JP4178243B2 - Gas analysis method and apparatus for total organic carbon in gas using low temperature plasma - Google Patents
Gas analysis method and apparatus for total organic carbon in gas using low temperature plasma Download PDFInfo
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Description
本発明は、低温プラズマを利用してガス中の総有機炭素（ＴＯＣ）を計測するガス分析に関するものである。 The present invention relates to a gas analysis that measures the total organic carbon (TOC) in a gas using low-temperature plasma.
現在、ガス中に含まれる総有機炭素（TOC）量を計測するには、試料ガスを燃焼法、触媒法などによりＣＯ２に酸化させ、得られたＣＯ２の濃度から有機炭素の濃度を求める方法が採用されている。ところが、これらの技術は、有機炭素をＣＯ ２ に酸化させるには６００℃以上の高温が必要であり、また、その装置を稼動させるためには触媒層の温度が設定値になるまでに長時間を要するという問題がある。さらに、使用する装置も高温に対応できる耐熱対策を必要とすることから、運転コストが高くなるという欠点があることから、分析ガス中のＴＯＣを簡易に計測できる方法の開発が求められている。 Currently, in order to measure the total organic carbon (TOC) amount contained in a gas, the sample gas is oxidized to CO 2 by a combustion method, a catalytic method, etc., and the concentration of organic carbon is obtained from the obtained CO 2 concentration. The method is adopted. However, these techniques require a high temperature of 600 ° C. or higher to oxidize organic carbon to CO 2, and in order to operate the apparatus, it takes a long time until the temperature of the catalyst layer reaches a set value. There is a problem that requires. Further, since the need for heat countermeasures also apparatus used can cope with high temperatures, since there is a drawback that the operation cost is high, development of a method that can measure the TOC in the analysis gas easily is demanded .
本発明は、従来の技術における上記した問題を解決するためになされたものである。すなわち、本発明の目的は、分析ガス中の総有機炭素（TOC）量を計測するに当たり、常温・常圧下で動作する低コストで簡易なガス分析方法及びそのガス分析に用いるガス分析装置を提供することにある。 The present invention has been made to solve the above-described problems in the prior art. An object of the present invention, when measuring the total organic carbon (TOC) Analysis of the amount of gas, the gas analyzer used in a simple gas analysis method and a gas analyzer at a low cost operating under normal temperature and pressure It is to provide.
本発明のガス分析方法は、有機炭素を含むガスを、酸素雰囲気下に金属を担持した触媒の存在する系内で低温プラズマ処理してガス中の総有機炭素量をＣＯ ２ に酸化させた後、得られたＣＯ ２ の濃度から総有機炭素を計測することを特徴とするものである。そのガス分析の対象とするガス中の総有機炭素が、揮発性有害有機物質及び悪臭物質であることが好ましい。 In the gas analysis method of the present invention, after gas containing organic carbon is subjected to low-temperature plasma treatment in a system in which a metal-supported catalyst exists in an oxygen atmosphere, the total amount of organic carbon in the gas is oxidized to CO 2. The total organic carbon is measured from the concentration of CO 2 obtained . The total organic carbon in the gas subject to gas analysis is preferably a volatile harmful organic substance and a malodorous substance.
また、本発明のガス分析装置は、有機炭素を含むガスを反応器に供給する手段と、酸素を反応器に供給する手段と、金属を担持した触媒を充填した低温プラズマ反応器と、反応器に電圧を印加する高電圧電源と、炭素量の計測装置と、低温プラズマ反応器で分解処理されたガスを放出する手段とを備えたことを特徴とするものである。 Further, the gas analyzer of the present invention includes means for supplying a gas containing organic carbon to a reactor, means for supplying oxygen to the reactor, a low-temperature plasma reactor filled with a metal-supported catalyst, and a reactor The apparatus includes a high voltage power source for applying a voltage, a carbon amount measuring device, and a means for releasing gas decomposed in the low temperature plasma reactor.
