JPH03170838A - Concentration analysis method and apparatus - Google Patents
Concentration analysis method and apparatusInfo
- Publication number
- JPH03170838A JPH03170838A JP1311617A JP31161789A JPH03170838A JP H03170838 A JPH03170838 A JP H03170838A JP 1311617 A JP1311617 A JP 1311617A JP 31161789 A JP31161789 A JP 31161789A JP H03170838 A JPH03170838 A JP H03170838A
- Authority
- JP
- Japan
- Prior art keywords
- carrier gas
- gas
- tube
- analyzer
- concentration
- 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.)
- Granted
Links
- 238000004458 analytical method Methods 0.000 title claims abstract description 30
- 239000012159 carrier gas Substances 0.000 claims abstract description 72
- 239000007789 gas Substances 0.000 claims abstract description 56
- 239000003463 adsorbent Substances 0.000 claims abstract description 10
- 239000012491 analyte Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 abstract description 16
- 239000012535 impurity Substances 0.000 abstract description 14
- 230000035945 sensitivity Effects 0.000 abstract description 12
- 238000005259 measurement Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000007670 refining Methods 0.000 abstract 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 230000006837 decompression Effects 0.000 abstract 1
- 230000007423 decrease Effects 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000004452 microanalysis Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 101100328887 Caenorhabditis elegans col-34 gene Proteins 0.000 description 1
- 230000035508 accumulation Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Sampling And Sample Adjustment (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利川分野〕
本発明は、桔製装置から導出される高純度ガス、又は容
器内に充填された高純度ガス等を拭料ガスとし、該ガス
中に含まれる微量の不純物（被分析成分）を濃縮分析方
法によって高感度に分析する方法及びその装置に関する
。[Detailed Description of the Invention] [Industrial field in Icheon] The present invention uses a high-purity gas derived from a steamer or a high-purity gas filled in a container as a wiping gas, and uses the gas contained in the gas as a cleaning gas. The present invention relates to a method and apparatus for highly sensitively analyzing trace amounts of impurities (components to be analyzed) using a concentration analysis method.
前記濃縮分析方法は、試料ガス中の被分析戊分を低温に
１．１１御した濃縮管山の吸着剤に低温吸着させて濃縮
した後、該濃縮管にキャリアガスを流しつつ該濃縮管を
加熱して前記被分析或分を脱着させて該キャリアガスに
同ｆ″１′させ、分Ｊｌ７ＡＩに導入して被分析成分を
ｌＩＩＪ定するもので、１１１１定Ｉｌｌ位がｐｐｍか
らｐｐｂ （ｉｐｐｍ − １ ０００ｐｐｂ ）へ
、更に、ｐｐｂからｐｐＬ （ＩＦ）ｐｂ − １
０００ｐｐＬ ）へと進行している近時の微量分析の要
求によく適応するものである。In the concentration analysis method, the fraction to be analyzed in the sample gas is concentrated by being adsorbed at a low temperature on the adsorbent of the concentrator tube, which is kept at a low temperature. The analyte is desorbed by heating to the carrier gas and introduced into the carrier gas to determine the analyte component. 1 000ppb) and then from ppb to ppL (IF) pb − 1
000 ppL), which is well suited to the recent demands for microanalysis.
以′ド、第２図に従来の濃縮分析装置のフローシートを
例示して従来の濃縮分析方法を説明する。Hereinafter, a conventional concentration analysis method will be explained by illustrating a flow sheet of a conventional concentration analysis apparatus in FIG.
図中、ＬＳＭは本体の摘みを操作することにより６つの
流路を同時に切り替えられるよう構或した六方コックで
、太線側に切り替えることにより各ポートＬ＋ ’＝Ｌ
６，Ｍ＋〜Ｍ６が実線で表示したように連通し、また、
破線側に切り替えることにより破線で表示したように連
通ずるようになっており、各ポートＬ，〜Ｌ６、Ｍ，〜
Ｍ６に各種ガス源及び機器が図のように連設されている
。In the figure, LSM is a hexagonal cock designed to switch six channels at the same time by operating the knob on the main body, and by switching to the thick line side, each port L + ' = L
6, M+ to M6 communicate as shown by solid lines, and
By switching to the dashed line side, communication is established as indicated by the dashed line, and each port L, ~L6, M, ~
Various gas sources and equipment are connected to M6 as shown in the figure.
即ち、六方コックＬのボートＬ１には減圧弁１を介して
高圧容器内にヘリウムガスを充填してなるキャリアガス
源Ｃが、ボートＬ３には元弁２を介して試料ガス源Ｓが
、ボートＬ４には稍密な流以計３が、ボートＬ ６には
試料ガス中の披分析成分の分離に適した充填剤を充填し
てなる分離力ラム４と被分析成分を検出する検出器５と
からなる分析計Ｄが各々連設され、また、六方コックＭ
のボートＭ，は六方コックＬのボー１・Ｌ２に、ポトＭ
６は六方コックＬのボートＬ，に夫々連設し、ボートＭ
２とボートＭ ｑの間には濃縮膏６が、ボートＭ，には
連成３１７，元弁８を介して真空ポンプＶが、ポートＭ
４には古Ｍ９が各々連設されている。That is, the boat L1 of the six-way cock L is connected to the carrier gas source C, which is a high-pressure container filled with helium gas, through the pressure reducing valve 1, and the sample gas source S is connected to the boat L3 through the main valve 2. L4 is equipped with a dense flow meter 3, boat L6 is equipped with a separation force ram 4 filled with a packing material suitable for separating the analyte components in the sample gas, and a detector 5 for detecting the analyte components. Analyzers D consisting of
Boat M, has six-way cock L on boats 1 and L2, and pot M
6 is connected to boat L with six-way cock L, and boat M
2 and boat Mq, a vacuum pump V is connected to the boat M via a coupling 317 and a main valve 8, and a vacuum pump V is connected to the boat M.
