JPH0727706A - Analyzer for nitrogen compounds and phosphorus compounds in water - Google Patents
Analyzer for nitrogen compounds and phosphorus compounds in waterInfo
- Publication number
- JPH0727706A JPH0727706A JP19796593A JP19796593A JPH0727706A JP H0727706 A JPH0727706 A JP H0727706A JP 19796593 A JP19796593 A JP 19796593A JP 19796593 A JP19796593 A JP 19796593A JP H0727706 A JPH0727706 A JP H0727706A
- Authority
- JP
- Japan
- Prior art keywords
- light
- measurement cell
- oxidation reaction
- sample water
- absorption
- 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.)
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Optical Measuring Cells (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
(57)【要約】
【目的】 試料水中の窒素化合物とリン化合物を１台の
装置でともに測定できるようにする。
【構成】 光酸化反応槽２には試料水と空気を供給する
ことができ、発色剤も添加することができる。光酸化反
応槽２内の試料水は酸化反応中は例えば９０℃に温度制
御される。光酸化反応槽２は取出し管８を介して吸光測
定セル５２に接続されている。酸化反応後の試料水は一
部が吸光測定セル５２に導入されて硝酸イオンが測定さ
れ、その後、試料水に発色剤が添加され、吸光測定セル
５２でリン酸イオンが測定される。吸光度測定のため
に、吸光測定セル５２にはキセノンフラッシュランプ５
４から測定光が照射され、吸光測定セル５２の透過光は
ハーフミラー６２で分波され、硝酸イオンとリン酸イオ
ンがそれぞれの波長でそれぞれの検出器６６，７０で検
出される。
(57) [Summary] [Purpose] To be able to measure both nitrogen compounds and phosphorus compounds in sample water with a single device. [Constitution] Sample water and air can be supplied to the photo-oxidation reaction tank 2, and a color former can also be added. During the oxidation reaction, the temperature of the sample water in the photo-oxidation reaction tank 2 is controlled to 90 ° C., for example. The photo-oxidation reaction tank 2 is connected to the absorption measurement cell 52 via the take-out tube 8. Part of the sample water after the oxidation reaction is introduced into the absorption measurement cell 52 to measure nitrate ions, and then a color developing agent is added to the sample water, and phosphate ions are measured in the absorption measurement cell 52. The xenon flash lamp 5 is provided in the absorption measurement cell 52 for measuring the absorbance.
The measurement light is irradiated from 4 and the transmitted light of the absorption measurement cell 52 is demultiplexed by the half mirror 62, and the nitrate ion and the phosphate ion are detected by the respective detectors 66 and 70 at their respective wavelengths.
Description
【０００１】[0001]
【産業上の利用分野】本発明は工場や事業所などから出
る排水や、河川や湖沼などの環境水に含まれる微量の窒
素化合物とリン化合物を分析する装置に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for analyzing a small amount of nitrogen compounds and phosphorus compounds contained in wastewater discharged from factories and business establishments and environmental water such as rivers and lakes.
【０００２】[0002]
【従来の技術】我が国においては水中の窒素化合物やリ
ン化合物の分析方法は、ＪＩＳのＫ０１０２や環境庁告
示１４０号によって公的に規格化されている。水中の窒
素化合物は硝酸イオン、亜硝酸イオン、アンモニウムイ
オン又は有機態窒素として存在している。これらの水中
窒素を全て測定するＴＮ（全窒素）分析方法では、全て
の窒素化合物を硝酸イオンに変えて測定するが、アンモ
ニウムイオンや有機体窒素は硝酸イオンに酸化されにく
い。そこで、ＴＮ測定では試料水にアルカリ性ペルオキ
ソ二硫酸カリウム溶液を加えて１２０℃で３０分間加熱
し、全ての窒素化合物を硝酸イオンに酸化する。それを
冷却した後、ｐＨを２〜３に調整し、硝酸イオンによる
波長２２０ｎｍでの紫外線吸光度を測定している。2. Description of the Related Art In Japan, analysis methods for nitrogen compounds and phosphorus compounds in water are officially standardized by JIS K0102 and Environmental Agency Notification No. 140. Nitrogen compounds in water are present as nitrate ions, nitrite ions, ammonium ions or organic nitrogen. In the TN (total nitrogen) analysis method for measuring all nitrogen in these water, all nitrogen compounds are converted into nitrate ions for measurement, but ammonium ions and organic nitrogen are not easily oxidized to nitrate ions. Therefore, in the TN measurement, an alkaline potassium peroxodisulfate solution is added to sample water and heated at 120 ° C. for 30 minutes to oxidize all nitrogen compounds into nitrate ions. After cooling it, the pH was adjusted to 2-3, and the ultraviolet absorbance at a wavelength of 220 nm due to nitrate ions was measured.
【０００３】一方、水中のリン化合物はリン酸イオン、
加水分解性リン、又は有機態リンとして存在している。
ＴＰ（全リン）測定では中性状態でペルオキソ二硫酸カ
リウムを酸化剤として添加し、１２０℃で３０分間加熱
することによって全てのリン化合物をリン酸イオンに酸
化する。リン酸イオンは特有の光吸収を持たないので、
リン酸イオンを測定するには、冷却後に発色剤としてモ
リブデン酸アンモニウム溶液とＬ−アスコルビン酸溶液
を添加して発色させ、波長８８０ｎｍでの吸光度を測定
している。On the other hand, phosphorus compounds in water are phosphate ions,
It exists as hydrolyzable phosphorus or organic phosphorus.
In TP (total phosphorus) measurement, potassium peroxodisulfate is added as an oxidant in a neutral state, and all phosphorus compounds are oxidized to phosphate ions by heating at 120 ° C. for 30 minutes. Since the phosphate ion does not have a unique light absorption,
To measure the phosphate ion, after cooling, an ammonium molybdate solution and an L-ascorbic acid solution are added as color formers to develop color, and the absorbance at a wavelength of 880 nm is measured.
【０００４】他のＴＮ測定方法では、酸化触媒を用いて
５００℃以上の高温で硝酸イオンに酸化した後、化学発
光法により窒素酸化物として測定したり、窒素酸化物を
さらに酸化還元反応管（約６００℃）に通して窒素ガス
に分解してガスクロマトグラフ法で窒素として測定して
いる。さらに他の方法としては、試料水にオゾンを供給
してオゾン酸化する方法も行なわれており、そのオゾン
酸化は、ＴＮ測定ではアルカリ性下、ＴＰ測定では酸性
下で行なわれている。In another TN measuring method, after oxidation to nitrate ions at a high temperature of 500 ° C. or higher using an oxidation catalyst, it is measured as a nitrogen oxide by a chemiluminescence method, or the nitrogen oxide is further analyzed in a redox reaction tube ( It is passed through about 600 ° C.) to decompose into nitrogen gas and measured as nitrogen by gas chromatography. As another method, a method of supplying ozone to sample water to oxidize ozone is also performed. The ozone oxidation is performed under alkaline conditions in TN measurement and under acidic conditions in TP measurement.
