JP2000298126A - Water quality analyzer - Google Patents
Water quality analyzerInfo
- Publication number
- JP2000298126A JP2000298126A JP11105818A JP10581899A JP2000298126A JP 2000298126 A JP2000298126 A JP 2000298126A JP 11105818 A JP11105818 A JP 11105818A JP 10581899 A JP10581899 A JP 10581899A JP 2000298126 A JP2000298126 A JP 2000298126A
- Authority
- JP
- Japan
- Prior art keywords
- sample
- oxidation catalyst
- tube
- analyzer
- vaporizing
- 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 Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Sampling And Sample Adjustment (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、池や川などの水質
を測定する水質分析計に関し、例えば生活用水や半導体
用水などのサンプルを気化・酸化してＮＯを含む気体を
発生させ、窒素含有率を連続的に測定する燃焼式水質分
析計に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water quality analyzer for measuring the quality of water in ponds and rivers. For example, a gas such as domestic water or semiconductor water is vaporized and oxidized to generate a gas containing NO and contain nitrogen. The present invention relates to a combustion type water quality analyzer for continuously measuring the rate.
【０００２】[0002]
【従来の技術】燃焼式水質分析計では有機物，Ｎ，Ｐ，
Ｓ，Ｃ，Ｂｒ，Ｎａ，Ｋ等が含まれるサンプルを気化・
酸化させ、その気体に含まれるたとえばＮを連続して測
定している。従来の燃焼式水質分析計では、サンプルの
気化・酸化を図４に示すような装置により行う。図４に
おいて、２１は石英やガラスなどからなる反応管であ
り、注入層２６、燃焼層２７及び注出層２８を備えてい
る。５は液体状のサンプルＳと空気あるいは不活性ガス
からなるキャリアガスＫとを反応管２１内へ注入するテ
フロン製の注入管であり、注入管５の上流側は分岐して
いて一方からはサンプルＳを、他方からはキャリアガス
Ｋを注入することができるようになっている。2. Description of the Related Art In a combustion type water quality analyzer, organic matter, N, P,
Evaporating a sample containing S, C, Br, Na, K, etc.
Oxidation is performed and, for example, N contained in the gas is continuously measured. In a conventional combustion type water quality analyzer, vaporization and oxidation of a sample are performed by an apparatus as shown in FIG. In FIG. 4, reference numeral 21 denotes a reaction tube made of quartz, glass, or the like, which includes an injection layer 26, a combustion layer 27, and a discharge layer 28. Reference numeral 5 denotes a Teflon injection tube for injecting a liquid sample S and a carrier gas K composed of air or an inert gas into the reaction tube 21. The upstream side of the injection tube 5 is branched and the sample is sampled from one side. S and the carrier gas K can be injected from the other side.
【０００３】注入管５と反応管２１は中央縦方向に注入
管５が挿通できる穴が設けられたＴ字形でステンレス製
の蓋部材２３により連通連結される。すなわち蓋部材２
３の下部が反応管２１の入口部３０に嵌め込まれ、シー
ル部材８，８’により蓋部材２３の下部外面と反応管２
１の上部内面の間が密閉されると共に、蓋部材２３と反
応管２１が固定される。また蓋部材２３の上部中央には
注入管５に外嵌された継手２４の雄ねじ部２４ａが螺着
できるための雌ねじ部２３ａが設けられており、継手２
４の雄ねじ部２４ａを蓋部材２３の雌ねじ２３ａに螺着
することで蓋部材２３と注入管５が固定される。更に注
入管５の下端部は蓋部材２３の下端部と同一面上となる
ように構成されている。The injection tube 5 and the reaction tube 21 are communicatively connected to each other by a T-shaped stainless steel lid member 23 provided with a hole through which the injection tube 5 can be inserted in the central longitudinal direction. That is, the lid member 2
3 is fitted into the inlet 30 of the reaction tube 21, and the lower outer surface of the lid member 23 and the reaction tube 2 are sealed by the sealing members 8 and 8 ′.
The space between the inner surfaces of the upper part 1 is sealed, and the lid member 23 and the reaction tube 21 are fixed. In the center of the upper part of the lid member 23, there is provided a female screw portion 23a into which the male screw portion 24a of the joint 24 externally fitted to the injection pipe 5 can be screwed.
By screwing the male screw portion 24 a of the fourth member 24 into the female screw 23 a of the lid member 23, the lid member 23 and the injection pipe 5 are fixed. Further, the lower end of the injection tube 5 is configured to be flush with the lower end of the lid member 23.
【０００４】前記反応管２１の燃焼層２７はＰｔ−Ａｌ
2 Ｏ3 又はＰｄ−Ａｌ2 Ｏ3 からなる酸化触媒２とネッ
ト１１，１１から構成され、注出層２８は注出管２９に
連通している。また２５は反応管２１の入口部３０を冷
却するための冷却用ファンであり、２２は反応管２１を
加熱するための電気炉である。The combustion layer 27 of the reaction tube 21 is made of Pt-Al
The oxidation catalyst 2 is composed of 2 O 3 or Pd—Al 2 O 3 and the nets 11, 11, and the pouring layer 28 communicates with the pouring pipe 29. Reference numeral 25 denotes a cooling fan for cooling the inlet 30 of the reaction tube 21, and reference numeral 22 denotes an electric furnace for heating the reaction tube 21.
