JP2003028851A - Measuring method for sulfur compound in exhaust gas - Google Patents
Measuring method for sulfur compound in exhaust gasInfo
- Publication number
- JP2003028851A JP2003028851A JP2001250896A JP2001250896A JP2003028851A JP 2003028851 A JP2003028851 A JP 2003028851A JP 2001250896 A JP2001250896 A JP 2001250896A JP 2001250896 A JP2001250896 A JP 2001250896A JP 2003028851 A JP2003028851 A JP 2003028851A
- Authority
- JP
- Japan
- Prior art keywords
- sulfur
- hydrogen
- sulfur compound
- exhaust gas
- measuring
- 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
- 150000003464 sulfur compounds Chemical class 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 34
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000007789 gas Substances 0.000 claims abstract description 68
- 239000001257 hydrogen Substances 0.000 claims abstract description 58
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 58
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 56
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000001301 oxygen Substances 0.000 claims abstract description 35
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 35
- 239000002737 fuel gas Substances 0.000 claims abstract description 32
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 230000005281 excited state Effects 0.000 claims abstract description 13
- 230000005283 ground state Effects 0.000 claims abstract description 12
- 238000002485 combustion reaction Methods 0.000 claims abstract description 10
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 239000001307 helium Substances 0.000 claims description 9
- 229910052734 helium Inorganic materials 0.000 claims description 9
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 8
- 230000007704 transition Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 238000011088 calibration curve Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、排ガス中の硫黄化
合物の測定方法に関する。さらに詳しくは、自動車から
排出される排ガス中に含まれる硫黄化合物の測定方法に
関する。TECHNICAL FIELD The present invention relates to a method for measuring a sulfur compound in exhaust gas. More specifically, it relates to a method for measuring a sulfur compound contained in exhaust gas emitted from an automobile.
【０００２】[0002]
【従来の技術】従来、空気中に含まれる硫黄化合物を測
定する方法として、特開２０００−８１３９１号公報が
知られている。この公知技術においては、低濃度、とく
に１ｐｐｍ以下の微量の硫黄化合物、たとえば、大気中
に含まれるｐｐｂオーダーの硫黄化合物を、硫黄の化学
ルミネサンス検出器（Ｓｕｌｆｅｒ Ｃｈｅｍｉｌｕｍ
ｉｎｅｓｅｎｃｅ Ｄｅｔｅｃｔｏｒ）を用いるＳＣＤ
法により測定する技術が開示されている。2. Description of the Related Art Conventionally, Japanese Patent Laid-Open No. 2000-81391 is known as a method for measuring a sulfur compound contained in air. In this known technique, a low concentration, particularly 1 ppm or less, of a trace amount of a sulfur compound, for example, a ppb-order sulfur compound contained in the atmosphere is detected as a sulfur chemiluminescence detector (Sulfur Chemium).
SCD with the use of the Presence Detector)
The technique of measuring by the method is disclosed.
【０００３】ＳＣＤ法は、下記反応式（１）ないし
（３）に示される反応機構を利用するものである。すな
わち、硫黄化合物（たとえば、二酸化硫黄ＳＯ２）を還
元雰囲気である水素炎の中心部で水素によって還元し
（反応式（１））、生成した亜酸化硫黄ＳＯをオゾンＯ
３によって酸化して励起状態の二酸化硫黄ＳＯ２ ＊を生
成させる（反応式（２））。励起状態の二酸化硫黄ＳＯ
２ ＊は、基底状態に遷移して二酸化硫黄ＳＯ２となる
が、このときに励起状態の二酸化硫黄ＳＯ２ ＊と基底状
態の二酸化硫黄ＳＯ２のエネルギ準位の差に応じたエネ
ルギｈνが発せられる（反応式（３））。このように、
励起した１つの二酸化硫黄ＳＯ２ ＊につきｈνで表され
るエネルギが発せられるため、励起状態の個々の二酸化
硫黄ＳＯ２ ＊が基底状態の二酸化硫黄ＳＯ２に遷移する
ときに発せられるエネルギの総量（発光強度）に基づい
て、励起した二酸化硫黄ＳＯ２ ＊の濃度、すなわち硫黄
化合物（二酸化硫黄ＳＯ２）の濃度を測定することがで
きる。The SCD method utilizes the reaction mechanism represented by the following reaction formulas (1) to (3). That is, a sulfur compound (for example, sulfur dioxide SO 2 ) is reduced by hydrogen in the central part of a hydrogen flame that is a reducing atmosphere (reaction formula (1)), and the generated sulfurous oxide SO is ozone O
Oxidation by 3 produces excited-state sulfur dioxide SO 2 * (reaction formula (2)). Excited Sulfur Dioxide SO
2 * is the sulfur dioxide SO 2 transitions to the ground state, the energy hν corresponding to the difference between the energy level of the sulfur dioxide SO 2 of the sulfur dioxide SO 2 * and the ground state of the excited state at this time issued (Reaction formula (3)). in this way,
Since one energy represented by hν per sulfur dioxide SO 2 * excited is emitted, the total amount of energy individual sulfur dioxide SO 2 * excited state is generated when transitioning to the sulfur dioxide SO 2 in the ground state ( Based on the emission intensity), the concentration of the excited sulfur dioxide SO 2 * , that is, the concentration of the sulfur compound (sulfur dioxide SO 2 ) can be measured.
