JP5266440B2 - Analyzers for halogens and sulfur in organic and inorganic compounds - Google Patents

Analyzers for halogens and sulfur in organic and inorganic compounds Download PDF

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JP5266440B2
JP5266440B2 JP2008333764A JP2008333764A JP5266440B2 JP 5266440 B2 JP5266440 B2 JP 5266440B2 JP 2008333764 A JP2008333764 A JP 2008333764A JP 2008333764 A JP2008333764 A JP 2008333764A JP 5266440 B2 JP5266440 B2 JP 5266440B2
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潜 長嶋
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an analyzer for analyzing halogens and sulfurs in an organic-inorganic compound which also enables analysis of inorganic compounds. <P>SOLUTION: The analyzer 10 for analyzing halogens and sulfurs within the organic-inorganic compound includes a sample combustion apparatus 20 for combusting and decomposing an organic-inorganic sample, containing four types of the halogens (fluorine, chlorine, bromine and iodine) and the sulfursin a combustion tube, and for generating a halide and a sulfur oxide. The sample combustion apparatus 20 includes a quartz combustion tube 30 for the sample of the organic compound, and a ceramic combustion tube 40 for the sample of the inorganic compound. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

本発明は、燃焼管内で４種ハロゲン（フッ素、塩素、臭素、ヨウ素）及び硫黄を含む有機・無機化合物の試料を燃焼分解して、ハロゲン化物、及び硫黄酸化物を生成する試料燃焼装置を備えたハロゲン及び硫黄の分析装置に関する。   The present invention includes a sample combustion apparatus that generates a halide and a sulfur oxide by burning and decomposing a sample of an organic / inorganic compound containing four types of halogens (fluorine, chlorine, bromine, iodine) and sulfur in a combustion tube. Relates to a halogen and sulfur analyzer.

従来の技術としては、例えば特開平８−２６２０００号公報に示すようなものがある。   As a conventional technique, for example, there is a technique disclosed in Japanese Patent Laid-Open No. 8-262000.

すなわち、分析装置は、石英燃焼管内で４種ハロゲン、及び硫黄を含む有機化合物の試料を燃焼分解して、ハロゲン化物、及び硫黄酸化物を生成する試料燃焼装置と、試料燃焼装置へ試料を自動供給するオートサンプラーと、試料燃焼装置で生成したハロゲン化物、及び硫黄酸化物を吸収液に通じて溶解し、ハロゲン化物及び硫酸イオンを生成する吸収装置と、吸収装置の吸収液に通じて溶解したハロゲン化物及び硫酸イオンを含む吸収液を試料溶液として取り込み、試料溶液中の各イオン種を分離定量するイオンクロマトグラフを備えているものである。   That is, the analyzer automatically burns and decomposes a sample of an organic compound containing four types of halogens and sulfur in a quartz combustion tube to generate a halide and sulfur oxide, and automatically sends the sample to the sample combustion device. The autosampler to be supplied, the halide and sulfur oxide generated in the sample combustion device are dissolved through the absorption liquid, the absorption apparatus for generating halide and sulfate ions, and the absorption liquid in the absorption apparatus are dissolved. An ion chromatograph that takes in an absorption solution containing halide and sulfate ions as a sample solution and separates and quantifies each ion species in the sample solution is provided.

特開平８−２６２０００号公報JP-A-8-262000

しかしながら、このような従来の技術では、燃焼管が石英製であるので有機化合物のみが対象とされ、無機化合物は分析できない、という問題点があった。   However, such a conventional technique has a problem that since the combustion tube is made of quartz, only an organic compound is targeted, and an inorganic compound cannot be analyzed.

本発明は、このような従来の技術が有する問題点に着目してなされたもので、より高温で燃焼させることにより無機化合物も分析することができるようにした有機・無機化合物中のハロゲン及び硫黄の分析装置を提供することを目的としている。   The present invention has been made paying attention to such problems of the prior art, and halogens and sulfur in organic and inorganic compounds that can analyze inorganic compounds by burning at higher temperatures. It aims at providing the analysis device of.

かかる目的を達成するための本発明の要旨とするところは、次の各項の発明に存する。   The gist of the present invention for achieving the object lies in the inventions of the following items.

［１］燃焼管内で４種ハロゲン（フッ素、塩素、臭素、ヨウ素）及び硫黄を含む有機・無機化合物の試料を燃焼分解して、ハロゲン化物、及び硫黄酸化物を生成する試料燃焼装置（２０）を備えたハロゲン及び硫黄の分析装置（１０）であって、
前記試料燃焼装置（２０）は、有機化合物の試料のための石英燃焼管（３０）と無機化合物の試料のためのセラミック燃焼管（４０）とを備えていることを特徴とする有機・無機化合物中のハロゲン及び硫黄の分析装置（１０）。 [1] Sample combustion apparatus (20) for generating a halide and sulfur oxide by burning and decomposing a sample of an organic / inorganic compound containing four types of halogens (fluorine, chlorine, bromine, iodine) and sulfur in a combustion tube A halogen and sulfur analyzer (10) comprising:
The sample combustion apparatus (20) includes a quartz combustion tube (30) for a sample of an organic compound and a ceramic combustion tube (40) for a sample of an inorganic compound. Analytical device for halogen and sulfur (10).