Old M9s are connected to each of the 4s.
濃縮管６は、吸着温度以下の低温下で試料ガス中の被分
析成分を１００％吸着できるように適宜選択された吸着
剤を充填してなるもので、冷却用コイル６ａと加熱川ヒ
ータ６ｂを有する。The concentrating tube 6 is filled with an adsorbent appropriately selected to adsorb 100% of the analyte in the sample gas at a low temperature below the adsorption temperature, and is equipped with a cooling coil 6a and a heating heater 6b. have
以下、この装置を用いた従来の分析方法を工程順に説明
する。Hereinafter, a conventional analysis method using this device will be explained step by step.
まず六方コックＬ，Ｍを実線側に切り替え、キャリアガ
スＭＣのヘリウムガスをキャリアガスとして減圧弁１で
所定の圧力に減圧した後、六方コックＬのボートｔ，，
ｌ Ｌｌ２ 、六方コックＭのボー｝Ｍ．，Ｍ．、
再び六方コックＬのボートＬ，、Ｌ６を介して分析計Ｄ
に導入して該分析計Ｄを安定状態に保持した後排気系１
０へ排気すると共に、試料ガスを元弁２から六方コック
ＬのボートＬ，，Ｌ４、流量計３を介して排気系１０へ
排気する。First, switch the hexagonal cocks L and M to the solid line side, and reduce the pressure to a predetermined pressure with the pressure reducing valve 1 using helium gas of the carrier gas MC as the carrier gas.
l Ll2, Bo of six-way cock M. ,M. ,
Analyzer D is connected again via boats L, L6 of hexagonal cock L.
After introducing the analyzer D into a stable state and maintaining the analyzer D, the exhaust system 1
At the same time, the sample gas is exhausted from the main valve 2 to the exhaust system 10 via the boats L, L4 of the six-way cock L and the flow meter 3.
また、この状態と併行して真空ボンブ■を作動し、真空
ボンブ■から元弁８、六方コックＭのボートＭ，，Ｍ２
、濃縮？Ｔ６、ボートＭ，，Ｍ４、盲蓋９に至る配管内
に残留する大気成分（酸素及び窒素）を排除した後停止
する。（待機工程）次に、冷却用コイル６ａに液化窒素
専の寒冷を流して濃縮管６を所定の温度以ドに冷却する
。In addition, in parallel with this state, the vacuum bomb ■ is operated, and from the vacuum bomb ■, the main valve 8, the boats M, , M2 of the six-way cock M,
,concentrated? After eliminating atmospheric components (oxygen and nitrogen) remaining in the piping leading to T6, boats M, M4, and blind lid 9, the operation is stopped. (Standby step) Next, cold water exclusively for liquefied nitrogen is passed through the cooling coil 6a to cool the concentrating tube 6 to a predetermined temperature or lower.
（ ｉａＮ青冷却［程）
そして、該冷却工捏のまま、六方コックＬ， Ｍをノ（
に破線側に切り替え、キャリアガスをポートＬ，，Ｌ６
を介して分析計Ｄに導入した後排気系１０に排気すると
共に、試料ガスを、ボートＬ ３ ，Ｌ２，Ｍ．，Ｍ，
を介して濃縮竹６に導入し、該試料ガス中の被分析成分
を濃縮管６内の吸着剤にａ（ｍ 吸着サセ、ポ ｝Ｍｑ
，Ｍ．，Ｌ ５，Ｌ４、流Ｗ４１３を介して排気系１
０に排気する。（濃縮１’． ｌ．’Ａ ）
次いで、六方コックＬを破線側にしたまま六方コックＭ
を実線側に切り替えて真空ボンプＶを再起動し、前記濃
縮］．程で被分析或分と共に濃縮骨６に低温吸着された
試料ガスの主成分を、ポートＭ２，Ｍ，を介して排出し
た後停Ｉ卜する。（主成分排出工捏）
次に、加熱ヒータ６ｂを作動して濃縮管６を加熱し、該
濃縮管６内に低温吸着された被分析成分を脱着した後、
六方コックＬを実線側に、六方コックＭを破線側に切り
替えてキャリアガスをボートＬ＋ ，Ｌ２ ，Ｍ＋ ，
Ｍ２を介して濃縮′ｒｐｒ６ニ流通して披分析成分をキ
ャリアガスに同佇させてボ｝ＭＳ ，Ｍ６，Ｌ５ ，Ｌ
６を介して分析計Ｄに導入する。これにより、披分１７
成分は分離カラム４で各々分離されて検１イ１器５に順
次導入され、該検出器５での検？Ｈ値と前記濃縮−１１
ｆ呈特に流量計３により計量された試料ガス量とから濃
度が定量される。（分析王糧）
〔発明が角ｑ決しようとする課題〕
しかし、前記従来方法では、待機１１１時の真空俳気に
よっても濃縮管６を含む配管系の速成計７，合蓋９等の
溜り部の大気成分が排出されずに残留するため濃縮工程
時に濃縮萱６内の吸着剤に吸着され、後に脱着して分析
計Ｄで測定されること、また、前記主威分排出工程を真
空排気により行い、かつ、前記六方コックＬ，Ｍを頻繁
に開閉操作すること等により大気成分が主に六方コック
Ｌ， Ｍのシート部等を透過して僅かに侵入すること等
によりバックグラウンドが大きくなり、ｐｐｂ以下のレ
ベルの濃度を１１確に測定することは困難だった。( iaN blue cooling process) Then, with the cooling process as it is, turn the six-way cocks L and M (
switch to the dashed line side and transfer the carrier gas to ports L,, L6.