【０００４】[0004]
【化１】 [Chemical 1]
【０００５】上記したＳＣＤ法では、検出器の出力と硫
黄化合物の濃度が一次直線の関係にあり、また水素炎中
で生成する亜酸化硫黄の比率も大きくその発光強度も３
４０〜３５０ｎｍの波長範囲のものであり、強力であ
る。したがって、低濃度、とくに１ｐｐｍ 以下の硫黄
化合物の濃度測定には適当な方法とされている（「エン
バイロンメンタル．サイエンス．テクノロジ（Ｅｎｖｉ
ｒｏｎ．Ｓｃｉ．Ｔｅｃｈｎｏｌ）」巻２４、ＮＯ．１
０，１５９２〜１５９６頁、１９９０年）。In the above-mentioned SCD method, the output of the detector and the concentration of the sulfur compound have a linear relationship, and the ratio of sulfurous oxide produced in the hydrogen flame is large, and the emission intensity thereof is 3 as well.
It is in the wavelength range of 40 to 350 nm and is strong. Therefore, it is considered to be an appropriate method for measuring the concentration of a sulfur compound at a low concentration, particularly 1 ppm or less (“Environmental Science Technology (Envi
ron. Sci. Technol) "volume 24, NO. 1
0, 1592-1596, 1990).
【０００６】以下、従来公知の技術について説明する。
図５は、大気中に含まれるｐｐｂオーダーの硫黄化合物
を、ＳＣＤ法により測定するために用いられる装置の概
略構成図である。図５において、硫黄化合物測定装置１
は、真空ライン１３によって減圧に保たれた反応セル２
を有しており、この反応セル２内には水素炎バーナー３
が配置されるとともに、支燃用ガス導入管６が接続され
ている。また、この水素炎バーナー３には、硫黄化合物
を含むサンプルガス導入管４、燃料ガス導入管５が接続
されている。A conventionally known technique will be described below.
FIG. 5 is a schematic configuration diagram of an apparatus used for measuring a ppb-order sulfur compound contained in the atmosphere by the SCD method. In FIG. 5, a sulfur compound measuring device 1
Is a reaction cell 2 kept under reduced pressure by a vacuum line 13.
And a hydrogen flame burner 3 in the reaction cell 2.
Is arranged, and the combustion-supporting gas introduction pipe 6 is connected. A sample gas introduction pipe 4 containing a sulfur compound and a fuel gas introduction pipe 5 are connected to the hydrogen flame burner 3.
【０００７】上記反応セル２においては、支燃用ガス導
入管６から導入した空気を支燃用ガスとし、上記水素炎
バーナー３に接続した燃料ガス導入管５から、水素／ヘ
リウム混合ガス（水素濃度、２０〜７０容量％）を導入
し、水素を燃焼させる。図２によく示されているよう
に、水素燃焼により形成された水素炎の中心部は還元炎
といわれ、その温度は８００〜１１００℃に達してい
る。このため、水素炎バーナー３に供給されたサンプル
ガス中の硫黄化合物は還元炎中７で還元され、その大部
分は亜酸化硫黄ＳＯとなる。そして、還元炎７の部分か
らピックアップノズル８によって亜酸化硫黄ＳＯを採取
する。In the reaction cell 2, the air introduced from the combustion supporting gas introduction pipe 6 is used as the combustion supporting gas, and the hydrogen / helium mixed gas (hydrogen) is supplied from the fuel gas introduction pipe 5 connected to the hydrogen flame burner 3. A concentration of 20-70% by volume) is introduced and hydrogen is burned. As shown in FIG. 2, the central part of the hydrogen flame formed by hydrogen combustion is called a reducing flame, and its temperature reaches 800 to 1100 ° C. Therefore, the sulfur compound in the sample gas supplied to the hydrogen flame burner 3 is reduced in the reducing flame 7 and most of it becomes sulfur suboxide SO. Then, the sulfurous oxide SO is collected from the portion of the reducing flame 7 by the pickup nozzle 8.
