JP4393801B2

JP4393801B2 - Method and apparatus for continuous separation / analysis of mixed fluid

Info

Publication number: JP4393801B2
Application number: JP2003177606A
Authority: JP
Inventors: 博実山崎
Original assignee: Nikkiso Co Ltd
Current assignee: Nikkiso Co Ltd
Priority date: 2003-06-23
Filing date: 2003-06-23
Publication date: 2010-01-06
Anticipated expiration: 2023-06-23
Also published as: JP2005010121A

Description

【０００１】
【発明の属する技術分野】
この発明は、例えば自動車の排気ガスのように多くの成分を含む混合流体から、特定の成分を選択して連続的に分離・分析・測定することのできる混合流体の連続分離・分析方法および装置に関するものである。
【０００２】
【従来の技術】
例えば自動車の排気ガスは、多くの気体成分を含む混合気体である。自動車の排気ガスの成分分析においては、エンジンの動作条件や負荷状態に応じて、排気ガスの特定の気体成分が時間的にどのような濃度変化を呈するのかを測定する必要がある。このような混合気体中の特定の成分を連続的に測定することのできる実用的な測定方法は、今のところ存在していない。
【０００３】
自動車の排気ガスのように多くの成分を含む混合気体から、例えばメタン等の特定の成分を定量的に測定するには、従来は、測定装置としてＦＩＤ（水素炎イオン化検出器）やＦＴＩＲ（フーリエ変換赤外分光計）が一般的に使用されていた。これらの測定では、テトラバッグ等の気体採取容器内に空気で希釈した排気ガスを採取して、バッチ処理によって特定成分の定量測定が行われていた。
【０００４】
【発明が解決しようとする課題】
従来のようなバッチ処理による定量測定では、混合気体中の特定成分の量の変化を連続的に測定するような、連続測定が行えないという問題点があった。また、混合気体を空気で希釈して測定するために、混合気体中の特定成分の濃度が薄くなって測定誤差が大きくなるという問題点があった。さらに、空気中にもともと含まれている気体成分が混合気体に混入するために、測定誤差が大きくなるという問題点もあった。
【０００５】
そこで、本発明は、例えば自動車の排気ガスのように多くの成分を含む混合気体から、特定の成分を選択して連続的に分離・分析・測定することのできる混合気体の連続分離・分析方法および装置を提供することを目的とする。
【０００６】
【課題を解決するための手段】
上記目的を達成するために、本発明の混合流体の連続分析方法は、複数の成分の流体が混合した試料流体を通過させ、各成分のカラム内の移動速度の相違により各成分が時間差を持って流出する複数のカラムと、前記試料流体中の目的成分流体を検出する検出手段と、複数の前記カラムの流入側に設けられ、前記試料流体と押し出し用の流体とを複数の前記カラムの少なくとも１つに選択的に流入させる流入側選択手段と、複数の前記カラムの流出側に設けられ、複数の前記カラムの１つから流出する前記目的成分流体を選択的に前記検出手段に供給する流出側選択手段とによる混合流体の連続分析方法であって、複数の前記カラムの１つを所定の時間間隔かつ所定の順序で順次選択し、選択した当該カラムに、前記目的成分流体が分離可能な所定時間幅だけ前記試料流体を流入させるとともに、続いて押し出し用の流体を流入させる手順と、それぞれの前記カラムから前記目的成分流体のみが流出する時間帯に、当該カラムから流出する流体を前記検出手段に供給するように時間によって切り換える手順と、前記カラムから前記目的成分流体が流出した後、前記流出側選択手段を介して当該カラムに清浄用流体を逆方向から流入させる手順と、前記検出手段により前記目的成分流体を連続的に測定する手順とを有するものである。
【００１０】
また、本発明の混合流体の連続分離装置は、複数の成分の流体が混合した試料流体を通過させ、各成分のカラム内の移動速度の相違により各成分が時間差を持って流出する複数のカラムと、前記試料流体から分離する目的成分流体を流出させる出力流路と、複数の前記カラムの流入側に設けられ、前記試料流体と押し出し用の流体とを複数の前記カラムの少なくとも１つに選択的に流入させる流入側選択手段と、複数の前記カラムの流出側に設けられ、複数の前記カラムの１つから流出する前記目的成分流体を前記出力流路に選択的に出力させる流出側選択手段と、前記流入側選択手段と前記流出側選択手段とを制御する制御手段とを有し、前記流出側選択手段は、前記カラムに清浄用流体を逆方向から流入させることが可能なものであり、前記制御手段は、複数の前記カラムの１つを所定の時間間隔かつ所定の順序で順次選択し、選択した当該カラムに、前記目的成分流体が分離可能な所定時間幅だけ前記試料流体を流入させるとともに、続いて押し出し用の流体を流入させるように流入側選択手段を制御する手順と、それぞれの前記カラムから前記目的成分流体のみが流出する時間帯に、当該カラムからの流出出力が前記出力流路に接続するように前記流出側選択手段を時間によって制御する手順と、前記カラムから前記目的成分流体が流出した後、前記流出側選択手段を介して当該カラムに清浄用流体を逆方向から流入させる手順とを実行するものである。
【００１１】
また、上記の混合流体の連続分離装置において、複数の前記カラムは、複数のカラムを円筒面上に集合配置した円筒状のカラム集合体として形成されたものとすることができる。その場合、前記流入側選択手段および前記流出側選択手段は、前記カラム集合体を中心軸の回りに回転させることにより、流体が流入および流出するカラムを切り換えるものとすることができる。
【００１２】
また、上記の混合流体の連続分離装置において、複数の前記カラムは、複数のカラムを縦横所定のピッチで格子状に配列したカラム集合体として形成されたものとすることができる。
【００１３】
また、本発明の混合流体の連続分析装置は、複数の成分の流体が混合した試料流体を通過させ、各成分のカラム内の移動速度の相違により各成分が時間差を持って流出する複数のカラムと、前記試料流体中の目的成分流体を検出する検出手段と、複数の前記カラムの流入側に設けられ、前記試料流体と押し出し用の流体とを複数の前記カラムの少なくとも１つに選択的に流入させる流入側選択手段と、複数の前記カラムの流出側に設けられ、複数の前記カラムの１つから流出する前記目的成分流体を選択的に前記検出手段に供給する流出側選択手段と、前記流入側選択手段と前記流出側選択手段とを制御する制御手段とを有し、前記流出側選択手段は、前記カラムに清浄用流体を逆方向から流入させることが可能なものであり、前記制御手段は、複数の前記カラムの１つを所定の時間間隔かつ所定の順序で順次選択し、選択した当該カラムに、前記目的成分流体が分離可能な所定時間幅だけ前記試料流体を流入させるとともに、続いて押し出し用の流体を流入させるように流入側選択手段を制御する手順と、それぞれの前記カラムから前記目的成分流体のみが流出する時間帯に、当該カラムからの流出出力を前記検出手段に供給するように前記流出側選択手段を時間によって制御する手順と、前記カラムから前記目的成分流体が流出した後、前記流出側選択手段を介して当該カラムに清浄用流体を逆方向から流入させる手順とを実行するものである。
