JPH0638079B2 - Gas analysis method and apparatus - Google Patents
Gas analysis method and apparatusInfo
- Publication number
- JPH0638079B2 JPH0638079B2 JP7225186A JP7225186A JPH0638079B2 JP H0638079 B2 JPH0638079 B2 JP H0638079B2 JP 7225186 A JP7225186 A JP 7225186A JP 7225186 A JP7225186 A JP 7225186A JP H0638079 B2 JPH0638079 B2 JP H0638079B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- chlorine
- sensor
- oxygen
- chlorine gas
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 23
- 238000004868 gas analysis Methods 0.000 title claims description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 48
- 239000007789 gas Substances 0.000 claims description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- 238000010521 absorption reaction Methods 0.000 claims description 24
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 22
- 229910001882 dioxygen Inorganic materials 0.000 claims description 22
- 239000012535 impurity Substances 0.000 claims description 16
- 238000005868 electrolysis reaction Methods 0.000 claims description 14
- 239000012159 carrier gas Substances 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003518 caustics Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 239000004155 Chlorine dioxide Substances 0.000 claims description 3
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000003014 ion exchange membrane Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000005398 Figaro Species 0.000 description 1
- 238000012369 In process control Methods 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010965 in-process control Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004457 water analysis Methods 0.000 description 1
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はたとえば塩化アルカリ電解槽より発生する塩素
ガス中に微量に含まれる不純物ガスの分析方法に関す
る。TECHNICAL FIELD The present invention relates to a method for analyzing an impurity gas contained in a minute amount in chlorine gas generated from an alkaline chloride electrolytic cell, for example.
（従来の技術） 塩化アルカリ電解槽より発生する塩素ガス中には水素ガ
ス，炭化水素ガスのような可燃性ガス又は炭素ガス，酸
素ガス等が微量に含まれている。たとえばイオン交換膜
法による塩化アルカリ溶液の電解工程では、陽イオン交
換膜の劣化あるいは亀裂により、陽極室で発生する塩素
ガスに陰極室で発生する水素ガスが混入して水素ガスが
約 5容量％以上になると塩素と水素との光反応による爆
発を起す危険性がある。したがって電解工程において、
塩素ガス中に含有する水素及び酸素等不純物ガスの分析
を行い、上記のような危険性を回避することは工程管理
上、重要な問題である。(Prior Art) Chlorine gas generated from an alkaline chloride electrolytic cell contains a trace amount of combustible gas such as hydrogen gas and hydrocarbon gas, carbon gas, oxygen gas, or the like. For example, in the electrolysis process of an alkali chloride solution by the ion exchange membrane method, hydrogen gas generated in the cathode chamber mixes with chlorine gas generated in the anode chamber due to deterioration or cracking of the cation exchange membrane, and hydrogen gas is contained at about 5% by volume. In the case above, there is a risk of causing an explosion due to a photoreaction of chlorine and hydrogen. Therefore, in the electrolysis process,
It is an important problem in process control to analyze the impurity gas such as hydrogen and oxygen contained in chlorine gas and avoid the above danger.
従来、このような塩素ガス中の水素ガスを分析するに
は、電解槽より発生する塩素ガスを分析器に採取して、
ヨウ化カリ溶液に純塩素ガスのみを吸収させ、残ガス中
の水素ガスはパラジウムアスベスト触媒を用いて燃焼さ
せ水として凝縮させ、容量減により定量分析を行ってい
る。またイオン交換膜の劣化あるいは亀裂により、陰極
液が陽極液に混入しＯＨイオンの放電による酸素発生が
起る場合には、塩素ガス中に酸素ガスが混入してくる。
酸素ガスの分析は、混入水素ガスの分析と同様に、ヨウ
化カリ溶液に純塩素のみを吸収させ、ピロガロール液よ
って酸素ガスを吸収させてその容量減によって定量す
る。これらの操作は手作業による容量分析であるため、
手間と時間を要する欠点がある。またこの方法では連続
的測定を行うことはできない。他の方法としては、ガス
クロマトグラフによる方法，あるいはこれらのガスに紫
外線を照射してガス組成の変化による熱伝導度の変化を
測定する方法，又は赤外吸収による方法等がある。Conventionally, in order to analyze hydrogen gas in such chlorine gas, chlorine gas generated from the electrolytic cell is sampled in an analyzer,
Only pure chlorine gas is absorbed in the potassium iodide solution, and hydrogen gas in the residual gas is burned using a palladium asbestos catalyst to be condensed as water, and quantitative analysis is performed by reducing the volume. When the catholyte mixes with the anolyte due to deterioration or cracks in the ion-exchange membrane to generate oxygen due to discharge of OH ions, oxygen gas mixes into the chlorine gas.