【０００５】[0005]
【発明が解決しようとする課題】試料水中のＴＮ測定と
ＴＰ測定を共通の分析計で分析するようにした装置はな
い。これは、酸化剤による酸化やオゾン酸化では、窒素
化合物の酸化をアルカリ性下で行ない、リン化合物の酸
化を中性下又は酸性下で行なうというように、酸化の際
のｐＨ条件が異なるためである。また、酸化剤による酸
化方法では水の沸点以上の１２０℃というような高温に
加熱するため、耐圧構造の反応釜を必要とし、酸化装置
の構造や操作が複雑になり、高価格になる問題がある。
酸化剤は消耗するため頻繁に補充しなければならず、ラ
ンニングコストが高くなる問題もある。There is no device that analyzes TN measurement and TP measurement in sample water with a common analyzer. This is because in the oxidation by an oxidant and the ozone oxidation, the pH condition at the time of oxidation is different such that the oxidation of the nitrogen compound is carried out under alkaline condition and the oxidation of the phosphorus compound is carried out under neutral condition or acidic condition. . In addition, in the oxidation method using an oxidant, since it is heated to a high temperature such as 120 ° C., which is higher than the boiling point of water, a reaction vessel having a pressure resistant structure is required, and the structure and operation of the oxidizer becomes complicated, resulting in high cost. is there.
Since the oxidant is consumed, it must be replenished frequently, which causes a problem of high running cost.
【０００６】触媒を用いて窒素化合物を酸化する方法
は、５００℃以上というような高温が必要であり、かつ
触媒の劣化が激しい。装置も構造が複雑になり、保守が
困難であるだけでなく、触媒を使用した分析法は一般に
モニタとして現場で使用するのに不向きである。オゾン
酸化法では中性域での酸化力が弱いため、窒素化合物の
酸化についてもリン化合物の酸化についてもそれぞれｐ
Ｈを調整する機構を要し、装置の構造が複雑になる。ま
た、酸とアルカリのｐＨ調整液も消耗品として必要にな
る。このように、従来の分析方法に基づく分析装置では
窒素化合物とリン化合物を共通に測定することができな
いだけでなく、コスト高にもなり、また連続モニタとし
て使用するのが困難である。The method of oxidizing a nitrogen compound using a catalyst requires a high temperature such as 500 ° C. or higher, and the deterioration of the catalyst is severe. Not only is the device complicated in structure and difficult to maintain, but also analytical methods using catalysts are generally unsuitable for on-site use as monitors. Since the ozone oxidation method has a weak oxidizing power in the neutral range, both the oxidation of nitrogen compounds and the oxidation of phosphorus compounds are p.
A mechanism for adjusting H is required, and the structure of the device becomes complicated. Further, a pH adjusting liquid of acid and alkali is also required as a consumable item. As described above, in the analyzer based on the conventional analysis method, not only the nitrogen compound and the phosphorus compound cannot be commonly measured, but also the cost becomes high, and it is difficult to use as a continuous monitor.
【０００７】そこで、本発明は試料水中の窒素化合物と
リン化合物を１台の装置でともに測定できるようにする
とともに、長時間連続して分析することも可能な分析装
置を提供することを目的とするものである。Therefore, an object of the present invention is to provide an analyzer capable of measuring both nitrogen compounds and phosphorus compounds in sample water with a single device and capable of continuously analyzing for a long time. To do.
【０００８】[0008]
【課題を解決するための手段】本発明の分析装置は、試
料水中の窒素化合物とリン化合物を同時に酸化して窒素
化合物から硝酸イオン、リン化合物からリン酸イオンを
生じさせる酸化反応槽と、酸化反応後の試料水の吸光度
を測定する石英ガラス製吸光測定セルと、酸化反応槽又
は吸光測定セルへリン酸イオンと選択的に反応する発色
剤を添加する発色剤添加用流路と、吸光測定セルへ測定
光を照射する光源部と、吸光測定セルの測定光透過光路
上にあって、その透過光を２つの光路に分波する分波手
段と、分波された一方の光路上にあって硝酸イオンに特
有の吸収波長を選択し、その波長の光を硝酸イオンの試
料光として検出する第１の光学系と、分波された他方の
光路上にあってリン酸イオンと反応した発色剤に特有の
吸収波長を選択し、その波長の光をリン酸イオンの試料
光として検出する第２の光学系と、第１及び第２の光学
系の検出信号を基にして窒素化合物濃度とリン化合物濃
度とを算出する演算処理部とを備えている。The analyzer of the present invention comprises an oxidation reaction tank for simultaneously oxidizing a nitrogen compound and a phosphorus compound in sample water to generate a nitrate ion from the nitrogen compound and a phosphate ion from the phosphorus compound, and an oxidation reactor. A quartz glass absorption measurement cell that measures the absorbance of the sample water after the reaction, a color-developing agent addition flow path that adds a coloring agent that selectively reacts with phosphate ions to the oxidation reaction tank or absorption measurement cell, and the absorption measurement A light source section for irradiating the cell with the measurement light, a demultiplexing means for demultiplexing the transmitted light into two optical paths on the absorption light of the absorption measurement cell, and a demultiplexing optical path on one of the demultiplexed optical paths. The first optical system that selects the absorption wavelength peculiar to nitrate ion and detects the light of that wavelength as the sample light of nitrate ion, and the color developed by reacting with phosphate ion on the other optical path of the demultiplexed Select the absorption wavelength specific to the agent A second optical system that detects light of that wavelength as sample light of phosphate ions, and an arithmetic processing unit that calculates the nitrogen compound concentration and the phosphorus compound concentration based on the detection signals of the first and second optical systems. It has and.
【０００９】好ましい態様では、酸化反応槽は酸素又は
オゾンを含有したガスを吹き込む手段と、試料水を５０
〜１００℃に加温する手段とを備え、少なくとも一部が
紫外線透過材料にてなる反応容器と、その反応容器の紫
外線透過材料部分から紫外線を照射する紫外光源とを備
えた光酸化反応槽である。他の態様では、光酸化反応槽
と吸光測定セルが１つのセルで共用されており、そのセ
ルは試料水が供給され、紫外線透過用石英窓を有し、加
熱手段を備え、供給された試料水に酸素又はオゾンを含
有したガスを吹き込む手段を備えて光酸化反応槽を兼ね
る吸光測定セルとなっている。In a preferred embodiment, the oxidation reaction tank has a means for injecting a gas containing oxygen or ozone and 50% sample water.
A photo-oxidation reaction tank comprising a reaction container having a heating means of up to 100 ° C., at least a part of which is made of an ultraviolet light transmitting material, and an ultraviolet light source which irradiates ultraviolet rays from the ultraviolet light transmitting material portion of the reaction container. is there. In another embodiment, the photooxidation reaction tank and the absorption measurement cell are shared by one cell, and the cell is supplied with sample water, has a quartz window for transmitting ultraviolet light, is provided with a heating means, and is supplied with the sample. The absorption measurement cell is equipped with a means for blowing a gas containing oxygen or ozone into water and also serves as a photooxidation reaction tank.