【００１４】
また、上記の混合流体の連続分析装置において、複数の前記カラムは、複数のカラムを円筒面上に集合配置した円筒状のカラム集合体として形成されたものとすることができる。その場合、前記流入側選択手段および前記流出側選択手段は、前記カラム集合体を中心軸の回りに回転させることにより、流体が流入および流出するカラムを切り換えるものとすることができる。
【００１５】
また、上記の混合流体の連続分析装置において、複数の前記カラムは、複数のカラムを縦横所定のピッチで格子状に配列したカラム集合体として形成されたものとすることができる。
【００１７】
【発明の実施の形態】
本発明の実施の形態について図面を参照して説明する。図１は、本発明の連続分析装置の全体構成を示す図である。この連続分析装置は、自動車の排気ガスのように複数の成分を含む混合気体の試料から、特定の目的成分を選択して連続的に分析・測定するものである。目的成分としては、例えばメタンがあげられる。目的成分以外のその他の成分（不要成分）としては、例えばエタン等がある。この連続分析装置は、第１カラムＣ１から第ｎカラムＣｎまでのｎ個のカラムを有している。
【００１８】
これらのカラムは、カラム内の目的成分と不要成分の移動速度が異なるものであり、目的成分の保持時間と不要成分の保持時間とが異なるものである。ここで、カラムへの流入開始から流出開始までの時間を保持時間とする。すなわち、カラムに目的成分と不要成分とを同時に流入させると、目的成分と不要成分とを時間的に分離して流出させることができる。
【００１９】
この事実を利用して、第１カラムＣ１から第ｎカラムＣｎまでのｎ個のカラムを用いて連続的に目的成分を分離することができる。すなわち、試料流路２１から供給された試料気体は、流入側選択手段２によって順次時間差を持って第１カラムＣ１から第ｎカラムＣｎまでのｎ個のカラムに流入される。各カラムへの試料気体の流入時間は目的成分が分離可能となる程度の短時間とし（またはカラムの各成分の保持時間の差を目的成分が分離可能となる程度とする）、その後は流路２２を介して供給されている押し出し用のパージガスを流入させる。パージガスとしては、ヘリウムや窒素等の不活性なガスが使用される。
【００２０】
そして、各カラムから目的成分が流出する時間帯に合わせて、そのカラムの流出先を流出側選択手段３によって出力流路３１に切り換える。そして目的成分は出力流路３１に接続された検出手段としての測定装置４に供給される。測定装置４として例示された検出手段としては、ＦＩＤ（水素炎イオン化検出器）、質量分析計、その他の検出器や測定機器、分析機器等が使用できる。なお、試料気体が流入されてから目的成分が流出を開始するまでの時間帯のカラムの流出先は排出流路３３に接続され、流出気体は排出流路３３を介して排出される。
【００２１】
このように、試料気体が流入するカラムを所定の時間差を持って順次切り換え、各カラムの流出出力を適切なタイミングで測定装置４側に切り換えることにより、試料気体から目的成分を分離して連続的に測定装置４に供給することができる。測定装置４では目的成分を連続して測定し、その質量、体積等を求め、さらには試料気体中の目的成分比率等を求めることができる。また、測定の終了したカラムに対しては、パージガスを流路３２を介して逆方向から流入させ再生清浄化を行う。清浄用のパージガスは流路２３から排出される。これにより、カラムを繰り返し使用して長時間連続的に測定を行うことができる。
【００２２】
制御部５は、流入側選択手段２を制御して、各カラムへの試料気体の流入開始およびパージガスの流入開始を所定のタイミングで行う。そして、制御部５は、流出側選択手段３を制御して、各カラムからの流出出力を出力流路３１に所定のタイミングで切り換える。また、制御部５は、流出側選択手段３を制御して、測定の終了したカラムに対して清浄用のパージガスを逆方向から流入させる。なお、この制御部５としては、時間経過に従って種々の制御を行うシーケンスコントローラ等が使用できる。または、制御部５を測定装置４の制御部と共通にして、コンピュータ等により実現することもできる。
【００２３】
次に、図２により、目的成分の分離動作を説明する。第１カラムＣ１には、図２（ａ）に示すように、時刻ｔ１から時刻ｔ２までの時間幅Δｔだけ試料気体が流入される。試料気体は、成分１，成分２，成分３，…からなる混合気体である。成分１を測定対象の目的成分とすることもできるし、成分１以外の成分２，成分３，…を目的成分とすることもできる。第１カラムＣ１に対しては、時刻ｔ２以降は押し出し用のパージガスを流入させる。そして第２カラムＣ２には、図２（ｂ）に示すように、時刻ｔ２から時刻ｔ３までの時間幅Δｔだけ試料気体を流入させ、時刻ｔ３以降は押し出し用のパージガスを流入させる。第３カラムＣ３以降に対しても、同様に順次、時間幅Δｔだけ試料気体を流入させ、その後、押し出し用のパージガスを流入させる。
【００２４】
第１カラムＣ１から流出する各成分は、それぞれの保持時間の相違により、図２（ｃ）に示すように、互いに分離して流出する。カラムの成分１，成分２，成分３，…に対する保持時間をｓ１，ｓ２，ｓ３，…とし、各成分の保持時間がｓ１＜ｓ２＜ｓ３…であるとする。それぞれの成分はｔ１＋ｓ１，ｔ１＋ｓ２，ｔ１＋ｓ３，…の時刻から流出を開始する。また、各カラムに試料気体を流入させる時間幅Δｔは、各成分が互いに分離して流出する程度の短時間とする。または、カラムの長さを十分に大きくして各成分が互いに分離するようにする。なお、必ずしも各成分が全て分離しなくてもよいが、少なくとも目的成分が分離するようにする
【００２５】
成分１と成分２とが分離するための条件はｔ１＋ｓ１＋Δｔ＜ｔ１＋ｓ２であり、すなわちΔｔ＜ｓ２−ｓ１である。成分１と成分２とが分離するには時間幅Δｔが保持時間ｓ２，ｓ１の差よりも小さければよい。同様に、成分２と成分３とが分離するための条件はΔｔ＜ｓ３−ｓ２となり、時間幅Δｔが保持時間ｓ３，ｓ２の差よりも小さければよい。このように、成分１，成分２，成分３，…が全て分離するためには、時間幅Δｔが各成分の保持時間の差よりも小さければよい。逆に、時間幅Δｔが測定結果の時間分解能等により決められている場合には、分離したい成分の保持時間の差が時間幅Δｔよりも大きくなるように、カラムの長さ、充填材の種類、充填量等を調整する必要がある。