［２］燃焼管内で４種ハロゲン（フッ素、塩素、臭素、ヨウ素）及び硫黄を含む有機・無機化合物の試料を燃焼分解して、ハロゲン化物、及び硫黄酸化物を生成する試料燃焼装置（２０）を備えたハロゲン及び硫黄の分析装置（１０）であって、
前記試料燃焼装置（２０）は、試料を予備燃焼する移動炉（２１）と試料を本燃焼させる固定炉（２５）と、無機化合物の試料のためのセラミック燃焼管（４０）と有機化合物の試料のための石英燃焼管（３０）とを備え、
前記石英燃焼管（３０）は前記移動炉（２１）及び固定炉（２５）で加熱される太管部（３１）と、燃焼ガス吸収管（５１）に接続する細管部（３５）とが一体に形成されて成り、前記セラミック燃焼管（４０）は前記移動炉（２１）及び固定炉（２５）で加熱される主管部（４１）を、石英製アダプタ（４５）で燃焼ガス吸収管（５１）に接続するよう構成されていることを特徴とする有機・無機化合物中のハロゲン及び硫黄の分析装置（１０）。 [2] Sample combustion apparatus (20) for generating a halide and a sulfur oxide by burning and decomposing a sample of an organic / inorganic compound containing four types of halogens (fluorine, chlorine, bromine, iodine) and sulfur in a combustion tube A halogen and sulfur analyzer (10) comprising:
The sample combustion apparatus (20) includes a mobile furnace (21) for pre-combustion of a sample, a fixed furnace (25) for main combustion of the sample, a ceramic combustion tube (40) for a sample of an inorganic compound, and a sample of an organic compound. A quartz combustion tube (30) for
In the quartz combustion tube (30), a thick tube portion (31) heated in the mobile furnace (21) and a fixed furnace (25) and a thin tube portion (35) connected to the combustion gas absorption tube (51) are integrated. The ceramic combustion tube (40) is composed of a main pipe portion (41) heated by the mobile furnace (21) and the fixed furnace (25), and a combustion gas absorption pipe (51) by a quartz adapter (45). And an analyzer for halogen and sulfur in organic and inorganic compounds (10).

［３］セラミック燃焼管（４０）で無機化合物の試料を加熱可能なよう、固定炉（２５）では、炭化ケイ素発熱体を用いることを特徴とする項２に記載の有機・無機化合物中のハロゲン及び硫黄の分析装置（１０）。 [3] The halogen in the organic / inorganic compound according to Item 2 , wherein a silicon carbide heating element is used in the fixed furnace (25) so that the sample of the inorganic compound can be heated by the ceramic combustion tube (40). And sulfur analyzer (10).

［４］無機化合物の試料では、移動炉（２１）で混在する有機物及び塩として存在するハロゲンを放出させてから、固定炉（２５）で加熱するようにしたことを特徴とする項２に記載の有機・無機化合物中のハロゲン及び硫黄の分析装置（１０）。 [4] The inorganic compound sample is characterized in that the organic substance mixed in the mobile furnace (21) and the halogen present as a salt are released and then heated in the fixed furnace (25). (10) for analyzing halogen and sulfur in organic and inorganic compounds.

［５］燃焼管内で４種ハロゲン（フッ素、塩素、臭素、ヨウ素）及び硫黄を含む有機・無機化合物の試料を燃焼分解して、ハロゲン化物、及び硫黄酸化物を生成する試料燃焼装置（２０）を備えたハロゲン及び硫黄の分析装置（１０）であって、
石英燃焼管（３０）内では有機化合物を対象として、セラミック燃焼管（４０）では無機化合物を対象として４種ハロゲン、及び硫黄を含む有機化合物の試料を燃焼分解し、ハロゲン化物、及び硫黄酸化物を生成する試料燃焼装置（２０）と、前記試料燃焼装置（２０）で生成したハロゲン化物、及び硫黄酸化物を吸収液に通じて溶解し、ハロゲン化物及び硫酸イオンを生成する吸収装置（５０）と、を備えたことを特徴とする有機・無機化合物中のハロゲン及び硫黄の分析装置（１０）。 [5] Sample combustion apparatus (20) for generating a halide and a sulfur oxide by burning and decomposing a sample of an organic / inorganic compound containing four types of halogen (fluorine, chlorine, bromine, iodine) and sulfur in a combustion tube A halogen and sulfur analyzer (10) comprising:
In the quartz combustion tube (30), an organic compound is targeted, and in the ceramic combustion tube (40), a sample of an organic compound containing four types of halogens and sulfur is combusted and decomposed to obtain a halide and sulfur oxide. Combustion apparatus (20) for generating a gas, and an absorption apparatus (50) for generating halides and sulfate ions by dissolving the halide and sulfur oxide generated in the sample combustion apparatus (20) through an absorption liquid And an analysis apparatus (10) for halogen and sulfur in organic and inorganic compounds.