【００１０】[0010]
【実施例】図１と図２は第１の実施例を表わす。図１は
反応部、図２は測定部を表している。２は紫外線照射に
より窒素化合物を硝酸イオンに酸化し、リン化合物をリ
ン酸イオンに酸化する光酸化反応槽である。光酸化反応
槽２は酸化反応容器４を備え、その酸化反応容器４の底
部には試料水、空気及び洗浄用上水を供給する供給管６
と、酸化反応終了後の試料水を取り出す取出し管８が接
続され、その酸化反応容器４の上部には溢れた試料水や
洗浄水、及び空気を排出するための排出管１０と、校正
液１２をバルブ１４を介して供給する校正液供給管１６
と、発色剤１８，２０をペリスターポンプ２２を介して
供給する発色剤供給管２４が接続されている。発色剤１
８，２０はリン酸イオンと反応して発色するものであ
り、発色剤１８はモリブデン酸アンモニウム溶液、発色
剤２０はＬ−アスコルビン酸溶液である。排出管１０に
は排出用バルブＶ５が接続され、そのバルブＶ５を経て
試料水等が排出される。1 and 2 show a first embodiment. FIG. 1 shows a reaction part and FIG. 2 shows a measurement part. Reference numeral 2 denotes a photo-oxidation reaction tank that oxidizes a nitrogen compound into a nitrate ion and a phosphorus compound into a phosphate ion by irradiating ultraviolet rays. The photo-oxidation reaction tank 2 includes an oxidation reaction container 4, and a supply pipe 6 for supplying sample water, air and clean water to the bottom of the oxidation reaction container 4.
And a take-out pipe 8 for taking out the sample water after the completion of the oxidation reaction, and a discharge pipe 10 for discharging the overflowing sample water, cleaning water, and air, and a calibration liquid 12 are connected to the upper part of the oxidation reaction container 4. For supplying calibration liquid through valve 14
And a color former supply pipe 24 for supplying the color formers 18 and 20 via a peristaltic pump 22. Coloring agent 1
Reference numerals 8 and 20 are those which develop a color by reacting with a phosphate ion, the color former 18 is an ammonium molybdate solution, and the color former 20 is an L-ascorbic acid solution. A discharge valve V5 is connected to the discharge pipe 10, and sample water or the like is discharged through the valve V5.
【００１１】酸化反応容器４内には光酸化反応用の光源
として、短波長の紫外線、例えば１８５ｎｍに輝度を有
する低圧水銀灯２６が配置されている。酸化分解時に低
圧水銀灯２６が電源２８により点灯されて紫外線が酸化
反応容器４内の試料水に照射される。酸化反応容器４は
例えばアルミニウムやステンレスなどの金属製であり、
その内面は紫外線を多重反射させるために、鏡面研磨さ
れてミラー構造になっている。酸化反応容器４をガラス
製とすることもできる。試料水が海水や塩分の多い水で
ある場合は、酸化反応容器４はガラス製であることが好
ましい。ガラス製の場合、ミラー構造とするには、パイ
レックスガラスは紫外線を透過しないので内面に銀鏡や
アルミニウム蒸着膜を形成し、紫外線透過ガラスの場合
は外面に銀鏡やアルミニウム蒸着膜を形成すればよい。
酸化反応容器４をミラー構造にすれば紫外線放射光を有
効に活用することができ、分解効率が著しく向上する。
光酸化反応槽２としては種々の構造のものを使用するこ
とができる。A low pressure mercury lamp 26 having a short wavelength ultraviolet ray, for example, a brightness of 185 nm, is arranged in the oxidation reaction container 4 as a light source for the photooxidation reaction. At the time of oxidative decomposition, the low-pressure mercury lamp 26 is turned on by the power supply 28, and ultraviolet rays are applied to the sample water in the oxidation reaction container 4. The oxidation reaction container 4 is made of metal such as aluminum or stainless steel,
Its inner surface is mirror-polished to have a mirror structure for multiple reflection of ultraviolet rays. The oxidation reaction container 4 can also be made of glass. When the sample water is seawater or water with high salt content, the oxidation reaction container 4 is preferably made of glass. In the case of glass, in order to form a mirror structure, since Pyrex glass does not transmit ultraviolet rays, a silver mirror or an aluminum vapor deposition film may be formed on the inner surface, and in the case of ultraviolet transmitting glass, a silver mirror or aluminum vapor deposition film may be formed on the outer surface.
If the oxidation reaction container 4 has a mirror structure, the ultraviolet radiation can be effectively used, and the decomposition efficiency is significantly improved.
As the photo-oxidation reaction tank 2, those having various structures can be used.
【００１２】光源としては低圧水銀灯２６以外にもエキ
シマレーザ、重水素ランプ、キセノンランプ、Ｈｇ−Ｚ
ｎ−Ｐｂランプなど、強いエネルギーで紫外線を放射で
きる光源であればいずれも使用することができる。低圧
水銀灯２６は寿命が長いという利点をもっており、モニ
タとして使用するのに好都合である。As the light source, in addition to the low-pressure mercury lamp 26, an excimer laser, a deuterium lamp, a xenon lamp, Hg-Z
Any light source, such as an n-Pb lamp, can be used as long as it can emit ultraviolet light with strong energy. The low-pressure mercury lamp 26 has an advantage that it has a long life and is convenient for use as a monitor.
【００１３】酸化反応容器４には酸化反応容器４内の試
料水を５０〜１００℃の所定の温度に保持するためにヒ
ータ３０が設けられ、温度センサ３２を介して温調器に
よって所定の温度に制御できるようになっている。酸化
反応容器４内の試料水は例えば９０℃に温度制御され
る。ヒータ３０をカートリッジヒータとして温度センサ
３２ともに酸化反応容器４に埋め込んでもよい。必要に
応じて酸化反応容器４の外側を断熱材で被ってもよい。
酸化反応容器４を紫外線透過ガラス製とした場合は、紫
外線光源を酸化反応容器４の外側に配置し、酸化反応容
器４の外側から紫外線照射するようにしてもよい。The oxidation reaction container 4 is provided with a heater 30 for keeping the sample water in the oxidation reaction container 4 at a predetermined temperature of 50 to 100 ° C. A temperature controller 32 is used to control a predetermined temperature via a temperature sensor 32. Can be controlled. The temperature of the sample water in the oxidation reaction container 4 is controlled to 90 ° C., for example. The heater 30 may be embedded in the oxidation reaction container 4 together with the temperature sensor 32 as a cartridge heater. If necessary, the outside of the oxidation reaction container 4 may be covered with a heat insulating material.
When the oxidation reaction container 4 is made of ultraviolet-transparent glass, the ultraviolet light source may be arranged outside the oxidation reaction container 4 and the ultraviolet irradiation may be performed from the outside of the oxidation reaction container 4.
【００１４】酸化反応容器４の下部の供給管６を経て試
料水を供給するために、試料水流路が弁３４とピンチ弁
Ｖ３を介して接続されている。弁３４とＶ３の間の流路
には弁Ｖ４を介して排水する流路が接続されている。供
給管６には酸化反応時に試料水を曝気するための空気を
供給するために、空気供給流路がフィルタ３８、ポンプ
４０、ニードル付き流量計４２及び弁Ｖ１を介して接続
されている。A sample water flow path is connected to the valve 34 via a pinch valve V3 in order to supply the sample water through the supply pipe 6 below the oxidation reaction container 4. A flow path for draining water is connected via a valve V4 to the flow path between the valve 34 and V3. An air supply flow path is connected to the supply pipe 6 through a filter 38, a pump 40, a needle-equipped flowmeter 42, and a valve V1 in order to supply air for aerating the sample water during the oxidation reaction.