【００２６】
第２カラムＣ２から流出する各成分も同様に、図２（ｄ）に示すように各成分が互いに分離して流出する。第２カラムＣ２には時刻ｔ２から試料気体を流入させているので、それぞれの成分はｔ２＋ｓ１，ｔ２＋ｓ２，ｔ２＋ｓ３，…の時刻から流出を開始する。
【００２７】
測定対象の目的成分として成分１を選択する場合は、図２（ｅ）に示すように、各カラムから成分１が流出する期間に、その流出出力を測定装置４に入力して測定を行うようにする。第１カラムＣ１、第２カラムＣ２、第３カラムＣ３、…からの成分１の出力を順次切り換えて測定装置４に入力するようにすれば、図２（ｅ）のように目的成分である成分１を連続して測定することができる。
【００２８】
図３は、第１カラムＣ１に対する流入側選択手段２および流出側選択手段３の動作タイミングを示す図である。まず、時刻ｔ１から時刻ｔ２までは、切替弁等の操作により試料気体を第１カラムＣ１に対して順方向に流入させる。そして、時刻ｔ２から時刻ｔ２＋ｓ１（第１カラムＣ１の測定終了時）までは、パージガスを順方向に流入させる。第１カラムＣ１の流出出力は、成分１が分離して流出される期間ｔ１＋ｓ１〜ｔ２＋ｓ１の間、出力流路３１すなわち測定装置４側に入力される。なお、時刻ｔ１＋ｓ１より前の第１カラムＣ１の流出出力は排出流路３３から排出される。
【００２９】
測定終了時の時刻ｔ２＋ｓ１以降は、カラム清浄再生用のパージガスを第１カラムＣ１に対して逆方向に流入させる。なお、清浄ガスは、押し出し用のパージガスと同一のガスを使用してもよいし、別の清浄用ガスを使用してもよい。ここでは第１カラムＣ１について説明したが、第２カラムＣ２、第３カラムＣ３、…第ｎカラムＣｎに対しても、同様の動作タイミングで試料気体およびパージガスを流入・流出させる。
【００３０】
次に、具体的なカラムの構成例を説明する。図４は、多数のカラムを円筒面上に集合配置して、円筒状のカラム集合体１としたものを示す図である。この円筒状のカラム集合体１を両端部から挟むように、流入側選択手段２および流出側選択手段３を配置する。そして、流入側選択手段２および流出側選択手段３には、図１と同符号で示す各流路が配置されている。なお、図４においては排出流路３３は図示を省略している。
【００３１】
測定時には、カラム集合体１を図示のように、所定時間ごとにカラムの１ピッチずつ間欠的に回転させる。試料気体、パージガス、清浄ガスの供給口は、それぞれ所定の期間だけ、各単位カラムに連通するように構成されている。カラム集合体１を間欠的に１ピッチずつ回転させることにより、それぞれのカラムに対して、順次、図３に示すようなタイミングで各気体を流入・流出させることができる。そして、測定装置では目的成分を連続して測定することができる。カラム集合体１の各カラムは、再生清浄化処理を行うため繰り返し使用することができるが、ある程度の性能劣化は免れない。性能劣化時には、カラム集合体１を新しいものに交換する。カラム集合体１ごと交換するので保守作業は容易である。
【００３２】
試料流路２１から供給された試料気体は、カラム集合体１の間欠的な回転により順次時間差を持ってカラム集合体１の各単位カラムに流入される。カラム集合体１は前述の時間幅Δｔごとに１ピッチずつ回転させるようにする。試料気体が時間幅Δｔだけ流入された後は、各単位カラムにパージガスが順方向に流入される。各単位カラムからの流出出力を出力流路３１に接続するタイミングは、試料流路２１と出力流路３１との回転方向の相対的な角度位置で決定される。
【００３３】
すなわち、出力流路３１の角度位置は目的成分が流出する位置に設定される。また、出力流路３１の角度位置を変更することにより、他の成分を目的成分として流出させることができる。出力流路３１の角度位置を変更可能にしておけば、混合成分の中から任意の成分を目的成分として選択することもできる。また、複数の出力流路を異なる角度位置に設置することにより、複数の成分を同時に分離することもできる。
【００３４】
図５は、カラム集合体１０、流入側選択手段２、流出側選択手段３の他の例を示す図である。このカラム集合体１０は、多数のカラムを縦横に所定のピッチで格子状に配列し、直方体状に形成したものである。このカラム集合体１０を両端部から挟むように、流入側選択手段２および流出側選択手段３を配置する。そして、流入側選択手段２および流出側選択手段３には、図１と同符号で示す各流路が配置されている。なお、図５では排出流路３３は図示を省略している。
【００３５】
流入側選択手段２には、各カラムの端部に各カラムに対応するマイクロバルブが設けられており、それぞれの気体の供給または排出用の流路に選択的に連通させることができる。流出側選択手段３も同様である。これらのマイクロバルブを所定の順序で制御することにより、それぞれのカラムに対して、順次、図３に示すようなタイミングで各気体を流入・流出させることができる。そして、測定装置では目的成分を連続して測定することができる。カラム集合体１０の各カラムは、再生清浄化処理を行うため繰り返し使用することができるが、ある程度の性能劣化は免れない。性能劣化時には、カラム集合体１０を新しいものに交換する。カラム集合体１０ごと交換するので保守作業は容易である。
【００３６】
このように、試料気体が流入するカラムを所定の時間差を持って順次切り換え、各カラムの流出出力を適切なタイミングで測定装置側に切り換えることにより、試料気体から目的成分を分離して連続的に測定装置に供給することができる。測定装置では目的成分を連続して測定し、その質量、体積、濃度等を求めることができる。また、測定の終了したカラムに対しては、パージガスを逆方向から流入させ再生清浄化を行うため、カラムを繰り返し使用して長時間連続的に測定を行うことができる。
【００３７】
図５の実施の形態でも、各カラムの流出出力をマイクロバルブによって出力流路３１に接続するタイミングを変更することにより、混合成分の中から任意の成分を目的成分として選択して分離することができる。また、複数の出力流路を設置しておき、各カラムの流出出力を異なるタイミングでこれらの出力流路に接続することにより、複数の成分を同時に分離することもできる。
【００３８】
なお、本発明における複数のカラムは、温度コントロールされて各カラムにおける目的成分の保持時間がほぼ同一となっていることが望ましい。また、流出側選択手段に接続され、目的成分の測定を行う測定装置としては、ＦＩＤ、単収束磁場質量分析計等の質量分析装置の他にも連続的に測定が可能な任意の分析器や分析装置が使用できる。
【００３９】
なお、以上の実施の形態においては、試料流体として混合気体を例にあげて説明しているが、本発明は液体等の他の試料流体にも適用可能である。また、試料流体の分離出力を検出手段としての測定装置によって連続的に分析・測定する例について説明しているが、試料流体の分離出力を他の処理装置によって処理するものであってもよいし、試料流体から目的成分の分離のみを行うものであってもよい。
【００４０】