【０００５】次に上記サンプル気化・酸化装置の動作に
ついて説明する。まず、電気炉２２によりあらかじめ反
応管２１内を熱しておくと共に冷却用ファン２５も作動
させておく。この状態で、所定量とされたサンプルＳを
注入管５へ流入させると同時にキャリアガスＫも注入管
５内へ流入させる。サンプルＳは重力あるいは加圧器等
により注入管５の下に設置された反応管２１内へ注入さ
れる。Next, the operation of the sample vaporizing / oxidizing apparatus will be described. First, the inside of the reaction tube 21 is heated in advance by the electric furnace 22 and the cooling fan 25 is also operated. In this state, a predetermined amount of the sample S is caused to flow into the injection pipe 5, and at the same time, the carrier gas K is also caused to flow into the injection pipe 5. The sample S is injected into the reaction tube 21 installed below the injection tube 5 by gravity or a pressurizer.
【０００６】反応管２１内へ注入されたサンプルＳは、
注入層２６及び燃焼層２７で気化するが、その大半は燃
焼層２７内にある酸化触媒２の熱により気化される。こ
のように気化したサンプルＳは燃焼層２７内の酸化触媒
２によって酸化される。つまり燃焼層２７の酸化触媒２
によってサンプルＳはほぼ同時に気化及び酸化する。The sample S injected into the reaction tube 21 is
The gas is vaporized in the injection layer 26 and the combustion layer 27, but most of the gas is vaporized by the heat of the oxidation catalyst 2 in the combustion layer 27. The sample S thus vaporized is oxidized by the oxidation catalyst 2 in the combustion layer 27. That is, the oxidation catalyst 2 of the combustion layer 27
As a result, the sample S is vaporized and oxidized almost simultaneously.
【０００７】この後、サンプルＳはキャリアガスＫによ
り注出層２８、注出管２９を経て分析計（図示せず）へ
と導かれる。After that, the sample S is guided by the carrier gas K to the analyzer (not shown) through the pouring layer 28 and the pouring pipe 29.
【０００８】ここでサンプルＳの気化及び酸化時の前記
サンプル気化・酸化装置における反応管２１の温度分布
について説明すると、シール部材８等が劣化するのを防
止するため冷却用ファン２５により蓋部材２３は３０°
Ｃ、入口部３０は３０〜３５°Ｃ程度に保たれており、
このためその下の注入層２６の上部は７０°Ｃ程度であ
り、注入層２６の下部から燃焼層２７、注出層２８は８
００〜８５０°Ｃ程度となっている。Here, the temperature distribution of the reaction tube 21 in the sample vaporizing / oxidizing apparatus at the time of vaporizing and oxidizing the sample S will be described. Is 30 °
C, the inlet 30 is maintained at about 30 to 35 ° C.
For this reason, the upper part of the injection layer 26 below is about 70 ° C., and the combustion layer 27 and the discharge layer 28
It is about 00 to 850 ° C.
【０００９】[0009]
【発明が解決しようとする課題】しかし、前記装置で
は、電気炉２２により間接的に熱せられる反応管２１内
の注入層２６及び燃焼層２７を分析に必要な温度である
８５０°Ｃにまで上げるための暖機時間が２０分もかか
り、また８５０°Ｃ程度の温度におかれるため酸化触媒
の劣化が早く、更に、燃焼層２７内の酸化触媒２が破損
した場合などの交換時には蓋部材２３及び注入管５を外
し、そこから酸化触媒２を取り出すため反応管２１を冷
却する必要があるが、その冷却の所要時間も２０分と長
い。また、前述したように反応管２１内の注入層２６の
上部が低温なため、気化していたサンプルＳの一部が冷
やされて、注入層２６の上部周辺の反応管２１の内側な
どに結露し、サンプルＳの全てがほぼ同時には分析計へ
と流れないことにより、測定誤差が生じる。However, in the above-mentioned apparatus, the temperature of the injection layer 26 and the combustion layer 27 in the reaction tube 21 heated indirectly by the electric furnace 22 is raised to 850 ° C., which is the temperature required for analysis. It takes as long as 20 minutes for warming up, and the temperature of about 850 ° C. causes rapid deterioration of the oxidation catalyst. Further, when the oxidation catalyst 2 in the combustion layer 27 is damaged, the lid member 23 is replaced. In addition, it is necessary to cool the reaction tube 21 in order to remove the injection tube 5 and take out the oxidation catalyst 2 therefrom, but the cooling time is as long as 20 minutes. Further, as described above, since the temperature of the upper part of the injection layer 26 in the reaction tube 21 is low, a part of the vaporized sample S is cooled and the dew forms on the inside of the reaction tube 21 around the upper part of the injection layer 26. However, a measurement error occurs because not all of the sample S flows to the analyzer almost at the same time.