In the analysis of oxygen gas, as in the case of analysis of mixed hydrogen gas, only potassium chloride is absorbed in a potassium iodide solution, oxygen gas is absorbed by a pyrogallol solution, and the volume of the oxygen gas is reduced. Since these operations are manual volumetric analyzes,
It has the drawback of requiring labor and time. Moreover, continuous measurement cannot be performed by this method. Other methods include a method using a gas chromatograph, a method of irradiating these gases with ultraviolet rays to measure a change in thermal conductivity due to a change in gas composition, or a method using infrared absorption.
しかしいずれの場合も塩素ガスが強烈な腐食性をもつた
め、材質面で大きな制約を受ける上、装置としてもかな
り大規模になるという欠点がある。However, in any case, since chlorine gas has a strong corrosive property, there are drawbacks that the material is greatly restricted and the device is considerably large-scaled.
（発明の目的） 本発明は上記の欠点に鑑み、比較的簡易な装置により材
質面の制約を顧慮することなく電解工程より発生する塩
素ガス中に微量の不純物ガスとして含まれる水素ガス，
酸素ガスを連続的に容易に分析しうる方法および装置を
提供することにある。(Object of the Invention) In view of the above-mentioned drawbacks, the present invention provides a hydrogen gas contained as a trace amount of impurity gas in chlorine gas generated from an electrolysis step without consideration of material restrictions by a relatively simple device,
An object of the present invention is to provide a method and an apparatus capable of continuously and easily analyzing oxygen gas.
（発明の構成） 本発明はすなわち、塩化物電解工程より発生する塩素ガ
ス中に微量の不純物ガスとして含まれる水素ガス，酸素
ガスを測定するにあたり、上記塩素ガスを連続的に採取
して、苛性アルカリ溶液を流下させた塩素ガス吸収塔に
導き、塩素及び不純物ガス中の炭酸ガスを吸収させ、残
存する不純物ガスを所定流量のキャリアガスにて水素ガ
ス及び酸素ガスの測定用センサーに送り、その濃度を連
続的に測定することを特徴とするガス分析方法およびこ
れに使用される装置である。(Structure of the Invention) In the present invention, in measuring hydrogen gas and oxygen gas contained as a trace amount of impurity gas in chlorine gas generated from a chloride electrolysis step, the chlorine gas is continuously sampled to obtain causticity. Lead the chlorine solution to the chlorine gas absorption tower, absorb the carbon dioxide gas in the chlorine and the impurity gas, and send the remaining impurity gas to the sensor for measuring hydrogen gas and oxygen gas with a carrier gas of a predetermined flow rate, A gas analysis method characterized by continuously measuring the concentration and an apparatus used for the method.
本発明方法及び装置を図面により説明すると、第 1図に
おいて貯槽（ 1）内の苛性アルカリ溶液（ 2）は、ポン
プ（ 3）により流量計 4）を通り、管（ 5）により塩素
ガス吸収塔（ 6）の上部に導かれ分散装置（ 7）により
分散され、吸収塔（ 6）の器壁に沿って濡壁状に流下さ
れる。一方塩化物電解工程（図示していない）より発生
した塩素ガスは管（ 8），流量計（ 9），管（10）によ
り所定流量にて吸収塔（ 6）の下部に導入され塔内を流
下する苛性アルカリ溶液と接触する。またキャリアガス
は管（11），流量計（12），管（10）により塩素ガスと
共に吸収塔（ 6）内に所定流量導入される。The method and apparatus of the present invention will be described with reference to the drawings. In FIG. 1, the caustic solution (2) in the storage tank (1) passes through the flow meter 4) by the pump (3) and the chlorine gas absorption tower by the pipe (5). It is guided to the upper part of (6) and dispersed by a dispersion device (7), and flows down like a wet wall along the wall of the absorption tower (6). On the other hand, chlorine gas generated from the chloride electrolysis process (not shown) is introduced into the lower part of the absorption tower (6) through the pipe (8), flow meter (9) and pipe (10) at a predetermined flow rate, Contact with a caustic solution flowing down. Further, the carrier gas is introduced into the absorption tower (6) at a predetermined flow rate together with chlorine gas through the pipe (11), the flow meter (12) and the pipe (10).