【０００８】ピックアップノズル８によって採取された
亜酸化硫黄ＳＯは、加熱された加熱導管１０を経由して
真空ライン１３によって、１０〜１０００Ｐａの減圧に
保たれたオゾン酸化セル９に導入される。このオゾン酸
化セル９には、オゾン発生装置１１からオゾンＯ３が供
給されており、オゾン酸化セル９内において、上記反応
式（２）にしたがい、亜酸化硫黄ＳＯがオゾンＯ３と反
応して励起した二酸化硫黄ＳＯ２ ＊となる。続いて反応
式（３）にしたがい、励起した二酸化硫黄ＳＯ２ ＊は基
底状態の二酸化硫黄ＳＯ２に遷移するが、このときに励
起状態の二酸化硫黄ＳＯ２ ＊のエネルギ準位と基底状態
の二酸化硫黄ＳＯ２のエネルギ準位との差に相当するエ
ネルギを発する。したがって、励起状態の個々の二酸化
硫黄ＳＯ２ ＊が基底状態の二酸化硫黄ＳＯ２に遷移する
ときに発するエネルギの総量（発光強度）を測定すれば
励起した二酸化硫黄ＳＯ２ ＊の濃度、すなわち、硫黄化
合物に由来する二酸化硫黄ＳＯ２の濃度を測定すること
ができる。The sulfurous oxide SO collected by the pick-up nozzle 8 is introduced into the ozone oxidation cell 9 kept at a reduced pressure of 10 to 1000 Pa by the vacuum line 13 via the heated heating conduit 10. Ozone O 3 is supplied to the ozone oxidation cell 9 from the ozone generator 11. In the ozone oxidation cell 9, sulfurous oxide SO reacts with ozone O 3 according to the above reaction formula (2). It becomes excited SO 2 * . Subsequently, according to the reaction formula (3), the excited sulfur dioxide SO 2 * transits to the sulfur dioxide SO 2 in the ground state. At this time, the energy level of the sulfur dioxide SO 2 * in the excited state and the dioxide in the ground state are changed. It emits energy corresponding to the difference from the energy level of sulfur SO 2 . Therefore, by measuring the total amount of energy (emission intensity) emitted when individual sulfur dioxide SO 2 * in the excited state transits to sulfur dioxide SO 2 in the ground state, the concentration of the excited sulfur dioxide SO 2 * , that is, sulfur The concentration of sulfur dioxide SO 2 derived from the compound can be measured.
【０００９】[0009]
【発明が解決しようとする課題】ところで、大気汚染防
止対策の一つとして、排ガス、とくにジーゼルエンジン
を搭載した自動車から排出される排ガス中の硫黄化合物
の量が規制される方向にある。そのためには、燃料とし
て用いる軽油に含まれる硫黄の量を規制することが必要
であり、軽油に含まれる硫黄濃度が現在の５００ｐｐｍ
以下から５０ｐｐｍ以下に規制が強化される予定であ
る。周知のように、軽油はジーゼルサイクルの最後の行
程で燃焼されてジーゼルエンジンの動力となるが、軽油
に含まれる硫黄も、軽油とともに燃焼されてジーゼルエ
ンジンから排出される。したがって、ジーゼルエンジン
からの排ガス中には、硫黄が酸化されて生成した二酸化
硫黄を始めとして、種々の硫黄化合物が含まれている。By the way, as one of the measures for preventing air pollution, the amount of sulfur compounds in exhaust gas, especially exhaust gas discharged from a vehicle equipped with a diesel engine, is being regulated. To do so, it is necessary to regulate the amount of sulfur contained in diesel fuel used as fuel, and the concentration of sulfur contained in diesel fuel is currently 500 ppm.
Regulations will be tightened from below to 50 ppm or less. As is well known, light oil is burned in the final stroke of the diesel cycle to power the diesel engine, but sulfur contained in the light oil is also burned together with the light oil and discharged from the diesel engine. Therefore, the exhaust gas from the diesel engine contains various sulfur compounds including sulfur dioxide produced by the oxidation of sulfur.
【００１０】現在、ジーゼルエンジンからの排ガスに含
まれる硫黄化合物の濃度は、主として炎光光度検出器
（ＦＰＤ）により測定されている。しかし、上記したよ
うに、軽油に含まれる硫黄濃度が５０ｐｐｍ以下に規制
されると、ＦＰＤ法による測定は困難で、より正確に排
ガス中に含まれる硫黄化合物の濃度を測定する方法が求
められている。そこで、既述のＳＣＤ法によって、ジー
ゼルエンジンからの排ガスに含まれている硫黄化合物の
濃度の測定を試みたが、安定して、精度よく測定するこ
とはできなかった。Presently, the concentration of sulfur compounds contained in the exhaust gas from diesel engines is mainly measured by a flame photometric detector (FPD). However, as described above, when the sulfur concentration contained in light oil is regulated to 50 ppm or less, measurement by the FPD method is difficult, and a method for more accurately measuring the concentration of sulfur compounds contained in exhaust gas is required. There is. Therefore, an attempt was made to measure the concentration of the sulfur compound contained in the exhaust gas from the diesel engine by the above-mentioned SCD method, but it could not be stably and accurately measured.
【００１１】その原因について検討したところ、水素炎
バーナーで形成した水素炎の還元炎部分に上記排ガスを
サンプルガスとして導入すると、上記排ガス中の酸素濃
度が約５〜２１％の範囲で変化するため、酸素の干渉を
受けて、炎の形状が微妙に変化することにあると判明し
た。そこで、本発明の課題は、排ガス中の酸素濃度が、
大気のように一定ではなく、変化したときでも、排ガス
中に含まれる微量の硫黄化合物の濃度を安定して、精度
よく、測定できる方法を提供することにある。When the cause was examined, when the above exhaust gas was introduced as a sample gas into the reducing flame portion of the hydrogen flame formed by the hydrogen flame burner, the oxygen concentration in the above exhaust gas changed in the range of about 5 to 21%. , It was found that the shape of the flame changed slightly due to the interference of oxygen. Therefore, the problem of the present invention is that the oxygen concentration in the exhaust gas is
An object of the present invention is to provide a method capable of stably and accurately measuring the concentration of a minute amount of a sulfur compound contained in exhaust gas even when it is not constant like the atmosphere but changes.