本発明によれば、低温プラズマと触媒を併用して分析対象ガス中の総有機炭素（TOC）量の計測を、常温・大気圧で動作するものであるから、使用する装置が簡単であるとともに、操作性及び経済性に優れ、また余熱に時間を要しないため測定の立ち上がり時間を短縮できるという利点を有している。 According to the present invention, since the measurement of the total organic carbon (TOC) amount in the analysis target gas is performed at room temperature and atmospheric pressure using a low-temperature plasma and a catalyst in combination, the apparatus to be used is simple. In addition, it has excellent operability and economical efficiency, and has the advantage that the rise time of the measurement can be shortened because time is not required for the residual heat.
本発明は、有機炭素物質を含む分析ガス中の総有機炭素（ＴＯＣ）量を計測する際に、全ての有機炭素のＣＯ２への転換を室温、常圧下において１段式の低温プラズマー触媒を用いて行うものであり、その装置の運転条件を純酸素とすることにより、ＣＯ２への転換を促進させることができるものである。特に、装置の動作温度が室温であるため耐熱構造の必要が無く、触媒層の余熱時間も必要としないものである。 In the present invention, when measuring the total organic carbon (TOC) amount in an analysis gas containing an organic carbon substance, the conversion of all organic carbon to CO 2 is performed at room temperature and atmospheric pressure using a one-stage low-temperature plasma catalyst. The conversion to CO 2 can be promoted by setting the operating condition of the apparatus to pure oxygen. In particular, since the operating temperature of the apparatus is room temperature, there is no need for a heat-resistant structure, and no preheating time for the catalyst layer is required.
本発明において、分解除去の対象とする分析ガス中に含まれる総有機炭素物質としては、ベンゼン、キシレン、トルエン、スチレン、トリクロロエチレン、アセトン、ホルムアルデヒド、メチルメルカプタン、トリメチルアミン、メタノール、イソブタノール、アセトアルデヒドなどが挙げられる。これらの分析ガス中の濃度は１００００ｐｐｍ以下であることが好ましい。 In the present invention, the total organic carbon substances contained in the analysis gas to be decomposed and removed include benzene, xylene, toluene, styrene, trichloroethylene, acetone, formaldehyde, methyl mercaptan, trimethylamine, methanol, isobutanol, acetaldehyde and the like. Can be mentioned. The concentration in these analysis gases is preferably 10,000 ppm or less.
本発明の低温プラズマ反応器には、金属を担持した触媒を充填したものである。その金属を担持する担体としては、例えば、酸化チタン、γ−アルミナなどのアルミナ、シリカ、モレキュラーシーブを含むゼオライト類（Ｘ型、Ｙ型、Ａ型など）、酸化セリウム、酸化亜鉛、酸化マグネシウムなどの無機材料を用いることができる。また、その金属触媒としては、有機物質の分解能に優れた金属を前記無機材料に担持させることが好ましく、その金属としてはＡｇ、Ｐｔ、Ｎｉ、Ｃｏ、Ｆｅ、Ｍｎなどから選ばれる１種または２種以上が用いられる。 The low-temperature plasma reactor of the present invention is packed with a metal-supported catalyst. Examples of the carrier supporting the metal include alumina such as titanium oxide and γ-alumina, silica, zeolites including molecular sieves (X type, Y type, A type, etc.), cerium oxide, zinc oxide, magnesium oxide and the like. Inorganic materials can be used. Further, as the metal catalyst, it is preferable to support the inorganic material with a metal excellent in the resolution of an organic substance, and the metal is one or two selected from Ag, Pt, Ni, Co, Fe, Mn and the like. More than seeds are used.
低温プラズマ装置としては、従来公知の常温で放電するいずれのプラズマ装置も使用可能であって、ＡＣ高電圧、パルス高電圧、マイクロウエーブなどの高電圧電源により電圧印加電極と接地電極の間に印加する電圧は、分析ガス中の総有機炭素の濃度などにより変動するが、通常１〜５０kV、好ましくは１０〜３５kVであり、またその周波数は数百Hz乃至数kHzのものである。 As the low-temperature plasma apparatus, any conventionally known plasma apparatus that discharges at room temperature can be used, and it is applied between the voltage application electrode and the ground electrode by a high-voltage power source such as an AC high voltage, a pulse high voltage, or a microwave. The voltage to be changed varies depending on the concentration of the total organic carbon in the analysis gas and the like, but is usually 1 to 50 kV, preferably 10 to 35 kV, and the frequency is several hundred Hz to several kHz.