［６］吸収液に、酸化剤と還元剤とを併せて添加したことを特徴とする項５に記載の有機・無機化合物中のハロゲン及び硫黄の分析装置（１０）。 [6] The analysis apparatus (10) for halogen and sulfur in an organic / inorganic compound as described in [5], wherein an oxidizing agent and a reducing agent are added to the absorbing solution.

前記本発明は次のように作用する。
分析装置（１０）は、試料燃焼装置（２０）により、燃焼管内で４種ハロゲン（フッ素、塩素、臭素、ヨウ素）及び硫黄を含む有機・無機化合物の試料を燃焼分解して、ハロゲン化物、及び硫黄酸化物を生成する。 The present invention operates as follows.
The analysis device (10) uses the sample combustion device (20) to burn and decompose a sample of an organic / inorganic compound containing four kinds of halogens (fluorine, chlorine, bromine, iodine) and sulfur in a combustion tube, and to obtain a halide, and Sulfur oxide is produced.

試料燃焼装置（２０）は、有機化合物の試料では、石英燃焼管（３０）で４種ハロゲン（フッ素、塩素、臭素、ヨウ素）及び硫黄を含む有機化合物の試料を燃焼分解し、無機化合物の試料では、セラミック燃焼管（４０）で必要な高温で有機化合物の試料を燃焼分解し、ハロゲン化物、及び硫黄酸化物を生成する。   In the sample combustion apparatus (20), an organic compound sample is combusted and decomposed in an organic compound sample containing four types of halogens (fluorine, chlorine, bromine, iodine) and sulfur in a quartz combustion tube (30), and an inorganic compound sample is obtained. Then, a sample of an organic compound is combusted and decomposed at a high temperature required in the ceramic combustion tube (40) to generate a halide and a sulfur oxide.

試料燃焼装置（２０）では、移動炉（２１）で試料を予備燃焼し、固定炉（２５）で試料を本燃焼させ、無機化合物の試料はセラミック燃焼管（４０）で燃焼され、有機化合物の試料は石英燃焼管（３０）で燃焼される。   In the sample combustion apparatus (20), the sample is pre-burned in the mobile furnace (21), the sample is burned in the fixed furnace (25), the inorganic compound sample is burned in the ceramic combustion tube (40), and the organic compound The sample is burned in a quartz combustion tube (30).

石英燃焼管（３０）では、太管部（３１）の前半部分で移動炉（２１）により試料が予備燃焼され、移動炉（２１）が太管部（３１）の前半部分を過ぎたところで太管部（３１）が固定炉（２５）で本燃焼される。   In the quartz combustion tube (30), the sample is pre-combusted by the moving furnace (21) in the first half portion of the thick tube portion (31), and when the moving furnace (21) passes the first half portion of the thick tube portion (31), the thick portion is obtained. The pipe section (31) is burned in the fixed furnace (25).

石英燃焼管（３０）は燃焼ガス吸収管（５１）に接続する細管部（３５）とが一体に形成されており、この細管部（３５）から燃焼ガス吸収管（５１）に移動する。有機化合物より高温を要する無機化合物では、セラミック燃焼管（４０）により、移動炉（２１）で主管部（４１）の試料が予備燃焼され、固定炉（２５）で、本燃焼される。燃焼ガスは燃焼ガス吸収管（５１）に接続された石英製のアダプタ（４５）から燃焼ガス吸収管（５１）に移動する。   The quartz combustion tube (30) is integrally formed with a narrow tube portion (35) connected to the combustion gas absorption tube (51), and moves from the narrow tube portion (35) to the combustion gas absorption tube (51). In the case of an inorganic compound that requires a higher temperature than the organic compound, the sample in the main pipe portion (41) is pre-combusted in the mobile furnace (21) by the ceramic combustion tube (40), and the main combustion is performed in the fixed furnace (25). The combustion gas moves from the quartz adapter (45) connected to the combustion gas absorption pipe (51) to the combustion gas absorption pipe (51).

固定炉（２５）での加熱には、セラミック燃焼管（４０）で高温で無機化合物の試料を加熱可能なよう、炭化ケイ素発熱体で加熱される。 The heating in the fixed furnace (25) is performed by a silicon carbide heating element so that the sample of the inorganic compound can be heated at a high temperature by the ceramic combustion tube (40).