【００１２】[0012]
【課題を解決するための手段】すなわち、本発明によれ
ば、支燃用ガスの供給下に水素を含む燃料ガスを水素炎
バーナーで燃焼させて、水素炎内に硫黄化合物を含むサ
ンプルガスを供給して亜酸化硫黄を生成させるステップ
と、生成した亜酸化硫黄を水素炎中から取り出してオゾ
ン酸化セルに供給し、オゾンと反応させて励起状態の二
酸化硫黄を生成させるステップと、励起状態の二酸化硫
黄が基底状態に遷移するときの発光強度を測定するステ
ップと、を含む排ガス中の硫黄化合物の測定方法であっ
て、上記水素を含む燃料ガスに窒素および酸素を添加す
ることを特徴とする、排ガス中の硫黄化合物の測定方法
が提供される。このとき、水素を含む燃料ガスは、水素
とヘリウムの混合ガスであることが好ましい。That is, according to the present invention, a fuel gas containing hydrogen is burned by a hydrogen flame burner while supplying a gas for supporting combustion to generate a sample gas containing a sulfur compound in the hydrogen flame. The step of supplying and generating sulfur dioxide, the step of taking out the generated sulfur oxide from the hydrogen flame and supplying it to the ozone oxidation cell, and reacting with ozone to generate excited state sulfur dioxide, and the excited state A step of measuring emission intensity when sulfur dioxide transits to a ground state; and a method of measuring a sulfur compound in exhaust gas, comprising adding nitrogen and oxygen to the fuel gas containing hydrogen. A method for measuring sulfur compounds in exhaust gas is provided. At this time, the fuel gas containing hydrogen is preferably a mixed gas of hydrogen and helium.
【００１３】上記構成とすることにより、水素炎の形状
が一定に保たれ、反応式（１）にしたがって、硫黄化合
物をＳＯに還元する際に利用する還元炎部分の位置も安
定し、ずれることがない。その結果、硫黄化合物のＳＯ
への還元が一定の割合で行われ、排ガス中の酸素濃度が
変化しても、酸素の干渉を排除して、精度よく硫黄化合
物の濃度を測定することができる。With the above structure, the shape of the hydrogen flame is kept constant, and the position of the reducing flame portion used when reducing the sulfur compound to SO is stabilized and deviated according to the reaction formula (1). There is no. As a result, the sulfur compound SO
Even if the oxygen concentration in the exhaust gas changes due to the reduction to a constant rate, the interference of oxygen can be eliminated, and the concentration of the sulfur compound can be accurately measured.
【００１４】上記燃料ガスラインに窒素および酸素を添
加して得られる効果について、その原因は明らかではな
いが、窒素が水素やヘリウムに比べて熱容量、粘性等が
大であるため、窒素の存在下、水素炎中の水素やヘリウ
ムの動きが抑制され、炎の中の温度勾配が少なくなるた
めと考えられる。さらに予め、燃料ガスラインに酸素を
加えておくことにより、酸素干渉のとくに顕著な、低酸
素領域での水素炎の形成を避けることができるためと考
えられる。The cause of the effect obtained by adding nitrogen and oxygen to the fuel gas line is not clear, but since nitrogen has a larger heat capacity, viscosity, etc. than hydrogen or helium, it does not exist in the presence of nitrogen. It is considered that the movement of hydrogen and helium in the hydrogen flame is suppressed and the temperature gradient in the flame is reduced. Further, it is considered that by adding oxygen to the fuel gas line in advance, formation of a hydrogen flame in a low oxygen region where oxygen interference is particularly remarkable can be avoided.
【００１５】[0015]
【発明の実施の形態】以下、本発明の好ましい実施の形
態について、公知の方法と対比しながら、図面を参照し
てより詳細に説明する。図１は、本発明にかかる排ガス
中の硫黄化合物の測定方法を実施するための装置の概略
構成図、図２は、図１の反応セルの周囲を拡大した断面
図である。図１において、上記硫黄化合物濃度測定装置
１は、真空ライン１３によって１０〜１０００Ｐａの減
圧に保たれた反応セル２を有しており、この反応セル２
内には水素炎バーナー３が配置されるとともに、支燃用
ガス導入管６が接続されている。また、この水素炎バー
ナー３には、硫黄化合物を含むサンプルガス導入管４、
燃料ガス導入管５が接続され、燃料ガス導入管５には、
燃料ガスに窒素を添加するための窒素導入管５１、酸素
を添加するための酸素導入管５２が接続されている。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to the drawings in comparison with known methods. FIG. 1 is a schematic configuration diagram of an apparatus for carrying out the method for measuring a sulfur compound in exhaust gas according to the present invention, and FIG. 2 is an enlarged sectional view of the periphery of the reaction cell of FIG. In FIG. 1, the sulfur compound concentration measuring apparatus 1 has a reaction cell 2 kept at a reduced pressure of 10 to 1000 Pa by a vacuum line 13.
A hydrogen flame burner 3 is arranged inside, and a combustion supporting gas introduction pipe 6 is connected. The hydrogen flame burner 3 is provided with a sample gas introduction pipe 4 containing a sulfur compound,
The fuel gas introduction pipe 5 is connected to the fuel gas introduction pipe 5,
A nitrogen introducing pipe 51 for adding nitrogen to the fuel gas and an oxygen introducing pipe 52 for adding oxygen are connected.