【００１０】この発明は、上述の事柄に留意してなされ
たもので、その目的は、前記サンプル気化・酸化装置を
改良することにより暖機及び冷却に要する時間を短縮
し、また酸化触媒を高温下におかないことで劣化を遅ら
せ、更に気化したサンプルをもれなく分析計へと供給で
きる構造からなるサンプル気化・酸化装置を有する水質
分析計を提供することである。The present invention has been made in consideration of the above-mentioned matters, and has as its object to reduce the time required for warm-up and cooling by improving the sample vaporizing / oxidizing apparatus, and to reduce the time required for the oxidation catalyst to a high temperature. An object of the present invention is to provide a water quality analyzer having a sample vaporizing / oxidizing device having a structure capable of delaying deterioration by not being placed below and supplying a vaporized sample to the analyzer without exception.
【００１１】[0011]
【課題を解決するための手段】上記目的を達成するため
に、本発明が講じた技術的手段は次の通りである。請求
項１に記載の発明は、流体流路の上流側に導電性で比熱
が小さい材料よりなる気化管を、下流側に酸化触媒を設
け、さらに前記酸化触媒を含む下流側を加熱するヒータ
を設け、電流を流して昇温した前記気化管に液体サンプ
ルを送って気化し、次いで気化したガスをキャリアガス
と共に前記下流側に送って酸化した後、その酸化したガ
スを前記キャリアガスと共に検出器へ送って前記液体サ
ンプル中の成分を分析するように構成した水質分析計で
ある。The technical means adopted by the present invention to achieve the above object are as follows. The invention according to claim 1 is to provide a vaporizing tube made of a conductive material having a small specific heat on the upstream side of the fluid flow path, an oxidation catalyst on the downstream side, and a heater for heating the downstream side including the oxidation catalyst. The liquid sample is sent to the vaporization tube heated by applying an electric current, and vaporized.Then, the vaporized gas is sent to the downstream side together with the carrier gas to be oxidized, and then the oxidized gas is sent to the detector together with the carrier gas. A water quality analyzer configured to be sent to a liquid sample analyzer to analyze components in the liquid sample.
【００１２】請求項２に記載の発明では、前記導電性で
比熱が小さい材料が黒鉛であり、さらに前記気化管に電
流を流すための電極が気化管のホルダーを兼ねている。According to the second aspect of the present invention, the conductive material having a small specific heat is graphite, and an electrode for supplying a current to the vaporization tube also serves as a holder for the vaporization tube.
【００１３】請求項３に記載の発明では、前記成分が窒
素又は炭素である。According to the third aspect of the present invention, the component is nitrogen or carbon.
【００１４】上記構成により、暖機及び冷却に要する時
間を短縮し、また酸化触媒を高温下におかないことで劣
化を遅らせ、更に、サンプルをもれなくほぼ同時に分析
計へと供給できる構造からなるサンプル気化・酸化装置
を有する水質分析計を提供できる。According to the above configuration, the time required for warm-up and cooling can be reduced, the deterioration can be delayed by keeping the oxidation catalyst at a high temperature, and the sample can be supplied to the analyzer almost at the same time. A water quality analyzer having a vaporization / oxidation device can be provided.
【００１５】[0015]
【発明の実施の形態】以下、この発明の詳細を、図を参
照しながら説明する。図１は、この発明の一実施形態に
係る水質分析計の構成を示す概略図である。同図におい
て、１２はサンプルＳを貯留しておくサンプルタンクで
あり、サンプルタンク１２からサンプル気化・酸化装置
ＤまでのサンプルＳの流路ＳＬには、上流側から順にフ
ィルタ１３と弁１４が設けられており、また同流路ＳＬ
において、図示していないが、サンプルＳの計量も行わ
れている。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below with reference to the drawings. FIG. 1 is a schematic diagram showing a configuration of a water quality analyzer according to one embodiment of the present invention. In the figure, reference numeral 12 denotes a sample tank for storing a sample S, and a filter 13 and a valve 14 are provided in the flow path SL of the sample S from the sample tank 12 to the sample vaporizing / oxidizing apparatus D in order from the upstream side. And the same flow path SL
Although not shown, the sample S is also weighed.
【００１６】一方、空気や不活性ガス（例えばＮ2 ，Ａ
ｒなど）をキャリアガスＫとして導入口１５より送り込
み、導入口１５からサンプル気化・酸化装置Ｄまでのキ
ャリアガスＫの流路ＫＬには、上流側から順にフィルタ
１６、弁１７、ポンプ１８、バッファタンク１９が設け
られている。On the other hand, air or an inert gas (for example, N 2 , A
r) as a carrier gas K from the inlet 15, and a filter 16, a valve 17, a pump 18, and a buffer are provided in order from the upstream side in the flow path KL of the carrier gas K from the inlet 15 to the sample vaporization / oxidation apparatus D A tank 19 is provided.
【００１７】２０は除湿用２段冷却システムで一次冷却
（室温冷却）用のドレンポット３１と二次冷却用の電子
冷却器３２から構成されている。また、ドレンポット３
１と電子冷却器３２の間には流量計３３が設けられてい
る。Reference numeral 20 denotes a two-stage cooling system for dehumidification, comprising a drain pot 31 for primary cooling (room temperature cooling) and an electronic cooler 32 for secondary cooling. Also, drain pot 3
A flow meter 33 is provided between 1 and the electronic cooler 32.
