JPH01248056A - Hydrogen concentration analyzing device in wet chlorine - Google Patents
Hydrogen concentration analyzing device in wet chlorineInfo
- Publication number
- JPH01248056A JPH01248056A JP7337488A JP7337488A JPH01248056A JP H01248056 A JPH01248056 A JP H01248056A JP 7337488 A JP7337488 A JP 7337488A JP 7337488 A JP7337488 A JP 7337488A JP H01248056 A JPH01248056 A JP H01248056A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- titanium
- valve
- chlorine gas
- chlorine
- 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.)
- Pending
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims description 14
- 239000000460 chlorine Substances 0.000 title claims description 14
- 229910052801 chlorine Inorganic materials 0.000 title claims description 14
- 239000007789 gas Substances 0.000 claims abstract description 52
- 238000005070 sampling Methods 0.000 claims abstract description 21
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 238000004458 analytical method Methods 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 15
- 238000001514 detection method Methods 0.000 claims description 9
- 238000010619 multiway switching Methods 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 2
- 229910052782 aluminium Inorganic materials 0.000 claims 2
- 229910052720 vanadium Inorganic materials 0.000 claims 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 101100204059 Caenorhabditis elegans trap-2 gene Proteins 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000000034 method Methods 0.000 description 23
- 238000004817 gas chromatography Methods 0.000 description 13
- 150000002431 hydrogen Chemical class 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005868 electrolysis reaction Methods 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000012159 carrier gas Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- -1 etc. Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ANUQVPMOKIYKBZ-UHFFFAOYSA-N [Ti].[Ni].[Mo] Chemical compound [Ti].[Ni].[Mo] ANUQVPMOKIYKBZ-UHFFFAOYSA-N 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- DPGAAOUOSQHIJH-UHFFFAOYSA-N ruthenium titanium Chemical compound [Ti].[Ru] DPGAAOUOSQHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000010206 sensitivity analysis Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Sampling And Sample Adjustment (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、塩素中のガス濃度を高感度で分析するための
装置に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an apparatus for analyzing gas concentration in chlorine with high sensitivity.
更に詳しくは湿塩素中の水素ガス濃度を高感度で分析す
るための装置に関する。More specifically, the present invention relates to an apparatus for analyzing hydrogen gas concentration in wet chlorine with high sensitivity.
〔従来の技術１
混合ガス中の各成分を分析することは化学工業において
日常頻繁に行なわれる操作である。[Prior Art 1] Analyzing each component in a mixed gas is an operation frequently performed on a daily basis in the chemical industry.
食塩電解工業において、電解セルより発生する塩素ガス
中の水素濃度を測定することもその一種であり、工程管
理上重要である。In the salt electrolysis industry, measuring the hydrogen concentration in chlorine gas generated from electrolytic cells is one type of measurement, and is important for process control.
従来、塩素ガス中の水素濃度を実験室的に測定する方法
として、ＪＩＳ−に１１０２に規定されている分析容器
を用い、塩素ガスをヨウ化カリウム溶液、苛性ソーダ溶
液、チオ硫酸ナトリウム溶液等に吸収させて不活性ガス
とし、この不活性ガスに対し、種々の分析方法例えば、
爆発ピペット法、パラジウム−アスベスト法、ガスクロ
マト法等を適用している。Conventionally, as a laboratory method for measuring the hydrogen concentration in chlorine gas, chlorine gas is absorbed into a potassium iodide solution, a caustic soda solution, a sodium thiosulfate solution, etc. using an analysis container specified in JIS-1102. This inert gas is then subjected to various analytical methods such as
The explosive pipette method, palladium-asbestos method, gas chromatography method, etc. are applied.
これらの方法は、あくまでも−次的い濃度を知るための
分析方法であり、又時間と労力を要し、かつ連続化する
ことは困難である。These methods are merely analytical methods for determining the next level of concentration, require time and effort, and are difficult to implement continuously.
一方、連続監視用分析計として、乾燥塩素ガスに対して
は、ガスクロマト装置を用いる計測器が実用化されてい
るが、腐蝕性の塩素ガスには適用できない。On the other hand, as a continuous monitoring analyzer, a measuring instrument using a gas chromatography device has been put into practical use for dry chlorine gas, but it cannot be applied to corrosive chlorine gas.