電解工程より発生する塩素ガス中に微量に含まれる不純
物ガスの成分は、主として水素，酸素，炭酸ガス等であ
り炭化水素ガスが極く微量に含まれる場合もあり、通常
塩素ガス濃度は90容量％以上である。キヤリアガスの種
類は測定しようとする不純物ガスによって異り、例えば
水素ガスを測定する際は空気であってもよく、酸素ガス
を測定する際は窒素，アルゴン等の不活性ガスが用いら
れる。The chlorine gas generated from the electrolysis process contains a small amount of impurities, such as hydrogen, oxygen, and carbon dioxide, which may contain a very small amount of hydrocarbon gas. % Or more. The type of carrier gas depends on the impurity gas to be measured. For example, when measuring hydrogen gas, it may be air, and when measuring oxygen gas, an inert gas such as nitrogen or argon is used.
塔内を流下する苛性アルカリ溶液と接触して、塩素及び
炭酸ガスが吸収され塔内に残存する不純物ガスは、ガス
によって塔内を上向し管（13）を通ってセンサー（14
Ａ），（14Ｂ），（14Ｃ）に導かれる。（14Ａ）は酸素
ガス測定用センサー，（14Ｂ）は水素ガス測定用センサ
ー，（14Ｃ）はもし排出ガス中に未吸収の塩素ガスが残
留して含まれる場合、これを検知するため補助的に設け
られた塩素ガス測定用センサーである。Impurity gas which is in contact with the caustic solution flowing down the inside of the tower and absorbs chlorine and carbon dioxide gas and remains inside the tower is directed upward by the gas through the tube (13) to the sensor (14
A), (14B), (14C). (14A) is a sensor for measuring oxygen gas, (14B) is a sensor for measuring hydrogen gas, and (14C) is an auxiliary sensor for detecting unabsorbed chlorine gas contained in the exhaust gas. It is a sensor for measuring chlorine gas provided.
これらのセンサーとしては半導体センサーが通常使用さ
れ、特に可燃性ガスの作用性が強い焼結型ｎ型酸化物半
導体が有効である。その半導体はＳｎＯ２，ＺｎＯ，Ｆ
ｅ２Ｏ３，Ｉｎ２Ｏ３，Ａｌ２Ｏ３等が挙げられ、これ
らの動作機構は、例えば水素ガス（電子供与型のガス）
が吸着すると、吸着分子から半導体への電子移行が行わ
れ、半導体の電子密度が増加して導電性が増加するとい
う現象を利用するもので、これによる抵抗変化をアンプ
にて増幅し、目的のガス濃度を検出する。本発明におい
てはその他、熱伝導素子又は接触燃焼式素子も使用でき
る。また塩素ガス検知用センサー（14Ｃ）は排出ガス中
の塩素ガスを検知して電解工程よりの塩素ガス導管（
8）に設けられた電磁弁（15）を停止させ、塩素ガスに
よるセンサー（14Ａ）（14Ｂ）の損傷を防止することが
できる。吸収塔（ 6）内を流下して塩素及び炭酸ガスを
吸収した吸収液は、吸収液排出管（16）により下方のシ
ールポット（17）に排出され、管（18）より溢流する。
排出管（16）の下端は吸収液により液封されており、塔
内のガスを封止している。管（19）はこの分析方法にお
いて基準となるガスを必要とする場合に管（10）に分枝
して設けられる導管である。As these sensors, a semiconductor sensor is usually used, and a sintered n-type oxide semiconductor having a strong action of combustible gas is particularly effective. The semiconductor is SnO 2 , ZnO, F
e 2 O 3, In 2 O 3, Al 2 O 3 and the like, these operating mechanisms, for example hydrogen gas (electron donating gas)
When is adsorbed, electrons are transferred from the adsorbed molecule to the semiconductor, and the phenomenon that the electron density of the semiconductor increases and conductivity increases is used. Detect gas concentration. In the present invention, a heat conduction element or a contact combustion type element can also be used. The chlorine gas detection sensor (14C) detects chlorine gas in the exhaust gas and detects the chlorine gas conduit (
The solenoid valve (15) provided in 8) can be stopped to prevent the chlorine gas from damaging the sensors (14A) and (14B). The absorption liquid which has flowed down the absorption tower (6) and has absorbed chlorine and carbon dioxide is discharged to the lower seal pot (17) by the absorption liquid discharge pipe (16) and overflows from the pipe (18).