【００１８】３４はＣＯ2 分析計で、サンプルＳ中の有
機物による影響を考慮して化学発光式ＮＯ分析計３５の
上流に設けられている。また、３５はＮＯ濃度を測定す
る化学発光式ＮＯ分析計である。Numeral 34 denotes a CO 2 analyzer, which is provided upstream of the chemiluminescent NO analyzer 35 in consideration of the influence of the organic matter in the sample S. Reference numeral 35 denotes a chemiluminescent NO analyzer for measuring NO concentration.
【００１９】サンプル気化・酸化装置Ｄ内で気化及び酸
化されたサンプルＳは、ドレンポット３１、流量計３
３、電子冷却器３２、ＣＯ2 分析計３４及び化学発光式
ＮＯ分析計３５を順に経て排出口３６に至る。The sample S vaporized and oxidized in the sample vaporizing / oxidizing apparatus D is supplied to a drain pot 31 and a flow meter 3.
3, leads to the electronic cooling device 32, CO 2 analyzer 34 and the discharge port 36 via the chemiluminescent NO analyzer 35 in order.
【００２０】図２は前記水質分析計におけるサンプル気
化・酸化装置Ｄの概略的な構成を示す図である。４はス
テンレス製で角筒状のブロックであり、そのほぼ中心を
通る長手方向には流体流路を形成する貫通孔６が設けら
れ、その中をキャリアガスＫが図中、左から右の方向に
流れる。前記ブロック４の上流側には、気化管１を挿脱
するための穴Ｈ及びこの穴Ｈを閉塞するための蓋９が設
けられ、さらに蓋９には注入管５からサンプルＳを注入
するための注入孔１０が設けられており、注入孔１０の
上部に注入管５が嵌め込まれ、注入管５及び注入孔１０
の上部はＯリングなどのシール部材８によって固定及び
密閉される。FIG. 2 is a diagram showing a schematic configuration of a sample vaporizing / oxidizing apparatus D in the water quality analyzer. Reference numeral 4 denotes a rectangular tube-shaped block made of stainless steel, and a through-hole 6 for forming a fluid flow path is provided in a longitudinal direction substantially passing through the center of the block, in which a carrier gas K flows from left to right in the figure. Flows to A hole H for inserting and removing the vaporizing tube 1 and a lid 9 for closing the hole H are provided on the upstream side of the block 4, and the lid 9 is used for injecting the sample S from the injection tube 5. The injection tube 5 is fitted over the injection hole 10, and the injection tube 5 and the injection hole 10 are provided.
Is fixed and sealed by a seal member 8 such as an O-ring.
【００２１】また注入管５の下部には、両端部３９，３
９’がそれぞれ貫通孔６と連通し上部のほぼ中央に注入
孔１０と連通する注入口３８が設けられた円筒状の気化
管１が設けられている。図３に示すように気化管１はほ
ぼＹ字形で黄銅製のホルダー７及び７’によって保持さ
れる。尚、４２，４２’はホルダー７，７’の脚部分４
１，４１’を挿入するための穴である。気化管１の材料
には導電性で比熱の小さい材料、例えば黒鉛などが使用
される。更に前記ホルダー７，７’は端部４１，４１’
においてそれぞれ大電流（数十Ａ）を流すことが可能な
電源４０の＋極と−極からの導線に接続され、スイッチ
ＳＷをＯＮにして通電すると、電流は導線を通りホルダ
ー７，気化管１，ホルダー７’と流れ、電源４０におい
て任意の電流量を設定すれば気化管１はそれに対応した
温度となる。このように前記ホルダー７，７’は、前記
気化管１の支持と、気化管１に通電するための電極とを
兼用している。また、ホルダー７，７’の脚部分４１，
４１’の端部は電源４０からの導線と接続するために、
ホルダー穴４２，４２’からブロック４の外部へ露出し
ている。At the lower part of the injection tube 5, both end portions 39, 3
The cylindrical vaporization tube 1 is provided with an injection port 9, each of which communicates with the injection hole 10 at the center of the upper portion of the cylinder 9 ′. As shown in FIG. 3, the vaporization tube 1 is substantially Y-shaped and held by brass holders 7 and 7 '. 42, 42 'are leg portions 4 of holders 7, 7'.
This is a hole for inserting 1, 41 '. As the material of the vaporization tube 1, a conductive material having a small specific heat, such as graphite, is used. Further, the holders 7, 7 'are end portions 41, 41'.
Are connected to conductors from the positive and negative poles of the power supply 40 capable of flowing a large current (several tens of amperes) respectively. , The holder 7 ′, and if an arbitrary amount of current is set in the power supply 40, the temperature of the vaporization tube 1 becomes corresponding to that. As described above, the holders 7 and 7 ′ serve both as a support for the vaporization tube 1 and as an electrode for supplying electricity to the vaporization tube 1. Also, the leg portions 41 of the holders 7, 7 ',
The end of 41 ′ is to be connected to the conductor from the power source 40,
It is exposed to the outside of the block 4 from the holder holes 42, 42 '.