湿塩素ガスに対応する分析方法として、非分散形光外線
ガス分析計が実用化されている。特開昭５４−３９１９
２号公報にはこの分析計が開示されているが、これは、
腐蝕性の湿塩素ガスの分析には適用できるが、検出感度
が低く一般に数千ｐｐ＋ｍ程度の水素濃度のものしか検
出されずその応用範囲は限定される。A non-dispersive optical external gas analyzer has been put into practical use as an analysis method for wet chlorine gas. Japanese Patent Publication No. 54-3919
This analyzer is disclosed in Publication No. 2, but it is
Although it can be applied to the analysis of corrosive wet chlorine gas, the detection sensitivity is low and generally only hydrogen concentrations of about several thousand pp+m can be detected, which limits its range of application.
例えば、イオン交換膜性食塩電解においては、塩素ガス
中の水素濃度は数百ｐｐｍ以下であるのでこの赤外線ガ
ス分析計の利用は困難である。For example, in ion-exchange membrane salt electrolysis, the hydrogen concentration in chlorine gas is several hundred ppm or less, so it is difficult to use this infrared gas analyzer.
又、塩素ガス中の水素を光化学反応により塩酸に変換し
、熱電導度ガス分析計にて定量分析する方法も公知であ
る。Furthermore, a method is also known in which hydrogen in chlorine gas is converted into hydrochloric acid by a photochemical reaction and quantitatively analyzed using a thermal conductivity gas analyzer.
しかしこの方法は、
１）検出セルがガラスコーティングされているため、検
出感度が低く、赤外線ガス分析計と同様に高感度分析に
は不適当である。However, this method has the following problems: 1) Since the detection cell is coated with glass, the detection sensitivity is low, and it is unsuitable for high-sensitivity analysis like an infrared gas analyzer.
２）試料ガス流量の変動により分析誤差が生ずるため、
試料ガスの精密な流量コントロールが必要となる。2) Analysis errors occur due to fluctuations in sample gas flow rate.
Precise flow rate control of sample gas is required.
３）塩素ガス中に共存する窒素、酸素、炭酸ガス、水分
の干渉により分析誤差が生じやすい。3) Analysis errors are likely to occur due to interference from nitrogen, oxygen, carbon dioxide, and moisture coexisting in chlorine gas.
４）水素濃度を正確に把握するための校正ガスの選定が
困難である。4) It is difficult to select a calibration gas to accurately determine the hydrogen concentration.
等々、この方法は種々の問題があり、工程管理の分析装
置としては必ずしも信頼性の高いものではない。This method has various problems and is not necessarily reliable as an analytical device for process control.
特開昭５５−４０９２２号公報には、塩素ガス中の水素
ガスを高感度で定量分析する方法として、ガスクロマト
法が開示されている。JP-A-55-40922 discloses a gas chromatography method as a method for quantitatively analyzing hydrogen gas in chlorine gas with high sensitivity.
この方法は、分析装置を腐蝕から保護するための装置面
での改良が開示されている。即ち、試料ガス中の塩素ガ
スと水分を一旦−１００”Ｃ以下の温度で凝結固化し、
水素ガスのみを取り出しこれをガスクロマト装置に導入
し分析する方法である。この方法は、冷却のために液体
窒素等の高価な冷媒が必要であり、又、凝縮器内での塩
素、水の固化によるラインの閉塞が起ることが多く、長
期間の連続分析には不適当であり、又、装置の試料ガス
流路内に固形物が発生するため、長期間の連続分析を必
要とするプロセス分析計としては使用できない。This method discloses improvements in the equipment to protect the analyzer from corrosion. That is, chlorine gas and moisture in the sample gas are once coagulated and solidified at a temperature of -100"C or less,
This method extracts only hydrogen gas and introduces it into a gas chromatography device for analysis. This method requires an expensive refrigerant such as liquid nitrogen for cooling, and the line is often blocked due to solidification of chlorine and water in the condenser, so it is not suitable for long-term continuous analysis. This method is unsuitable, and solid matter is generated in the sample gas flow path of the device, so it cannot be used as a process analyzer that requires continuous analysis over a long period of time.
［発明が解決しようとする問題点］
本発明は、特に金属等に対して腐蝕性の高い、水分を含
んだ湿塩素中に混在するガスを、直接、且つ精度良く定
量分析でき又、次の点を満足できる工程分析装置を提供
することを目的とするものである。[Problems to be Solved by the Invention] The present invention enables direct and accurate quantitative analysis of gases mixed in wet chlorine containing water, which is particularly corrosive to metals, etc. The purpose of this invention is to provide a process analysis device that satisfies the above points.
