JP3316664B2 - Method and apparatus for measuring total phosphorus by ultraviolet oxidation decomposition method - Google Patents
Method and apparatus for measuring total phosphorus by ultraviolet oxidation decomposition methodInfo
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- JP3316664B2 JP3316664B2 JP02995696A JP2995696A JP3316664B2 JP 3316664 B2 JP3316664 B2 JP 3316664B2 JP 02995696 A JP02995696 A JP 02995696A JP 2995696 A JP2995696 A JP 2995696A JP 3316664 B2 JP3316664 B2 JP 3316664B2
- Authority
- JP
- Japan
- Prior art keywords
- total phosphorus
- acid
- sample water
- condensed phosphoric
- orthophosphoric acid
- 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.)
- Expired - Lifetime
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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)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、試料水中の縮合リ
ン酸を含めた全リンを定量分析するための紫外線酸化分
解法による全リン測定方法および装置に関する。 BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for measuring total phosphorus by an ultraviolet oxidative decomposition method for quantitatively analyzing total phosphorus including condensed phosphoric acid in sample water .
【０００２】[0002]
【発明が解決しようとする課題】種々の形態で存在する
リン化合物を酸化分解する方法として試料に酸化剤を添
加した後、これをオートクレーブと称される加水分解槽
内に投入し、加圧下で１２０℃に加熱した状態を３０分
間保持するオートクレーブ法がよく知られ、この方法を
採用した全リン自動測定装置も実用に供されており、そ
の状態では、縮合リン酸を含めた全リンの測定が可能で
ある。As a method for oxidatively decomposing a phosphorus compound existing in various forms, an oxidizing agent is added to a sample, and the oxidizing agent is introduced into a hydrolysis tank called an autoclave, and is subjected to pressurization. An autoclave method in which a state heated to 120 ° C. is maintained for 30 minutes is well known, and a total phosphorus automatic measuring apparatus employing this method is also practically used. In this state, measurement of total phosphorus including condensed phosphoric acid is performed. Is possible.
【０００３】しかし、前記オートクレーブは高い耐熱
性、耐圧性、耐薬品性等が求められるため、セラミック
スや特殊金属合金材等の特殊な材料が用いられ、高価に
なり、また、寿命も短いという難点があった。However, since the autoclave is required to have high heat resistance, pressure resistance, chemical resistance and the like, special materials such as ceramics and special metal alloys are used, and the autoclave becomes expensive and has a short life. was there.
【０００４】一方、紫外線を照射させることにより、比
較的低温（１００℃以下）かつ常圧下で酸化分解を行う
紫外線酸化分解法では、分解容器の耐熱性や耐圧性の負
担は軽減されるが、縮合リン酸の測定は困難であった。On the other hand, in the ultraviolet oxidative decomposition method of performing oxidative decomposition at a relatively low temperature (100 ° C. or lower) and normal pressure by irradiating ultraviolet rays, the heat resistance and pressure resistance of the decomposition vessel are reduced. Measurement of condensed phosphoric acid was difficult.
【０００５】本発明は、このような実情に鑑みてなさ
れ、試料水中の縮合リン酸を含めた全リンを定量分析す
ることのできる紫外線酸化分解法による全リン測定方法
および装置を提供することを目的としている。The present invention has been made in view of such circumstances, and quantitatively analyzes total phosphorus including condensed phosphoric acid in sample water.
Of total phosphorus by UV oxidation decomposition method
And devices .