【発明の効果】
本発明は、以上に説明したように構成されているので、以下のような効果を奏する。
【００４１】
試料流体が流入するカラムを所定の時間差で順次切り換え、各カラムの流出出力を適切なタイミングで検出手段側に切り換えることにより、試料流体から目的成分を分離して連続的に検出手段に供給することができる。検出手段では目的成分を連続して測定し、その質量、体積、濃度等を求めることができる。
【００４２】
測定の終了したカラムに対しては、清浄用流体を逆方向から流入させて再生清浄化を行うため、カラムを繰り返し使用して長時間連続的に測定を行うことができる。
【００４３】
カラムを円筒状のカラム集合体として形成したので、カラム集合体を間欠的に回転させるだけで、流入側と流出側の切り換え制御を行うことができ、切り換え制御が簡単になる。また、カラムの性能劣化時には、カラム集合体ごと交換することができ保守作業が容易となる。
【００４４】
カラムを縦横所定のピッチで格子状に配列したカラム集合体を使用するようにしたので、カラム集合体に含まれるカラムの数を増大することができ、カラム集合体を小型化することができる。また、カラムの性能劣化時には、カラム集合体ごと交換することができ保守作業が容易となる。
【図面の簡単な説明】
【図１】図１は、本発明の連続分析装置の全体構成を示す図である。
【図２】図２は、本発明における目的成分の分離動作を示す図である。
【図３】図３は、カラムの各選択手段の動作タイミングを示す図である。
【図４】図４は、カラム集合体、流入側選択手段、流出側選択手段を示す図である。
【図５】図５は、カラム集合体、流入側選択手段、流出側選択手段の他の例を示す図である。
【符号の説明】
１，１０…カラム集合体
２…流入側選択手段
３…流出側選択手段
４…測定装置
５…制御部
２１…試料流路
２２，２３，３２…流路
３１…出力流路
３３…排出流路
Ｃ１…第１カラム
Ｃ２…第２カラム
Ｃｎ…第ｎカラム[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method and apparatus for continuous separation / analysis of a mixed fluid capable of continuously separating, analyzing and measuring a specific component from a mixed fluid containing many components, such as automobile exhaust gas. It is about.
[0002]
[Prior art]
For example, automobile exhaust gas is a mixed gas containing many gas components. In the component analysis of automobile exhaust gas, it is necessary to measure the concentration change of a specific gas component of the exhaust gas over time according to the engine operating conditions and load conditions. At present, there is no practical measurement method capable of continuously measuring a specific component in such a mixed gas.
[0003]
In order to quantitatively measure a specific component such as methane from a mixed gas containing many components such as automobile exhaust gas, conventionally, as a measuring device, FID (hydrogen flame ionization detector) or FTIR (Fourier) Conversion infrared spectrometers) were commonly used. In these measurements, exhaust gas diluted with air is collected in a gas collection container such as a tetra bag, and quantitative measurement of specific components is performed by batch processing.
[0004]
[Problems to be solved by the invention]
Conventional quantitative measurement by batch processing has a problem that continuous measurement such as continuous measurement of changes in the amount of a specific component in a mixed gas cannot be performed. Moreover, since the gas mixture is diluted with air and measured, the concentration of the specific component in the gas mixture becomes thin, resulting in a large measurement error. Furthermore, since the gas component originally contained in the air is mixed into the mixed gas, there is a problem that the measurement error increases.
[0005]
Accordingly, the present invention provides a continuous separation / analysis method for a mixed gas that can select, isolate, analyze, and measure a specific component continuously from a mixed gas that contains many components, such as automobile exhaust gas. And an object to provide an apparatus.