ｌ）連続的に自動計測できること。l) Capable of continuous automatic measurement.
２）低濃度の水素ガスが測定できること。2) Capable of measuring low concentration hydrogen gas.
３）サンプリングガスラインが閉塞しないこと。3) The sampling gas line must not be blocked.
４）耐久性があり、保守が容易であること。4) It must be durable and easy to maintain.
［問題解決のための手段］
本発明は、ガスサンプリング部、第一の多方切替えバル
ブ、第二の多方切替えバルブ、及びガスクロマト検出部
が夫々この順序で連結され、前記バルブの少なくとも一
方がチタン又はチタン合金で構成されたものである湿塩
素中の水素濃度分析装置に関するものである。[Means for Solving the Problem] The present invention provides a gas sampling section, a first multi-way switching valve, a second multi-way switching valve, and a gas chromatograph detection section, each of which is connected in this order, and at least one of the valves is made of titanium. The present invention also relates to a hydrogen concentration analyzer in wet chlorine that is made of a titanium alloy.
本発明の一実施態様は次のとうりである。One embodiment of the present invention is as follows.
試料ガスは、ポンプにより吸引され、必要に応じてフィ
ルター又はトラップを経てサンプリングバルブにて一定
量試料ガス計量管に採取される、次にプレカットカラム
を付帯する切替バルブ（好ましくは自動切替バルブ）に
導かれる。次いでバルブの流路切り替え操作により、塩
素及び水は系外へ排出され、それ以外の水素、酸素、窒
素、炭酸ガス、−酸化炭素等の混在ガス成分がガスクロ
マト装置へ導入され定量分析されるもので、本発明では
、少なくとも試料の検出部への導入部、特に前述のバル
ブ部分をチタン又はチタン合金で構成したことが特徴で
ある。The sample gas is sucked by a pump, passes through a filter or a trap as necessary, and is collected in a fixed amount into a sample gas metering tube by a sampling valve.Then, it is transferred to a switching valve (preferably an automatic switching valve) attached to a pre-cut column. be guided. Next, by switching the flow path of the valve, chlorine and water are discharged from the system, and other mixed gas components such as hydrogen, oxygen, nitrogen, carbon dioxide, and carbon oxide are introduced into a gas chromatograph and quantitatively analyzed. The present invention is characterized in that at least the part for introducing the sample into the detection part, especially the above-mentioned valve part, is made of titanium or a titanium alloy.
本発明の対象となる試料ガスは、水分を含有する腐蝕性
の塩素である。The sample gas targeted by the present invention is corrosive chlorine containing moisture.
又、サンプリング時の温度における水蒸気圧に相当する
水を含有する塩素にも適用されるが、塩素中の水分量は
特に限定されるものではない。The present invention also applies to chlorine containing water corresponding to the water vapor pressure at the temperature at the time of sampling, but the amount of water in chlorine is not particularly limited.
一般に食塩電解、塩化カリ電解、塩酸電解等の工程にお
いて、隔膜法並びにイオン交換膜法の電解セルより発生
する湿塩素ガスに対して好適に適用される。Generally, in processes such as salt electrolysis, potassium chloride electrolysis, and hydrochloric acid electrolysis, it is suitably applied to wet chlorine gas generated from electrolysis cells using the diaphragm method and the ion exchange membrane method.
本発明で検出の対象となる成分は主として水素であるが
、塩素中に含有される酸素、窒素、炭酸ガス、−酸化炭
素等も精度良く分析可能である。The component to be detected in the present invention is mainly hydrogen, but oxygen, nitrogen, carbon dioxide, carbon oxide, etc. contained in chlorine can also be analyzed with high accuracy.
本発明をガスクロマト分析装置に適用した際の構成につ
いて詳述する。The configuration when the present invention is applied to a gas chromatography analyzer will be described in detail.