無機化合物の試料を対象とする場合は、移動炉（２１）で混在する有機物及び塩として存在するハロゲンを放出させてから、固定炉（２５）で加熱する。例えば、無機化合物の試料を移動炉（２１）の中心部に置き、５〜１０分加熱してから、固定炉（２５）内に挿入し、１３５０℃程度で５〜１５分加熱する。   When a sample of an inorganic compound is used as a target, the organic substance mixed in the mobile furnace (21) and the halogen present as a salt are released, and then heated in the fixed furnace (25). For example, a sample of an inorganic compound is placed in the center of the mobile furnace (21), heated for 5 to 10 minutes, inserted into the fixed furnace (25), and heated at about 1350 ° C. for 5 to 15 minutes.

試料燃焼装置（２０）で生成したハロゲン化物、及び硫黄酸化物は吸収液に溶解し、吸収装置（５０）によりハロゲン化物及び硫酸イオンの試料溶液が生成される。試料溶液中の各イオン種はイオンクロマトグラフにより分離定量される。   The halide and sulfur oxide generated in the sample combustion device (20) are dissolved in the absorption liquid, and a sample solution of halide and sulfate ions is generated by the absorption device (50). Each ion species in the sample solution is separated and quantified by an ion chromatograph.

吸収液には、酸化剤として例えば過酸化水素を、還元剤として例えば抱水ヒドラジンを併せて添加してあり、酸化・還元反応に同時に対応している。すなわち、フッ素・塩素では燃焼に伴い、純水に容易に吸収されてフッ化物・塩化物イオンが発生するが、臭素及びヨウ素では燃焼に伴い、ハロゲン化物と分子状の遊離体（Ｂｒ２、Ｉ２）を生成する。この遊離体のイオン化には還元剤の存在が必要である。   For example, hydrogen peroxide as an oxidizing agent and hydrazine hydrate as a reducing agent, for example, are added to the absorbing solution, and simultaneously support oxidation / reduction reactions. That is, fluoride and chloride ions are easily absorbed in pure water during combustion in fluorine and chlorine, and generate fluoride and chloride ions. In bromine and iodine, halides and molecular free bodies (Br2, I2) are generated along with combustion. Is generated. The ionization of this educt requires the presence of a reducing agent.

また、硫黄は、燃焼・吸収に伴い、硫酸・亜硫酸イオンを生成し、酸化剤の存在が必要である。これに対し酸化剤として例えば過酸化水素を、還元剤として例えば抱水ヒドラジンを吸収液に併せて添加することにより、酸化・還元反応に対し同時に分析できるようになった。   In addition, sulfur generates sulfuric acid and sulfite ions with combustion and absorption, and the presence of an oxidizing agent is necessary. On the other hand, for example, hydrogen peroxide is added as an oxidizing agent, and hydrazine hydrate as a reducing agent is added to the absorbing solution, thereby enabling simultaneous analysis of the oxidation / reduction reaction.

本発明にかかる有機・無機化合物中のハロゲン及び硫黄の分析装置によれば、セラミック燃焼管を備えることにより無機化合物の試料を対象とする高温の燃焼をすることができるようになる。   According to the apparatus for analyzing halogen and sulfur in organic / inorganic compounds according to the present invention, it is possible to perform high-temperature combustion for a sample of an inorganic compound by providing a ceramic combustion tube.

石英燃焼管とセラミック燃焼管とにより、有機化合物の試料および無機化合物の試料のハロゲン及び硫黄を分析することができるので、従来技術では有機化合物のみが対象となったものの分析範囲を広げることができる。   The quartz combustion tube and the ceramic combustion tube allow analysis of halogen and sulfur in organic compound samples and inorganic compound samples, so that the analysis range of only organic compounds in the prior art can be expanded. .

酸化剤として例えば過酸化水素を、還元剤として例えば抱水ヒドラジンを吸収液に併せて添加することにより、硫黄の酸化反応及び、ハロゲンのハロゲン化物への還元反応に対し同時に分析できるようになる。   By adding, for example, hydrogen peroxide as the oxidizing agent and hydrazine hydrate as the reducing agent together with the absorbing solution, it becomes possible to simultaneously analyze the oxidation reaction of sulfur and the reduction reaction of halogen to a halide.

以下、図面に基づき本発明の好適な一実施の形態を説明する。
図１〜図３は本発明の一実施の形態を示している。 Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings.
1 to 3 show an embodiment of the present invention.

ハロゲン及び硫黄の分析装置１０は、燃焼管内で４種ハロゲン（フッ素、塩素、臭素、ヨウ素）及び硫黄を含む有機・無機化合物の試料を燃焼分解して、ハロゲン化物、及び硫黄酸化物を生成するものであり、燃焼管内で４種ハロゲン（フッ素、塩素、臭素、ヨウ素）及び硫黄を含む有機・無機化合物の試料を燃焼してハロゲン化物、及び硫黄酸化物を生成する試料燃焼装置２０と、試料燃焼装置２０で生成したハロゲン化物、及び硫黄酸化物を吸収液に通じて溶解し、ハロゲン化物及び硫酸イオンを生成する吸収装置５０と、を備えている。   The halogen and sulfur analyzer 10 burns and decomposes a sample of an organic / inorganic compound containing four types of halogens (fluorine, chlorine, bromine, iodine) and sulfur in a combustion tube to generate a halide and a sulfur oxide. A sample combustion apparatus 20 for burning a sample of an organic / inorganic compound containing four types of halogens (fluorine, chlorine, bromine, iodine) and sulfur in a combustion tube to generate a halide and a sulfur oxide; And an absorption device 50 that dissolves the halide and sulfur oxide generated in the combustion device 20 through an absorption liquid to generate halide and sulfate ions.