[0006]
[Means for Solving the Problems]
In order to achieve the above object, the mixed fluid continuous analysis method of the present invention allows a sample fluid mixed with a plurality of component fluids to pass through, and each component has a time difference due to the difference in moving speed of each component in the column. A plurality of columns flowing out, detection means for detecting a target component fluid in the sample fluid, and a plurality of columns provided on the inflow side of the plurality of columns, wherein the sample fluid and the fluid for extrusion are at least of the plurality of columns An inflow side selection means for selectively inflowing into one, and an outflow provided on the outflow side of the plurality of columns, and selectively supplying the target component fluid flowing out from one of the plurality of columns to the detection means A method for continuously analyzing a mixed fluid using a side selection means, wherein one of a plurality of the columns is sequentially selected in a predetermined time interval and in a predetermined order, and the target component fluid can be separated into the selected column. The flow of the sample fluid is allowed to flow in for a predetermined time width, and then the extrusion fluid is flown in, and the fluid flowing out from the column is detected in the time zone in which only the target component fluid flows out from each column. A procedure for switching by time so as to supply to the means, a procedure for allowing the cleaning fluid to flow into the column in the reverse direction via the outflow side selection means after the target component fluid has flowed out of the column, and the detection means And continuously measuring the target component fluid .
[0010]
The mixed fluid continuous separation device of the present invention allows a sample fluid mixed with a plurality of component fluids to pass therethrough, and a plurality of columns in which each component flows out with a time difference due to a difference in moving speed of each component in the column. And an output flow path for flowing out the target component fluid separated from the sample fluid, and an inflow side of the plurality of columns, and the sample fluid and the extrusion fluid are selected as at least one of the plurality of columns Inflow side selection means for allowing inflow, and outflow side selection means for selectively outputting the target component fluid flowing out from one of the plurality of columns to the output flow path, provided on the outflow side of the plurality of columns And control means for controlling the inflow side selection means and the outflow side selection means, and the outflow side selection means is capable of allowing a cleaning fluid to flow into the column from the opposite direction. , The control means sequentially selects one of the plurality of columns in a predetermined time interval and in a predetermined order, and causes the sample fluid to flow into the selected column for a predetermined time width in which the target component fluid can be separated. At the same time, in the procedure of controlling the inflow side selection means so that the fluid for extrusion flows in, and in the time zone when only the target component fluid flows out from each column, the outflow output from the column is output to the output flow. A procedure for controlling the outflow side selecting means according to time so as to connect to the channel, and after the target component fluid has flowed out of the column, the cleaning fluid flows into the column in the reverse direction through the outflow side selecting means. The procedure to perform is performed.
[0011]
In the continuous fluid separation device, the plurality of columns may be formed as a cylindrical column aggregate in which a plurality of columns are arranged and arranged on a cylindrical surface. In that case, the inflow side selection means and the outflow side selection means can switch the column through which the fluid flows in and out by rotating the column assembly around the central axis.
[0012]
In the above-described continuous fluid separation apparatus, the plurality of columns may be formed as a column aggregate in which a plurality of columns are arranged in a grid pattern at a predetermined vertical and horizontal pitch.
[0013]
In addition, the continuous analysis apparatus for mixed fluid of the present invention allows a sample fluid mixed with a plurality of component fluids to pass therethrough, and a plurality of columns in which each component flows out with a time difference due to a difference in moving speed of each component in the column. And a detection means for detecting a target component fluid in the sample fluid, and the sample fluid and the fluid for extrusion are selectively provided to at least one of the plurality of columns. Inflow side selection means for inflow, Outflow side selection means provided on the outflow side of the plurality of columns, and selectively supplying the target component fluid flowing out from one of the plurality of columns to the detection means, Control means for controlling the inflow side selection means and the outflow side selection means, wherein the outflow side selection means is capable of allowing a cleaning fluid to flow into the column from the reverse direction, and the control means One of the plurality of columns is sequentially selected in a predetermined time interval and in a predetermined order, and the sample fluid is allowed to flow into the selected column for a predetermined time width in which the target component fluid can be separated. In order to supply the outflow output from the column to the detection means in the procedure for controlling the inflow side selection means so that the fluid for extrusion flows in, and only the target component fluid flows out from each column. And a procedure for controlling the outflow side selection means according to time and a procedure for allowing the cleaning fluid to flow into the column in the reverse direction via the outflow side selection means after the target component fluid has flowed out of the column. To do.
[0014]
In the above-described continuous analysis apparatus for a mixed fluid, the plurality of columns may be formed as a cylindrical column aggregate in which a plurality of columns are arranged and arranged on a cylindrical surface. In that case, the inflow side selection means and the outflow side selection means can switch the column through which the fluid flows in and out by rotating the column assembly around the central axis.
[0015]
In the mixed fluid continuous analysis apparatus, the plurality of columns may be formed as a column aggregate in which a plurality of columns are arranged in a grid pattern at a predetermined vertical and horizontal pitch.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a diagram showing the overall configuration of the continuous analysis apparatus of the present invention. This continuous analyzer selects and analyzes and measures a specific target component continuously from a mixed gas sample containing a plurality of components such as automobile exhaust gas. Examples of the target component include methane. Examples of other components (unnecessary components) other than the target component include ethane. This continuous analyzer has n columns from the first column C1 to the nth column Cn.
[0018]
These columns have different moving speeds of the target component and the unnecessary component in the column, and the holding time of the target component and the holding time of the unnecessary component are different. Here, the time from the start of flow into the column to the start of flow is defined as the holding time. That is, when the target component and the unnecessary component are allowed to flow into the column at the same time, the target component and the unnecessary component can be temporally separated and discharged.
[0019]
Utilizing this fact, the target component can be continuously separated using n columns from the first column C1 to the nth column Cn. That is, the sample gas supplied from the sample flow path 21 is sequentially introduced into the n columns from the first column C1 to the nth column Cn with a time difference by the inflow side selection means 2. The flow time of the sample gas into each column is set to a short time such that the target component can be separated (or the difference in the retention time of each component of the column is set to such a level that the target component can be separated), and thereafter the flow path Extrusion purge gas supplied through 22 is introduced. As the purge gas, an inert gas such as helium or nitrogen is used.