【００１５】供給管６にはさらに、酸化反応容器４や測
定セルなどの流路を洗浄するための上水を供給するため
に、上水供給路がボール弁４４、電磁弁Ｖ２、純水器４
６、逆止弁４８を介して接続されている。供給管６には
排水用弁５０が接続され、その弁５０を介して酸化反応
容器４や供給管６に残った液を排出できるようになって
いる。酸化反応容器４の底部に設けられた取出し管８は
弁Ｖ６を介して吸光測定セル５２の底部に接続されてい
る。吸光測定セル５２はその底部から弁Ｖ８を介して排
水できるようになっており、その上部には溢れた試料水
や洗浄水を排出するために弁Ｖ７をもつ排出管が接続さ
れている。The supply pipe 6 is further provided with a ball valve 44, a solenoid valve V2, and a deionizer for supplying clean water for cleaning the flow paths such as the oxidation reaction container 4 and the measuring cell. Four
6. Connected via a check valve 48. A drainage valve 50 is connected to the supply pipe 6, and the liquid remaining in the oxidation reaction container 4 and the supply pipe 6 can be discharged through the valve 50. The take-out pipe 8 provided at the bottom of the oxidation reaction container 4 is connected to the bottom of the absorption measurement cell 52 via a valve V6. The absorption measurement cell 52 can be drained from its bottom through a valve V8, and a drain pipe having a valve V7 is connected to the top thereof for draining overflowing sample water and washing water.
【００１６】吸光測定セル５２は試料水を流通させるこ
とができるとともに、紫外から近赤外に及ぶ領域の測定
光を透過させるために石英ガラス製の透過窓を備えてい
る。吸光測定セル５２へ測定光を照射するために、キセ
ノンフラッシュランプ５４が設けられている。測定用光
源としては短波長側に重水素ランプ、長波長側にタング
ステンランプを用いることもできる。しかし、光源が２
種類になると構造が複雑になるので、測定に必要な波長
範囲をカバーできるキセノンランプが好ましい。連続点
灯するキセノンランプでは高温になり、かつ寿命が短い
ので、キセノンフラッシュランプが好都合である。キセ
ノンフラッシュランプ５４は発熱が少なく、寿命が長
い。５６は光源の電源である。発色剤を添加する手段は
吸光測定セル５２に設け、吸光測定セル５２において試
料水に発色剤を添加するようにしてもよい。The absorption measuring cell 52 allows the sample water to flow therethrough, and is provided with a transmission window made of quartz glass for transmitting the measurement light in the region from ultraviolet to near infrared. A xenon flash lamp 54 is provided to irradiate the absorption measurement cell 52 with measurement light. As the light source for measurement, a deuterium lamp can be used on the short wavelength side and a tungsten lamp can be used on the long wavelength side. However, the light source is 2
A xenon lamp that can cover the wavelength range necessary for measurement is preferable because the structure becomes complicated depending on the type. A xenon flash lamp is convenient because a xenon lamp that lights continuously has a high temperature and has a short life. The xenon flash lamp 54 generates less heat and has a long life. 56 is a power source for the light source. The means for adding the color former may be provided in the absorption measurement cell 52, and the color developer may be added to the sample water in the absorption measurement cell 52.
【００１７】吸光測定セル５２は紫外線透過可能な石英
窓が測定光路上に配置される。吸光測定セル５２の光路
長は１０ｍｍである。吸光測定セル５２の透過光光路上
には透過光を分波するハーフミラー６２が設置され、吸
光測定セル５２とハーフミラー６２の間の光路上には石
英製集光レンズ５８が配置され、吸光測定セル５２の透
過光がハーフミラー６２上に集光されるようになってい
る。集光レンズ５８とハーフミラー６２の間の光路上に
は校正フィルタ６２が配置されている。In the absorption measuring cell 52, a quartz window capable of transmitting ultraviolet rays is arranged on the measuring optical path. The optical path length of the absorption measurement cell 52 is 10 mm. A half mirror 62 for demultiplexing the transmitted light is installed on the optical path of the transmitted light of the absorption measuring cell 52, and a quartz condenser lens 58 is arranged on the optical path between the absorption measuring cell 52 and the half mirror 62 to absorb the light. The transmitted light of the measurement cell 52 is focused on the half mirror 62. A calibration filter 62 is arranged on the optical path between the condenser lens 58 and the half mirror 62.
【００１８】ハーフミラー６２としては反射光が８００
ｎｍ以上の光となり、透過光が２４０ｎｍ以下の波長の
光となるように波長特性が設定されたものを用い、ハー
フミラー６２の透過光路が窒素化合物測定用、反射光路
がリン化合物測定用となる。ハーフミラー６２の透過光
路上にはシリコンフォトダイオード６６が窒素側光検出
器として配置され、ハーフミラー６２とフォトダイオー
ド６６の間の光路上には透過波長が２２０ｎｍの光学フ
ィルタ６４が配置されている。一方、ハーフミラーの反
射光路上にはシリコンフォトダイオード７０がリン側光
検出器として配置され、ハーフミラー６２とフォトダイ
オード７０の間の光路上には透過波長が８８０ｎｍの光
学フィルタ６８が配置されている。光学フィルタ６４，
６８の半値幅は１０〜３０ｎｍである。光検出器のシリ
コンフォトダイオード６６，７０は紫外〜近赤外域にわ
たって広範囲な感度を有する特性のものを使用する。As the half mirror 62, the reflected light is 800
The wavelength characteristic of the half mirror 62 is set so that the transmitted light has a wavelength of 240 nm or less, and the transmitted light path of the half mirror 62 is for nitrogen compound measurement, and the reflected light path is for phosphorus compound measurement. . A silicon photodiode 66 is arranged as a nitrogen-side photodetector on the transmission optical path of the half mirror 62, and an optical filter 64 having a transmission wavelength of 220 nm is arranged on the optical path between the half mirror 62 and the photodiode 66. . On the other hand, a silicon photodiode 70 is arranged as a phosphorus-side photodetector on the reflection optical path of the half mirror, and an optical filter 68 having a transmission wavelength of 880 nm is arranged on the optical path between the half mirror 62 and the photodiode 70. There is. Optical filter 64,
The full width at half maximum of 68 is 10 to 30 nm. As the silicon photodiodes 66 and 70 of the photodetector, those having characteristics having a wide range of sensitivity in the ultraviolet to near infrared region are used.