試料燃焼装置２０は、試料を予備燃焼する移動炉２１と試料を本燃焼させる固定炉２５と、無機化合物の試料のためのセラミック燃焼管４０と有機化合物の試料のための石英燃焼管３０とを備えている。   The sample combustion apparatus 20 includes a mobile furnace 21 for pre-combustion of a sample, a fixed furnace 25 for main combustion of the sample, a ceramic combustion tube 40 for a sample of an inorganic compound, and a quartz combustion tube 30 for a sample of an organic compound. I have.

石英燃焼管３０は、有機化合物を対象として、セラミック燃焼管４０は、無機化合物を対象として４種ハロゲン、及び硫黄を含む有機・無機化合物の試料を燃焼分解するよう対応している。   The quartz combustion tube 30 is intended for organic compounds, and the ceramic combustion tube 40 is adapted for combustion decomposition of organic / inorganic compound samples containing four types of halogens and sulfur for inorganic compounds.

図２でわかるように、石英燃焼管３０は移動炉２１及び固定炉２５で加熱される太管部３１と、燃焼ガス吸収管５１に中継部５５を介して接続する細管部３５とが一体に形成されて成る。   As shown in FIG. 2, the quartz combustion tube 30 includes a thick tube portion 31 heated by the moving furnace 21 and the fixed furnace 25 and a narrow tube portion 35 connected to the combustion gas absorption tube 51 via a relay portion 55. Formed.

図１でわかるように、セラミック燃焼管４０は移動炉２１及び固定炉２５で加熱される主管部４１を、石英製アダプタ４５で燃焼ガス吸収管５１に接続するよう構成されている。石英製アダプタ４５は、石英燃焼管３０の太管部３１の末端から細管部３５にかけた形態と似ており、主管部４１の末端の嵌合部４６と燃焼ガス吸収管５１に中継部５５を介して接続する細径部４７とにより構成されている。   As can be seen in FIG. 1, the ceramic combustion tube 40 is configured to connect the main pipe portion 41 heated in the moving furnace 21 and the fixed furnace 25 to the combustion gas absorption pipe 51 by a quartz adapter 45. The quartz adapter 45 is similar to the configuration in which the end of the thick tube portion 31 of the quartz combustion tube 30 is applied to the thin tube portion 35. It is comprised by the thin diameter part 47 connected via.

セラミック燃焼管４０で無機化合物の試料を加熱可能なよう、固定炉２５では、炭化ケイ素発熱体であるシリコニット発熱体（「シリコニット」は、炭化珪素質電気発熱体を指定商品とする株式会社シリコニットの登録商標である。）が採用されている。また、無機化合物の試料では、移動炉２１で混在する有機物及び塩として存在するハロゲンを放出させてから、固定炉２５で加熱するようにし、吸収液には、酸化剤と還元剤とを併せて添加してある。 In the fixed furnace 25, a siliconite heating element (“siliconite”) is a silicon carbide heating element designated as a silicon carbide electric heating element so that the sample of the inorganic compound can be heated by the ceramic combustion tube 40. Is a registered trademark) . Moreover, in the sample of an inorganic compound, the organic substance mixed in the mobile furnace 21 and the halogen present as a salt are released, and then heated in the fixed furnace 25, and the absorbent includes an oxidizing agent and a reducing agent. It has been added.

次に作用を説明する。
分析装置１０は、試料燃焼装置２０により、燃焼管内で４種ハロゲン（フッ素、塩素、臭素、ヨウ素）及び硫黄を含む有機・無機化合物の試料を燃焼分解して、ハロゲン化物、及び硫黄酸化物を生成する。 Next, the operation will be described.
The analyzer 10 burns and decomposes a sample of an organic / inorganic compound containing four types of halogens (fluorine, chlorine, bromine, iodine) and sulfur in the combustion tube by the sample combustion device 20 to obtain halides and sulfur oxides. Generate.

試料燃焼装置２０は、有機化合物の試料では、石英燃焼管３０で４種ハロゲン（フッ素、塩素、臭素、ヨウ素）及び硫黄を含む有機化合物の試料を燃焼分解し、無機化合物の試料では、セラミック燃焼管４０で必要な高温で無機化合物の試料を燃焼分解し、ハロゲン化物、及び硫黄酸化物を生成する。   The sample combustion apparatus 20 combusts and decomposes an organic compound sample containing four types of halogens (fluorine, chlorine, bromine, iodine) and sulfur in a quartz combustion tube 30 for an organic compound sample, and ceramic combustion for an inorganic compound sample. A sample of the inorganic compound is combusted and decomposed at a high temperature required in the tube 40 to generate a halide and a sulfur oxide.