[0020]
Then, the outflow destination of the column is switched to the output flow path 31 by the outflow side selection means 3 in accordance with the time zone in which the target component flows out from each column. Then, the target component is supplied to the measuring device 4 as detection means connected to the output flow path 31. As a detection means exemplified as the measuring device 4, an FID (hydrogen flame ionization detector), a mass spectrometer, other detectors, measuring devices, analytical devices, and the like can be used. In addition, the outflow destination of the column during the time period from when the sample gas is introduced to when the target component starts to flow out is connected to the discharge flow path 33, and the outflow gas is discharged through the discharge flow path 33.
[0021]
In this way, by sequentially switching the column into which the sample gas flows in with a predetermined time difference and switching the outflow output of each column to the measuring device 4 side at an appropriate timing, the target component is separated from the sample gas and continuously. Can be supplied to the measuring device 4. The measuring device 4 can continuously measure the target component, determine its mass, volume, etc., and further determine the target component ratio in the sample gas. In addition, the column that has been measured is regenerated and cleaned by flowing a purge gas from the reverse direction through the flow path 32. The purge gas for cleaning is discharged from the flow path 23. Thereby, it is possible to perform measurement continuously for a long time by repeatedly using the column.
[0022]
The control unit 5 controls the inflow side selection unit 2 to start inflow of the sample gas and purge gas into each column at a predetermined timing. And the control part 5 controls the outflow side selection means 3, and switches the outflow output from each column to the output flow path 31 at a predetermined timing. In addition, the control unit 5 controls the outflow side selection unit 3 to allow the purging purge gas to flow into the column after the measurement from the reverse direction. In addition, as this control part 5, the sequence controller etc. which perform various control according to progress of time can be used. Alternatively, the control unit 5 can be realized by a computer or the like in common with the control unit of the measuring device 4.
[0023]
Next, the separation operation of the target component will be described with reference to FIG. As shown in FIG. 2A, the sample gas flows into the first column C1 for a time width Δt from time t1 to time t2. The sample gas is a mixed gas composed of component 1, component 2, component 3,. Component 1 can be the target component to be measured, and component 2, component 3,... Other than component 1 can be the target component. For the first column C1, the purge gas for extrusion is caused to flow after time t2. Then, as shown in FIG. 2B, the sample gas is allowed to flow into the second column C2 for a time width Δt from time t2 to time t3, and the purge gas for extrusion is allowed to flow after time t3. Similarly, the sample gas is sequentially introduced into the third column C3 and the subsequent time by the time width Δt, and then the purge gas for extrusion is introduced.
[0024]
The components flowing out from the first column C1 are separated from each other and flow out as shown in FIG. It is assumed that the retention times for the column component 1, component 2, component 3,... Are s1, s2, s3,..., And each component retention time is s1 <s2 <s3. Each component starts to flow out at time t1 + s1, t1 + s2, t1 + s3,. The time width Δt for allowing the sample gas to flow into each column is set to a short time such that the components are separated from each other and flow out. Alternatively, the length of the column is made sufficiently large so that the components are separated from each other. It is not always necessary to separate all the components, but at least the target component should be separated.
The condition for separating component 1 and component 2 is t1 + s1 + Δt <t1 + s2, that is, Δt <s2-s1. In order for the component 1 and the component 2 to be separated, the time width Δt only needs to be smaller than the difference between the holding times s2 and s1. Similarly, the condition for separating the component 2 and the component 3 is Δt <s3−s2, and the time width Δt only needs to be smaller than the difference between the holding times s3 and s2. In this way, in order to separate all of component 1, component 2, component 3,..., It is sufficient that the time width Δt is smaller than the difference between the retention times of the components. Conversely, when the time width Δt is determined by the time resolution of the measurement result, the column length and the type of packing material so that the difference in the retention time of the components to be separated is greater than the time width Δt. It is necessary to adjust the filling amount.
[0026]
Similarly, the components flowing out from the second column C2 are separated from each other and flow out as shown in FIG. Since the sample gas is allowed to flow into the second column C2 from the time t2, the respective components start to flow out from the time t2 + s1, t2 + s2, t2 + s3,.
[0027]
When component 1 is selected as the target component to be measured, as shown in FIG. 2 (e), during the period in which component 1 flows out from each column, the outflow output is input to measuring device 4 for measurement. To. If the output of the component 1 from the first column C1, the second column C2, the third column C3,... Is sequentially switched and input to the measuring device 4, the component which is the target component as shown in FIG. 1 can be measured continuously.
[0028]
FIG. 3 is a diagram illustrating operation timings of the inflow side selection unit 2 and the outflow side selection unit 3 with respect to the first column C1. First, from time t1 to time t2, the sample gas is caused to flow in the forward direction with respect to the first column C1 by operating a switching valve or the like. Then, from time t2 to time t2 + s1 (at the end of measurement of the first column C1), the purge gas is allowed to flow in the forward direction. The outflow output of the first column C1 is input to the output flow path 31, that is, the measuring device 4 side during the period t1 + s1 to t2 + s1 in which the component 1 is separated and outflows. The outflow output of the first column C1 before time t1 + s1 is discharged from the discharge flow path 33.
[0029]
After the time t2 + s1 at the end of the measurement, the purge gas for regenerating the column clean is caused to flow in the reverse direction with respect to the first column C1. The cleaning gas may be the same gas as the purge purge gas or a different cleaning gas. Here, the first column C1 has been described. However, the sample gas and the purge gas are allowed to flow into and out of the second column C2, the third column C3,.
[0030]
Next, a specific configuration example of the column will be described. FIG. 4 is a view showing a cylindrical column assembly 1 in which a large number of columns are gathered and arranged on a cylindrical surface. The inflow side selection means 2 and the outflow side selection means 3 are arranged so as to sandwich the cylindrical column assembly 1 from both ends. The inflow side selection means 2 and the outflow side selection means 3 are provided with respective flow paths indicated by the same reference numerals as in FIG. In FIG. 4, the discharge channel 33 is not shown.