本発明において、得られたＣＯ２の計測には、従来公知の赤外線吸収法を適用することが好ましい。また、使用する反応器の材質としては、セラミックス，石英，ガラスなどの誘電体を用い、スパークを起こさない構造からなるものが用いられる。 In the present invention, it is preferable to apply a conventionally known infrared absorption method for measuring the obtained CO 2 . Moreover, as a material of the reactor to be used, the thing using the dielectric materials, such as ceramics, quartz, glass, and the structure which does not raise | generate a spark is used.
本発明において、１００００ｐｐｍ以下の総有機炭素物質を含むガスの分析には、図1に示すプロセスで行うことが望ましい。図1において、１は連続酸素供給装置、２は試料ガス注入口、３はプラズマ−触媒反応器、４はＣＯ２の検出装置であって、２に流入した試料ガスをプラズマ反応器３に導入して全ての有機炭素をＣＯ２に酸化させ、４の検出装置でＣＯ２濃度を計測し、５のデータ解析装置により出力する。 In the present invention, it is desirable to analyze the gas containing 10000 ppm or less of the total organic carbon material by the process shown in FIG. In FIG. 1, 1 is a continuous oxygen supply device, 2 is a sample gas inlet, 3 is a plasma-catalyst reactor, 4 is a CO 2 detection device, and the sample gas flowing into 2 is introduced into the plasma reactor 3. to oxidize all of the organic carbon to CO 2 by the CO 2 concentration measured by the fourth detector, and outputs the fifth data analyzer.
実施例
以下、本発明を実施例によりさらに具体的に説明するが、本発明はこの実施例によって何ら限定されるものではない。
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples.
Ａｇ１．０重量％を担持した酸化チタン粒子（平均粒径1.8ｍ）２３ｇを内部に装填した石英管反応器（ 長さ２０ｃｍ、内径１３ｍｍ）の一方の口から、分析ガスとしてベンゼン２１０ｐｐｍを含む酸素を流速２Ｌ／分で流通させながら、高電圧電源より３０ｋV、５００Ｈｚの電圧を印加し、プラズマエネルギー４００Ｊ／Ｌを投与し、常温で分解反応を行った。 Oxygen containing 210 ppm of benzene as an analysis gas from one port of a quartz tube reactor (length: 20 cm, inner diameter: 13 mm) in which 23 g of titanium oxide particles (average particle size: 1.8 m) loaded with 1.0% by weight of Ag was loaded. Was circulated at a flow rate of 2 L / min, a voltage of 30 kV and 500 Hz was applied from a high-voltage power supply, plasma energy of 400 J / L was administered, and a decomposition reaction was performed at room temperature.
実施例１において分析ガスとして用いたベンゼン２１０ｐｐｍを含む酸素を、
５００ｐｐｍを含む酸素に代えたこと以外は、実施例と同様にして分解反応を行った。
Oxygen containing 210 ppm of benzene used as the analysis gas in Example 1 was
The decomposition reaction was performed in the same manner as in the example except that the oxygen was changed to 500 ppm.
実施例１及び２で得られた結果を図３に示す。図３に見られるように、酸素雰囲気下ではベンゼンは１００％分解されて全てＣＯ２に転換された。ベンゼン分解の選択性が１００％であるため、ＣＯ２の濃度を計測することにより総有機炭素量を測定できる。 The results obtained in Examples 1 and 2 are shown in FIG. As can be seen in FIG. 3, under an oxygen atmosphere, benzene was 100% decomposed and all converted to CO 2 . Since the selectivity of benzene decomposition is 100%, the total amount of organic carbon can be measured by measuring the concentration of CO 2 .
１ 連続酸素供給装置
２ 分析ガス注入口
３ 低温プラズマ−触媒反応器
４ ＣＯ２計測装置
５ データ解析・出力装置
1 continuous
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