioned condensate demineralizer, and catalytic decomposition is carried out by heating catalyst. In this case, there is a field of controlling the injection amount of the nitrite. In this case, it is advantageous to inject nitrite in an amount of about 1 to 3 times the required amount determined by the method of the present invention. The conditions for the thermal decomposition treatment of ammonia are preferably set to be the same as in the ammonium ion concentration measuring method of the present invention. Further, the method of the present invention can be effectively applied to the control of the amount of hydrogen donor (such as methanol) added in the biological denitrification process and the control of the amount of chlorine added during the decomposition of ammonia by chlorine.

【0010】[0010]

【実施例】次に実施例により本発明をさらに詳細に説明
するが、本発明はこれらの例によってなんら限定される
ものではない。
EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

【0011】実施例1 A火力発電所の復水脱塩装置の再生排水について分析し
た例を示す。従来法では、1000倍に希釈してインド
フェノール比色法にて測定した。比色分析するまでに4
0分間程度を要した。本発明方法では、20倍に希釈し
たのち、10wt%NaNO2溶液をNO2濃度が100mg
-N/リットルとなるように添加し、0.5wt%Pt−チタ
ニア触媒を充填した触媒分解塔(温度200℃、帯留時
間5分)にて反応させた。反応後の液を島津製作所製U
V検出器(SPD6A、セル長0.5mm)により、波長
220nmにて残留NO2濃度(N換算)を検出した。N
4濃度(N換算)は減少したNO2の化学反応量(N換
算)として算出した。この算出まで8分間を要した。な
お、この再生排水は希釈後、NaNO2溶液添加前に0.
026の吸光度があったため、吸光度の測定値はこの値
を差引いたものとした。結果を第1表に示す。
Example 1 An example of analysis of reclaimed waste water from a condensate demineralizer of a thermal power plant A will be shown. In the conventional method, it was diluted 1000 times and measured by the indophenol colorimetric method. 4 by colorimetric analysis
It took about 0 minutes. In the method of the present invention, after diluting 20 times, a 10 wt% NaNO 2 solution was added to a NO 2 concentration of 100 mg.
-N / liter was added and the reaction was carried out in a catalytic decomposition tower (temperature 200 ° C, distillation time 5 minutes) packed with 0.5 wt% Pt-titania catalyst. The liquid after the reaction is U made by Shimadzu Corporation
The residual NO 2 concentration (N conversion) was detected at a wavelength of 220 nm with a V detector (SPD6A, cell length 0.5 mm). N
The H 4 concentration (N conversion) was calculated as the reduced NO 2 chemical reaction amount (N conversion). It took 8 minutes for this calculation. The regenerated waste water was diluted to 0. 0 before the NaNO 2 solution was added.
Since the absorbance was 026, the measured value of the absorbance was obtained by subtracting this value. The results are shown in Table 1.

【0012】[0012]

【表1】 [Table 1]

【0013】[0013]

【発明の効果】本発明の水中のアンモニウムイオン濃度
の測定方法は、(1)発色試薬などの特別の薬品が不用
である、(2)連続して測定可能である、(3)比較的
高濃度域も測定でき、希釈操作が軽減できる、(4)ほ
ぼリアルタイムに測定できる、(5)妨害イオンの影響
を排除することが可能である、などの優れた特徴を有し
ている。本発明方法は、例えば復水脱塩装置の再生排水
など、アンモニア濃度が高く、実質上有機物を含まない
排水に亜硝酸塩を添加し、加熱触媒接触分解するに際
し、該亜硝酸塩の注入量を制御するのに、好適に適用す
ることができる。
The method for measuring ammonium ion concentration in water according to the present invention is (1) no special chemical such as a coloring reagent is necessary, (2) continuous measurement is possible, and (3) relatively high. It has excellent features such that the concentration range can be measured, the diluting operation can be reduced, (4) it can be measured almost in real time, and (5) the influence of interfering ions can be eliminated. The method of the present invention, for example, regenerated waste water of a condensate desalination apparatus, which has a high ammonia concentration, is added with nitrite to waste water containing substantially no organic matter, and the amount of nitrite injected is controlled during catalytic decomposition by heating. However, it can be suitably applied.

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】被検体のアンモニウムイオン含有水に、既
知量の亜硝酸塩を添加したのち、これを加熱下に貴金属
担持触媒を充填したアンモニア分解装置に供給し、得ら
れる流出水の紫外部吸光度を測定して前記亜硝酸塩の消
費量を求め、この消費量から該被検体中のアンモニウム
イオン濃度を算出することを特徴とする水中のアンモニ
ウムイオン濃度の測定方法。
1. A known amount of nitrite is added to water containing ammonium ions as a test substance, which is then supplied to an ammonia decomposing device filled with a noble metal-supported catalyst under heating to obtain an ultraviolet absorbance of the resulting effluent. Is calculated to obtain the consumption amount of the nitrite, and the ammonium ion concentration in the sample is calculated from the consumption amount.
JP35903692A 1992-12-25 1992-12-25 Measurement method of ammonium ion concentration in water Expired - Fee Related JP3287040B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP35903692A JP3287040B2 (en) 1992-12-25 1992-12-25 Measurement method of ammonium ion concentration in water

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP35903692A JP3287040B2 (en) 1992-12-25 1992-12-25 Measurement method of ammonium ion concentration in water

Publications (2)

Publication Number Publication Date
JPH06201588A true JPH06201588A (en) 1994-07-19
JP3287040B2 JP3287040B2 (en) 2002-05-27

Family

ID=18462414

Family Applications (1)

Application Number Title Priority Date Filing Date
JP35903692A Expired - Fee Related JP3287040B2 (en) 1992-12-25 1992-12-25 Measurement method of ammonium ion concentration in water

Country Status (1)

Country Link
JP (1) JP3287040B2 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006105709A (en) * 2004-10-04 2006-04-20 Mitsui Mining & Smelting Co Ltd Quantitative analyzing method of unstable material and pretreatment method
CN105009962A (en) * 2015-08-10 2015-11-04 中国科学院地球化学研究所 Method for determining ammonium plundering capacity of a plant
CN108911320A (en) * 2018-06-06 2018-11-30 东南大学 A kind of nitrite decomposing processor and method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006105709A (en) * 2004-10-04 2006-04-20 Mitsui Mining & Smelting Co Ltd Quantitative analyzing method of unstable material and pretreatment method
CN105009962A (en) * 2015-08-10 2015-11-04 中国科学院地球化学研究所 Method for determining ammonium plundering capacity of a plant
CN108911320A (en) * 2018-06-06 2018-11-30 东南大学 A kind of nitrite decomposing processor and method

Also Published As

Publication number Publication date
JP3287040B2 (en) 2002-05-27

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