【００２２】また、気化管１とホルダー７，７’におい
て、両者が接触していない部分には、その周辺（ブロッ
ク４及び蓋９）への断熱及び絶縁の目的で例えば石英ウ
ールやガラスウールなど３７が設けられている。The portions of the vaporizing tube 1 and the holders 7 and 7 ′ that are not in contact with each other are, for example, quartz wool or glass wool for the purpose of heat insulation and insulation around the periphery (block 4 and lid 9). 37 are provided.
【００２３】前記ブロック体４及び貫通孔６の下流側に
はヒータ３及びＰｔ−Ａｌ2 Ｏ3 又はＰｄ−Ａｌ2 Ｏ3
よりなる酸化触媒２が設けられ、貫通孔６内に設けられ
た前記酸化触媒２はネット１１によって保持されてい
る。A heater 3 and Pt-Al 2 O 3 or Pd-Al 2 O 3 are provided downstream of the block 4 and the through hole 6.
An oxidation catalyst 2 is provided, and the oxidation catalyst 2 provided in the through hole 6 is held by a net 11.
【００２４】次に前記水質分析計の動作について説明す
る。まず、準備段階として、分析に用いる系内の洗浄を
した後、図２に示すサンプル気化・酸化装置Ｄ内のヒー
タ３を２００°Ｃにまで昇温しておく。Next, the operation of the water quality analyzer will be described. First, as a preparatory step, after cleaning the inside of the system used for analysis, the heater 3 in the sample vaporizing / oxidizing apparatus D shown in FIG.
【００２５】次に、サンプルタンク１２内のサンプルＳ
を流路ＳＬに通し、所定量（数十μＬ）だけサンプル気
化・酸化装置Ｄに注入し、気化及び酸化した後キャリア
ガスＫと共に前記除湿用２段冷却システムへと流す。こ
こで前記サンプル気化・酸化装置Ｄにおける動作を図２
を用いて詳述する。Next, the sample S in the sample tank 12 is
Is injected into the sample vaporizing / oxidizing apparatus D by a predetermined amount (several tens of μL), and after vaporizing and oxidizing, flows into the two-stage cooling system for dehumidification together with the carrier gas K. Here, the operation of the sample vaporizing / oxidizing apparatus D is shown in FIG.
It will be described in detail with reference to FIG.
【００２６】流路ＳＬを経て所定量とされた液体状のサ
ンプルＳは注入管５内へ流入し、注入孔１０及び注入口
３８を経て常温のままの気化管１内へと落下する。この
とき、サンプルＳはまだ液体状態を保っているが、微量
（数十μＬ）であり、また気化管１はほぼ水平に設置さ
れているため、サンプルＳが気化管１の両端３９，３
９’から流出することはない。A predetermined amount of the liquid sample S flows into the injection pipe 5 through the flow path SL, and falls into the vaporization pipe 1 at room temperature through the injection hole 10 and the injection port 38. At this time, although the sample S is still in a liquid state, it is in a very small amount (several tens μL), and since the vaporization tube 1 is installed almost horizontally, the sample S is supplied to both ends 39, 3 of the vaporization tube 1.
It does not flow out of 9 '.
【００２７】サンプルＳが気化管１内に落下した後、電
源４０から気化管１へ通電し、約１０秒間、気化管１内
を１５０〜２００°Ｃとする。更にその後の１０秒間は
気化管１へ流す電流を大にし気化管１内を６００〜８０
０°Ｃとする。このように昇温過程を２段階に分けたの
は、サンプルＳを早くかつ確実に気化させるためであ
る。After the sample S has fallen into the vaporization tube 1, power is supplied from the power supply 40 to the vaporization tube 1, and the inside of the vaporization tube 1 is kept at 150 to 200 ° C. for about 10 seconds. Further, for the next 10 seconds, the current flowing through the vaporization tube 1 is increased to increase the current within the vaporization tube 1 by 600 to 80.
0 ° C. The reason for dividing the heating process into two stages is to vaporize the sample S quickly and surely.
【００２８】そして、気化したサンプルＳはキャリアガ
スＫを流すことで、サンプル気化・酸化装置Ｄの下流側
へと運ばれる。下流側にはヒータ３により２００°Ｃ位
にまで昇温した酸化触媒２があり、この酸化触媒２によ
って気化したしたサンプルＳ中のＮはＮＯへと変換され
ると同時に、気化管１が炭素である黒鉛からできている
ために発生するＣＯなどもＣＯ2 へと変換される。The vaporized sample S is carried to the downstream side of the sample vaporizing / oxidizing apparatus D by flowing the carrier gas K. On the downstream side, there is an oxidation catalyst 2 whose temperature has been raised to about 200 ° C. by a heater 3. The N in the sample S vaporized by the oxidation catalyst 2 is converted into NO, and at the same time, the vaporization tube 1 CO, which is generated from graphite, is also converted to CO 2 .