本発明を構成する上で好ましいの機器類は、サンプリン
グポンプ、フィルター又はトラップ、試料ガスサンプリ
ングバルブ、プレカットカラム付帯の試料ガス導入バル
ブ、及びガスクロマト分析装置、更に必要に応じてデー
タ処理部、自動制御のコントローラーである。試料ガス
サンプリングバルブは、多方向への切替え口を持つ切替
えバルブ、例えば、Ｇ方流路、８方流路の切替えバルブ
が用いられる。Preferable equipment for configuring the present invention includes a sampling pump, a filter or a trap, a sample gas sampling valve, a sample gas introduction valve attached to a pre-cut column, a gas chromatograph analyzer, and, if necessary, a data processing unit, an automatic It is a controller of control. As the sample gas sampling valve, a switching valve having switching ports in multiple directions, for example, a switching valve with a G-way flow path or an 8-way flow path is used.
試料ガスサンプリングバルブは、好ましくは自励作動の
バルブでチタン又はチタン合金製の多方向切替えバルブ
である。本バルブは、通常チタン又はチタン合金製のガ
ス計量管（１０μＬ〜数＋ｍＬ）を付帯している。試料
ガスのサンプリングを円滑且つ効率的に行なうためには
通常サンプリング用ポンプが使用される。The sample gas sampling valve is preferably a self-operating valve and a multi-way switching valve made of titanium or a titanium alloy. This valve is usually accompanied by a gas measuring tube (10 μL to several + mL) made of titanium or titanium alloy. A sampling pump is normally used to sample the sample gas smoothly and efficiently.
又、フィルター、トラップは、試料ガス中の微粒子等の
固形物が混在する場合に用い、これによりガス流路の閉
塞を防止する。ガスクロマト分析装置への試料ガス導入
装置は、検出部への試料ガス導入前に試料ガス中の水及
び塩素ガス成分と水素、酸素及び窒素成分とを分離する
ためのプレカットカラム（充填材としては、塩素ガス、
水分に対して一定の保持容量をＦ！ｊち、水素、酸素、
窒素等と親和力の弱いもの、例えばポーラスなポリマー
等）及び分離された水と塩素成分を系外へ排出し、カラ
ムの劣化を防止するためのバックフラッシュ流路、更に
キャリアガスと共に水素、酸素及び窒素成分をガスクロ
マト装置へ導入するための出口部等の機能を有するもの
である。Further, filters and traps are used when solid substances such as particulates are present in the sample gas, thereby preventing clogging of the gas flow path. The sample gas introduction device to the gas chromatograph analyzer uses a pre-cut column (filling material: , chlorine gas,
F has a certain holding capacity for moisture! j, hydrogen, oxygen,
There is also a backflush flow path to prevent column deterioration by discharging separated water and chlorine components (such as porous polymers, etc.) that have a weak affinity with nitrogen, etc., as well as hydrogen, oxygen, and It has a function such as an outlet section for introducing nitrogen components into the gas chromatography device.
このような構成とすることにより、プレカットカラム入
口付近で保持されている塩素ガス、水分を、バルブ操作
により、出口側よりキャリアーガスと共に系外に排出で
き、塩素ガスによるＴＣＤ検出器の腐蝕を防止できる。With this configuration, the chlorine gas and moisture held near the inlet of the pre-cut column can be discharged from the outlet side along with the carrier gas by operating the valve, preventing corrosion of the TCD detector due to chlorine gas. can.
本発明による分析操作に使用するキャリアーガスは、通
常のガスクロマトグラフィー法で使用するガスを使用で
きるが、アルゴンガスが好ましい。As the carrier gas used in the analytical operation according to the present invention, gases used in ordinary gas chromatography methods can be used, but argon gas is preferable.
本発明の装置では、前記したように少なくとも検出部へ
の試料導入部をチタン又はチタン合金で構成されていれ
ば良いが、その他のプレカットカラム、ガス導管等の付
帯機器についても、これらの金属で構成することは何等
さしつかえない。In the device of the present invention, as described above, at least the sample introduction part to the detection part may be made of titanium or a titanium alloy, but other ancillary equipment such as pre-cut columns and gas pipes may also be made of these metals. There is nothing wrong with configuring it.
プレカットカラムで分離した水素、酸素、窒素等は、キ
ャリアーガスに同伴され、ガスクロマト検出部で検出さ
れ、検出量は電気信号に変換されデータ処理装置へ入力
され定量計算される。尚、ガスクロマトのカラム充填剤
は、通常用いられるモレキュラーシーブ、活性アルミナ
、モレキュラーシービングカーボン等が用いられる。Hydrogen, oxygen, nitrogen, etc. separated by the pre-cut column are accompanied by a carrier gas and detected by a gas chromatography detection section, and the detected amount is converted into an electrical signal and input to a data processing device for quantitative calculation. As the column packing material for gas chromatography, commonly used molecular sieves, activated alumina, molecular sieving carbon, etc. are used.