【００１９】フォトダイオード６６，７０の検出出力を
増幅するために、それぞれにプリアンプ７２，７４が接
続され、プリアンプ７２，７４で増幅された検出出力は
前処理回路７６を経て演算部７８へ取り込まれる。前処
理部７６では差動増幅と対数増幅がなされ、演算部７８
で窒素化合物とリン化合物の濃度が算出され、表示部８
０へ表示される。８４は演算部の電源である。測定値は
アナログ出力としても取り出すことができ、例えばＤＣ
０〜１Ｖ又はＤＣ４〜２０ｍＡの値として出力すること
ができる。測定時の温度制御、各電磁弁（ピンチ弁、電
磁弁）及びペリスターポンプ、空気ポンプなどのシーケ
ンス制御は制御部８２によって行なわれる。Preamplifiers 72 and 74 are connected to the detection outputs of the photodiodes 66 and 70, respectively, and the detection outputs amplified by the preamplifiers 72 and 74 are taken into a computing unit 78 via a preprocessing circuit 76. . In the preprocessing unit 76, differential amplification and logarithmic amplification are performed, and the calculation unit 78
The concentrations of nitrogen compounds and phosphorus compounds are calculated by the display unit 8
Displayed at 0. Reference numeral 84 is a power supply for the arithmetic unit. The measured value can also be taken out as an analog output, for example DC
It can be output as a value of 0 to 1 V or DC 4 to 20 mA. The temperature control during measurement, sequence control of each solenoid valve (pinch valve, solenoid valve), perister pump, air pump, etc. is performed by the controller 82.
【００２０】前処理部７６及び演算部７８の詳細を図３
に示す。窒素側フォトダイオード６６の検出信号がプリ
アンプ７２で増幅され、その増幅出力を対数値に変換す
るためにプリアンプ７２の出力側に対数増幅器８４が接
続されている。対数増幅器８４の出力はＶ／Ｉ変換器９
６で電流値に変換されて出力として取り出される。リン
側ではプリアンプ７４で増幅された検出出力を対数値に
変換するためにプリアンプ７４の出力側に対数増幅器８
６，８４が並列に接続されている。対数増幅器８６の出
力もＶ／Ｉ変換器１００で電流値に変換されて出力を取
り出すことができる。窒素化合物及びリン化合物の濃度
と吸光度の関係はランベルト−ベアーの法則に従うの
で、出力信号が濃度に比例するようにフォトダイオード
６６，７０の信号が対数変換される。Details of the preprocessor 76 and the arithmetic unit 78 are shown in FIG.
Shown in. A detection signal of the nitrogen-side photodiode 66 is amplified by the preamplifier 72, and a logarithmic amplifier 84 is connected to the output side of the preamplifier 72 to convert the amplified output into a logarithmic value. The output of the logarithmic amplifier 84 is the V / I converter 9
At 6, it is converted into a current value and taken out as an output. On the phosphorus side, the logarithmic amplifier 8 is provided on the output side of the preamplifier 74 in order to convert the detection output amplified by the preamplifier 74 into a logarithmic value.
6, 84 are connected in parallel. The output of the logarithmic amplifier 86 can be converted into a current value by the V / I converter 100, and the output can be taken out. Since the relationship between the concentrations of the nitrogen compound and the phosphorus compound and the absorbance follows Lambert-Beer's law, the signals of the photodiodes 66 and 70 are logarithmically converted so that the output signal is proportional to the concentration.
【００２１】９０は窒素側の差動増幅器であり、対数増
幅器８４と８６で変換された対数値の差を増幅して窒素
側測定値としてＶ／Ｉ変換器９８から出力を取り出すこ
とができる。対数増幅器８６の対数変換値はまたホール
ド回路９２に保持され、リン側差動増幅器９４はリン側
測定値を対数増幅器８８から入力し、ホールド回路９２
に保持された窒素側測定時の対数増幅器８６の出力を入
力して両者の差を増幅し、Ｖ／Ｉ変換器１０２からリン
側測定値として出力する。Reference numeral 90 denotes a nitrogen-side differential amplifier, which can amplify the difference between the logarithmic values converted by the logarithmic amplifiers 84 and 86 and take the output from the V / I converter 98 as the nitrogen-side measured value. The logarithmic converted value of the logarithmic amplifier 86 is also held in the hold circuit 92, and the phosphorus side differential amplifier 94 inputs the phosphorus side measured value from the logarithmic amplifier 88, and the hold circuit 92.
The output of the logarithmic amplifier 86 at the time of the nitrogen side measurement held at is input, the difference between the two is amplified, and the V / I converter 102 outputs it as the phosphorus side measurement value.
【００２２】窒素化合物濃度測定の場合はハーフミラー
６２の透過光が試料光になり反射光が比較光になる。両
フォトダイオード６６，７０の同時検出信号の差が差動
増幅器９０で求められてＶ／Ｉ変換器９８から窒素化合
物濃度測定値として出力される。リン化合物濃度測定の
場合は、窒素化合物濃度測定時のフォトダイオード７０
による検出信号が比較光としてホールド回路９２に保持
されており、リン化合物測定時の測定液（試料水に発色
剤を添加したもの）によるハーフミラー６２での反射光
が試料光になり、差動増幅器９４で対数増幅器８８から
の信号とホールド回路９２に保持された信号との差が増
幅されてリン化合物濃度測定値としてＶ／Ｉ変換器１０
２から出力される。In the case of measuring the nitrogen compound concentration, the light transmitted through the half mirror 62 becomes the sample light and the reflected light becomes the comparison light. The difference between the simultaneous detection signals of the two photodiodes 66 and 70 is obtained by the differential amplifier 90 and output from the V / I converter 98 as a nitrogen compound concentration measurement value. In the case of phosphorus compound concentration measurement, the photodiode 70 at the time of nitrogen compound concentration measurement
The detection signal by the light is held in the hold circuit 92 as the comparison light, and the light reflected by the half mirror 62 by the measurement liquid (the one in which the color former is added to the sample water) at the time of measuring the phosphorus compound becomes the sample light, and the differential light is obtained. The difference between the signal from the logarithmic amplifier 88 and the signal held in the hold circuit 92 is amplified by the amplifier 94, and the V / I converter 10 is used as the phosphorus compound concentration measurement value.
It is output from 2.
【００２３】硝酸イオンとリン酸イオンを測定するとき
の吸収スペクトルを図４に示す。（Ａ）は硝酸イオンの
標準試料としてＫＮＯ3をそれぞれ５ｐｐｍ，１０ｐｐ
ｍ，２０ｐｐｍの濃度で含む標準試料水を測定したもの
である。２４０ｎｍ以下に吸収をもつので、光学フィル
タ６４により２２０ｎｍの波長の光を選択する。（Ｂ）
は標準試料としてＫＨ2ＰＯ4を３ｐｐｍ含む試料水に発
色剤としてモリブデンブルー（モリブデン酸アンモニウ
ム溶液とＬ−アスコルビン酸溶液）を添加した標準試料
水を測定したものである。リン酸イオンの測定には光学
フィルタ６８により８８０ｎｍの波長の光を選択する。FIG. 4 shows absorption spectra when measuring nitrate ion and phosphate ion. (A) KNO 3 as a standard sample of nitrate ion, 5 ppm and 10 pp, respectively
m is a standard sample water contained at a concentration of 20 ppm. Since it has absorption at 240 nm or less, light having a wavelength of 220 nm is selected by the optical filter 64. (B)
Is a standard sample water obtained by adding molybdenum blue (ammonium molybdate solution and L-ascorbic acid solution) as a color developing agent to sample water containing 3 ppm of KH 2 PO 4 as a standard sample. For the measurement of phosphate ions, light having a wavelength of 880 nm is selected by the optical filter 68.