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するた
め、本発明では、試料水中の縮合リン酸を含めた全リン
を定量分析する紫外線酸化分解法による全リン測定方法
において、採取した試料水に酸化剤と硫酸を添加した
後、加熱条件下で所定時間紫外線を照射して縮合リン酸
を含むリン化合物を酸化分解してオルトリン酸に変化さ
せ、その後、前記オルトリン酸を含む試料水に還元剤と
発色剤を添加して吸光度法により前記オルトリン酸を定
量するようにしている。 そして、本発明では、試料水中
の縮合リン酸を含めた全リンを定量分析する紫外線酸化
分解法による全リン測定装置において、採取した試料水
に酸化剤と硫酸を添加した後、加熱条件下で所定時間紫
外線を照射して縮合リン酸を含むリン化合物を酸化分解
してオルトリン酸に変化させ、その後、前記オルトリン
酸を含む試料水に還元剤と発色剤を添加して吸光度法に
より前記オルトリン酸を定量するようにしている。 Means for Solving the Problems To achieve the above object,
Therefore, in the present invention, total phosphorus including condensed phosphoric acid in sample water
Of Total Phosphorus by UV Oxidation Decomposition Method for Quantitative Analysis of Phosphorus
In, after addition of oxidizing agent and sulfuric acid in samples taken water, condensed phosphoric acid by irradiating a predetermined time ultraviolet under heating
Change of the orthophosphoric acid and oxidative decomposition of the phosphorus compound containing
Then, a reducing agent and a color former are added to the sample water containing orthophosphoric acid, and the orthophosphoric acid is determined by an absorbance method.
I try to weigh. In the present invention, the sample water
Oxidation for Quantitative Analysis of Total Phosphorus Including Condensed Phosphoric Acid
Sample water collected by the total phosphorus measurement device using the decomposition method
After adding an oxidizing agent and sulfuric acid to the
Oxidative degradation of phosphorus compounds containing condensed phosphoric acid by irradiation with external light
To orthophosphoric acid, and then
Add a reducing agent and a color former to sample water containing acid
More specifically, the orthophosphoric acid is determined.
【０００７】縮合リン酸をオルトリン酸に変化させるプ
ロセスは加水分解であり、酸性・高温下で分解速度が大
となる。そこで、試料水に酸を添加してから紫外線照射
を行うことにより、縮合リン酸の測定が可能となる。[0007] The process of converting condensed phosphoric acid to orthophosphoric acid is hydrolysis, and the rate of decomposition increases under acidic and high temperatures. Therefore, by adding an acid to the sample water and then irradiating the sample with ultraviolet light, it becomes possible to measure the condensed phosphoric acid.
【０００８】[0008]
【発明の実施の形態】以下に本発明の紫外線酸化分解法
による全リン測定方法および装置の実施の形態について
詳細に説明する。図２は本発明の方法を実施するための
全リン自動測定装置の要部構成図で、符号１は試料水取
入口、２は試料計量管、３は希釈槽、４は混合槽、５は
紫外線酸化分解器で、紫外線ランプ５１、分解槽５２、
ヒータ５３等を有する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the total phosphorus measurement method and apparatus according to ultraviolet oxidation decomposition method of the present invention will be described in detail. FIG. 2 is a main part configuration diagram of an apparatus for automatically measuring total phosphorus for carrying out the method of the present invention. With an ultraviolet oxidation decomposer, an ultraviolet lamp 51, a decomposition tank 52,
It has a heater 53 and the like.
【０００９】６は紫外線による酸化分解後の試料水を計
量するための計量管、７は測定セルで光源７１、セル本
体７２、検出器７３等よりなる。８は排出口、９はブラ
ンク水の取入口、１０は希釈槽３および混合槽４にブラ
ンク水を供給するためのブランク水タンクである。Reference numeral 6 denotes a measuring tube for measuring the sample water after oxidative decomposition by ultraviolet rays, and reference numeral 7 denotes a measuring cell comprising a light source 71, a cell body 72, a detector 73 and the like. 8 is a discharge port, 9 is an inlet for blank water, and 10 is a blank water tank for supplying blank water to the dilution tank 3 and the mixing tank 4.
【００１０】１１はモリブデン酸アンモニウム・酒石酸
アンチモニルカリウム水溶液を貯留する発色剤用のタン
ク、１２はＬ−アスコルビン酸水溶液を貯留する還元剤
用のタンク、１３はペルオキソニ硫酸カリウム水溶液を
貯留する酸化剤用のタンク、１４は硫酸を貯留するタン
クである。なお、１５は三方切換弁、Ｐは送給用のポン
プである。Reference numeral 11 denotes a tank for a coloring agent for storing an aqueous solution of ammonium molybdate / potassium antimonyl tartrate, 12 a tank for a reducing agent for storing an aqueous solution of L-ascorbic acid, and 13 an oxidizing agent for storing an aqueous solution of potassium peroxodisulfate. Is a tank for storing sulfuric acid. In addition, 15 is a three-way switching valve, and P is a pump for feeding.