又、検出器としては、水素、酸素、窒素等の一連のガス
に高感度な熱電導度型検出器が用いられるがこれらに限
定されるものではない。Further, as a detector, a thermal conductivity type detector is used which is highly sensitive to a series of gases such as hydrogen, oxygen, nitrogen, etc., but is not limited thereto.
本発明で用いるチタン合金はチタン・パラジウム、チタ
ン・ルテニウム、チタン・ニッケル・モリブデン、チタ
ン・アルミニウム、チタン・バナジウム、チタン・アル
ミニウム・バナジウムの群から選ばれる１種でチタンを
主成分とする合金である。The titanium alloy used in the present invention is one selected from the group of titanium-palladium, titanium-ruthenium, titanium-nickel-molybdenum, titanium-aluminum, titanium-vanadium, and titanium-aluminum-vanadium, and is an alloy whose main component is titanium. be.
［発明の効果］
従来、イオン交換脱法食塩電解工業においては、塩素ガ
ス中の水素濃度が数十〜数百ｐｐｍと低いため、又、発
生ガスが水を含有する腐蝕性の湿塩素ガスであるため、
水素濃度の高感度分析をプロセスガスクロマトグラフに
て連続的に実施することは困難であった。[Effect of the invention] Conventionally, in the ion-exchange demethod salt electrolysis industry, the hydrogen concentration in chlorine gas is as low as several tens to hundreds of ppm, and the generated gas is corrosive wet chlorine gas containing water. For,
It has been difficult to continuously perform highly sensitive analysis of hydrogen concentration using a process gas chromatograph.
本発明に基づくチタン又はチタン合金製の装置の使用に
より、電解セルより発生した湿塩素ガスを直接分析シス
ティムへ導入することができ又、塩素ガス中の水素のみ
ならず窒素、酸素を高感度で定量分析が可能となった。By using the device made of titanium or titanium alloy according to the present invention, wet chlorine gas generated from the electrolytic cell can be directly introduced into the analysis system, and not only hydrogen but also nitrogen and oxygen in chlorine gas can be detected with high sensitivity. Quantitative analysis became possible.
又、本発明の装置をガスクロマト装置と組み合せること
により、電解工程管理用のプロセス分析装置として利用
できるので、その工業的利用価値は極めて大きい。Further, by combining the device of the present invention with a gas chromatography device, it can be used as a process analysis device for controlling electrolytic processes, so its industrial utility value is extremely large.
又、湿塩素ガスの前処理過程では固体析出物が全く発生
しないため、長期間安定に分析装置を運転することがで
き、簡便な操作性を有する分析システィムとすることが
できる。Furthermore, since no solid precipitates are generated during the wet chlorine gas pretreatment process, the analyzer can be operated stably for a long period of time, and the analyzer system can be easily operated.
本発明を用いた場合、ガスクロマト装置部へ導入される
ガスは、水及び塩素を含をしていないため、検出部に高
感度用熱電導度針の使用が可能となり、低濃度の水素を
精度良く測定することが可能となる。When the present invention is used, the gas introduced into the gas chromatography unit does not contain water or chlorine, so it is possible to use a high-sensitivity thermoconductivity needle in the detection unit, allowing low concentration hydrogen to be used. It becomes possible to measure with high precision.
［実施例］
以下に本発明を実施例により更に詳細に説明するが、本
発明はこの実施例のみに限定されるものではない。[Example] The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples.
実施例 図−１に示した構成の分析装置を使用した。Example An analyzer with the configuration shown in Figure 1 was used.
ガスクロマト装置（８）はキャリアー（Ａｒ）を流し、
１’ＣＤ検出器を安定化させる。The gas chromatography device (8) flows a carrier (Ar),
Stabilize the 1'CD detector.