After introducing the sample gas into the analyzer D via the exhaust system 10, the sample gas is introduced into the analyzer D through the boats L 3 , L2, M. ,M,
The sample gas is introduced into the concentrating tube 6 through the sample gas, and the analyte component in the sample gas is transferred to the adsorbent in the concentrating tube 6 by
,M. , L 5, L4, exhaust system 1 via flow W413
Exhaust to 0. (Concentration 1'.l.'A) Next, turn the hexagonal cock M while leaving the hexagonal cock L on the dotted line side.
to the solid line side, restart the vacuum pump V, and perform the concentration]. At this point, the main component of the sample gas adsorbed at a low temperature on the concentrated bone 6 together with a certain amount of the sample to be analyzed is discharged through ports M2, M, and then the process is stopped. (Main component discharge process) Next, the heater 6b is activated to heat the concentrating tube 6, and after desorbing the component to be analyzed that has been adsorbed at low temperature in the concentrating tube 6,
Switch the six-way cock L to the solid line side and the six-way cock M to the broken line side to supply carrier gas to the boats L+, L2, M+,
The analyte is passed through M2 to the concentrated RPR6 to keep the analyte components present in the carrier gas.MS, M6, L5, L
6 into analyzer D. As a result, 17
The components are separated in the separation column 4 and sequentially introduced into the detector 5, where they are detected. H value and the concentration-11
The concentration is determined from the sample gas amount measured by the flow meter 3. (Analysis King Food) [Problem that the invention attempts to solve] However, in the conventional method, the vacuum exhaust during standby 111 also causes accumulations in the rapid conversion meter 7, cover 9, etc. of the piping system including the concentrating tube 6. Since some of the atmospheric components remain without being discharged, they are adsorbed by the adsorbent in the concentrator 6 during the concentration process, and are later desorbed and measured with the analyzer D. In addition, by frequently opening and closing the hexagonal cocks L and M, atmospheric components mainly pass through the seats of the hexagonal cocks L and M and enter slightly, resulting in a large background. , it has been difficult to accurately measure concentrations below the ppb level.
また、分析ｔｆｘでは、濃縮管６を加熱して披分析成分
を脱青した後、該濃縮管６にキャリアガスを流通して波
分析成分をキャリアガスに同（’Ｆさせるため、被分Ｏ
Ｔ成分の一部が真空ボンブＶの系統にｐｍ留して被分析
成分の全量を分Ｈｊ ａｔ Ｄに導入することができず
、また、主成分排出上捏で脱着しなかった主成分がノＪ
１熱によって脱着し、これによって濃縮管系の圧力か上
昇して披分析成分の一部が主成分とノ（に大気に漏洩す
ることもあり正確な測定を困難にしていた。In addition, in the analysis TFX, after heating the concentrating tube 6 to deblue the analyte components, a carrier gas is passed through the concentrating tube 6 to convert the analyte components into the carrier gas.
Part of the T component was distilled into the system of the vacuum bomb V, making it impossible to introduce the entire amount of the component to be analyzed into the component Hj at D. Also, the main component that was not desorbed during the main component discharge and mixing was removed. J
The desorption occurs due to heat, which increases the pressure in the concentrator tube system, causing some of the analyzed components to leak into the atmosphere along with the main components, making accurate measurements difficult.
本発明はこのｔｉな不都合を解決することを１１的とし
た濃縮分析方法及びその装置を１１Δ１』（ずるにある
。The present invention is directed to a concentration analysis method and an apparatus for the same, which are aimed at solving this serious disadvantage.
前記１１的を達成する本発明の濃縮分析方法は、キャリ
アガスを濃縮管に流通した後分析別を介して排気する詩
機工程、濃縮管を所定の温度以下に冷却する濃縮管冷却
玉捏、前記キャリアガスを前記濃縮管を介さずに前記分
析計に導入した後排気すると共に試料ガスを該濃縮管に
流通して該試料ガス中の披分析成分を該濃縮管内の吸着
剤に低温眼着させた後排出す・る濃縮工程、前記キャリ
アガスを濃縮管に流通して前記濃縮工程で被分析或分と
共に低温吸着された主或分を同伴させて分ＦｒＩに導入
した後排出する主威分排Ｈｉ ’！．−． ｌ、該主或
分排出−［捏のまま濃縮管を所定の温度以上に加熱して
該濃縮管に低温吸着された前記被分析或分を脱着させて
キャリアガスに同１ｆさせて分析計に導入する分析工程
を順次行うことを特徴とし、また、前記キャリアガスは
、帖製器を介して供給されていることを特徴とし、更に
、前記キャリアガスと試料ガスの流路切り替えをシール
付多方コックで行うことを特徴とする。The concentration analysis method of the present invention which achieves the above-mentioned 11 objectives includes a step of discharging a carrier gas through a concentrating tube and then exhausting it through an analysis chamber, a concentrating tube cooling process that cools the concentrating tube to a predetermined temperature or lower, The carrier gas is introduced into the analyzer without going through the concentrator tube and then evacuated, and the sample gas is passed through the concentrator tube to transfer the analyte components in the sample gas to the adsorbent in the concentrator tube. A concentration step in which the carrier gas is passed through a concentrating tube to bring together the main fraction adsorbed at a low temperature with the fraction to be analyzed in the concentration step, and the main fraction is introduced into the fraction FrI and then discharged. Separation Hi'! ．． −． l. Discharge of the main fraction - [heat the concentrating tube as it is kneaded to a predetermined temperature or higher to desorb the fraction to be analyzed that has been adsorbed at low temperature to the concentrating tube, and transfer it to the carrier gas to the analyzer. The method is characterized in that the analysis steps for introduction are carried out sequentially, and the carrier gas is supplied through a maker, and the flow path switching between the carrier gas and the sample gas is performed in multiple directions with a seal. It is characterized by being performed with a cook.
