JPH0554062B2

JPH0554062B2 -

Info

Publication number: JPH0554062B2
Application number: JP59046895A
Authority: JP
Inventors: Takeshi Murayama
Original assignee: Yokogawa Electric Corp
Current assignee: Yokogawa Electric Corp
Priority date: 1984-03-12
Filing date: 1984-03-12
Publication date: 1993-08-11
Also published as: JPS60190858A

Description

【発明の詳細な説明】〔発明の属する分野〕本発明は、大量の水酸化ナトリウム等が共存す
る被測定液に含まれている陰イオンを、イオンク
ロマトグラフイを用いて分析する方法およびその
方法を用いた装置に関する。[Detailed Description of the Invention] [Field to which the invention pertains] The present invention relates to a method for analyzing anions contained in a liquid to be measured in which a large amount of sodium hydroxide, etc. coexists, using ion chromatography, and a method thereof. The present invention relates to an apparatus using the method.

[Description of prior art]

第１図は、このような陰イオン分析方法および
その装置に関する従来例の構成説明図であり、本
願の発明者らが発明して本願の出願人がすでに出
願済みのものである（特開昭57−69251号公報；
発明の名称「サンプル液に含まれる陰イオンを分
析する方法および装置」）。第１図において、１ａ
は例えば濃度が4mmol／dm³のNa₂CO₃／
NaHCO₃の水溶液からなる溶離液を貯留してな
る溶離液槽、２ａは該溶離液を例えば2ml／min
で圧送するポンプ、３はポンプ２ａにより溶離液
の脈動を防止するダンパー、４は溶離液の圧力を
検出する圧力計、５は第１〜第６の接続口５ａ〜
５ｆおよび計量管５ｇを有し第１図の実線接続状
態と破線接続状態にその内部流路が切換えられる
インジエクタ、６は例えば外径4.6mmで長さ50mm
のプレカラム、７は例えば外径4.6mmで長さ250mm
の分離カラム、８は例えば陽イオン交換膜でなる
チユーブ８ａによつて内部が内室８ｂと外室８ｃ
に区分けされた二重管構造のサプレツサ、９は例
えば導電率計でなる検出器、１０はプレカラム
６、分離カラム７、サプレツサ８、および検出器
９を収容しこれらを所定温度（例えば40℃）に保
つ恒温槽、１ｂは例えば50mmol／dm³のドデシ
ルベンゼンスルホン酸溶液でなる除去液が貯留さ
れてなるスキヤベンジヤ液槽、２ｂは該除去液を
例えば2ml／minで圧送するポンプ、１ｃは例え
ば、5ppmのF^-イオン、10ppmのC1^-イオン、
15ppmのNO₂ ^-イオン、30ppmのPO₄ ^3-イオン、
10ppmのBr^-イオン、30ppmのNO₃ ^-イオン、お
よび40ppmのSO₄ ^2-イオンを含む被測定液（以下
「第１測定液」という）を貯留してなる被測定液
槽、２ｃは該被測定液を例えば0.4ml／minで圧
送するポンプ、１ｄ〜１ｆは廃液槽である。第２
図は、このような陰イオン分析装置を用いて得ら
れた、上記第１測定液のクロマトグラムであり、
種々の陰イオンがわずか８分という短時間のうち
に高感度で測定できることを示している。 FIG. 1 is an explanatory diagram of the configuration of a conventional example of such an anion analysis method and apparatus, which was invented by the inventors of the present application and has already been applied for by the applicant of the present application (Japanese Patent Application Laid-Open No. Publication No. 57-69251;
Title of the invention: ``Method and apparatus for analyzing anions contained in a sample liquid.'' In Figure 1, 1a
For example, Na ₂ CO ₃ / with a concentration of 4 mmol/dm ³
An eluent tank 2a stores an eluent consisting of an aqueous solution of _NaHCO3 , and the eluent tank 2a stores the eluent at a rate of, for example, 2 ml/min.
3 is a damper that prevents pulsation of the eluent by the pump 2a, 4 is a pressure gauge that detects the pressure of the eluent, and 5 is the first to sixth connection ports 5a to 5.
The injector 6 has an outer diameter of 4.6 mm and a length of 50 mm.
For example, precolumn 7 has an outer diameter of 4.6 mm and a length of 250 mm.
The separation column 8 has an inner chamber 8b and an outer chamber 8c formed by a tube 8a made of, for example, a cation exchange membrane.
9 is a detector made of, for example, a conductivity meter, and 10 houses a precolumn 6, a separation column 7, a suppressor 8, and a detector 9, which are kept at a predetermined temperature (for example, 40°C). 1b is a scavenging liquid tank in which a removal liquid consisting of, for example, 50 mmol/dm ³ dodecylbenzenesulfonic acid solution is stored; 2b is a pump that pumps the removal liquid at a rate of, for example, 2 ml/min; 1c is, for example, 5ppm F ^- ions, 10ppm C1 ^- ions,
15ppm NO ₂ ^-ions , 30ppm PO ₄ ^3- ions,
A liquid to be measured tank 2c stores a liquid to be measured (hereinafter referred to as "first measurement liquid") containing 10 ppm of Br ^- ions, 30 ppm of NO ₃ ^- ions, and 40 ppm of SO ₄ ^2- ions; The pumps 1d to 1f which pump the measurement liquid at a rate of, for example, 0.4 ml/min are waste liquid tanks. Second
The figure is a chromatogram of the first measurement liquid obtained using such an anion analyzer,
This shows that various anions can be measured with high sensitivity in just 8 minutes.