【００２９】また前記キャリアガスＫは、図１に示す導
入口１５から流路ＫＬを通し、サンプル気化・酸化装置
Ｄ，ドレンポット３１，流量計３３，電子冷却器３２，
ＣＯ 2 分析計３４，化学発光式ＮＯ分析計３５を順に経
て排出口３６まで流れるので、サンプルＳをサンプル気
化・酸化装置Ｄから排出口３６まで運搬できるのは勿論
だが、高温になったサンプルＳを冷却し、水質分析計の
損傷を防止する役目も果たす。Further, the carrier gas K is supplied as shown in FIG.
Sample vaporization / oxidation device through the flow path KL from the inlet 15
D, drain pot 31, flow meter 33, electronic cooler 32,
CO TwoAn analyzer 34 and a chemiluminescent NO analyzer 35 are sequentially passed.
Flow to the outlet 36, so that the sample S
Of course, it can be transported from the oxidation / oxidation unit D to the outlet 36.
However, the high temperature sample S is cooled and the water quality analyzer
It also serves to prevent damage.
【００３０】気化及び酸化されたサンプルＳは除湿用２
段冷却システム２０へと運ばれ、ＣＯ2 分析計３４及び
化学発光式ＮＯ分析計３５により測定されたあと排出口
３６へと至る。化学発光式ＮＯ分析計３５はオゾンとサ
ンプルガスＳ中のＮＯとを反応発光させ、それによりＮ
Ｏ濃度を検出し、それに基づいてＮの量を測定するもの
であるが、サンプルＳ中の有機物や気化管１中の炭素か
ら変換されたＣＯ2 による影響が考えられるため、化学
発光式ＮＯ分析計３５の上流に設けられているＣＯ2 分
析計３４を補正手段として用い、ＣＯ2 分析計３４での
ＣＯ2 の検出結果によりＮＯの分析結果は補正される。
また、ＣＯ2 分析計３４を単独でＣＯ2の分析に使用す
ることでＣの量が測定できるのは勿論のこと、ＣＯ2 分
析計３４と化学発光式ＮＯ分析計３５を両方用いること
でＮとＣの計測を同時に行うことも可能である。The vaporized and oxidized sample S is used for dehumidification 2
It is conveyed to the stage cooling system 20 and reaches the outlet 36 after being measured by the CO 2 analyzer 34 and the chemiluminescent NO analyzer 35. The chemiluminescence NO analyzer 35 reacts and emits light between ozone and NO in the sample gas S, and
The O concentration is detected, and the amount of N is measured based on the O concentration. However, the influence of the organic matter in the sample S or CO 2 converted from the carbon in the vaporization tube 1 is considered, so that the chemiluminescence NO analysis is performed. using CO 2 analyzer 34 provided upstream of the meter 35 as a correction means, analysis of NO by the detection result of the CO 2 in the CO 2 analyzer 34 is corrected.
In addition, by using the CO 2 analyzer 34 alone for CO 2 analysis, the amount of C can be measured, and by using both the CO 2 analyzer 34 and the chemiluminescent NO analyzer 35, And C can be measured at the same time.
【００３１】また、前記気化管１を直接加熱するため電
力を効率良く熱に変換でき、また気化管１には比熱の小
さな黒鉛が用いられているため、熱し易く冷め易く、暖
機時間が殆ど不要で、また劣化した気化管１の取り換え
は前記蓋９を外して行うが、冷却時間も短いため取り換
えを早く行うことができる。更に従来はサンプルの気化
と酸化を同じポイントで行っていたのに対し、本発明で
は気化する場所と酸化する場所を分けたことから酸化す
る場所を気化する場所に必要なほど高温にしなくて済む
ので電力の消費を更に節減でき、また酸化する場所にあ
る酸化触媒２の劣化が遅くなる。更に劣化した酸化触媒
２の取り換えは前記ブロック４の下流側から行われる
が、酸化触媒２の温度が低温であることから冷却時間が
短くなり、酸化触媒２の取り換えを早く行うことができ
る。Further, since the vaporizing tube 1 is directly heated, electric power can be efficiently converted into heat. Further, since the vaporizing tube 1 is made of graphite having a small specific heat, it is easy to heat and cool, and the warm-up time is almost completely reduced. Replacement of the unnecessary and deteriorated vaporization tube 1 is performed with the lid 9 removed, but since the cooling time is short, the replacement can be performed quickly. Further, in contrast to the conventional method of vaporizing and oxidizing a sample at the same point, in the present invention, a place to be vaporized and a place to be oxidized are separated, so that the place to be oxidized does not have to be heated to a temperature necessary for the place to be vaporized. Therefore, the power consumption can be further reduced, and the deterioration of the oxidation catalyst 2 at the oxidizing place is delayed. Further, the replacement of the deteriorated oxidation catalyst 2 is performed from the downstream side of the block 4. However, since the temperature of the oxidation catalyst 2 is low, the cooling time is shortened, and the replacement of the oxidation catalyst 2 can be performed quickly.