【００１１】上述のような全リン自動測定装置によっ
て、以下のようにして縮合リン酸を含めた全リンの定量
分析を信頼性よく行うことができる（図１の測定フロー
参照）。まず、試料計量管２で一定量の試料水を計量
し、これを希釈槽３内に導入し、必要な場合には、ブラ
ンク水タンク１０からブランク水を導入して希釈する。
次に、この試料水を混合槽４に導入する。With the above-described automatic analyzer for total phosphorus, quantitative analysis of total phosphorus including condensed phosphoric acid can be reliably performed as described below (see the measurement flow in FIG. 1). First, a predetermined amount of sample water is measured by the sample measuring tube 2 and introduced into the dilution tank 3, and if necessary, blank water is introduced from the blank water tank 10 to dilute the sample water.
Next, the sample water is introduced into the mixing tank 4.
【００１２】次いで、必要な場合には、ブランク水を導
入して希釈し、タンク１３から酸化剤であるペルオキソ
二硫酸カリウム水溶液を注入し、さらに、タンク１４か
ら硫酸を注入する。これにより前処理が終了する。Next, if necessary, blank water is introduced for dilution, an aqueous solution of potassium peroxodisulfate as an oxidizing agent is injected from the tank 13, and sulfuric acid is injected from the tank 14. Thus, the pre-processing ends.
【００１３】混合槽４内での前処理が終了した後、試料
水を分解槽５２内に導入し、常圧下で、ヒータ５３によ
り９５℃に加熱した状態にて４５分間紫外線ランプ５１
を照射させ、リン化合物をオルトリン酸イオンに変え
る。After the pretreatment in the mixing tank 4 is completed, the sample water is introduced into the decomposition tank 52, and heated at 95 ° C. by the heater 53 under normal pressure for 45 minutes using the ultraviolet lamp 51.
To convert the phosphorus compound into orthophosphate ions.
【００１４】このリン化合物をオルトリン酸に変化させ
るプロセスは加水分解であるが、前処理段階で硫酸を添
加しているので、酸性かつ高温の条件下でその分解速度
が大となるため、縮合リン酸をもオルトリン酸に変化さ
せることができることになる。The process of converting this phosphorus compound into orthophosphoric acid is hydrolysis, but since sulfuric acid is added in the pretreatment step, its decomposition rate is high under acidic and high temperature conditions, and condensed phosphorus The acid can also be changed to orthophosphoric acid.
【００１５】次いで、酸化分解後の試料水を計量管６に
導入し所定量計量し、タンク１２からＬ−アスコルビン
酸水溶液を注入した後、セル本体７２内に導入して、タ
ンク１１からモリブデン酸アンモニウム・酒石酸アンチ
モニルカリウム水溶液を注入して、モリブデン青を発生
させ、８８０ｎｍの吸光度を測定してダーク補正とゼロ
点補正を行い縮合リン酸を含む全リン濃度を求める。な
お、より信頼性の高い測定を行うために、測定毎にブラ
ンク水をゼロ水として用いた自動ゼロ校正を行うのが好
ましい。Next, the oxidatively decomposed sample water is introduced into the measuring tube 6 and measured in a predetermined amount. An aqueous solution of L-ascorbic acid is injected from the tank 12 and then introduced into the cell body 72. An aqueous solution of ammonium / potassium antimonyl tartrate is injected to generate molybdenum blue, and the absorbance at 880 nm is measured to perform dark correction and zero point correction to obtain the total phosphorus concentration including condensed phosphoric acid. In addition, in order to perform more reliable measurement, it is preferable to perform automatic zero calibration using blank water as zero water for each measurement.