然し乍ら、上記従来例においては、微量の被測
定イオンを固体試料等から溶出させて測定した
り、被測定イオンが強いアルカリ性でないと安定
しないというような理由のため被測定液中に強ア
ルカリを加えたりして、被測定液中に水酸化ナト
リウム等が多量に共存する場合、陰イオンの測定
が著しく困難になるという欠点があつた。即ち、
上記第１測定液に例えば１規定の水酸化ナトリウ
ム（NaOH）を注入したもの（以下、「第２測定
液」という）を被測定液槽１ｃに貯留して、上述
の陰イオン分析装置を用いて第２測定液中の陰イ
オンを測定すると、第３図に示すようなクロマト
グラムとなり、各陰イオンの定性や定量が著しく
困難となる。 However, in the above conventional example, a trace amount of the ion to be measured is eluted from a solid sample, etc. for measurement, or a strong alkali is added to the liquid to be measured because the ion to be measured is not stable unless it is strongly alkaline. However, when a large amount of sodium hydroxide or the like coexists in the liquid to be measured, it becomes extremely difficult to measure anions. That is,
For example, 1N sodium hydroxide (NaOH) is injected into the first measurement liquid (hereinafter referred to as "second measurement liquid") and stored in the liquid to be measured tank 1c, and the anion analyzer described above is used. When the anions in the second measurement solution are measured using this method, a chromatogram as shown in FIG. 3 is obtained, and the qualitative and quantitative determination of each anion becomes extremely difficult.

[Purpose of the invention]

本発明は、かかる欠点に鑑みてなされたもので
あり、その目的は、高濃度の水酸化ナトリウム等
が共存する被測定液中の陰イオンをも、迅速且つ
容易に測定できるような陰イオン分析方法および
その装置を提供することにある。 The present invention has been made in view of these drawbacks, and its purpose is to provide an anion analysis method that can quickly and easily measure anions in a liquid to be measured in which high concentrations of sodium hydroxide, etc. coexist. An object of the present invention is to provide a method and a device thereof.