また、本発明の濃縮分析装置は、多方コックの各ボート
に、キャリアガス源に接続されるキャリアガス菅路と、
試料ガス源に接続される拭料ガス菅路と、冷却手段及び
加熱手段を備えた濃縮管の導入部及び導出部にそれぞれ
接続される濃縮管導八管路及び濃縮管導出管路と、分析
計に接続される分析管路と、流量計に接続される流量測
定管路とをそれぞれ接続するとＪ（に、該多方コックは
、少なくとも、キャリアガスを濃縮骨に流通した後に分
析別に導入する経路と、キャリアガスを濃縮管を介さず
に分析３１に導入する経路と、試料ガスを濃縮管に流通
した後に流量計に導入する経路とを切り替えｉｉＪ能に
備えていることを特徴としている。In addition, the concentration analysis device of the present invention includes a carrier gas channel connected to a carrier gas source in each boat of the multi-way cock;
A wiping gas pipe connected to a sample gas source, a concentrating tube conduit and a concentrating tube outlet conduit respectively connected to an inlet and an outlet of a concentrating tube equipped with a cooling means and a heating means, and an analyzer. When the analysis pipe line connected to J and the flow measurement pipe line connected to the flow meter are respectively connected, the multi-way cock at least serves as a route for introducing the carrier gas for each analysis after passing through the concentrated bone. It is characterized by the ability to switch between a route for introducing the carrier gas into the analysis 31 without going through the concentrator tube and a route for introducing the sample gas into the flowmeter after passing through the concentrator tube.
本発明方法及び装置によれば、待機＋’−ｔａでの濃縮
管系統の人気成分の排除を、濃縮管出にキャリアガスを
流して行うので確実に排除できる。According to the method and apparatus of the present invention, the removal of popular components from the concentrating tube system in standby +'-ta is carried out by flowing carrier gas to the concentrating tube outlet, so that the components can be reliably eliminated.
また、主成分排出玉捏での主成分の排除を、濃縮管内に
キャリアガスを流して行うので、主威分の排除を真空排
只で行うより効率的に実施できると共に、主成分の脱着
による急激な圧力上昇を抑制して被分析成分の漏洩を防
＋１することができる。In addition, since the main component is removed by flowing the carrier gas into the concentrating tube, the main component can be removed more efficiently than by vacuum evacuation. By suppressing a sudden pressure rise, leakage of the analyzed component can be prevented by +1.
史には、主成分をキャリアガスに同１′Ｆシて分析計に
送るようにしたのでコックの［１７Ｊり替え操作を減少
でき、大気成分の侵入を大幅に減少できる。分析工捏で
は、主成分排出］−捏の状態のまま濃縮管を加熱して被
分析成分を脱着するので被分析成分の全量がキャリアガ
スに同伴されて分析計に導入される。Historically, the main components were sent to the analyzer at the same 1'F as the carrier gas, which reduced the need to change the cock and greatly reduced the intrusion of atmospheric components. In analytical processing, the main component is discharged] - The concentrating tube is heated in the kneaded state to desorb the analyte component, so that the entire amount of the analyte component is introduced into the analyzer along with the carrier gas.
このように、本発明方法によれば、従来の真空排気を不
要として装置構或を簡略化すると共に、大気成分の侵入
をより効果的に防ｌトしたので従来よりバックグラウン
ドを低減でき高感度の測定が可能になる〇
次に、キャリナガスは、通常、前記のように高圧容器出
に充填されたものを用いるので減圧弁を介して減圧して
使用するが、この場合、発明者の知見によると、キャリ
アガスは減圧弁通過時に大気成分の侵入を受ける。従っ
て、高江容器内のガスが極めて高純度のものであっても
減圧弁通過時に一部汚染されるので、減圧弁通過後のキ
ャリアガスを精製器に流通し、該キャリアガス中の不純
物を予め除去しておくと、濃縮工程時に試料ガスと共に
キャリアガスを低温に制御された濃縮管に流しても該キ
ャリアガス中の不純物は極めて減少しているので濃縮管
内の吸着剤に代温吸着されることがほとんどな＜、測定
時におけるバックグラウンドを史に０（減して、感度を
史に向上することができる。As described above, the method of the present invention simplifies the device structure by eliminating the need for conventional vacuum evacuation, and more effectively prevents the intrusion of atmospheric components, resulting in lower background and higher sensitivity than in the past. It becomes possible to measure When the carrier gas passes through the pressure reducing valve, atmospheric components enter the carrier gas. Therefore, even if the gas in the Takae container is of extremely high purity, it will be partially contaminated when it passes through the pressure reducing valve, so the carrier gas after passing through the pressure reducing valve is passed through a purifier to remove impurities in the carrier gas. If they are removed in advance, even if the carrier gas is flowed together with the sample gas into the concentrator tube controlled at low temperature during the concentration process, the impurities in the carrier gas will be extremely reduced, so that they will be adsorbed thermothermally by the adsorbent in the concentrator tube. In most cases, the background during measurement can be reduced to zero, and the sensitivity can be dramatically improved.
また、キャリアガスと試料ガスの流踏切り替えをシール
付多方コックで行うと、該コックを操作して流路切り替
えを行う際の該コック内への人気の侵入を防ＩＬできる
ので感度向上にＨ効である。In addition, if the carrier gas and sample gas flows are switched using a multi-way cock with a seal, it is possible to prevent the intrusion into the cock when operating the cock to switch the flow paths, thereby improving sensitivity. It is effective.