The lower end of the discharge pipe (16) is liquid-sealed with an absorbing liquid to seal the gas in the tower. The pipe (19) is a conduit provided by branching to the pipe (10) when a reference gas is required in this analysis method.
なお苛性アルカリ溶液貯槽（ 1）には液面計（20）を取
りつけて、溶液が少なくなるとこれを補充するようにす
れば便利である。It is convenient to attach a level gauge (20) to the caustic solution storage tank (1) and replenish it when the solution becomes low.
上記の装置により、所定流量の苛性アルカリ溶液を吸収
塔（ 6）内に流下させながら、管（ 9）より微量の不純
物ガスを含む電解工程より発生した塩素ガスを、管（1
1）よりキャリアガスをそれぞれ所定流量吸収塔内に供
給すると、苛性アルカリ溶液により脱塩素及び脱炭酸ガ
スされた不純物ガスは塔頂よりセンサー（14Ａ）（14
Ｂ）（14Ｃ）に導かれ、精度の良い水素ガス及び酸素ガ
スの分析を行うことができる。With the above apparatus, while flowing a caustic solution at a predetermined flow rate into the absorption tower (6), chlorine gas generated from the electrolysis process containing a trace amount of impurity gas from the tube (9) is removed from the tube (1
When the carrier gas is supplied into the absorption tower at a predetermined flow rate from 1), the impurity gas dechlorinated and decarbonated by the caustic solution is discharged from the sensor (14A)
B) Guided by (14C), hydrogen gas and oxygen gas can be analyzed with high accuracy.
実施例１ 第 1図に示す装置により塩素ガスと微量の水素ガスとを
混合して分析を行った。すなわち塩素ガス吸収塔（内径
8mm，長さ100 mm）の内壁表面に濃度10重量％の苛性ソ
ーダ溶液を0.5 ml／min の割合で通液し、塩化酸素ボン
ベより純塩素ガスを10ml／min の割合で連続的に吸収塔
に注入し、かつキャリアガスとして空気を10ml／min の
割合で同様に連続的に注入したところ、水素ガスセンサ
ー及び塩素ガスセンサーによるそれぞれのガス検出は零
であった。次に基準ガス注入管により、小型の水電解槽
より発生させた水素ガスを希釈空気中水素ガス濃度が 0
〜20,000ｐｐｍになるよう、電解電流を可変させて、上
記塩素ガス，空気と共に吸収塔に注入し水素ガスセンサ
ーで測定した。Example 1 Chlorine gas and a trace amount of hydrogen gas were mixed and analyzed by the apparatus shown in FIG. That is, chlorine gas absorption tower (inner diameter
A caustic soda solution with a concentration of 10% by weight was passed through the inner wall surface (8 mm, length 100 mm) at a rate of 0.5 ml / min, and pure chlorine gas was continuously supplied from an oxygen chloride cylinder to an absorption tower at a rate of 10 ml / min. When the carrier gas was injected and air was also continuously injected at a rate of 10 ml / min in the same manner, the respective gas detections by the hydrogen gas sensor and the chlorine gas sensor were zero. Next, using the reference gas injection pipe, the hydrogen gas generated from the small-sized water electrolyzer was adjusted to zero concentration in the diluted air.