[Summary of the invention]

本発明の特徴は、イオンクロマトグラフイを用
いた陰イオン分析方法およびその装置において、
被測定液が大量の陰イオン測定阻害イオンを含む
場合に際しては、予め陰イオン測定阻害イオンを
陰イオンの測定を阻害しない程度に除去した後、
前記溶離液と共に前記分離カラムに搬送するよう
にしたことにある。 The present invention is characterized by an anion analysis method using ion chromatography and an apparatus thereof.
If the liquid to be measured contains a large amount of anion measurement-inhibiting ions, remove the anion measurement-inhibiting ions in advance to the extent that they do not inhibit anion measurement, and then
The present invention is characterized in that the eluent is transported to the separation column together with the eluent.

[Explanation of Examples]

以下、本発明について図を用いて詳細に説明す
る。第４図は本発明実施例の構成説明図であり、
図中、第１図と同一記号は同一意味をもたせて使
用しここでの重複説明は省略する。また、８′は
例えば陽イオン交換膜でなり例えば内径0.45mm、
外径0.55mm、長さ５ｍのチユーブ８′ａによつて
内部が内室８′ｂと外室８′ｃに区分けされた二重
管構造のサプレツサ、１１はサプレツサ８′の内
室８′ｂに被測定液を注入する例えば注射器でな
るシリンジである。このような構成からなる本発
明の実施例において、ポンプ２ａが駆動すると、
槽１ａ内の被測定液は、ポンプ２ａ→ダンパー３
→圧力計４→インジエクタ５の第１および第２接
続口５ａ，５ｂ→プレカラム６→分離カラム７→
サプレツサ８の内室８ｂ→検出器９→廃液槽１ｄ
の流路で流れる。また、ポンプ２ｂが駆動する
と、槽１ｂ内の除去液は、ポンプ２ｂ→サプレツ
サ８の外室８ｃ→サプレツサ８′の外室８′ｃ→廃
液槽１ｅの流路で流れる。この状態で、前記第２
測定液（前記第１測定液に例えば１規定の
NaOHを注入してもの）を、シリンジ１１でサ
プレツサ８′の内室８′ｂに注入する。サプレツサ
８′の外室８′ｃには除去液が流れているため、該
除去液中のH⁺イオンと上記第２測定液中の測定
妨害イオン（例えばNa⁺イオン）がチユーブ８′
ａを介してイオン交換する。このため、インジエ
クタ５の計量管５ｇ内には、上記測定妨害イオン
が除去された上記第２測定液が供給されるように
なる。従つて、インジエクタ５がオンとなつて、
計量管５ｇ内の被測定液が溶離液でもつて分離カ
ラム７に搬送されても、該カラム７における陰イ
オンの分離が上記所定妨害イオンの影響を受ける
ようなことはない。即ち、検出器９の出力信号を
図示しない記録計等に導いてクロマトグラムを描
かせると第５図に示すようになり、F^-イオン以
外のイオンは良好なピーク形状を与える。第２図
および第３図のクロマトグラムと第５図のクロマ
トグラムを比較すれば明らかなように、第５図の
クロマトグラムの方が、(イ)F^-イオンの位置に所
定妨害イオン（Na⁺イオン等）の悪影響が若干現
われている。(ロ)残りのイオンのピークも低くなつ
ている。(イ)は、サプレツサ８′で第２測定液中の
測定妨害イオンが完全に除去しきれなかつたため
生じているものであり、除去液の成分を調整する
ことによつて改善できるものである。また、(ロ)
は、サプレツサ８′でチユーブ８′ａを透過して、
除去液中の水が第２測定液中に混入するために生
ずるものであるが、各イオンの相対的な定量分析
等には何ら悪影響を与えないものである。尚、本
発明は、上述の実施例に限定されることなく種々
の変更が可能である。例えば、第４図のシリンジ
１１の代りに、被測定液が貯留された槽と送液ポ
ンプを用いるようにしてもよい。また、サプレツ
サ８′の外室８′ｂへの除去液をサプレツサ８の外
室８ｂから導く代りに、サプレツサ８′専用の除
去液槽と送液ポンプから供給するようにしてもよ
い。更に、上記測定妨害イオンとして、Na⁺イオ
ンの代りに、K⁺イオン、NH₄ ⁺イオン、Fe⁺⁺イ
オン、Al⁺⁺イオン、若しくはZn⁺⁺イオン等であ
つてもよい。 Hereinafter, the present invention will be explained in detail using figures. FIG. 4 is an explanatory diagram of the configuration of an embodiment of the present invention,
In the figure, the same symbols as in FIG. 1 are used with the same meaning, and repeated explanation will be omitted here. Further, 8' is a cation exchange membrane, for example, with an inner diameter of 0.45 mm,
A suppressor with a double tube structure, the inside of which is divided into an inner chamber 8'b and an outer chamber 8'c by a tube 8'a with an outer diameter of 0.55 mm and a length of 5 m, 11 is the inner chamber 8' of the suppressor 8'. A syringe, such as a syringe, is used to inject the liquid to be measured into b. In the embodiment of the present invention having such a configuration, when the pump 2a is driven,