【００１６】上記反応セル２においては、支燃用ガス導
入管６から導入した空気を支燃用ガスとし、上記水素炎
バーナー３に接続した燃料ガス導入管５から、水素を含
む燃料ガスを導入し水素を燃焼させる。燃料ガスとして
は水素／ヘリウム混合ガスを用い、混合ガス中の水素濃
度は２０〜７０容量％とすることが好ましい。このと
き、燃料ガス導入管５に接続された窒素導入管５１と酸
素導入管５２から、窒素および酸素を添加する。その添
加量は、窒素の場合、燃料ガス１００容量に対して５〜
５０容量の割合で添加することが好ましい。また、酸素
の場合、燃料ガス１００容量に対して０．１〜５容量の
割合で添加することが好ましい。In the reaction cell 2, the air introduced from the combustion-supporting gas introduction pipe 6 is used as the combustion-supporting gas, and the fuel gas containing hydrogen is introduced from the fuel gas introduction pipe 5 connected to the hydrogen flame burner 3. Then burn the hydrogen. A hydrogen / helium mixed gas is used as the fuel gas, and the hydrogen concentration in the mixed gas is preferably 20 to 70% by volume. At this time, nitrogen and oxygen are added from the nitrogen introducing pipe 51 and the oxygen introducing pipe 52 connected to the fuel gas introducing pipe 5. In the case of nitrogen, the amount added is 5 to 100 volumes of fuel gas.
It is preferable to add it at a ratio of 50 volumes. Further, in the case of oxygen, it is preferable to add it in a ratio of 0.1 to 5 volumes with respect to 100 volumes of fuel gas.
【００１７】上記窒素と酸素を添加した燃料ガスが燃焼
することにより、水素炎が形成され、既述と同様に水素
炎の中心部の還元炎で、サンプル中に含まれる硫黄化合
物は還元され、その大部分は亜酸化硫黄ＳＯとなる。そ
して、図２によく表れているように還元炎７の部分から
ピックアップノズル８によって亜酸化硫黄ＳＯを採取し
て、これを真空ライン１３によって１０〜１０００Ｐａ
の減圧に保たれたオゾン酸化セル９に供給する。A hydrogen flame is formed by burning the fuel gas to which nitrogen and oxygen are added, and the sulfur compound contained in the sample is reduced by the reducing flame at the center of the hydrogen flame as described above. Most of it is sulfurous oxide SO. Then, as clearly shown in FIG. 2, sulfur dioxide SO is collected from the portion of the reducing flame 7 by the pickup nozzle 8 and is collected by the vacuum line 13 at 10 to 1000 Pa.
And is supplied to the ozone oxidation cell 9 maintained under reduced pressure.
【００１８】なお、上記した燃焼条件において水素炎の
中から亜酸化硫黄ＳＯを採取するという観点から反応セ
ル２の高さは少なくとも７０ｍｍ以上であることが好ま
しい。ピックアップノズル８は、その内径が０．１ｍｍ
〜１．０ｍｍ、その長さが内径の５０〜４００倍とされ
る。また、その材質は高温下、長時間安定してサンプリ
ングを行えるものが好ましく、通常、石英を用いる。The height of the reaction cell 2 is preferably at least 70 mm or more from the viewpoint of collecting sulfurous oxide SO from the hydrogen flame under the above combustion conditions. The pick-up nozzle 8 has an inner diameter of 0.1 mm.
˜1.0 mm, the length of which is 50 to 400 times the inner diameter. Further, the material is preferably one capable of stable sampling at high temperature for a long time, and quartz is usually used.
【００１９】ピックアップノズル８によって採取された
亜酸化硫黄ＳＯは、１１０℃以上に加熱された加熱導管
１０を経由し、真空ライン１３によって１０〜１０００
Ｐａの減圧下に保たれたオゾン酸化セル９に導入され
る。このオゾン酸化セル９には、オゾン発生装置１１か
らオゾンＯ３が供給されており、オゾン酸化セル９内に
おいて、亜酸化硫黄ＳＯがオゾンＯ３と反応して励起し
た二酸化硫黄ＳＯ２ ＊となる。励起した二酸化硫黄ＳＯ
２ ＊は基底状態の二酸化硫黄ＳＯ２に遷移するが、この
ときに励起状態の二酸化硫黄ＳＯ２ ＊のエネルギ準位と
基底状態の二酸化硫黄ＳＯ２のエネルギ準位との差に相
当するエネルギを発する。したがって、励起状態の個々
の二酸化硫黄ＳＯ２ ＊が基底状態の二酸化硫黄ＳＯ２に
遷移するときに発するエネルギの総量（発光強度）を測
定すれば励起した二酸化硫黄ＳＯ２ ＊の濃度、すなわ
ち、硫黄化合物由来の二酸化硫黄ＳＯ２の濃度を測定す
ることができる。The sulfurous oxide SO collected by the pick-up nozzle 8 passes through a heating conduit 10 heated to 110 ° C. or higher and a vacuum line 13 causes 10 to 1000.