【００３２】ここで、ＮＯ濃度の測定時間に触れると、
ＮＯ濃度の１回の測定所要時間は、系内洗浄並びにサン
プルＳを所定量とするための計量に約１２０秒要し、気
化管１内へのサンプルＳ注入後の化学発光応答時間の６
０秒を合わせて約３分である。よって、例えば１時間測
定を行った場合、２０回の測定ができ、その結果は２０
回の結果の平均を求めることで得られる。Here, when touching the measurement time of the NO concentration,
The time required for one measurement of the NO concentration is about 120 seconds for cleaning the inside of the system and weighing the sample S to a predetermined amount, and is 6 times the chemiluminescence response time after the injection of the sample S into the vaporization tube 1.
It takes about 3 minutes including 0 seconds. Therefore, for example, when measuring for 1 hour, 20 measurements can be performed, and the result is 20 times.
It is obtained by averaging the results of the rounds.
【００３３】また、上記実施例では、気化管１全体が熱
せられ気化管１内に極端に低温な場所が無いため気化さ
れたサンプルＳが冷えて結露したり付着することなどが
なく、そのままもれなくほぼ同時に気化管１内から排出
される。Further, in the above embodiment, since the entire vaporizing tube 1 is heated and there is no extremely low temperature place in the vaporizing tube 1, the vaporized sample S does not cool down and is not condensed or adhered. Almost simultaneously, the gas is discharged from the vaporization tube 1.
【００３４】上記実施例では、サンプル気化・酸化装置
Ｄ内のブロック４を角筒状としたが円筒状でも問題な
く、また貫通孔６と気化管１内部の形状は、両者の断面
が共通していれば円形でも多角形でもよい。また、サン
プル気化・酸化装置Ｄ内のヒータ３の設定温度を２００
°Ｃとしたが、必要に応じて６００°Ｃなどの高温に設
定しても勿論良い。In the above-described embodiment, the block 4 in the sample vaporizing / oxidizing apparatus D has a rectangular cylindrical shape. However, it is not a problem if the block 4 is cylindrical, and the shapes of the through hole 6 and the vaporizing tube 1 have the same cross section. If so, it may be circular or polygonal. Further, the set temperature of the heater 3 in the sample vaporizing / oxidizing apparatus D is set to 200.
Although it was set to ° C, it is needless to say that a high temperature such as 600 ° C may be set as needed.
【００３５】[0035]
【発明の効果】以上説明したように、本発明では、流体
流路の上流側に導電性で比熱が小さい材料よりなる気化
管を、下流側に酸化触媒を設け、さらに前記酸化触媒を
含む下流側を加熱するヒータを設け、電流を流して昇温
した前記気化管に液体サンプルを送って気化し、次いで
気化したガスをキャリアガスと共に前記下流側に送って
酸化した後、その酸化したガスを前記キャリアガスと共
に検出器へ送って前記液体サンプル中の成分を分析する
ように構成したことにより、暖機及び冷却に要する時間
を短縮し、また酸化触媒を高温下におかないことで劣化
を遅らせ、更にサンプルをもれなくほぼ同時に分析計へ
と供給できる構造からなるサンプル気化・酸化装置を有
する水質分析計を提供できる。As described above, according to the present invention, a vaporization tube made of a conductive material having a small specific heat is provided on the upstream side of the fluid flow path, an oxidation catalyst is provided on the downstream side, and the downstream side including the oxidation catalyst is further provided. A heater for heating the side is provided, a liquid sample is sent to the vaporization tube heated by flowing an electric current, and the liquid sample is vaporized.Then, the vaporized gas is sent to the downstream side along with the carrier gas to be oxidized, and then the oxidized gas is discharged. By sending components to the detector together with the carrier gas to analyze the components in the liquid sample, the time required for warming up and cooling is reduced, and the degradation is delayed by keeping the oxidation catalyst at a high temperature. Further, it is possible to provide a water quality analyzer having a sample vaporizing / oxidizing device having a structure capable of supplying a sample to the analyzer almost simultaneously without any leakage.
【図１】本発明の一実施形態に係る水質分析計の構成を
概略的に示す図である。FIG. 1 is a diagram schematically showing a configuration of a water quality analyzer according to one embodiment of the present invention.
【図２】上記水質分析計におけるサンプル気化・酸化装
置の概略的な構成を示す図である。FIG. 2 is a diagram showing a schematic configuration of a sample vaporization / oxidation device in the water quality analyzer.
【図３】上記サンプル気化・酸化装置における気化管及
びホルダーの斜視図である。FIG. 3 is a perspective view of a vaporizing tube and a holder in the sample vaporizing / oxidizing apparatus.
【図４】サンプル気化・酸化装置の従来例を示す概略的
構成図である。FIG. 4 is a schematic configuration diagram showing a conventional example of a sample vaporizing / oxidizing apparatus.