The liquid to be measured in the tank 1a is transferred from the pump 2a to the damper 3.
→Pressure gauge 4→First and second connection ports 5a, 5b of injector 5→Precolumn 6→Separation column 7→
Inner chamber 8b of suppressor 8 → detector 9 → waste liquid tank 1d
It flows through the flow path. Further, when the pump 2b is driven, the removed liquid in the tank 1b flows through the flow path of the pump 2b, the outer chamber 8c of the suppressor 8, the outer chamber 8'c of the suppressor 8', and the waste liquid tank 1e. In this state, the second
Measurement liquid (for example, 1N to the first measurement liquid)
Inject NaOH into the inner chamber 8'b of the suppressor 8' using the syringe 11. Since the removal liquid is flowing into the outer chamber 8'c of the suppressor 8', H ⁺ ions in the removal liquid and measurement-interfering ions (for example, Na ⁺ ions) in the second measurement liquid are transferred to the tube 8'.
ion exchange via a. Therefore, the second measurement liquid from which the measurement-interfering ions have been removed is supplied into the measuring tube 5g of the injector 5. Therefore, the injector 5 is turned on,
Even if the liquid to be measured in the measuring tube 5g is conveyed to the separation column 7 along with the eluent, the separation of anions in the column 7 will not be affected by the predetermined interfering ions. That is, when the output signal of the detector 9 is guided to a recorder (not shown) and a chromatogram is drawn, it becomes as shown in FIG. 5, and ions other than F ^- ions give a good peak shape. As is clear from comparing the chromatograms in Figures 2 and 3 with the chromatogram in Figure 5, the chromatogram in Figure ⁵ has a predetermined interfering ion (Na ⁺ ions, etc.) have some negative effects. (b) The peaks of the remaining ions are also lower. (a) occurs because the suppressor 8' cannot completely remove the measurement interfering ions in the second measurement liquid, and can be improved by adjusting the components of the removal liquid. Also, (b)
is transmitted through tube 8'a by suppressor 8',
Although this is caused by water in the removal solution mixing into the second measurement solution, it does not have any adverse effect on the relative quantitative analysis of each ion. Note that the present invention is not limited to the above-described embodiments, and can be modified in various ways. For example, instead of the syringe 11 shown in FIG. 4, a tank storing a liquid to be measured and a liquid pump may be used. Further, instead of leading the removal liquid to the outer chamber 8'b of the suppressor 8' from the outer chamber 8b of the suppressor 8, it may be supplied from a removal liquid tank and a liquid feeding pump exclusively for the suppressor 8'. Further, the measurement interfering ions may be K ⁺ ions, NH ₄ ⁺ ions, Fe ⁺⁺ ions, Al ⁺⁺ ions, Zn ⁺⁺ ions, etc. instead of Na ⁺ ions.