多流路切替えバルブ（４） （５）を実線流路とし、ポ
ンプ（１）により試料の湿塩素ガスはトラップ（２）を
通過し、試料ガスサンプリングバルブ（４）に付帯した
サンプリングチューブ（３）を通り置換、サンプリング
する。試料導入バルブを点線流路に切替える。更に一定
時間経過すると試料ガスサンプリングバルブ（４）は点
線流路に切替わり、試料ガスを試料カス導入バルブ（５
）に付帯したプレカットカラム（７）に導く。試料ガス
サンプリングバルブ（４）は一定時間経過後、次の試料
をサンプリングするために実践流路に切替わる。バルブ
の切替わりはあらかじめ時間を設定したタイマー等によ
り作動させる。The multi-channel switching valve (4) (5) is set as a solid line flow channel, and the wet chlorine gas of the sample is passed through the trap (2) by the pump (1), and the sampling tube (3) attached to the sample gas sampling valve (4) is connected to the sample gas sampling valve (4). ) to replace and sample. Switch the sample introduction valve to the dotted line flow path. After a further certain period of time has elapsed, the sample gas sampling valve (4) switches to the dotted line flow path, and the sample gas is transferred to the sample waste introduction valve (5).
) into a pre-cut column (7) attached to the column. The sample gas sampling valve (4) switches to the practical flow path after a certain period of time to sample the next sample. The switching of the valve is activated by a timer or the like with a preset time.
データ処理装置の始動は、前記の試料ガスサンプリング
バルブ（４）が実線流路から点線流路へ切替わる時点で
行なう。The data processing device is started at the time when the sample gas sampling valve (4) switches from the solid line flow path to the dotted line flow path.
プレカットカラム（７）で湿塩素ガス中の塩素ガス、水
分と水素、酸素、窒素等は分離され、水素、酸素、窒素
等はキャリアーガスと共に分離カラム（９）に導入され
、夫々のカス成分に分離され、ＴＣＤ検出器で検出され
その結果得られる電気信号により、データ処理装置（１
１）に入力され定量計算される。Chlorine gas, moisture, hydrogen, oxygen, nitrogen, etc. in the wet chlorine gas are separated in the pre-cut column (7), and the hydrogen, oxygen, nitrogen, etc. are introduced into the separation column (9) together with the carrier gas, and are separated into their respective residue components. The electrical signal is separated and detected by the TCD detector, and the resulting electrical signal is transmitted to the data processing device (1
1) and quantitatively calculated.
このような操作を繰返し行なうことにより連続測定が可
能となる。Continuous measurement becomes possible by repeating such operations.
イオン交換膜電解により発生する湿塩素ガスに対し、何
ら前処理を行なわず直接本発明の分析装置に導入しても
、水分、塩素ガスはバックフラッシュ操作により系外に
排出するので、イオン交換膜電解セルにより発生した湿
塩素ガスを２０００時間連続して測定し、水素０．Ｏ１
〜０．３％、酸素ｔ −ｔ、ａ％、窒素０．Ｏ１〜０．
０３％の測定値を得たが測定は定常的に行なわれた。Even if wet chlorine gas generated by ion-exchange membrane electrolysis is directly introduced into the analyzer of the present invention without any pretreatment, the water and chlorine gas will be discharged from the system by backflushing. The wet chlorine gas generated by the electrolytic cell was continuously measured for 2,000 hours, and hydrogen 0. O1
~0.3%, oxygen t-t, a%, nitrogen 0. O1~0.
Although a measured value of 0.3% was obtained, measurements were carried out regularly.
比較のため、切替えバルブを５Ｏ８−３１８の材質のも
のにし、同様の測定を行なったが、測定開始後１００時
間でバルブの切替えに変調を来たし、ガス洩れが発生し
た。For comparison, similar measurements were performed using a switching valve made of 5O8-318 material, but 100 hours after the start of the measurement, the switching of the valve became irregular and gas leakage occurred.
図−１は本発明の一実施態様を示す経路図で１はガスサ
ンプリングポンプ、 ２はトラップ、３はサンプリング
チューブ、４は試料ガスサンプリングバルブ、５は試料
ガス導入バルブ、６はダミーカラム、７はプレカットカ
ラム、８はガスクロマト装置、９は分離カラム、ｌＯは
ＴＣＤ検出器、１１はデータ処理装置、１２はキャリア
ーガス導入口、１３はベントロを夫々示す。Figure 1 is a route diagram showing one embodiment of the present invention, in which 1 is a gas sampling pump, 2 is a trap, 3 is a sampling tube, 4 is a sample gas sampling valve, 5 is a sample gas introduction valve, 6 is a dummy column, 7 8 is a pre-cut column, 8 is a gas chromatography device, 9 is a separation column, 10 is a TCD detector, 11 is a data processing device, 12 is a carrier gas inlet, and 13 is a ventilator.