It is introduced into the ozone oxidation cell 9 kept under a reduced pressure of Pa. Ozone O 3 is supplied to the ozone oxidation cell 9 from the ozone generator 11. In the ozone oxidation cell 9, sulfur dioxide SO reacts with ozone O 3 to become excited sulfur dioxide SO 2 *. . Excited sulfur dioxide SO
2 * transits to sulfur dioxide SO 2 in the ground state. At this time, the energy corresponding to the difference between the energy level of sulfur dioxide SO 2 * in the excited state and the energy level of sulfur dioxide SO 2 in the ground state is set. Emit. Therefore, by measuring the total amount of energy (emission intensity) emitted when individual sulfur dioxide SO 2 * in the excited state transits to sulfur dioxide SO 2 in the ground state, the concentration of the excited sulfur dioxide SO 2 * , that is, sulfur The concentration of sulfur dioxide SO 2 derived from the compound can be measured.
【００２０】このときの発光強度の測定には、光電子増
倍管１２が用いられる。この光電子増倍管１２では入射
された光の光量に応じて光電子が放出され、ダイノード
に衝突した電子が次々と増倍されて、電圧値として光電
子増倍管１２に入射した光の量が表される。そして、既
知の濃度の硫黄化合物を上記と同じ操作をして得られた
電圧値との関係から、予め作成した検量線を用いて、測
定された電圧値から試料中の硫黄化合物の濃度を測定す
る。The photomultiplier tube 12 is used for measuring the emission intensity at this time. In this photomultiplier tube 12, photoelectrons are emitted according to the amount of incident light, and the electrons colliding with the dynodes are multiplied one after another, and the amount of light incident on the photomultiplier tube 12 is displayed as a voltage value. To be done. Then, from the relationship with the voltage value obtained by performing the same operation as above with a sulfur compound of known concentration, using a calibration curve created in advance, measure the concentration of the sulfur compound in the sample from the measured voltage value. To do.
【００２１】まず、従来法により硫黄化合物の濃度測定
を行った。すなわち、４０容量％の水素を含む、水素と
ヘリウムの混合ガスを燃料ガスとして、これを４００ｍ
ｌ／分の流量で燃料ガス導入管５を介して約１３０℃に
維持された反応セル２に導入した。一方、支燃用ガス導
入管６を介して活性炭塔を通して清浄にした空気を流量
６００ｍｌ／分で導入し、上記水素−ヘリウム混合ガス
に点火した。ついで、硫黄化合物としてＳＯ２５ｐｐｍ
を含む標準ガス（窒素バランス）に種々の濃度の酸素を
存在させ、流量２５ｍｌ／分でサンプルガス導入管４か
ら水素炎バーナー３に導き、水素炎の中心部の還元炎７
で、上記標準ガス中に含まれる硫黄化合物を亜酸化硫黄
ＳＯに還元した。生成した亜酸化硫黄ＳＯは、ピックア
ップノズル８によって採取され、１１０℃以上に加熱さ
れた加熱導管１０を経由し、真空ライン１３によって１
００〜１０００Ｐａの減圧下に保たれたオゾン酸化セル
９に導入された。このオゾン酸化セル９には、オゾン発
生装置１１からオゾンＯ３が１００ｍｌ／分の流量で供
給されており、オゾン酸化セル９内において亜酸化硫黄
ＳＯとオゾンＯ３の反応を行った。この反応の際、上記
した理由により発光するが、この発光強度を光電子増倍
管１２により測定し、増幅器で増幅した後、電圧値とし
て出力させた。First, the sulfur compound concentration was measured by the conventional method. That is, a mixed gas of hydrogen and helium containing 40% by volume of hydrogen was used as a fuel gas, and this was 400 m.
It was introduced into the reaction cell 2 maintained at about 130 ° C. through the fuel gas introduction pipe 5 at a flow rate of 1 / min. On the other hand, purified air was introduced at a flow rate of 600 ml / min through the activated carbon tower through the combustion-supporting gas introducing pipe 6 and the hydrogen-helium mixed gas was ignited. Then, as a sulfur compound, SO 2 5ppm
Various concentrations of oxygen are made to exist in a standard gas (nitrogen balance) containing hydrogen, and the sample gas is introduced into the hydrogen flame burner 3 from the sample gas introduction pipe 4 at a flow rate of 25 ml / min.
Then, the sulfur compound contained in the standard gas was reduced to sulfur dioxide. The generated sulfurous oxide SO is collected by the pick-up nozzle 8, passes through the heating conduit 10 heated to 110 ° C. or higher, and the vacuum line 13
It was introduced into the ozone oxidation cell 9 kept under a reduced pressure of 00 to 1000 Pa. Ozone O 3 was supplied to the ozone oxidation cell 9 from the ozone generator 11 at a flow rate of 100 ml / min, and the sulfur dioxide SO and ozone O 3 were reacted in the ozone oxidation cell 9. During this reaction, light is emitted for the reason described above, but the emission intensity was measured by the photomultiplier tube 12, amplified by an amplifier, and then output as a voltage value.