〔Effect of the invention〕

以上詳しく説明したような本発明の実施例によ
れば、被測定液が大量の陰イオン測定阻害イオン
を含む場合に際しては、第２サプレツサを用いて
予め陰イオン測定阻害イオンを陰イオンの測定を
阻害しない程度に除去した後インジエクタに送り
込むようにしたので、第１サプレツサで十分に陽
イオンを除去することができる。その結果、高濃
度の水酸化ナトリウム等が共存する被測定液中の
陰イオンを迅速且つ容易に測定できるようになる
利点がある。 According to the embodiment of the present invention as described in detail above, when the liquid to be measured contains a large amount of anion measurement-inhibiting ions, the second suppressor is used to suppress the anion measurement-inhibiting ions in advance. Since the cations are removed to the extent that they are not inhibited and then sent to the injector, the first suppressor can sufficiently remove the cations. As a result, there is an advantage that anions in a liquid to be measured in which a high concentration of sodium hydroxide or the like coexists can be measured quickly and easily.

[Brief explanation of the drawing]

第１図は従来例の構成説明図、第２図および第
３図は従来例を用いて作成したクロマトグラム、
第４図は本発明実施例の構成説明図、第５図は本
発明実施例を用いて作成したクロマトグラムであ
る。１ａ〜１ｆ……槽、２ａ〜２ｃ……ポンプ、３
……ダンパー、４……圧力計、５……インジエク
タ、６……プレカラム、７……分離カラム、８，
８′……サプレツサ、８ａ，８′ａ……チユーブ、
９……検出器、１０……恒温槽、１１……シリン
ジ。 Figure 1 is an explanatory diagram of the configuration of the conventional example, Figures 2 and 3 are chromatograms created using the conventional example,
FIG. 4 is an explanatory diagram of the configuration of the embodiment of the present invention, and FIG. 5 is a chromatogram prepared using the embodiment of the present invention. 1a to 1f...tank, 2a to 2c...pump, 3
...damper, 4 ... pressure gauge, 5 ... injector, 6 ... precolumn, 7 ... separation column, 8,
8'...Suppressa, 8a, 8'a...Tube,
9...Detector, 10...Thermostat, 11...Syringe.

Claims

[Claims] 1. A predetermined amount of a liquid to be measured containing a large amount of anion measurement-inhibiting ions is collected and transported to a separation column using an eluent, and a predetermined cation contained in the liquid eluted from the separation column is cationized. The first part has a double-tube structure that is divided into an inner chamber and an outer chamber by a tube made of an ion exchange membrane.
In a method of analyzing anions in the measurement solution by removing them using a suppressor and then detecting the physical quantity of the eluate, It is characterized in that after removal using a second suppressor with a double tube structure that is divided into an inner chamber and an outer chamber by a tube made of a cation exchange membrane, the eluent is transported to the separation column. Anion analysis method. 2. The anion analysis method according to claim 1, wherein the measurement-inhibiting ion is a sodium ion. 3. The anion analysis method according to claim 1, wherein the measurement-inhibiting ion is a potassium ion. 4. The anion analysis method according to claim 1, wherein the measurement-inhibiting ion is an ammonium ion. 5. The anion analysis method according to claim 1, wherein the measurement-inhibiting ions are lithium ions. 6 Claim 1 in which the physical quantity is electrical conductivity
- The anion analysis method according to any one of Items 5 to 5. 7. An injector that collects a predetermined amount of a liquid to be measured containing a large amount of anion measurement-inhibiting ions, and a separation device that separates anions in the liquid to be measured when the liquid to be measured collected by the injector is transported by an eluent. The first tube has a double tube structure and is divided into an inner chamber and an outer chamber by a tube consisting of a column and a cation exchange membrane that removes predetermined cations in the eluate when the eluate from the column is introduced. In an anion analyzer having a suppressor and a detector for detecting the physical quantity of the eluate eluted from the suppressor, cation exchange is performed to remove in advance the anion measurement-inhibiting ions to an extent that does not inhibit anion measurement. An anion analyzer characterized by comprising a second suppressor having a double tube structure divided into an inner chamber and an outer chamber by a tube made of a membrane. 8. The anion analyzer according to claim 7, wherein the detector is a conductivity detector.