Claims (1)
二の多方切替えバルブ、及びガスクロマト検出部が夫々
この順序で連結され、前記バルブの少なくとも一方のバ
ルブがチタン又はチタン合金で構成されたものである湿
塩素中の水素濃度分析装置。 ２）第一の多方切替えバルブがガスサンプリング用計量
管を持つ多方切替えバルブであり、第二の多方切替えバ
ルブがプレカットカラム及びバックフラッシュ機構を持
つ多方切替えバルブである特許請求の範囲１項記載の分
析装置。 ３）チタン合金がチタン・パラジウム、チタン・ルテニ
ウム、チタン・ニッケル・モリブデン、チタン・アルミ
ニウム、チタン・バナジウム、チタン・アルミニウム・
バナジウムの群から選ばれる１種である特許請求の範囲
１又は２項記載の分析装置。[Claims] 1) A gas sampling section, a first multi-way switching valve, a second multi-way switching valve, and a gas chromatograph detection section are connected in this order, and at least one of the valves is made of titanium or titanium. A device for analyzing hydrogen concentration in wet chlorine, which is made of an alloy. 2) The first multi-way switching valve is a multi-way switching valve having a metering tube for gas sampling, and the second multi-way switching valve is a multi-way switching valve having a pre-cut column and a backflush mechanism. Analysis equipment. 3) Titanium alloys include titanium/palladium, titanium/ruthenium, titanium/nickel/molybdenum, titanium/aluminum, titanium/vanadium, titanium/aluminum/
The analyzer according to claim 1 or 2, which is one type selected from the group of vanadium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7337488A JPH01248056A (en) | 1988-03-29 | 1988-03-29 | Hydrogen concentration analyzing device in wet chlorine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7337488A JPH01248056A (en) | 1988-03-29 | 1988-03-29 | Hydrogen concentration analyzing device in wet chlorine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01248056A true JPH01248056A (en) | 1989-10-03 |
Family
ID=13516341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7337488A Pending JPH01248056A (en) | 1988-03-29 | 1988-03-29 | Hydrogen concentration analyzing device in wet chlorine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01248056A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105510503A (en) * | 2015-12-31 | 2016-04-20 | 上海正帆科技股份有限公司 | Analysis device and method of electronic-grade chlorine gas |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49130794A (en) * | 1973-03-30 | 1974-12-14 | ||
| JPS51111391A (en) * | 1975-03-26 | 1976-10-01 | Hitachi Ltd | Liquid chromatograph |
| JPS5713355A (en) * | 1980-06-27 | 1982-01-23 | Yokogawa Hokushin Electric Corp | Gas chromatographic apparatus |
| JPS586906A (en) * | 1981-07-04 | 1983-01-14 | Sumitomo Electric Ind Ltd | Manufacture of nonequilibrium state sintered body |
| JPS6166960A (en) * | 1984-09-10 | 1986-04-05 | Yokogawa Hokushin Electric Corp | Coating method of pipe inside |
| JPS62145137A (en) * | 1985-12-20 | 1987-06-29 | Hitachi Ltd | Analyzing device for incineration gas |
-
1988
- 1988-03-29 JP JP7337488A patent/JPH01248056A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49130794A (en) * | 1973-03-30 | 1974-12-14 | ||
| JPS51111391A (en) * | 1975-03-26 | 1976-10-01 | Hitachi Ltd | Liquid chromatograph |
| JPS5713355A (en) * | 1980-06-27 | 1982-01-23 | Yokogawa Hokushin Electric Corp | Gas chromatographic apparatus |
| JPS586906A (en) * | 1981-07-04 | 1983-01-14 | Sumitomo Electric Ind Ltd | Manufacture of nonequilibrium state sintered body |
| JPS6166960A (en) * | 1984-09-10 | 1986-04-05 | Yokogawa Hokushin Electric Corp | Coating method of pipe inside |
| JPS62145137A (en) * | 1985-12-20 | 1987-06-29 | Hitachi Ltd | Analyzing device for incineration gas |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105510503A (en) * | 2015-12-31 | 2016-04-20 | 上海正帆科技股份有限公司 | Analysis device and method of electronic-grade chlorine gas |
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