試料燃焼装置２０では、移動炉２１で試料を予備燃焼し、固定炉２５で試料を本燃焼させ、無機化合物の試料はセラミック燃焼管４０で燃焼され、有機化合物の試料は石英燃焼管３０で燃焼される。固定炉２５の温度推移を図４に示す。   In the sample combustion apparatus 20, the sample is pre-combusted in the mobile furnace 21, the sample is subjected to main combustion in the fixed furnace 25, the inorganic compound sample is combusted in the ceramic combustion tube 40, and the organic compound sample is combusted in the quartz combustion tube 30. Is done. The temperature transition of the fixed furnace 25 is shown in FIG.

石英燃焼管３０では、太管部３１の前半部分で移動炉２１により試料が予備燃焼され、移動炉２１が太管部３１の前半部分を過ぎたところで太管部３１中で固定炉２５により本燃焼される。   In the quartz combustion tube 30, the sample is pre-combusted by the moving furnace 21 in the first half portion of the thick tube portion 31, and when the moving furnace 21 passes the first half portion of the thick tube portion 31, the sample is fixed in the thick tube portion 31 by the fixed furnace 25. Burned.

石英燃焼管３０は燃焼ガス吸収管５１に接続する細管部３５が一体に形成されており、この細管部３５から燃焼ガス吸収管５１に移動する。有機化合物より高温を要する無機化合物では、セラミック燃焼管４０により、移動炉２１で主管部４１が予備燃焼され、固定炉２５で主管部４１にある試料が固定炉２５により本燃焼される。燃焼ガスは燃焼ガス吸収管５１に接続された石英製のアダプタ（４５）から燃焼ガス吸収管５１に移動する。   The quartz combustion tube 30 is integrally formed with a narrow tube portion 35 connected to the combustion gas absorption tube 51, and moves from the narrow tube portion 35 to the combustion gas absorption tube 51. For inorganic compounds that require a higher temperature than the organic compound, the main pipe portion 41 is pre-combusted in the moving furnace 21 by the ceramic combustion tube 40, and the sample in the main pipe portion 41 is burned in the fixed furnace 25 by the fixed furnace 25. The combustion gas moves from the quartz adapter (45) connected to the combustion gas absorption pipe 51 to the combustion gas absorption pipe 51.

固定炉２５での加熱には、セラミック燃焼管４０で高温で無機化合物の試料を加熱可能なよう、シリコニット発熱体で加熱される。   The heating in the fixed furnace 25 is performed by a siliconite heating element so that the sample of the inorganic compound can be heated at a high temperature by the ceramic combustion tube 40.

無機試料を対象とする場合は、移動炉２１で混在する有機物及び塩として存在するハロゲンを放出させてから、固定炉２５で加熱する。例えば、無機化合物の試料を移動炉２１の中心部に置き、５〜１０分加熱してから、固定炉２５内に挿入し、１３５０℃程度で５〜１５分加熱する。すなわち、図６に示すように、先ず、位置Ａで移動炉２１により加熱して燃焼させた後、位置Ｂで固定炉２５により加熱して燃焼させる。   When an inorganic sample is a target, organic substances mixed in the mobile furnace 21 and halogens present as salts are released and then heated in the fixed furnace 25. For example, a sample of an inorganic compound is placed in the center of the mobile furnace 21 and heated for 5 to 10 minutes, then inserted into the fixed furnace 25 and heated at about 1350 ° C. for 5 to 15 minutes. That is, as shown in FIG. 6, first, the fuel is heated and burned at the position A by the moving furnace 21, and then heated and burned at the position B by the fixed furnace 25.

試料燃焼装置２０で生成したハロゲン化物、及び硫黄酸化物は吸収液に溶解し、吸収装置５０によりハロゲン化物及び硫酸イオンの試料溶液が生成される。試料溶液中の各イオン種はイオンクロマトグラフにより分離定量される。なお、標準試料のデータと比較することにより精度を上げることが出来る。図５に標準試料の分析結果を示す。   The halide and sulfur oxide generated in the sample combustion device 20 are dissolved in the absorbing solution, and the absorbing device 50 generates a sample solution of halide and sulfate ions. Each ion species in the sample solution is separated and quantified by an ion chromatograph. The accuracy can be increased by comparing with the data of the standard sample. FIG. 5 shows the analysis result of the standard sample.