特に、前記ｌｉ製器とシール付多方コックの両ノｊをＯ
Ｆ用すると、不純物を含まない消浄なキャリアガスが消
浄なまま濃縮膏内を流通するので濃縮管内にキャリアガ
ス中の不純物がａｍせず感度の向上に極めて効果的であ
る。In particular, both the nozzles of the li maker and the multi-way cock with seals are
When F is used, a clean carrier gas containing no impurities flows through the concentrate in a clean state, so that impurities in the carrier gas do not enter the concentration tube, which is extremely effective in improving sensitivity.
第１図は、本発明方法に係る大施例装置のフローシ一ト
で、図中前記第２図と同一安索には同一付号を付してあ
る。FIG. 1 is a flowchart of a large-scale embodiment of the apparatus according to the method of the present invention, in which the same cables as in FIG. 2 are given the same reference numbers.
本実施例装置は、シール付六方コックＥの各ボートＥ１
〜Ｅ６に、キャリアガス源Ｃに接続されるキャリアガス
管路１１と、拭料ガス源Ｓに接続される試料ガス管路１
２と、冷却ｆ段である冷却コイル６ａ及び加熱手段であ
る加熱ヒータ６ｂを備えた濃縮管６の導入部及び導出部
にそれぞれ接続される濃縮管導入管路１３及び濃縮管導
出管路１４と、分析計Ｄに接続される分析管路１５と、
流量計３に接続される流ｍ測定管路１６とをそれぞれ接
続してなるもので、前記キャリアガス管路１１に、該キ
ャリアガス中の不純物成分を除去するｌｒｆｆ製器２０
が設けられている。This embodiment device has a hexagonal cock E with a seal for each boat E1.
~E6, a carrier gas line 11 connected to a carrier gas source C, and a sample gas line 1 connected to a wiping gas source S.
2, and a concentrating tube inlet line 13 and a concentrating tube outlet line 14 connected to the inlet and outlet parts of the concentrator tube 6, respectively, which are equipped with a cooling coil 6a as a cooling stage F and a heater 6b as a heating means. , an analysis pipe line 15 connected to the analyzer D;
A flow meter measuring pipe 16 connected to the flow meter 3 is connected to the carrier gas pipe 11, and an lrff device 20 for removing impurity components in the carrier gas is connected to the carrier gas pipe 11.
is provided.
このシール付六方コックＥは、内部の切り替え流路をケ
ーシングＥＣで気密に覆い、かつ、該ケーシングＥＣと
切り替え流路との間に形成される空間にキャリアガスと
同等のガスを導入管２１，導出骨２２を介して流通する
ようにして大気の侵入をより完全に防１１−できるよう
にしたものである。This hexagonal cock E with a seal has an internal switching channel airtightly covered with a casing EC, and a gas equivalent to a carrier gas is introduced into the space formed between the casing EC and the switching channel through an introduction pipe 21, By allowing the air to flow through the derived bone 22, the intrusion of the atmosphere can be more completely prevented.
また、精製器２０は、キャリアガス導入．導出部を有す
る適宜な気密容器内にモレキュラシーブス，活性炭等の
吸着剤を充填すると共に冷却手段（図示略）を設けてな
るもので、キャリアがス中の不純物を除上ずるものであ
る。Further, the purifier 20 is configured to introduce a carrier gas. An appropriate airtight container having an outlet part is filled with an adsorbent such as molecular sieves or activated carbon, and a cooling means (not shown) is provided so that the carrier removes impurities in the gas.
通常、本発明が対象とするような微量分析にあっては、
キャリアガスは直純度のものを用いるので、キャリアガ
ス源Ｃのキャリアガス中には不純物は殆どないのである
が、キャリアガス源Ｃのキャリアガスは、通堂ボンベ専
の高圧容器内に高圧で充填されているため、前記減圧弁
１を用いて所定の圧力まで減圧して使用する。そして、
キャリアガスが減圧弁１を通過した際に人気が侵入する
ので、これによる不純物を除去するのである。Normally, in the kind of microanalysis targeted by the present invention,
Since the carrier gas used is of direct purity, there are almost no impurities in the carrier gas of carrier gas source C. However, the carrier gas of carrier gas source C is filled at high pressure into a high-pressure container made exclusively for Tsudo cylinders. Therefore, the pressure is reduced to a predetermined pressure using the pressure reducing valve 1 before use. and,
When the carrier gas passes through the pressure reducing valve 1, impurities that enter the carrier gas are removed.
なお、減庄弁通過後のキャリアガスの圧力は、大気圧よ
り高いので、通常大気は侵入しないものと考えられるが
、ｐｐｂ以ドの１１１１定では桔製器を設けた場合と設
けなかった場合とで測定値が異なることから、キャリア
ガスを、たとえ人気圧より高い状態で減圧したとしても
大気かわずがに侵入することを知見したものである。更
に、前記減圧弁１と拭料ガス源Ｓの元弁２のような通常
の仕切弁とを比較すると、減圧弁１の方が人気の侵入程
度が大きいが、これは、減圧弁１が減江機構を有し複雑
な構成になることと、この減圧機構が機械的に作動する
ためであろうと推定される。Note that the pressure of the carrier gas after passing through the pressure reduction valve is higher than atmospheric pressure, so normally it is thought that the atmosphere does not enter, but at 1111 constants of less than ppb, there are two cases with and without a pressure regulator. Since the measured values were different between the two, it was discovered that even if the carrier gas was depressurized to a level higher than human pressure, it would infiltrate into the atmosphere. Furthermore, when comparing the pressure reducing valve 1 with a normal gate valve such as the main valve 2 of the wiping gas source S, the pressure reducing valve 1 has a greater degree of popularity. It is presumed that this is because the mechanism is complicated and the pressure reducing mechanism operates mechanically.