[0031]
During measurement, the column assembly 1 is intermittently rotated by one pitch of the column every predetermined time as shown in the figure. Sample gas, purge gas, and clean gas supply ports are configured to communicate with each unit column for a predetermined period. By rotating the column assembly 1 intermittently one pitch at a time, each gas can be flowed into and out of each column sequentially at the timing shown in FIG. The measuring device can continuously measure the target component. Each column of the column assembly 1 can be repeatedly used to perform the regeneration cleaning process, but a certain degree of performance deterioration is inevitable. When the performance deteriorates, the column assembly 1 is replaced with a new one. Since the column assembly 1 is replaced, maintenance work is easy.
[0032]
The sample gas supplied from the sample channel 21 is sequentially introduced into each unit column of the column assembly 1 with a time difference due to the intermittent rotation of the column assembly 1. The column assembly 1 is rotated by one pitch every time width Δt described above. After the sample gas has flowed in for the time width Δt, the purge gas flows in the forward direction into each unit column. The timing for connecting the outflow output from each unit column to the output flow path 31 is determined by the relative angular position of the sample flow path 21 and the output flow path 31 in the rotation direction.
[0033]
That is, the angular position of the output channel 31 is set to a position where the target component flows out. Further, by changing the angular position of the output flow path 31, it is possible to cause other components to flow out as target components. If the angular position of the output channel 31 can be changed, an arbitrary component can be selected as a target component from the mixed components. In addition, a plurality of components can be separated simultaneously by installing a plurality of output channels at different angular positions.
[0034]
FIG. 5 is a diagram illustrating another example of the column assembly 10, the inflow side selection unit 2, and the outflow side selection unit 3. The column assembly 10 is formed by arranging a large number of columns vertically and horizontally in a lattice shape at a predetermined pitch and forming a rectangular parallelepiped shape. The inflow side selection means 2 and the outflow side selection means 3 are arranged so as to sandwich the column assembly 10 from both ends. The inflow side selection means 2 and the outflow side selection means 3 are provided with respective flow paths indicated by the same reference numerals as in FIG. In FIG. 5, the discharge flow path 33 is not shown.
[0035]
The inflow side selection means 2 is provided with a microvalve corresponding to each column at the end of each column, and can be selectively communicated with each gas supply or discharge flow path. The same applies to the outflow side selection means 3. By controlling these microvalves in a predetermined order, each gas can be flowed into and out of each column sequentially at the timing shown in FIG. The measuring device can continuously measure the target component. Each column of the column assembly 10 can be repeatedly used to perform the regeneration cleaning process, but a certain degree of performance deterioration is inevitable. When the performance deteriorates, the column assembly 10 is replaced with a new one. Since the entire column assembly 10 is exchanged, maintenance work is easy.
[0036]
In this way, the column in which the sample gas flows in is sequentially switched with a predetermined time difference, and the outflow output of each column is switched to the measuring device side at an appropriate timing to separate the target component from the sample gas and continuously It can be supplied to a measuring device. The measuring device can continuously measure the target component and determine its mass, volume, concentration and the like. In addition, since the purge gas is flowed in the reverse direction and the regeneration cleaning is performed on the column for which the measurement has been completed, the measurement can be continuously performed for a long time by repeatedly using the column.
[0037]
In the embodiment of FIG. 5 as well, by changing the timing at which the outflow output of each column is connected to the output flow path 31 by the microvalve, it is possible to select and separate any component from the mixed components as the target component. it can. Also, a plurality of components can be separated simultaneously by installing a plurality of output channels and connecting the outflow outputs of the respective columns to these output channels at different timings.
[0038]
The plurality of columns in the present invention are desirably temperature-controlled so that the retention time of the target component in each column is substantially the same. Moreover, as a measuring device connected to the outflow side selecting means and measuring a target component, in addition to a mass spectrometer such as an FID or a single-focusing magnetic field mass spectrometer, any analyzer capable of continuous measurement, An analysis device can be used.
[0039]
In the above embodiment, the mixed gas is described as an example of the sample fluid. However, the present invention can be applied to other sample fluids such as a liquid. Further, the example in which the separation output of the sample fluid is continuously analyzed and measured by the measurement device as the detection means has been described, but the separation output of the sample fluid may be processed by another processing device. Alternatively, only the target component may be separated from the sample fluid.
[0040]
【The invention's effect】
Since the present invention is configured as described above, the following effects can be obtained.
[0041]
The target fluid is separated from the sample fluid and continuously supplied to the detection means by sequentially switching the column into which the sample fluid flows at a predetermined time difference and switching the outflow output of each column to the detection means at an appropriate timing. Can do. The detection means can continuously measure the target component and determine its mass, volume, concentration, and the like.
[0042]
Since the column for which the measurement has been completed is regenerated and cleaned by flowing a cleaning fluid from the opposite direction, the column can be repeatedly used for continuous measurement for a long time.
[0043]
Since the column is formed as a cylindrical column assembly, switching control between the inflow side and the outflow side can be performed only by intermittently rotating the column assembly, and the switching control is simplified. Further, when the performance of the column deteriorates, the entire column assembly can be replaced, and maintenance work is facilitated.
[0044]
Since the column aggregate in which the columns are arranged in a grid pattern at a predetermined vertical and horizontal pitch is used, the number of columns included in the column aggregate can be increased, and the column aggregate can be reduced in size. Further, when the performance of the column deteriorates, the entire column assembly can be replaced, and maintenance work is facilitated.
[Brief description of the drawings]
FIG. 1 is a diagram showing an overall configuration of a continuous analysis apparatus according to the present invention.
FIG. 2 is a diagram showing a separation operation of a target component in the present invention.
FIG. 3 is a diagram illustrating the operation timing of each selection unit in a column.
FIG. 4 is a diagram showing a column assembly, inflow side selection means, and outflow side selection means.