The electrolytic current was varied so that the concentration became ˜20,000 ppm, and the chlorine gas and air were injected into the absorption tower and the hydrogen gas sensor measured.
この水素ガスセンサー（フィガロ技研社製ＴＧＳ＃812
型）信号の取出しは、センサーの抵抗変化を電流アンプ
にて変換し、電圧出力としたものである。その測定結果
は第 2図に示すように良好な直線性を示した。This hydrogen gas sensor (TGS # 812 manufactured by Figaro Giken Co., Ltd.
(Type) signal is taken out by converting the resistance change of the sensor into a voltage output by a current amplifier. The measurement results showed good linearity as shown in Fig. 2.
実施例２ 実施例１と同様の装置を使用し、苛性ソーダ溶液注入
量，塩素ガス注入量は実施例１と同様であり、キャリア
ガスとして窒素ガスを20ml／min の割合で連続的に注入
し、酸素ガスセンサーにて酸素濃度，塩素ガスセンサー
にて塩素濃度を測定したところそれぞれの検出値は零で
あった。次に基準ガス注入管より小型の水電解槽より発
生させた酸素ガスを希釈用窒素ガス中の酸素ガス濃度が
0〜10容量％になるよう、電解電流を可変させて、上記
塩素ガス，窒素ガスと共に吸収塔に注入し酸素ガスセン
サーで測定した。酸素ガスセンサーとしてはセラミック
酸素センサー（藤倉電線社製，ＦＣＸ−Ｕ型）を使用し
た。その測定結果は第 3図に示すように良好な直線性を
示した。Example 2 The same apparatus as in Example 1 was used, the caustic soda solution injection amount and chlorine gas injection amount were the same as in Example 1, and nitrogen gas was continuously injected as a carrier gas at a rate of 20 ml / min. When the oxygen concentration was measured with an oxygen gas sensor and the chlorine concentration was measured with a chlorine gas sensor, the detected values were zero. Next, the oxygen gas concentration generated in the diluting nitrogen gas from the small water electrolysis tank is smaller than that of the reference gas injection pipe.
The electrolysis current was varied so that it was from 0 to 10% by volume, and the chlorine gas and the nitrogen gas were injected into the absorption tower and measured with an oxygen gas sensor. A ceramic oxygen sensor (FCX-U type, manufactured by Fujikura Electric Cable Co., Ltd.) was used as the oxygen gas sensor. The measurement results showed good linearity as shown in Fig. 3.
実施例３ イオン交換膜法食塩電解槽より発生する塩素ガス（濃度
約95容量％）を直接試料ガスとし、第 1図に示す装置に
接続し、該塩素ガス中の水素ガス，酸素ガス濃度を測定
した。吸収塔，吸収液及びその流量は実施例１と同様で
あるが、キャリアガスとして窒素ガスを10ml／min の割
合で使用し、実施例１，２と同様のガスセンサーにて測
定したところ水素ガス濃度は0.1 容量％以下、酸素濃度
は 1〜1.2 容量％であり、塩素ガス濃度は零であった。Example 3 Chlorine gas (concentration: about 95% by volume) generated from an ion-exchange membrane method salt electrolysis tank was directly used as a sample gas and connected to the apparatus shown in FIG. 1 to determine the concentration of hydrogen gas and oxygen gas in the chlorine gas. It was measured. The absorption tower, the absorption liquid, and the flow rate thereof are the same as in Example 1, but nitrogen gas was used as a carrier gas at a rate of 10 ml / min, and hydrogen gas was measured by the same gas sensor as in Examples 1 and 2. The concentration was 0.1 vol% or less, the oxygen concentration was 1 to 1.2 vol%, and the chlorine gas concentration was zero.