次に、上記のように構成した実施例装置の操作方法を説
明すると、まず六方コックＥを実線側にし、キャリアガ
スを減圧弁１を介してＬｆ ！’２ 姦２ ０に導入し
、該キャリアガス中の不純物を除大した後、六方コック
ＥのポートＥ＋ ，Ｅ２＋ １６縮管６，ボートＥ−，
，Ｅ６を介して分析３１Ｄに導入し、該分ｔｌＦ ６１
’ Ｄを安に状態に保持した後排気系１〔｝に排｝Ｉ１
する。一方、試料ガスを元弁２からボー｝Ｅ，，Ｅ４を
介して流量計３に流したあと排出し系内のパージを行な
う。（待機−Ｌ捏）
次に、上記待機−［程の状態のまま、冷却コイル６ａに
液化窒素等の寒冷を流して濃縮管６を所定の温度まで冷
却する。（濃縮管冷却Ｅ−． ｆｆｆ ）次に、六方コ
ックＥを破線側に切り替えて、キャリアガスをボートＥ
，，Ｅ，，を介して分ＩＦ Ｊ’ Ｄに導入すると共に
、試料ガスをボートＥ．，Ｅ２を介して濃縮管６に導入
し、該試料ガス中の波分析成分を該濃縮管６内の吸着剤
に低温吸着させた後、ボートＥ５，Ｅ．、流量計３を介
して排気系１０から排出する。（ａ縮■二捏）
次に、六ｈ′コックＥを再び実線側に切り替え、前連の
ごとく濃縮管６１ノ４にキャリアガスを導入して披分ｉ
１？成分と共に吸着された主成分を脱着して分析，：１
に導入する。（主成分排出Ｌ程）所定１１与間後、加熱
ヒータ６ｂを作動して濃縮管６を所定温度以上に加熱し
、前記濃縮１二捏で濃縮管６に吸着された披分析成分を
キャリアガスに同１１ｌシてボー｝Ｅ，，Ｅ，，を介し
て分析ａｌＤに導入する。これにより、披分析成分は分
離カラム４で各々分離されて検出器５に順次導入され、
該検出器５での検出値と前記濃縮［程時に流量羽３によ
り÷１量された試料ガス量とから濃度が定量される。Next, the operating method of the embodiment device configured as described above will be explained. First, the six-way cock E is set to the solid line side, and the carrier gas is supplied through the pressure reducing valve 1 to Lf! '2 After introducing the carrier gas into the carrier gas and removing impurities in the carrier gas, port E+ of the six-way cock E, E2+ 16 contraction tube 6, boat E-,
, E6 into analysis 31D, and the fraction tIF 61
' After holding D in a stable state, exhaust to exhaust system 1 [} I1
do. On the other hand, the sample gas is passed from the main valve 2 to the flow meter 3 via bows E, , E4 and then discharged to purge the system. (Standby-L kneading) Next, while in the above-mentioned standby state, cold such as liquefied nitrogen is flowed through the cooling coil 6a to cool the concentrating tube 6 to a predetermined temperature. (Concentrator tube cooling E-. fff) Next, switch the hexagonal cock E to the dotted line side and supply the carrier gas to the boat E.
, , E, , into minute IF J' D, and the sample gas is introduced into boat E. , E2 into the concentrating tube 6, and the wave analysis components in the sample gas are adsorbed at low temperature on the adsorbent in the concentrating tube 6, and then transferred to the boats E5, E2. , is discharged from the exhaust system 10 via the flow meter 3. (a reduction ■2) Next, switch the 6h' cock E to the solid line side again, and introduce the carrier gas into the concentrating tube 61-4 as in the previous series.
1? Desorb and analyze the main components adsorbed together with the components: 1
to be introduced. (Main component discharge L step) After a predetermined 11 minutes, the heater 6b is activated to heat the concentrating tube 6 to a predetermined temperature or higher, and the analyte components adsorbed on the concentrating tube 6 during the concentration 12 times are transferred to the carrier gas. Then, the same 11l is introduced into the analysis alD via }E,,E,,. As a result, the analyte components are separated by the separation column 4 and sequentially introduced into the detector 5.
The concentration is determined from the detected value by the detector 5 and the sample gas amount divided by 1 by the flow rate vane 3 during the concentration.
なお、試料ガスは前記待機工程と同様に排気系１｛）に
排出される。（分析［程）
本発明に係る濃縮分析方法は前記の如く実施されるが、
コックの切り替え操作を従来方法と比較したものを第１
表に示す。なお、表中〔一〕は尖線側、〔・・・〕は破
線側への切り替えを、また「１」は切り替え操作を示す
。Note that the sample gas is discharged to the exhaust system 1{) similarly to the standby process. (Analysis) The concentration analysis method according to the present invention is carried out as described above.
The first comparison of the cock switching operation with the conventional method
Shown in the table. In the table, [1] indicates switching to the pointed line side, [...] indicates switching to the broken line side, and "1" indicates switching operation.
第１表
上記第１表から明らかなように、従来の方法では、コッ
クの切り替えを５回行って測定するのに対し、本発明方
法では２同の切り替え操作で測定することができる。Table 1 As is clear from Table 1 above, in the conventional method, measurement is performed by switching the cock five times, whereas in the method of the present invention, measurement can be performed by switching the cock twice.
次に、高純度水素ガスを拭料ガスとして第１図の実施例
装置を用いて不純物をａＰ１定した場合と、前記第２図
に例示した従来装置を用いてａｌｌ定した場八との測定
限界を比較する丈験を行った。大施例装置を川いた測定
では、稍製器２０を使用した場合と、使用しなかった場
合、及びシール付コックＥを使用した場合と通常の六方
コックを使用した場合もそれぞれ比較した。Next, we will compare the measurement limits when impurities are determined by aP1 using the example device shown in FIG. We conducted an experiment to compare the In measurements taken using the large example device, comparisons were made between using and not using the fine molding device 20, and between using a cock with a seal E and using a normal six-way cock.