【００２４】次に、図１，２の実施例の動作について詳
細に説明する。光酸化反応部２のヒータ３０をオンにし
て９０℃に温調する。同時に光源の電源２８もオンにし
て低圧水銀灯２６の点灯を安定化させる。試料水は初め
バルブＶ３をオフ、バルブＶ４をオンにして排水状態に
しておく。その後、バルブＶ３をオン、バルブＶ４をオ
フにし、バルブ５０をオフにして試料水を反応容器３０
へ導入し、オーバーフローした試料水はバルブＶ５を経
て排出する。その後、バルブＶ３をオフ、Ｖ４をオンに
する。次に、バルブＶ１をオンにして空気を反応容器３
０へ導入して、光酸化反応部に保持された試料水を曝気
しながら約２０分間にわたって紫外線を照射し、試料水
中の窒素酸化物とリン酸化物を同時に酸化反応させる。Next, the operation of the embodiment shown in FIGS. 1 and 2 will be described in detail. The heater 30 of the photo-oxidation reaction section 2 is turned on to control the temperature to 90 ° C. At the same time, the power source 28 of the light source is turned on to stabilize the lighting of the low-pressure mercury lamp 26. First, the sample water is drained by turning off the valve V3 and turning on the valve V4. Thereafter, the valve V3 is turned on, the valve V4 is turned off, the valve 50 is turned off, and the sample water is added to the reaction container 30.
The sample water that has been introduced into and has overflowed is discharged through the valve V5. Then, the valve V3 is turned off and the valve V4 is turned on. Next, the valve V1 is turned on to supply air to the reaction container 3
0, and while irradiating the sample water held in the photooxidation reaction section, the sample water is irradiated with ultraviolet rays for about 20 minutes to simultaneously oxidize nitrogen oxides and phosphorus oxides in the sample water.
【００２５】光酸化反応終了後、酸化反応容器３０内の
半分の試料水をバルブＶ６をオンにして測定セル５２に
導入し、測定セル５２からオーバーフローした試料水は
バルブＶ７を経て排出する。測定セル５２に保持された
試料水に光源５４から測定光を照射し、波長２２０ｎｍ
で硝酸イオン濃度を測定する。この測定の間に、酸化反
応容器３０には発色剤１８，２０を添加しておく。測定
セル５２での硝酸イオンの光吸収測定を終了した後、バ
ルブＶ８をオンにして測定セル５２内の試料水を排出す
る。このときバルブＶ６はオフになっている。測定セル
５２の試料水の排出を完了した後、バルブＶ８をオフに
し、バルブＶ６をオンにして光酸化反応部２の残り試料
水（発色している）試料セル５２に導入し、オーバーフ
ローした試料水はバルブＶ７を経て排出する。リン酸イ
オンは発色剤の８８０ｎｍの波長で測定する。測定後、
バルブＶ８をオンにして測定セル５２内の試料水を排出
する。After the photo-oxidation reaction is completed, half of the sample water in the oxidation reaction container 30 is introduced into the measuring cell 52 by turning on the valve V6, and the sample water overflowing from the measuring cell 52 is discharged through the valve V7. The sample water held in the measuring cell 52 is irradiated with the measuring light from the light source 54, and the wavelength is 220 nm.
To measure the nitrate ion concentration. During this measurement, the coloring agents 18 and 20 are added to the oxidation reaction container 30. After the light absorption measurement of nitrate ions in the measurement cell 52 is completed, the valve V8 is turned on and the sample water in the measurement cell 52 is discharged. At this time, the valve V6 is off. After the discharge of the sample water from the measurement cell 52 is completed, the valve V8 is turned off and the valve V6 is turned on to introduce the remaining sample water (coloring) in the photooxidation reaction part 2 into the sample cell 52 and overflow the sample. The water is discharged via the valve V7. The phosphate ion is measured at the wavelength of 880 nm of the color former. After measurement,
The valve V8 is turned on and the sample water in the measurement cell 52 is discharged.
【００２６】その後、バルブＶ６をオフにした状態で、
洗浄のためにバルブＶ２をオンにして酸化反応容器４へ
上水を洗浄水として供給して洗浄する。次に、バルブＶ
６をオンにし、酸化反応容器４を経て洗浄水を測定セル
５２にも供給し測定セル５２も洗浄する。このときバル
ブＶ８をオフ、Ｖ７をオンにしておく。測定セル５２の
洗浄終了後、洗浄水の供給を停止し、バルブＶ８をオン
にして測定セル５２内の洗浄水を排出する。これにより
測定系内の洗浄水は全て排出される。その後、光酸化反
応部２へ試料水を導入する工程に戻って測定を繰り返
す。Then, with the valve V6 turned off,
For cleaning, the valve V2 is turned on and clean water is supplied to the oxidation reaction container 4 as cleaning water for cleaning. Next, the valve V
6 is turned on, washing water is also supplied to the measurement cell 52 via the oxidation reaction container 4, and the measurement cell 52 is also washed. At this time, the valve V8 is turned off and V7 is turned on. After the cleaning of the measurement cell 52 is completed, the supply of cleaning water is stopped, the valve V8 is turned on, and the cleaning water in the measurement cell 52 is discharged. As a result, all washing water in the measurement system is discharged. Then, the measurement is repeated by returning to the step of introducing the sample water into the photooxidation reaction section 2.
【００２７】図１，２の実施例は酸化反応槽として光酸
化反応を行なうものを示しているが、窒素化合物とリン
化合物を同時に酸化して硝酸イオンとリン酸イオンを発
生させるものであれば、酸化反応槽は他の方式のもので
もよい。The embodiment shown in FIGS. 1 and 2 shows a photo-oxidation reaction as an oxidation reaction tank. However, as long as it produces a nitrate ion and a phosphate ion by simultaneously oxidizing a nitrogen compound and a phosphorus compound. The oxidation reaction tank may be of another type.
【００２８】図５は第２の実施例を表わす。図１，２の
実施例と比較すると、測定セル５２ａが光酸化反応部の
機能を果ねている点で異なる。そのため、測定セル５２
ａとしては、紫外線透過石英ガラスからなる窓を有し、
その窓から光酸化反応用光源と吸光測定用光源とを兼ね
るキセノンランプ５４ａの光が入射する。測定セル５２
ａには試料水と空気が供給され、洗浄用の上水も供給さ
れる。試料セル５２ａには光酸化反応時に試料水温度を
加温するために、ヒータ３０ａと温度検出器３２ａが設
けられている。リン酸イオン測定時の発色剤１８，２０
はペリスターポンプ２２を経て測定セル５２ａに供給さ
れる。FIG. 5 shows a second embodiment. Compared with the embodiment of FIGS. 1 and 2, the measurement cell 52a is different in that it functions as a photooxidation reaction portion. Therefore, the measurement cell 52
a has a window made of UV transparent quartz glass,
Light from the xenon lamp 54a, which also serves as a light source for photooxidation reaction and a light source for absorption measurement, enters from the window. Measuring cell 52
Sample water and air are supplied to a, and clean water for cleaning is also supplied. The sample cell 52a is provided with a heater 30a and a temperature detector 32a for heating the sample water temperature during the photooxidation reaction. Coloring agents for measuring phosphate ions 18, 20
Is supplied to the measuring cell 52a via the perister pump 22.