FIG. 5 is a diagram illustrating another example of the column assembly, the inflow side selection unit, and the outflow side selection unit.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1,10 ... Column assembly 2 ... Inflow side selection means 3 ... Outflow side selection means 4 ... Measuring apparatus 5 ... Control part 21 ... Sample flow path 22, 23, 32 ... Flow path 31 ... Output flow path 33 ... Discharge flow path C1 ... 1st column C2 ... 2nd column Cn ... nth column

Claims

A plurality of columns (C1, C2,..., Cn) through which a sample fluid mixed with a plurality of component fluids passes and each component flows out with a time difference due to a difference in moving speed of each component in the column; Detection means (4) for detecting a target component fluid in the fluid, and provided on the inflow side of the plurality of columns (C1, C2,..., Cn), and the sample fluid and the extrusion fluid are supplied to the plurality of columns. (C1, C2,..., Cn) are provided on the outflow side of the plurality of columns (C1, C2,..., Cn). In the continuous analysis method of the mixed fluid by the outflow side selection means (3) for selectively supplying the target component fluid flowing out from one of the columns (C1, C2,..., Cn) to the detection means (4). There,
One of the plurality of columns (C1, C2,..., Cn) is sequentially selected in a predetermined time interval and in a predetermined order, and the sample is applied to the selected column for a predetermined time width in which the target component fluid can be separated. A procedure for injecting fluid and subsequently injecting fluid for extrusion;
A procedure for switching according to time so that the fluid flowing out from the column is supplied to the detection means (4) in a time zone when only the target component fluid flows out from each of the columns (C1, C2,..., Cn);
After the target component fluid has flowed out of the column (C1, C2,..., Cn), a procedure for allowing the cleaning fluid to flow into the column in the reverse direction via the outflow side selection means (3);
A continuous analysis method of a mixed fluid, comprising a step of continuously measuring the target component fluid by the detection means (4).

A plurality of columns (C1, C2,..., Cn) through which a sample fluid mixed with a plurality of component fluids passes and each component flows out with a time difference due to a difference in moving speed of each component in the column;
An output channel (31) for flowing out the target component fluid separated from the sample fluid;
Provided on the inflow side of the plurality of columns (C1, C2,..., Cn), the sample fluid and the extrusion fluid are selectively used as at least one of the plurality of columns (C1, C2,..., Cn). Inflow side selection means (2) for flowing into
Provided on the outflow side of the plurality of columns (C1, C2,..., Cn), the target component fluid flowing out from one of the plurality of columns (C1, C2,. ) The outflow side selection means (3) to be selectively output,
Control means (5) for controlling the inflow side selection means (2) and the outflow side selection means (3);
The outflow side selecting means (3) is capable of allowing a cleaning fluid to flow into the columns (C1, C2,..., Cn) from the reverse direction,
The control means (5)
One of the plurality of columns (C1, C2,..., Cn) is sequentially selected in a predetermined time interval and in a predetermined order, and the sample is applied to the selected column for a predetermined time width in which the target component fluid can be separated. A procedure for controlling the inflow side selection means (2) so as to allow the fluid to flow in and then to allow the extrusion fluid to flow;
The outflow side selection means so that the outflow output from the column is connected to the output flow path (31) in a time zone when only the target component fluid flows out from each of the columns (C1, C2,..., Cn). A procedure for controlling (3) according to time ;
After the target component fluid has flowed out of the columns (C1, C2,..., Cn), a procedure for performing a procedure for allowing the cleaning fluid to flow into the column in the reverse direction via the outflow side selection means (3) A continuous separator for a fluid mixture.

A continuous separation apparatus for mixed fluid according to claim 2 ,
The plurality of columns are formed as a cylindrical column aggregate (1) in which a plurality of columns are arranged on a cylindrical surface.
The inflow side selection means (2) and the outflow side selection means (3) are for switching the column through which the fluid flows in and out by rotating the column assembly (1) around the central axis. A continuous separator for fluid.

A continuous separation apparatus for mixed fluid according to claim 2 ,
A plurality of the columns are formed as a column assembly (10) in which a plurality of columns are arranged in a grid pattern at predetermined pitches in the vertical and horizontal directions.

A plurality of columns (C1, C2,..., Cn) through which a sample fluid mixed with a plurality of component fluids passes and each component flows out with a time difference due to a difference in moving speed of each component in the column;
Detection means (4) for detecting a target component fluid in the sample fluid;
Provided on the inflow side of the plurality of columns (C1, C2,..., Cn), the sample fluid and the extrusion fluid are selectively used as at least one of the plurality of columns (C1, C2,..., Cn). Inflow side selection means (2) for flowing into
The detection means is provided on the outflow side of the plurality of columns (C1, C2,..., Cn) and selectively detects the target component fluid flowing out from one of the plurality of columns (C1, C2,..., Cn). Outflow side selection means (3) to be supplied to (4),
Control means (5) for controlling the inflow side selection means (2) and the outflow side selection means (3);
The outflow side selecting means (3) is capable of allowing a cleaning fluid to flow into the columns (C1, C2,..., Cn) from the reverse direction,
The control means (5)
One of the plurality of columns (C1, C2,..., Cn) is sequentially selected in a predetermined time interval and in a predetermined order, and the sample is applied to the selected column for a predetermined time width in which the target component fluid can be separated. A procedure for controlling the inflow side selection means (2) so as to allow the fluid to flow in and then to allow the extrusion fluid to flow;
In the time zone when only the target component fluid flows out from each of the columns (C1, C2,..., Cn), the outflow side selecting means ( 3) the procedure for controlling by time ,
After the target component fluid has flowed out of the columns (C1, C2,..., Cn), a procedure for performing a procedure for allowing the cleaning fluid to flow into the column in the reverse direction via the outflow side selection means (3) A continuous analysis device for fluid mixture.

It is a continuous analysis apparatus of the fluid mixture according to claim 5 ,
The plurality of columns are formed as a cylindrical column aggregate (1) in which a plurality of columns are arranged on a cylindrical surface.
The inflow side selection means (2) and the outflow side selection means (3) are for switching the column through which the fluid flows in and out by rotating the column assembly (1) around the central axis. Fluid continuous analysis device.

It is a continuous analysis apparatus of the fluid mixture according to claim 5 ,
A plurality of the columns are formed as a column assembly (10) in which a plurality of columns are arranged in a grid pattern at predetermined pitches in the vertical and horizontal directions.