検出器５には熱伝導度検出器を用い、梢製器２０には内
径４關で長さ１ｍのカラムにモレキュラシーブス５Ａを
充填したものを、また、濃縮管６には、内径３ｌｌｍで
長さ１５０ｌｌＩのカラムにポーラスボリマービーズを
充填したものを用いて各々液化窒素でマイナス１８５℃
以下に冷却した。また、濃縮後の濃縮汀６の加熱は該濃
縮管６に巻き付けたヒータにより行い、昇温速度は毎分
１５０℃とした。この実験桔果を第２表に示す。A thermal conductivity detector was used as the detector 5, a column with an inner diameter of 4 mm and a length of 1 m filled with molecular sieves 5A was used as the column maker 20, and a long column with an inner diameter of 3 llm was used for the concentrator tube 6. Using a 150llI column filled with porous polymer beads, each was heated to -185°C with liquefied nitrogen.
Cooled below. Further, the concentrated sludge 6 after concentration was heated by a heater wrapped around the concentrating tube 6, and the temperature rising rate was 150° C./min. The results of this experiment are shown in Table 2.
ｍ２表
第２表から明らかなように、本発明方法によれば、精製
器２０， シール付コックＥの両方を使用しなくとも
、従来より高感度の測定ができ、情製”Ｊ：４ ２ ０
， シール付コックＥの一方を用いれば更に感度を
向上でき、両方川いると更に感度が向上することがｉり
る。As is clear from Table 2, according to the method of the present invention, even without using both the purifier 20 and the seal cock E, it is possible to perform measurements with higher sensitivity than before. 0
If one of the cocks with a seal E is used, the sensitivity can be further improved, and if both are used, the sensitivity can be further improved.
以上説明したように、本発明によれば、濃縮管Ｉｑにキ
ャリアガスを流しつつ該濃縮管を冷却するので大気の侵
入を防止して従来より高Ｔ＋’ｔ度の濃縮分析を実施す
ることができ、また、配青系統を簡略化することができ
る。As explained above, according to the present invention, since the concentrating tube Iq is cooled while the carrier gas is flowing through the concentrating tube Iq, it is possible to prevent the intrusion of the atmosphere and perform concentration analysis at a higher T+'t degree than before. In addition, the blue distribution system can be simplified.
また、従来の真空排気を不要として装置構成を簡略化す
ると共に、大気或分の侵入をより効果的に防止したので
従来よりバックグラウンドを低減でき高感度のＡｔＪ定
か可能になる。In addition, the device configuration is simplified by eliminating the need for conventional vacuum evacuation, and the intrusion of atmospheric air to a certain extent is more effectively prevented, so that background can be reduced and AtJ with high sensitivity can be determined.
特に、濃縮管に流す前のキャリアガスをｌｌｆｆ製器に
通して該キャリアガス中の不純物を除去するか、又は、
シール付多方コックを使用することにより測定感度を高
めることができ、両方設けることにより史に高感度の測
定がｉｉＪ能になる。In particular, impurities in the carrier gas are removed by passing the carrier gas through an llff device before flowing into the concentrator tube, or
By using a multi-way cock with a seal, measurement sensitivity can be increased, and by providing both, it is possible to perform measurements with the highest sensitivity ever.
第１図は本発明の一丈施例を示す濃縮分ＩＦ装置のブロ
ーシーｊ・、第２図は従来の濃縮分＃ｌτ装１１奮のフ
ローシートである。
Ｃ・・・キャリアガス源 Ｄ・・・分１ｉ ｊｌＥ・
・シール付六Ｊｊコック Ｓ・・・試料ガス源 ３
・・・流抗１：１ ６・・冒農縮青 ２０・・
・Ｌ’ｉ製器特 苧′１ 出 ４６ 人 １１本酸素
株式会ｌｉ代ｐｐ人 井Ｐｐ十 木 戸 傳一
郎同
木 Ｆ ＋Ｊ同
小 川 眞FIG. 1 is a flow sheet of a concentrated fraction IF device showing one embodiment of the present invention, and FIG. 2 is a flow sheet of a conventional concentrated fraction #lτ system. C...Carrier gas source D...minute 1i jlE・
・6 Jj cock with seal S...Sample gas source 3
...Flow resistance 1:1 6...Farming shrinkage 20...