【００１６】オルトリン酸の定量は、一般に、モリブデ
ンブルー吸光光度法が採用されており、これは硫酸酸性
下で行うため、通常は、硫酸水溶液に溶かした発色剤を
用いるが、本発明では、発色剤を水溶液とし、その硫酸
を紫外線照射前に添加している。[0016] Determination of orthophosphate generally motor re Bude <br/> Nburu are absorption spectrophotometry is adopted, which is for performing in an acidic sulfate, are usually used color former dissolved in aqueous sulfuric acid solution In the present invention, the color former is used as an aqueous solution, and the sulfuric acid is added before the ultraviolet irradiation.
【００１７】全リン濃度の測定は、種々のリン化合物を
酸化分解によってオルトリン酸に変化させ、そのオルト
リン酸を定量することにより全リン濃度を求めるのであ
るが、本発明では、酸性・高温下で、縮合リン酸のオル
トリン酸への分解速度を大きくし、縮合リン酸を定量的
に回収できるようになった。ちなみに、表１に標準試料
の回収率を掲載する。なお、実験条件は、試料：０．２
または０．５ｍｇＰ／Ｌ、計器：０〜０．５ｍｇＰ／Ｌ
計、室温：２２〜２５℃、手分析：ＪＩＳ Ｋ０１０２
−１９９３であった。In the measurement of the total phosphorus concentration, various phosphorus compounds are converted into orthophosphoric acid by oxidative decomposition, and the total phosphorus concentration is determined by quantifying the orthophosphoric acid. Thus, the decomposition rate of condensed phosphoric acid to orthophosphoric acid was increased, and condensed phosphoric acid could be recovered quantitatively. Table 1 shows the standard sample recovery rates. The experimental conditions were as follows: sample: 0.2
Or 0.5 mgP / L, instrument: 0 to 0.5 mgP / L
Total, room temperature: 22-25 ° C, manual analysis: JIS K0102
-1993.
【００１８】[0018]
【表１】 [Table 1]
【００１９】以上のように、紫外線酸化分解法で縮合リ
ン酸を含む全リンの測定が可能となり、分解容器に耐圧
性が不要となり、また耐熱性も緩和されることとなるた
め、本方法による全リン自動測定装置では、オートクレ
ーブ法による従来装置に比べてコスト安となり、また保
守性も高くなる。As described above, the total phosphorous including condensed phosphoric acid can be measured by the ultraviolet oxidative decomposition method, and the decomposition vessel does not need to have pressure resistance and the heat resistance is reduced. The total phosphorus automatic measuring device is lower in cost and higher in maintainability than the conventional device based on the autoclave method.
【００２０】[0020]
【発明の効果】以上説明したように、本発明の紫外線酸
化分解法による全リン測定方法および装置においては、
採取した試料水に酸化剤と硫酸を添加した後、加熱条件
下で所定時間紫外線を照射して縮合リン酸を含むリン化
合物を酸化分解してオルトリン酸に変化させ、その後、
前記オルトリン酸を含む試料水に還元剤と発色剤を添加
して吸光度法により前記オルトリン酸を定量するように
しているので、縮合リン酸を定量的に回収できるように
なり、従来からのオートクレーブ法による場合に比し
て、低価格で保守性にすぐれた測定装置を構成でき、か
つ信頼性の高い全リン測定値を得ることができる。As described above, the ultraviolet acid of the present invention
In the method and apparatus for measuring total phosphorus by the chemical decomposition method ,
After adding an oxidizing agent and sulfuric acid to the sampled water, irradiate it with ultraviolet light for a predetermined time under heating conditions, and
The compound is oxidatively decomposed into orthophosphoric acid, and then
To add a reducing agent and a color former to the sample water containing the orthophosphoric acid and determine the orthophosphoric acid by an absorbance method
As a result , condensed phosphoric acid can be quantitatively recovered, making it possible to construct a low-cost, highly maintainable measuring device and a highly reliable total system compared to the conventional autoclave method. A phosphorus measurement can be obtained.
【図１】本発明の紫外線酸化分解法による全リン測定方
法の測定フローを示す図である。[1] total phosphorus measurement direction by ultraviolet oxidation decomposition method of the present invention
It is a figure which shows the measurement flow of a method .