【００２９】測定セル５２ａを用いて窒素化合物濃度と
リン化合物濃度を測定する光学系は図１，２のものと同
じである。光源５４ａは光酸化反応用と吸光測定用の両
方の光源を兼ねて大きな光量を必要とするため、連続発
光のキセノンランプを用いる。図５の実施例では測定セ
ル５２ａに試料水を導入し、空気を吹き込んで曝気しな
がら２０〜３０分間にわたって光酸化反応を起こさせ
る。その後、まず窒素化合物濃度を測定するために２２
０ｎｍでの吸光度測定を行なう。その後、発色剤１８，
２０が測定セル５２ａに一定量注入され、約５分間静置
された後、８８０ｎｍでの吸光度測定によりリン化合物
濃度が測定される。The optical system for measuring the nitrogen compound concentration and the phosphorus compound concentration using the measuring cell 52a is the same as that shown in FIGS. Since the light source 54a serves as both a light source for photooxidation reaction and a light source for absorption measurement and requires a large amount of light, a continuous emission xenon lamp is used. In the embodiment of FIG. 5, sample water is introduced into the measurement cell 52a, and air is blown in to aerate it to cause a photooxidation reaction for 20 to 30 minutes. Then, first, to measure the nitrogen compound concentration, 22
Perform absorbance measurement at 0 nm. After that, the coloring agent 18,
After a fixed amount of 20 was injected into the measurement cell 52a and left standing for about 5 minutes, the phosphorus compound concentration is measured by measuring the absorbance at 880 nm.
【００３０】[0030]
【発明の効果】本発明では試料水中の窒素化合物とリン
化合物を同時に酸化して窒素化合物から硝酸イオン、リ
ン化合物からリン酸イオンを生じさせ、その試料水に測
定光を照射し、硝酸イオンとリン酸イオンを同じ装置内
で逐次測定できるようにしたので、試料水中の窒素化合
物とリン化合物を１台の装置でともに測定できるように
なる。酸化反応の際、試料水に酸素又はオゾンを含有し
たガスを吹き込みながら試料水を加温し、試料水に紫外
線を照射するようにすれば、効率よく光酸化反応を行な
わせることができ、酸化剤などの消耗剤を補充する必要
がないので、作業が用意で、長時間連続して分析するこ
とができる。光酸化反応槽と吸光測定セルを１つのセル
で共用するようにすれば、装置の構造が簡単になる。INDUSTRIAL APPLICABILITY In the present invention, nitrogen compounds and phosphorus compounds in sample water are simultaneously oxidized to generate nitrate ions from the nitrogen compounds and phosphate ions from the phosphorus compounds, and the sample water is irradiated with measuring light to generate nitrate ions. Since phosphate ions can be sequentially measured in the same device, both nitrogen compounds and phosphorus compounds in the sample water can be measured by one device. At the time of the oxidation reaction, if the sample water is heated while blowing a gas containing oxygen or ozone into the sample water and the sample water is irradiated with ultraviolet rays, the photooxidation reaction can be efficiently performed, and the oxidation can be performed. Since it is not necessary to replenish consumable agents such as agents, work is ready and continuous analysis can be performed for a long time. If the photo-oxidation reaction tank and the absorption measurement cell are shared by one cell, the structure of the device is simplified.
【図１】第１の実施例の反応部を示す構成図である。FIG. 1 is a configuration diagram showing a reaction unit of a first embodiment.
【図２】第１の実施例の測定部を示す構成図である。FIG. 2 is a configuration diagram showing a measurement unit of the first embodiment.
【図３】同実施例における光学系及び信号処理系を示す
ブロック図である。FIG. 3 is a block diagram showing an optical system and a signal processing system in the example.
【図４】硝酸イオンとリン酸イオン（発色剤添加）の吸
収スペクトルを示す図である。FIG. 4 is a diagram showing absorption spectra of nitrate ion and phosphate ion (adding a color former).
【図５】第２の実施例の主要部を示す構成図である。FIG. 5 is a configuration diagram showing a main part of a second embodiment.
２ 光酸化反応槽 ４ 酸化反応容器 ６ 供給管 ８ 取出し管 ２４ 発色剤供給管 ２６ 低圧水銀灯 ５２ 吸光測定セル ５２ａ 光酸化反応槽を兼ねる吸光測定セル ５４ キセノンフラッシュランブ ５４ａ キセノンランブ ６０ ハーフミラー ６４，６８ 光学フィルタ ６６，７０ シリコンフォトダイオード ７６ 前処理部 ７８ 演算部 2 Photooxidation reaction tank 4 Oxidation reaction container 6 Supply pipe 8 Extraction pipe 24 Coloring agent supply pipe 26 Low pressure mercury lamp 52 Absorption measurement cell 52a Absorption measurement cell that also serves as photooxidation reaction tank 54 Xenon flash lamp 54a Xenon lamp 60 Half mirror 64, 68 Optical filter 66, 70 Silicon photodiode 76 Pre-processing unit 78 Computing unit
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｇ０１Ｎ 31/00 Ｎ 33/18 Ａ 7055−2Ｊ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location G01N 31/00 N 33/18 A 7055-2J
Claims (2)
時に酸化して窒素化合物から硝酸イオン、リン化合物か
らリン酸イオンを生じさせる酸化反応槽と、 前記酸化反応槽と流路で結ばれ、前記酸化反応槽からの
試料水が供給される石英ガラス製吸光測定セルと、 前記酸化反応槽又は前記吸光測定セルへリン酸イオンと
選択的に反応する発色液を添加する発色液添加用流路
と、 前記吸光測定セルへ測定光として紫外線及び近赤外線を
照射する光源部と、 前記吸光測定セルの測定光透過光路上にあって、その透
過光を２つの光路に分波する分波手段と、 分波された一方の光路上にあって硝酸イオンに特有の吸
収波長を選択し、その波長の光を硝酸イオンの試料光と
して検出する第１の光学系と、 分波された他方の光路上にあってリン酸イオンと反応し
た発色液に特有の吸収波長を選択し、その波長の光をリ
ン酸イオンの試料光として検出する第２の光学系と、 前記第１及び第２の光学系の検出信号を基にして窒素化
合物濃度とリン化合物濃度とを算出する演算処理部とを
備えたことを特徴とする分析装置。1. An oxidation reaction tank for simultaneously oxidizing a nitrogen compound and a phosphorus compound in sample water to generate a nitrate ion from the nitrogen compound and a phosphate ion from the phosphorus compound, and a flow path connected to the oxidation reaction tank, A quartz glass absorption measurement cell to which sample water is supplied from an oxidation reaction tank, and a channel for addition of a coloring solution for adding a coloring solution that selectively reacts with phosphate ions to the oxidation reaction tank or the absorption measurement cell, A light source unit that irradiates the absorption measurement cell with ultraviolet rays and near infrared rays as measurement light; and a demultiplexing unit that is on the measurement light transmission optical path of the absorption measurement cell and that demultiplexes the transmission light into two optical paths. A first optical system that selects the absorption wavelength unique to nitrate ions on one of the demultiplexed optical paths and detects the light of that wavelength as sample light of nitrate ions, and the other optical path on the demultiplexed other optical path. In the phosphate ion Based on the detection signals of the second optical system that selects an absorption wavelength specific to the color developing liquid that has reacted with and detects light of that wavelength as sample light of phosphate ions, And an arithmetic processing unit for calculating a nitrogen compound concentration and a phosphorus compound concentration.