１…気化管、２…酸化触媒、３…ヒータ、Ｓ…サンプ
ル、Ｋ…キャリアガス。DESCRIPTION OF SYMBOLS 1 ... Vaporization pipe, 2 ... Oxidation catalyst, 3 ... Heater, S ... Sample, K ... Carrier gas.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｇ０１Ｎ 31/00 Ｇ０１Ｎ 31/00 Ｖ 31/10 31/10 (72)発明者 南 孝明 京都府京都市南区吉祥院宮の東町２番地 株式会社堀場製作所内 Ｆターム(参考） 2G042 AA01 BA01 BA05 BB05 BB07 CA02 CB03 DA04 FA08 2G054 AA02 BB12 BB13 BB20 CA10 CE08 EA01 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification code FI Theme coat ゛ (Reference) G01N 31/00 G01N 31/00 V 31/10 31/10 (72) Inventor Takaaki Minami Kyoto City, Kyoto 2 Higashi-cho, Kichijo-in, Ward F-term in Horiba, Ltd. F-term (reference) 2G042 AA01 BA01 BA05 BB05 BB07 CA02 CB03 DA04 FA08 2G054 AA02 BB12 BB13 BB20 CA10 CE08 EA01
Claims (3)
い材料よりなる気化管を、下流側に酸化触媒を設け、さ
らに前記酸化触媒を含む下流側を加熱するヒータを設
け、電流を流して昇温した前記気化管に液体サンプルを
送って気化し、次いで気化したガスをキャリアガスと共
に前記下流側に送って酸化した後、その酸化したガスを
前記キャリアガスと共に検出器へ送って前記液体サンプ
ル中の成分を分析するように構成した水質分析計。1. A vaporization tube made of a conductive material having a small specific heat is provided on the upstream side of a fluid flow path, an oxidation catalyst is provided on a downstream side, and a heater for heating a downstream side including the oxidation catalyst is provided. The liquid sample is sent to the vaporization tube that has flowed and heated, and vaporized. A water quality analyzer configured to analyze components in a liquid sample.
あり、さらに前記気化管に電流を流すための電極が気化
管のホルダーを兼ねている請求項１に記載の水質分析
計。2. The water quality analyzer according to claim 1, wherein the conductive material having a small specific heat is graphite, and an electrode for flowing a current through the vaporization tube also serves as a holder for the vaporization tube.
又は２に記載の水質分析計。3. The method according to claim 1, wherein said component is nitrogen or carbon.
Or the water quality analyzer according to 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10581899A JP3595461B2 (en) | 1999-04-13 | 1999-04-13 | Water quality analyzer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10581899A JP3595461B2 (en) | 1999-04-13 | 1999-04-13 | Water quality analyzer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000298126A true JP2000298126A (en) | 2000-10-24 |
| JP3595461B2 JP3595461B2 (en) | 2004-12-02 |
Family
ID=14417669
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10581899A Expired - Fee Related JP3595461B2 (en) | 1999-04-13 | 1999-04-13 | Water quality analyzer |
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| Country | Link |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008241623A (en) * | 2007-03-28 | 2008-10-09 | Shimadzu Corp | Water quality analyzer |
| JP2017040539A (en) * | 2015-08-19 | 2017-02-23 | 東亜ディーケーケー株式会社 | Container lid, lid unit, and reaction vessel |
| JP2017089935A (en) * | 2015-11-05 | 2017-05-25 | 住友電気工業株式会社 | Airtight joint and heat treatment method using airtight joint |
| JP2018533730A (en) * | 2016-04-27 | 2018-11-15 | エルジー・ケム・リミテッド | Apparatus for measuring moisture of solid sample, method of measuring moisture content of solid sample, and method of analyzing imidation ratio |
| CN110208309A (en) * | 2019-06-11 | 2019-09-06 | 邯郸学院 | A kind of coal water slurry gasification test device and its application |
| KR102214542B1 (en) * | 2020-06-22 | 2021-02-10 | 에이티티(주) | Measuring device for total organic carbon |
| WO2022224312A1 (en) * | 2021-04-19 | 2022-10-27 | 株式会社島津製作所 | Gas chromatograph |
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1999
- 1999-04-13 JP JP10581899A patent/JP3595461B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008241623A (en) * | 2007-03-28 | 2008-10-09 | Shimadzu Corp | Water quality analyzer |
| JP2017040539A (en) * | 2015-08-19 | 2017-02-23 | 東亜ディーケーケー株式会社 | Container lid, lid unit, and reaction vessel |
| JP2017089935A (en) * | 2015-11-05 | 2017-05-25 | 住友電気工業株式会社 | Airtight joint and heat treatment method using airtight joint |
| JP2018533730A (en) * | 2016-04-27 | 2018-11-15 | エルジー・ケム・リミテッド | Apparatus for measuring moisture of solid sample, method of measuring moisture content of solid sample, and method of analyzing imidation ratio |
| US10928301B2 (en) | 2016-04-27 | 2021-02-23 | Lg Chem, Ltd. | Apparatus for measuring moisture of solid sample, method for measuring moisture content of solid sample, and method for analyzing imidization ratio |
| CN110208309A (en) * | 2019-06-11 | 2019-09-06 | 邯郸学院 | A kind of coal water slurry gasification test device and its application |
| KR102214542B1 (en) * | 2020-06-22 | 2021-02-10 | 에이티티(주) | Measuring device for total organic carbon |
| WO2022224312A1 (en) * | 2021-04-19 | 2022-10-27 | 株式会社島津製作所 | Gas chromatograph |
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|---|---|
| JP3595461B2 (en) | 2004-12-02 |
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