【図２】本発明の紫外線酸化分解法による全リン測定方
法を実施するための全リン自動測定装置の構成図であ
る。[2] total phosphorus measurement direction by ultraviolet oxidation decomposition method of the present invention
1 is a configuration diagram of a total phosphorus automatic measuring device for performing a method . FIG.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 分析化学便覧，第164ページ，昭和56 年９月20日，丸善株式会社発行 Жу РНАЛ АНАЛИТИЧЕ СКОИ ХИМИИ 第1615−1623 頁、1990年発行 (58)調査した分野(Int.Cl.7，ＤＢ名) G01N 31/00 G01N 21/77 ＪＩＣＳＴファイル（ＪＯＩＳ)────────────────────────────────────────────────── ─── Continuation of the front page (56) References Analytical Chemistry Handbook, page 164, September 20, 1981, published by Maruzen Co., Ltd. Жу РНАЛ АНАЛИТИЧЕ СКОИ ХИМИИ pp. 1615-1623, published in 1990 (58) Survey Field (Int.Cl. 7 , DB name) G01N 31/00 G01N 21/77 JICST file (JOIS)
Claims (2)
定量分析する紫外線酸化分解法による全リン測定方法に
おいて、採取した試料水に酸化剤と硫酸を添加した後、
加熱条件下で所定時間紫外線を照射して縮合リン酸を含
むリン化合物を酸化分解してオルトリン酸に変化させ、
その後、前記オルトリン酸を含む試料水に還元剤と発色
剤を添加して吸光度法により前記オルトリン酸を定量す
ることを特徴とする紫外線酸化分解法による全リン測定
方法。(1) total phosphorus including condensed phosphoric acid in a sample water;
Quantitative analysis of total phosphorus by UV oxidation decomposition method
Oite, after addition of oxidizing agent and sulfuric acid collected water samples,
Irradiate ultraviolet light for a predetermined time under heating conditions to contain condensed phosphoric acid.
Oxidatively decomposes phosphorus compounds to orthophosphoric acid,
Thereafter, a reducing agent and a color former are added to the sample water containing orthophosphoric acid, and the orthophosphoric acid is quantified by an absorbance method.
How .
定量分析する紫外線酸化分解法による全リン測定装置にFor quantitative analysis of total phosphorus by ultraviolet oxidation decomposition method
おいて、採取した試料水に酸化剤と硫酸を添加した後、After adding the oxidizing agent and sulfuric acid to the sample water collected,
加熱条件下で所定時間紫外線を照射して縮合リン酸を含Irradiate ultraviolet light for a predetermined time under heating conditions to contain condensed phosphoric acid.
むリン化合物を酸化分解してオルトリン酸に変化させ、Oxidatively decomposes phosphorus compounds to orthophosphoric acid,
その後、前記オルトリン酸を含む試料水に還元剤と発色After that, a reducing agent is added to the sample water containing orthophosphoric acid and color is developed.
剤を添加して吸光度法により前記オルトリン酸を定量すThe orthophosphoric acid is quantified by an absorbance method after adding an agent.
ることを特徴とする紫外線酸化分解法による全リン測定Of total phosphorus by ultraviolet oxidative decomposition method
装置。apparatus.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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|---|---|
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| JP5234053B2 (en) * | 2010-05-12 | 2013-07-10 | 三浦工業株式会社 | Determination of total phosphorus |
| KR101340767B1 (en) * | 2012-04-12 | 2013-12-11 | 서울시립대학교 산학협력단 | the detecting method for low concentration of phosphate |
| CN102998266A (en) * | 2012-11-21 | 2013-03-27 | 合肥星宇化学有限责任公司 | Method for analyzing total phosphorus in industrial sewage sample |
-
1996
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Non-Patent Citations (2)
| Title |
|---|
| Жу РНАЛ АНАЛИТИЧЕСКОИ ХИМИИ 第１６１５−１６２３頁、１９９０年発行 |
| 分析化学便覧，第１６４ページ，昭和５６年９月２０日，丸善株式会社発行 |
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