を有し、加熱手段を備え、供給された試料水に酸素又は
オゾンを含有したガスを吹き込む手段を備えて光酸化反
応槽を兼ねる吸光測定セルと、 前記吸光測定セルへリン酸イオンと選択的に反応する発
色剤を添加する発色剤添加用流路と、 前記吸光測定セルへ測定光として紫外線及び近赤外線を
照射する光源部と、 前記吸光測定セルの測定光透過光路上にあって、その透
過光を２つの光路に分波する分波手段と、 分波された一方の光路上にあって硝酸イオンに特有の吸
収波長を選択し、その波長の光を硝酸イオンの試料光と
して検出する第１の光学系と、 分波された他方の光路上にあってリン酸イオンと反応し
た発色液に特有の吸収波長を選択し、その波長の光をリ
ン酸イオンの試料光として検出する第２の光学系と、 前記第１及び第２の光学系の検出信号を基にして窒素化
合物濃度とリン化合物濃度とを算出する演算処理部とを
備えたことを特徴とする分析装置。2. A sample water is supplied, a quartz window for transmitting ultraviolet rays is provided, a heating means is provided, and a means for blowing a gas containing oxygen or ozone into the supplied sample water is provided, which also serves as a photooxidation reaction tank. Absorption measurement cell, a color-developing agent-adding channel for adding a color-developing agent that selectively reacts with phosphate ions to the absorption measurement cell, and a light source unit for irradiating the absorption measurement cell with ultraviolet rays and near-infrared rays as measurement light. , A demultiplexing means for demultiplexing the transmitted light into two optical paths on the measured light transmission optical path of the absorption measurement cell, and an absorption wavelength peculiar to nitrate ions on one of the demultiplexed optical paths. Select the first optical system that detects the light of that wavelength as the sample light of nitrate ions, and the absorption wavelength peculiar to the coloring liquid that has reacted with phosphate ions on the other optical path of the branched light. , The light of that wavelength is the sample light of phosphate ion A second optical system for detecting the concentration of nitrogen compound and an arithmetic processing unit for calculating the concentration of nitrogen compound and the concentration of phosphorus compound based on the detection signals of the first and second optical systems. Analysis equipment.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19796593A JP3269196B2 (en) | 1993-07-14 | 1993-07-14 | Analyzer for nitrogen compounds and phosphorus compounds in water |
| US08/272,747 US5567621A (en) | 1993-07-14 | 1994-07-11 | Method of and apparatus for analyzing nitrogen compound and phosphorus compound contained in water |
| EP94110835A EP0634646B1 (en) | 1993-07-14 | 1994-07-12 | Method of and apparatus for analyzing nitrogen compounds and phosphorus compounds contained in water |
| DE69416207T DE69416207T2 (en) | 1993-07-14 | 1994-07-12 | Method and device for the determination of phosphorus compounds and nitrogen compounds in water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19796593A JP3269196B2 (en) | 1993-07-14 | 1993-07-14 | Analyzer for nitrogen compounds and phosphorus compounds in water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0727706A true JPH0727706A (en) | 1995-01-31 |
| JP3269196B2 JP3269196B2 (en) | 2002-03-25 |
Family
ID=16383273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19796593A Expired - Fee Related JP3269196B2 (en) | 1993-07-14 | 1993-07-14 | Analyzer for nitrogen compounds and phosphorus compounds in water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3269196B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08285834A (en) * | 1995-04-13 | 1996-11-01 | Yokogawa Electric Corp | Water quality continuous measurement device |
| JP2002311011A (en) * | 2001-04-18 | 2002-10-23 | Kosu:Kk | Total nitrogen and/or total phosphor measuring device |
| JP2004093509A (en) * | 2002-09-03 | 2004-03-25 | Dkk Toa Corp | Total nitrogen and total phosphorus measuring device |
| DE102007004339A1 (en) | 2007-01-29 | 2008-08-07 | Lar Process Analysers Ag | Method and device for determining the phosphorus content of an aqueous sample |
| KR200468248Y1 (en) * | 2011-02-21 | 2013-08-02 | 주식회사 코비 | container for thermal reactor of total nitrogen analysis apparatus |
| WO2013121577A1 (en) * | 2012-02-17 | 2013-08-22 | 株式会社島津製作所 | Total nitrogen measurement apparatus |
| JP2015187595A (en) * | 2014-03-14 | 2015-10-29 | 株式会社島津製作所 | Analysis equipment |
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| CN108982388A (en) * | 2018-08-31 | 2018-12-11 | 青岛卓建海洋装备科技有限公司 | The test method of seawater total nitrogen content |
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| KR101817447B1 (en) * | 2016-12-28 | 2018-01-10 | 주식회사 휴비스워터 | Method and device for analyzing low concentration boron using online photometer |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08285834A (en) * | 1995-04-13 | 1996-11-01 | Yokogawa Electric Corp | Water quality continuous measurement device |
| JP2002311011A (en) * | 2001-04-18 | 2002-10-23 | Kosu:Kk | Total nitrogen and/or total phosphor measuring device |
| JP2004093509A (en) * | 2002-09-03 | 2004-03-25 | Dkk Toa Corp | Total nitrogen and total phosphorus measuring device |
| DE102007004339A1 (en) | 2007-01-29 | 2008-08-07 | Lar Process Analysers Ag | Method and device for determining the phosphorus content of an aqueous sample |
| US7993930B2 (en) | 2007-01-29 | 2011-08-09 | Lar Process Analysers Ag | Method and device for determining the phosphorus content of an aqueous sample |
| KR200468248Y1 (en) * | 2011-02-21 | 2013-08-02 | 주식회사 코비 | container for thermal reactor of total nitrogen analysis apparatus |
| WO2013121577A1 (en) * | 2012-02-17 | 2013-08-22 | 株式会社島津製作所 | Total nitrogen measurement apparatus |
| JPWO2013121577A1 (en) * | 2012-02-17 | 2015-05-11 | 株式会社島津製作所 | Total nitrogen measuring device |
| US9588050B2 (en) | 2012-02-17 | 2017-03-07 | Shimadzu Corporation | Total nitrogen measurement apparatus |
| JP2015187595A (en) * | 2014-03-14 | 2015-10-29 | 株式会社島津製作所 | Analysis equipment |
| WO2016163024A1 (en) * | 2015-04-10 | 2016-10-13 | 株式会社島津製作所 | Water quality analysis device |
| JPWO2016163024A1 (en) * | 2015-04-10 | 2017-11-09 | 株式会社島津製作所 | Water quality analyzer |
| US10458968B2 (en) | 2015-04-10 | 2019-10-29 | Shimadzu Corporation | Water quality analysis device |
| CN108982388A (en) * | 2018-08-31 | 2018-12-11 | 青岛卓建海洋装备科技有限公司 | The test method of seawater total nitrogen content |
| CN109668848A (en) * | 2019-02-27 | 2019-04-23 | 苏州奥特福环境科技有限公司 | A kind of ozone concentration on-line detecting system and method |
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