（発明の効果） 本発明法および装置によれば、電解工程より発生する塩
素ガス中に微量の不純物ガスとして含まれる水素ガスの
濃度及び酸素ガスの濃度を分析装置の腐食を来たすこと
なく連続的に正確に測定することができる。したがって
水素ガス等の可燃性ガスの含有量が増加し塩素ガスと反
応して電解槽の爆発等事故を起す危険性を防止するのに
有効であり、またイオン交換膜の損傷を予知できる等、
工業的に有用である。(Effects of the Invention) According to the method and apparatus of the present invention, the concentration of hydrogen gas and the concentration of oxygen gas contained as a trace amount of impurity gas in chlorine gas generated in the electrolysis step are continuously measured without causing corrosion of the analyzer. Can be accurately measured. Therefore, the content of combustible gas such as hydrogen gas is increased and it is effective in preventing the risk of causing an accident such as explosion of the electrolytic cell by reacting with chlorine gas, and it is also possible to predict damage to the ion exchange membrane,
It is industrially useful.
第 1図は本発明装置を例示する概略説明図，第 2図は実
施例１におけるセンサーの水素濃度と出力電圧との関係
を示すグラフ、第 3図は実施例２におけるセンサーの酸
素濃度と出力電圧との関係を示すグラフである。 （ 2）……苛性アルカリ溶液，（ 6）……塩素ガス吸収
塔，（ 8）……塩素ガス管，（11）……キャリアガス
管，（14Ａ）（14Ｂ）（14Ｃ）……ガスンセンサー，
（17）……シールポットFIG. 1 is a schematic explanatory view illustrating the device of the present invention, FIG. 2 is a graph showing the relationship between the hydrogen concentration and output voltage of the sensor in Example 1, and FIG. 3 is the oxygen concentration and output of the sensor in Example 2. It is a graph which shows the relationship with a voltage. (2) ... caustic solution, (6) ... chlorine gas absorption tower, (8) ... chlorine gas tube, (11) ... carrier gas tube, (14A) (14B) (14C) ... gasn sensor,
(17) …… Seal pot
Claims (4)
微量の不純物ガスとして含まれる水素ガス，酸素ガスを
測定するにあたり、上記塩素ガスを連続的に採取して、
塩素ガス吸収塔に導き塔内を流下する苛性アルカリ溶液
と接触させて塩素及び不純物ガス中の炭酸ガスを吸収さ
せ、残存する不純物ガスを所定流量のキャリアガスにて
水素ガス及び酸素ガスの測定用センサーに送り、その濃
度を連続的に測定することを特徴とするガス分析方法。1. When measuring hydrogen gas and oxygen gas contained as a trace amount of impurity gas in chlorine gas generated in a chloride electrolysis step, the chlorine gas is continuously sampled,
Chlorine and carbon dioxide in impurity gas are absorbed by contacting the caustic solution flowing down the tower to the chlorine gas absorption tower, and the remaining impurity gas is used as a carrier gas at a predetermined flow rate for measuring hydrogen gas and oxygen gas. A gas analysis method, characterized in that the gas is sent to a sensor and its concentration is continuously measured.
特許請求の範囲第１項に記載のガス分析方法。2. The gas analysis method according to claim 1, wherein the carrier gas is air or an inert gas.
半導体ガスセンサーである特許請求の範囲第１項もしく
は第２項記載のガス分析方法。3. The gas analysis method according to claim 1, wherein the sensor for measuring hydrogen gas and oxygen gas is a semiconductor gas sensor.