吸収液には、酸化剤として例えば過酸化水素を、還元剤として例えば抱水ヒドラジンを併せて添加してあり、酸化・還元反応に同時に対応している。すなわち、フッ素・塩素では燃焼に伴い、純水に容易に吸収されるフッ化物・塩化物イオンが発生するが、臭素及びヨウ素では燃焼に伴い、ハロゲン化物と分子状の遊離体（Ｂｒ２、Ｉ２）を生成する。この遊離体のイオン化には還元剤の存在が必要である。 For example, hydrogen peroxide as an oxidizing agent and hydrazine hydrate as a reducing agent, for example, are added to the absorbing solution, and simultaneously support oxidation / reduction reactions. That is, fluoride and chloride ions that are easily absorbed in pure water are generated with combustion in fluorine and chlorine, but halides and molecular free bodies (Br 2 , I) are generated with combustion in bromine and iodine. 2 ) is generated. The ionization of this educt requires the presence of a reducing agent.

また、硫黄は、燃焼・吸収に伴い、硫酸・亜硫酸イオンを生成し。酸化剤の存在が必要である。これに対し酸化剤として例えば過酸化水素を、還元剤として例えば抱水ヒドラジンを吸収液に併せて添加することにより、酸化・還元反応に対し同時に分析できるようになった。図７〜図９に各種分析対象についての分析結果を示す。   In addition, sulfur generates sulfuric acid and sulfite ions with combustion and absorption. The presence of an oxidant is necessary. On the other hand, for example, hydrogen peroxide is added as an oxidizing agent, and hydrazine hydrate as a reducing agent is added to the absorbing solution, thereby enabling simultaneous analysis of the oxidation / reduction reaction. FIG. 7 to FIG. 9 show the analysis results for various analysis objects.

本発明の一実施の形態に係るセラミック燃焼管を用いた場合の分析装置の要部を示す説明図である。It is explanatory drawing which shows the principal part of the analyzer at the time of using the ceramic combustion tube which concerns on one embodiment of this invention. 本発明の一実施の形態に係る石英燃焼管を用いた場合の分析装置の要部を示す説明図である。It is explanatory drawing which shows the principal part of the analyzer at the time of using the quartz combustion tube which concerns on one embodiment of this invention. 本発明の一実施の形態に係る分析装置を示す概念図である。It is a conceptual diagram which shows the analyzer which concerns on one embodiment of this invention. 本発明の一実施の形態に係る分析装置における固定炉の温度推移を示す図表である。It is a graph which shows the temperature transition of the fixed furnace in the analyzer which concerns on one embodiment of this invention. 本発明の一実施の形態に係る分析装置において標準試料の分析結果を示す図表である。It is a graph which shows the analysis result of a standard sample in the analyzer which concerns on one embodiment of this invention. 本発明の一実施の形態に係る分析装置における無機化合物の試料を燃焼させる場合を示す説明図である。It is explanatory drawing which shows the case where the sample of the inorganic compound in the analyzer which concerns on one embodiment of this invention is burned. 本発明の一実施の形態に係る分析装置により廃電気電子機器材料を分析した結果を示す図表である。It is a graph which shows the result of having analyzed waste electrical and electronic equipment material with the analyzer which concerns on one embodiment of this invention. 本発明の一実施の形態に係る分析装置により廃電気電子機器材料を分析した結果を示すグラフである。It is a graph which shows the result of having analyzed the waste electrical and electronic equipment material with the analyzer which concerns on one embodiment of this invention. 本発明の一実施の形態に係る分析装置によりはんだフレックスを分析した結果を示すグラフを示す図表である。It is a graph which shows the graph which shows the result of having analyzed the solder flex by the analyzer which concerns on one embodiment of this invention.

符号の説明Explanation of symbols

１０…ハロゲン及び硫黄の分析装置
２０…試料燃焼装置
２１…移動炉
２５…固定炉
３０…石英燃焼管
３１…太管部
３５…細管部
４０…セラミック燃焼管
４１…主管部
４５…石英製アダプタ
４６…嵌合部
４７…細径部
５０…吸収装置
５１…燃焼ガス吸収管
５５…中継部 DESCRIPTION OF SYMBOLS 10 ... Analytical apparatus of halogen and sulfur 20 ... Sample combustion apparatus 21 ... Moving furnace 25 ... Fixed furnace 30 ... Quartz combustion pipe 31 ... Thick pipe part 35 ... Thin pipe part 40 ... Ceramic combustion pipe 41 ... Main pipe part 45 ... Quartz adapter 46 ... Fitting part 47 ... Small diameter part 50 ... Absorber 51 ... Combustion gas absorption pipe 55 ... Relay part

Claims (6)