【００２２】一方、精製窒素ＺＥＲＯ−Ａ（住友精化製
ＳＯ２フリーガス）を上記の方法で測定し、その時の発
光強度を濃度ゼロとして、ゼロ点を設定し、濃度既知の
ＳＯ２を含む標準ガス（窒素バランス）を用いて同様に
発光強度を測定し、増幅器で増幅した後、その電圧指示
値を１００％として検量線を作成した。この検量線を用
いて、上記標準ガス中のＳＯ２を種々の酸素濃度におい
て測定した。得られた測定値を５ｐｐｍを１００％とし
た振れ幅で図３に示す。図３から明らかなように、ＳＯ
２の測定値が酸素濃度によって大きく干渉されることが
明らかである。On the other hand, purified nitrogen ZERO-A (SO 2 free gas manufactured by Sumitomo Seika) was measured by the above method, the emission intensity at that time was set to zero, and a zero point was set to contain SO 2 of known concentration. Similarly, the emission intensity was measured using a standard gas (nitrogen balance), amplified with an amplifier, and then a calibration curve was created with the indicated voltage value as 100%. Using this calibration curve, SO 2 in the standard gas was measured at various oxygen concentrations. The obtained measured value is shown in FIG. 3 as a swing range with 5 ppm as 100%. As is clear from FIG.
It is clear that the measured value of 2 is greatly interfered by the oxygen concentration.
【００２３】本発明における好ましい実施形態において
は、燃料ガス導入管５に接続された窒素導入管５１と酸
素導入管５２から、窒素および酸素を、燃料ガスとして
用いた４０容量％の水素を含む水素とヘリウムの混合ガ
スに添加する。その添加量は、燃料ガス４００ｍｌ／分
に対して、窒素５０ｍｌ／分、そして酸素２ｍｌ／分で
ある。窒素および酸素を、燃料ガスに添加すること以外
は、前出と同じ条件で、硫黄化合物としてＳＯ２５ｐｐ
ｍを含む標準ガス（窒素バランス）に種々の濃度の酸素
を存在させ、流量２５ｍｌ／分でサンプルガス導入管４
から水素炎バーナー３に導き、ＳＯ２の測定を行った。
前出と同様に、検量線法によって、種々の酸素濃度にお
けるＳＯ２を測定した。図４に種々の酸素濃度における
ＳＯ２の測定値を５ｐｐｍを１００％とした振れ幅で示
す。図４から明らかなように、ＳＯ２の測定値は酸素濃
度によって干渉されることなく、ほぼ、正確に標準ガス
中のＳＯ２濃度を示していることが明らかである。In a preferred embodiment of the present invention, hydrogen containing 40% by volume of hydrogen, which is nitrogen and oxygen used as a fuel gas, is supplied from a nitrogen introducing pipe 51 and an oxygen introducing pipe 52 connected to the fuel gas introducing pipe 5. And helium mixed gas. The amount added is 400 ml / min of fuel gas, 50 ml / min of nitrogen, and 2 ml / min of oxygen. SO 2 5pp as a sulfur compound under the same conditions as the above except that nitrogen and oxygen are added to the fuel gas.
Various concentrations of oxygen are present in the standard gas containing nitrogen (nitrogen balance), and the sample gas introduction pipe 4 is used at a flow rate of 25 ml / min.
Was introduced into a hydrogen flame burner 3 and SO 2 was measured.
Similarly to the above, SO 2 at various oxygen concentrations was measured by the calibration curve method. FIG. 4 shows the measured values of SO 2 at various oxygen concentrations by the swing width with 5 ppm as 100%. As is clear from FIG. 4, it is clear that the measured value of SO 2 almost exactly indicates the concentration of SO 2 in the standard gas without being interfered by the oxygen concentration.
【００２４】[0024]
【発明の効果】以上述べたように、本発明は、大気に含
まれる微量の硫黄化合物をＳＣＤ法によって測定する方
法を、自動車の排ガスの測定に適用したものである。本
発明の方法を実施すれば、自動車の排ガスにおける場合
のように、排ガス中の酸素濃度が約５〜２１％と大きく
変動する場合においても、酸素による干渉を巧みに排除
して、排ガスに含まれる微量の硫黄化合物の濃度を安定
かつ、精度よく測定することが可能となる。INDUSTRIAL APPLICABILITY As described above, the present invention applies the method for measuring a trace amount of sulfur compounds contained in the atmosphere by the SCD method to the measurement of exhaust gas from automobiles. When the method of the present invention is carried out, even when the oxygen concentration in the exhaust gas fluctuates greatly to about 5 to 21%, as in the case of the exhaust gas of an automobile, the interference by oxygen is skillfully excluded and it is contained in the exhaust gas. Thus, it becomes possible to measure the concentration of a trace amount of sulfur compound stably and accurately.
【図１】本発明にかかる排ガス中の硫黄化合物の測定方
法を実施するための装置の概略構成図である。FIG. 1 is a schematic configuration diagram of an apparatus for carrying out a method for measuring a sulfur compound in exhaust gas according to the present invention.
【図２】図１の反応セルの周囲を拡大した断面図である2 is an enlarged cross-sectional view of the periphery of the reaction cell of FIG.
【図３】従来法による種々の酸素濃度におけるＳＯ２の
測定値の振れ幅を示すグラフである。FIG. 3 is a graph showing a fluctuation range of SO 2 measured values at various oxygen concentrations according to a conventional method.