微量の不純物ガスとして含まれる水素ガス，酸素ガスを
測定する装置であって、塩素ガス吸収塔及び該ガス吸収
塔頂部と導管により連結された上記水素ガス及び酸素ガ
スの測定用センサーよりなり、上記塩素ガス吸収塔の上
部には苛性アルカリ溶液導入管及び該溶液の分散装置、
下部にはキャリアガス及び電解工程より発生する塩素ガ
スの導入管、底部には塩素ガス吸収液の排出管をそれぞ
れ設け、かつ上記排出管の先端には塩素ガス吸収液によ
る液封手段を設けたことを特徴とするガス分析装置。4. A device for measuring hydrogen gas and oxygen gas contained as a trace amount of impurity gas in chlorine gas generated in a chloride electrolysis step, which is connected to a chlorine gas absorption tower and the top of the gas absorption tower by a conduit. The sensor for measuring hydrogen gas and oxygen gas, and a caustic solution introducing pipe and a dispersion device for the solution above the chlorine gas absorption tower,
An inlet pipe for the chlorine gas generated from the carrier gas and the electrolysis process was provided at the bottom, a discharge pipe for the chlorine gas absorption liquid was provided at the bottom, and a liquid sealing means for the chlorine gas absorption liquid was provided at the tip of the discharge pipe. A gas analyzer characterized by the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7225186A JPH0638079B2 (en) | 1986-03-29 | 1986-03-29 | Gas analysis method and apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7225186A JPH0638079B2 (en) | 1986-03-29 | 1986-03-29 | Gas analysis method and apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62228162A JPS62228162A (en) | 1987-10-07 |
| JPH0638079B2 true JPH0638079B2 (en) | 1994-05-18 |
Family
ID=13483888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7225186A Expired - Lifetime JPH0638079B2 (en) | 1986-03-29 | 1986-03-29 | Gas analysis method and apparatus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0638079B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6849239B2 (en) | 2000-10-16 | 2005-02-01 | E. I. Du Pont De Nemours And Company | Method and apparatus for analyzing mixtures of gases |
| JP7471978B2 (en) * | 2020-09-29 | 2024-04-22 | 東邦チタニウム株式会社 | Method for measuring oxygen gas concentration in chlorine-containing gas, method for calculating current efficiency, and method for producing metallic magnesium |
| CN117849287B (en) * | 2024-03-07 | 2024-05-31 | 深圳市瑞盛环保科技有限公司 | Gaseous composition detection device for chlorine recovery system |
-
1986
- 1986-03-29 JP JP7225186A patent/JPH0638079B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62228162A (en) | 1987-10-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5132094A (en) | Method and apparatus for the determination of dissolved carbon in water | |
| CN105842234B (en) | Self-calibration formula nitrogen dioxide continuous on-line detection device and detection method | |
| US7879134B2 (en) | Conditioning system and method for use in the measurement of mercury in gaseous emissions | |
| CN204330674U (en) | For detecting the equipment of Volatile Organic Compounds in Soil | |
| CN101788522B (en) | Chemical oxygen demand (COD) on-line monitoring device and method based on boron-doped diamond membrane electrode | |
| CN103364385B (en) | Utilize the device and method of fluorescence spectrophotometry on-line checkingi water sample medium sulphide content concentration | |
| CN103389279B (en) | The device and method of sub-methyl blue spectrum analysis on-line checkingi water quality medium sulphide content concentration | |
| CN108287157A (en) | A kind of fluorine gas analysis reforming unit | |
| CN102564823A (en) | Device and method for continuously determining total organic carbon (TOC) concentration of sea water and high-salinity waste water | |
| CN205607866U (en) | From maring continuous on -line measuring device of formula nitrogen dioxide | |
| US5250171A (en) | Sensor for carbon monoxide | |
| JPH0638079B2 (en) | Gas analysis method and apparatus | |
| US3003932A (en) | Apparatus for the galvanic analysis of hydrogen | |
| CN221326431U (en) | Continuous automatic monitoring system for non-methane total hydrocarbons in ambient air | |
| US3296098A (en) | Method and apparatus for gas analysis | |
| US20100281950A1 (en) | Method and apparatus for analysis of mixed streams | |
| CN112986453B (en) | A method and system for high-resolution determination of organic carbon isotopes in stalagmites | |
| CN115586149A (en) | Automatic distillation device and method for volatile pollutants in water | |
| CN111537496A (en) | A Titration Analyzer Based on Detection by Tip Discharge Atomic Emission Spectrometry | |
| CN114910593A (en) | High-temperature molten carbonate enriched carbon dioxide gas purification system and use method thereof | |
| CN208188035U (en) | A kind of oxygen analyzer | |
| US3700568A (en) | Electrochemical carbon meter | |
| CN219935765U (en) | System for detecting content of trace halide in gas | |
| US7799113B2 (en) | Conditioning system and method for use in the measurement of mercury in gaseous emissions | |
| CN207689371U (en) | Ultralow memory effect atomic fluorescence trace mercury vapourmeter is miniaturized |