燃焼管内で４種ハロゲン（フッ素、塩素、臭素、ヨウ素）及び硫黄を含む有機・無機化合物の試料を燃焼分解して、ハロゲン化物、及び硫黄酸化物を生成する試料燃焼装置を備えたハロゲン及び硫黄の分析装置であって、
前記試料燃焼装置は、有機化合物の試料のための石英燃焼管と無機化合物の試料のためのセラミック燃焼管とを備えていることを特徴とする有機・無機化合物中のハロゲン及び硫黄の分析装置。 Halogen and sulfur equipped with a sample combustion device that generates organic halides and sulfur oxides by burning and decomposing samples of organic and inorganic compounds containing four types of halogens (fluorine, chlorine, bromine, iodine) and sulfur in the combustion tube An analysis device,
The sample combustion apparatus includes a quartz combustion tube for a sample of an organic compound and a ceramic combustion tube for a sample of an inorganic compound, and an analysis apparatus for halogen and sulfur in an organic / inorganic compound. 燃焼管内で４種ハロゲン（フッ素、塩素、臭素、ヨウ素）及び硫黄を含む有機・無機化合物の試料を燃焼分解して、ハロゲン化物、及び硫黄酸化物を生成する試料燃焼装置を備えたハロゲン及び硫黄の分析装置であって、
前記試料燃焼装置は、試料を予備燃焼する移動炉と試料を本燃焼させる固定炉と、無機化合物の試料のためのセラミック燃焼管と有機化合物の試料のための石英燃焼管とを備え、
前記石英燃焼管は前記移動炉及び固定炉で加熱される太管部と、燃焼ガス吸収管に接続する細管部とが一体に形成されて成り、前記セラミック燃焼管は前記移動炉及び固定炉で加熱される主管部を、石英製アダプタで燃焼ガス吸収管に接続するよう構成されていることを特徴とする有機・無機化合物中のハロゲン及び硫黄の分析装置。 Halogen and sulfur equipped with a sample combustion device that generates organic halides and sulfur oxides by burning and decomposing samples of organic and inorganic compounds containing four types of halogens (fluorine, chlorine, bromine, iodine) and sulfur in the combustion tube An analysis device,
The sample combustion apparatus includes a mobile furnace for pre-combusting the sample, a fixed furnace for main-combustion of the sample, a ceramic combustion tube for the inorganic compound sample, and a quartz combustion tube for the organic compound sample,
The quartz combustion tube is formed by integrally forming a thick tube portion heated in the mobile furnace and a fixed furnace and a thin tube portion connected to a combustion gas absorption tube, and the ceramic combustion tube is formed in the mobile furnace and the fixed furnace. An apparatus for analyzing halogen and sulfur in organic and inorganic compounds, wherein the heated main pipe is connected to a combustion gas absorption pipe with a quartz adapter. セラミック燃焼管で無機化合物の試料を加熱可能なよう、固定炉では、炭化ケイ素発熱体を用いることを特徴とする請求項２に記載の有機・無機化合物中のハロゲン及び硫黄の分析装置。 The apparatus for analyzing halogen and sulfur in an organic / inorganic compound according to claim 2 , wherein a silicon carbide heating element is used in the fixed furnace so that the sample of the inorganic compound can be heated by the ceramic combustion tube. 無機化合物の試料では、移動炉で混在する有機物及び塩として存在するハロゲンを放出させてから、固定炉で加熱するようにしたことを特徴とする請求項２に記載の有機・無機化合物中のハロゲン及び硫黄の分析装置。   3. The halogen in an organic / inorganic compound according to claim 2, wherein in the inorganic compound sample, the organic substance mixed in the mobile furnace and the halogen present as a salt are released and then heated in the fixed furnace. And sulfur analyzer. 燃焼管内で４種ハロゲン（フッ素、塩素、臭素、ヨウ素）及び硫黄を含む有機・無機化合物の試料を燃焼分解して、ハロゲン化物、及び硫黄酸化物を生成する試料燃焼装置を備えたハロゲン及び硫黄の分析装置であって、
石英燃焼管内では有機化合物を対象として、セラミック燃焼管では無機化合物を対象として４種ハロゲン、及び硫黄を含む有機化合物の試料を燃焼分解し、ハロゲン化物、及び硫黄酸化物を生成する試料燃焼装置と、前記試料燃焼装置で生成したハロゲン化物、及び硫黄酸化物を吸収液に通じて溶解し、ハロゲン化物及び硫酸イオンを生成する吸収装置と、を備えたことを特徴とする有機・無機化合物中のハロゲン及び硫黄の分析装置。 Halogen and sulfur equipped with a sample combustion device that generates organic halides and sulfur oxides by burning and decomposing samples of organic and inorganic compounds containing four types of halogens (fluorine, chlorine, bromine, iodine) and sulfur in the combustion tube An analysis device,
A sample combustion apparatus for burning and decomposing a sample of an organic compound containing four kinds of halogens and sulfur to target an organic compound in a quartz combustion tube and an inorganic compound in a ceramic combustion tube to generate a halide and a sulfur oxide; In the organic / inorganic compound, characterized in that the halide and the sulfur oxide generated in the sample combustion apparatus are dissolved in the absorption liquid to generate halide and sulfate ions. Halogen and sulfur analyzer. 吸収液に、酸化剤と還元剤とを併せて添加したことを特徴とする請求項５に記載の有機・無機化合物中のハロゲン及び硫黄の分析装置。   6. The analyzer for halogen and sulfur in an organic / inorganic compound according to claim 5, wherein an oxidizing agent and a reducing agent are added to the absorbing solution.
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