・L'i Seiki Toku 苧'1 Output 46 people 11 Oxygen Co., Ltd. pp people I Pp 10 Kido Denichiro Doki F + J Dou Makoto Ogawa
Claims (1)
排気する待機工程、濃縮管を所定の温度以下に冷却する
濃縮管冷却工程、前記キャリアガスを前記濃縮管を介さ
ずに前記分析計に導入した後排気すると共に試料ガスを
濃縮管に流通して該試料ガス中の被分析成分を該濃縮管
内の吸着剤に低温吸着させた後排出する濃縮工程、前記
キャリアガスを濃縮管に流通して前記濃縮工程で被分析
成分と共に低温吸着された主成分を同伴させて分析計に
導入した後排出する主成分排出工程、該主成分排出工程
のまま濃縮管を所定の温度以上に加熱して該濃縮管に低
温吸着された前記被分析成分を脱着させてキャリアガス
に同伴させて分析計に導入する分析工程を順次行うこと
を特徴とする濃縮分析方法。 ２、前記キャリアガスは、精製器を介して供給されるこ
とを特徴とする請求項１記載の濃縮分析方法。 ３、前記キャリアガスと試料ガスの流路切り替えをシー
ル付多方コックで行うことを特徴とする請求項１記載の
濃縮分析方法。 ４、多方コックの各ポートに、キャリアガス源に接続さ
れるキャリアガス管路と、試料ガス源に接続される試料
ガス管路と、冷却手段及び加熱手段を備えた濃縮管の導
入部及び導出部にそれぞれ接続される濃縮管導入管路及
び濃縮管導出管路と、分析計に接続される分析管路と、
流量計に接続される流量測定管路とをそれぞれ接続する
と共に、該多方コックは、少なくとも、キャリアガスを
濃縮管に流通した後に分析計に導入する経路と、キャリ
アガスを濃縮管を介さずに分析計に導入する経路と、試
料ガスを濃縮管に流通した後に流量計に導入する経路と
を切り替え可能に備えていることを特徴とする濃縮分析
装置。[Claims] 1. A standby step in which the carrier gas is passed through the concentrating tube and then exhausted through an analyzer; a concentrating tube cooling step in which the concentrating tube is cooled to a predetermined temperature or below; and the carrier gas is passed through the concentrating tube. a concentration step in which the sample gas is introduced into the analyzer without passing through the analyzer and then evacuated, and the sample gas is passed through a concentrator tube to cause the analyte components in the sample gas to be adsorbed at a low temperature on an adsorbent in the concentrator tube, and then discharged; A main component discharge step in which the gas is passed through a concentrating tube and the main component adsorbed at a low temperature along with the analyzed component in the concentration step is introduced into the analyzer and then discharged; 1. A concentration analysis method comprising successively performing an analysis step of heating the component to a temperature higher than or equal to the temperature of the concentration tube to desorb the component to be analyzed that has been adsorbed at a low temperature in the concentration tube, and introducing the desorbed component into a carrier gas into an analyzer. 2. The concentration analysis method according to claim 1, wherein the carrier gas is supplied through a purifier. 3. The concentration analysis method according to claim 1, wherein the flow path switching between the carrier gas and the sample gas is performed using a multi-way cock with a seal. 4. Each port of the multi-way cock has a carrier gas line connected to a carrier gas source, a sample gas line connected to a sample gas source, and an inlet and outlet of a concentrator tube equipped with a cooling means and a heating means. a concentrating tube introduction conduit and a concentrating tube deriving conduit respectively connected to the section, and an analysis conduit connected to the analyzer;
In addition to connecting the flow rate measuring pipes connected to the flowmeter, the multi-way cock also connects at least a route for introducing the carrier gas into the analyzer after passing through the concentrator pipe, and a route for introducing the carrier gas into the analyzer without passing through the concentrator pipe. A concentration analysis device characterized by being switchable between a path for introducing the sample gas into the analyzer and a path for introducing the sample gas into the flowmeter after passing through the concentration tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1311617A JP2858143B2 (en) | 1989-11-30 | 1989-11-30 | Concentration analysis method and apparatus therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1311617A JP2858143B2 (en) | 1989-11-30 | 1989-11-30 | Concentration analysis method and apparatus therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03170838A true JPH03170838A (en) | 1991-07-24 |
| JP2858143B2 JP2858143B2 (en) | 1999-02-17 |
Family
ID=18019409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1311617A Expired - Lifetime JP2858143B2 (en) | 1989-11-30 | 1989-11-30 | Concentration analysis method and apparatus therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2858143B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5435169A (en) * | 1993-06-14 | 1995-07-25 | New Jersey Institute Of Technology | Continuous monitoring of organic pollutants |
| WO2002063275A1 (en) * | 2001-02-07 | 2002-08-15 | Japan Tobacco Inc. | Apparatus and method of extracting volatime components |
| US7031520B2 (en) | 2003-07-24 | 2006-04-18 | Sap Ag | Method and system for identifying multiple questionnaire pages |
| JP2009236590A (en) * | 2008-03-26 | 2009-10-15 | Yazaki Corp | Gas chromatograph device and gas component desorption method |
| JP2011106873A (en) * | 2009-11-13 | 2011-06-02 | Japan Agengy For Marine-Earth Science & Technology | Pretreatment apparatus for elemental analysis, and elemental analyzer |
| CN110095541A (en) * | 2019-05-06 | 2019-08-06 | 南京工业大学 | Gas separation characterization device and mixed gas separation performance detection method |
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|---|---|---|---|---|
| KR101348540B1 (en) * | 2007-02-22 | 2014-01-07 | 동우 화인켐 주식회사 | Outgas Analysis Apparatus Having Concentrating Device |
| KR101707864B1 (en) * | 2015-09-07 | 2017-02-17 | 한국표준과학연구원 | Low temperature pre-concentrator comprising adsorption trap for chemical analysis |
-
1989
- 1989-11-30 JP JP1311617A patent/JP2858143B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5435169A (en) * | 1993-06-14 | 1995-07-25 | New Jersey Institute Of Technology | Continuous monitoring of organic pollutants |
| WO2002063275A1 (en) * | 2001-02-07 | 2002-08-15 | Japan Tobacco Inc. | Apparatus and method of extracting volatime components |
| US7082849B2 (en) | 2001-02-07 | 2006-08-01 | Japan Tobacco Inc. | Apparatus and method for extracting volatile constituents |
| US7031520B2 (en) | 2003-07-24 | 2006-04-18 | Sap Ag | Method and system for identifying multiple questionnaire pages |
| US7684621B2 (en) | 2003-07-24 | 2010-03-23 | Sap Ag | Method and system for identifying multiple questionnaire pages |
| JP2009236590A (en) * | 2008-03-26 | 2009-10-15 | Yazaki Corp | Gas chromatograph device and gas component desorption method |
| JP2011106873A (en) * | 2009-11-13 | 2011-06-02 | Japan Agengy For Marine-Earth Science & Technology | Pretreatment apparatus for elemental analysis, and elemental analyzer |
| CN110095541A (en) * | 2019-05-06 | 2019-08-06 | 南京工业大学 | Gas separation characterization device and mixed gas separation performance detection method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2858143B2 (en) | 1999-02-17 |
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