【図４】本発明の方法による種々の酸素濃度におけるＳ
Ｏ２の測定値の振れ幅を示すグラフである。FIG. 4 S at various oxygen concentrations according to the method of the present invention
It is a graph which shows the fluctuation range of the measured value of O 2 .
【図５】大気中の硫黄化合物の濃度を測定するための従
来装置の概略構成図である。FIG. 5 is a schematic configuration diagram of a conventional device for measuring the concentration of a sulfur compound in the atmosphere.
１ 硫黄化合物濃度測定装置 ２ 反応セル ３ 水素炎バーナー ４ サンプルガス導入管 ５ 燃料ガス導入管 ５１ 窒素導入管 ５２ 酸素導入管 ６ 支燃用ガス導入管 ７ 還元炎 ８ ピックアップノズル ９ オゾン酸化セル １０ 加熱導管 １１ オゾン発生装置 １２ 光電子増倍管 １３ 真空ライン 1 Sulfur compound concentration measuring device 2 reaction cells 3 hydrogen flame burner 4 Sample gas introduction tube 5 Fuel gas introduction pipe 51 Nitrogen introduction tube 52 Oxygen introduction tube 6 Combustion support gas introduction pipe 7 reducing flame 8 pickup nozzles 9 Ozone oxidation cell 10 heating conduit 11 Ozone generator 12 Photomultiplier tube 13 Vacuum line
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山田 光正 静岡県三島市光ケ丘３−35−14 Ｆターム(参考） 2G042 AA01 BA08 BB12 CA01 CB01 DA04 2G054 AA01 CA10 EA10 GB10 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Mitsumasa Yamada 3-35-14 Hikarigaoka, Mishima City, Shizuoka Prefecture F term (reference) 2G042 AA01 BA08 BB12 CA01 CB01 DA04 2G054 AA01 CA10 EA10 GB10
Claims (6)
スを水素炎バーナーで燃焼させて、水素炎内に硫黄化合
物を含むサンプルガスを供給して亜酸化硫黄を生成させ
るステップと、生成した亜酸化硫黄を水素炎中から取り
出してオゾン酸化セルに供給し、オゾンと反応させて励
起状態の二酸化硫黄を生成させるステップと、励起状態
の二酸化硫黄が基底状態に遷移するときの発光強度を測
定するステップと、を含む排ガス中の硫黄化合物の測定
方法であって、上記水素を含む燃料ガスに窒素および酸
素を添加することを特徴とする、排ガス中の硫黄化合物
の測定方法。1. A step of combusting a fuel gas containing hydrogen while supplying a combustion supporting gas with a hydrogen flame burner to supply a sample gas containing a sulfur compound into the hydrogen flame to generate sulfur suboxide. The generated sulfur dioxide is taken out from the hydrogen flame and supplied to the ozone oxidation cell to react with ozone to generate excited state sulfur dioxide, and the emission intensity when the excited state sulfur dioxide transits to the ground state And a step of measuring the sulfur compound in the exhaust gas, which comprises adding nitrogen and oxygen to the fuel gas containing hydrogen.
ウムの混合ガスである、請求項１に記載の排ガス中の硫
黄化合物の測定方法。2. The method for measuring a sulfur compound in exhaust gas according to claim 1, wherein the fuel gas containing hydrogen is a mixed gas of hydrogen and helium.
２０〜７０容量％である、請求項１に記載の排ガス中の
硫黄化合物の測定方法。3. The method for measuring a sulfur compound in exhaust gas according to claim 1, wherein the hydrogen concentration in the fuel gas containing hydrogen is 20 to 70% by volume.
て５〜５０容量の割合で添加する、請求項１に記載の排
ガス中の硫黄化合物の測定方法。4. The method for measuring a sulfur compound in exhaust gas according to claim 1, wherein the nitrogen is added in a ratio of 5 to 50 volumes with respect to 100 volumes of the fuel gas.
て０．１〜５容量の割合で添加する、請求項１に記載の
排ガス中の硫黄化合物の測定方法。5. The method for measuring a sulfur compound in exhaust gas according to claim 1, wherein the oxygen is added at a ratio of 0.1 to 5 volume with respect to 100 volume of the fuel gas.
に記載の排ガス中の硫黄化合物の測定方法。6. The combustion supporting gas is air.
The method for measuring a sulfur compound in exhaust gas according to [4].
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|---|---|---|---|
| JP2001250896A JP2003028851A (en) | 2001-07-16 | 2001-07-16 | Measuring method for sulfur compound in exhaust gas |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001250896A JP2003028851A (en) | 2001-07-16 | 2001-07-16 | Measuring method for sulfur compound in exhaust gas |
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ID=19079626
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013242158A (en) * | 2012-05-17 | 2013-12-05 | Shimadzu Corp | Component analysis device and component analysis method |
| CN105136973A (en) * | 2015-08-26 | 2015-12-09 | 常州大学 | Neutralization method sulphur meter with sodium hydroxide calibration function |
-
2001
- 2001-07-16 JP JP2001250896A patent/JP2003028851A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013242158A (en) * | 2012-05-17 | 2013-12-05 | Shimadzu Corp | Component analysis device and component analysis method |
| CN105136973A (en) * | 2015-08-26 | 2015-12-09 | 常州大学 | Neutralization method sulphur meter with sodium hydroxide calibration function |
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