JPH0830989B2 - Pressure control device for supercritical fluid - Google Patents
Pressure control device for supercritical fluidInfo
- Publication number
- JPH0830989B2 JPH0830989B2 JP62008652A JP865287A JPH0830989B2 JP H0830989 B2 JPH0830989 B2 JP H0830989B2 JP 62008652 A JP62008652 A JP 62008652A JP 865287 A JP865287 A JP 865287A JP H0830989 B2 JPH0830989 B2 JP H0830989B2
- Authority
- JP
- Japan
- Prior art keywords
- valve
- pressure
- supercritical fluid
- closing
- control device
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000012530 fluid Substances 0.000 title claims description 35
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 description 17
- 239000000126 substance Substances 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000000194 supercritical-fluid extraction Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000004808 supercritical fluid chromatography Methods 0.000 description 2
- 101100165177 Caenorhabditis elegans bath-15 gene Proteins 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Control Of Fluid Pressure (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、超臨界流体抽出装置や超臨界クロマトグラ
フ等に用いられる超臨界流体用圧力制御装置に関する。TECHNICAL FIELD The present invention relates to a pressure control device for a supercritical fluid used in a supercritical fluid extraction device, a supercritical chromatograph, or the like.
［従来技術及びその問題点］ 従来の圧力制御装置では、圧力をある範囲内に大ざっ
ぱに保つための簡単な制御には、不連続的なオン・オフ
制御が用いられ（例えば実開昭57−106014号公報）、一
方、圧力を目標値に保つための精密な制御には、圧力調
整弁の開度を連続的に調整するのが常識となっていた
（例えば実開昭58−40671号公報）。温度や流量等の他
の物理量の制御においても同様であった。[Prior Art and Problems Thereof] In a conventional pressure control device, discontinuous on / off control is used for simple control for roughly maintaining a pressure within a certain range (for example, in actual development 57- On the other hand, it has been common knowledge that the opening of the pressure regulating valve is continuously adjusted for precise control for maintaining the pressure at the target value (for example, Japanese Utility Model Laid-Open No. 58-40671). ). The same applies to the control of other physical quantities such as temperature and flow rate.
しかし、この圧力調整弁はシートとポペットの間隙の
開度を調整する構成となっているために、該間隙の前後
の空間の体積が比較的大きくなり、弁内部の流体滞留量
が少なくとも数ml乃至数十mlになる。このため、例えば
超臨界流体クロマトグラフにおいては、カラム内部で分
離が完全であっても、圧力調整弁内にカラム溶出流体が
流入すると、分離された各成分の再混合が生ずることに
なる。However, since this pressure adjusting valve is configured to adjust the opening of the gap between the seat and the poppet, the volume of the space before and after the gap becomes relatively large, and the fluid retention amount inside the valve is at least several ml. To tens of ml. Therefore, for example, in a supercritical fluid chromatograph, even if the separation is complete inside the column, when the column elution fluid flows into the pressure regulating valve, the separated components are remixed.
この再混合を防ぐために、キャピラリーカラムを用い
る超臨界クロマトグラフにおいては、内径10μｍ以下の
キャピラリーチューブをカラムの下流側に接続し、その
流体の粘性抵抗を利用して必要な圧力を保つようになっ
ている。In order to prevent this re-mixing, in a supercritical chromatograph using a capillary column, a capillary tube with an inner diameter of 10 μm or less is connected to the downstream side of the column, and the necessary pressure is maintained by utilizing the viscous resistance of the fluid. There is.
しかし、圧力を変化させるためには移動相流体の流量
をも変化させなればならず、保持時間を決定する圧力及
び流量を同時に変化させることになるため、圧力または
流量の変化に対する保持時間の特性の詳細を知ることが
できない。However, in order to change the pressure, the flow rate of the mobile phase fluid must also be changed, and since the pressure and the flow rate that determine the retention time are also changed at the same time, the characteristics of the retention time with respect to changes in pressure or flow rate. Can't know the details of.
また、超臨界流体抽出装置では、圧力を低下させるこ
とにより流体中における抽出物の溶解度を低下させ、溶
質を流体から分離回収する減圧分離法が広く用いられて
いる。Further, in the supercritical fluid extraction apparatus, a reduced pressure separation method is widely used in which the solubility of the extract in the fluid is reduced by lowering the pressure and the solute is separated and recovered from the fluid.
しかし、小型の臨界流体抽出装置に弁開度を調整する
圧力調整弁を用いた場合には、圧力調整弁内の流体滞留
量が多いため、分画された異なる抽出物質が圧力調整弁
内で再混合し、各抽出物質を分取できない。しかも、抽
出物質の弁内滞留時間が長いために、抽出物質が弁内壁
に付着し易く、全抽出物質を分取できず、また付着物質
の離脱により異なる抽出物質が混合される。However, when a pressure control valve that adjusts the valve opening is used in a small critical fluid extraction device, the amount of fluid retention in the pressure control valve is large, and thus different fractionated extraction substances are stored in the pressure control valve. Re-mixing cannot separate each extracted substance. Moreover, since the extraction substance stays in the valve for a long time, the extraction substance easily adheres to the inner wall of the valve, and it is impossible to separate all the extraction substances.
本発明の目的は、上記問題点に鑑み、弁内流体の平均
滞留量を低減でき且つ流体に含まれている物質が弁内壁
に付着し難い超臨界流体用圧力制御装置を提供すること
にある。In view of the above problems, an object of the present invention is to provide a pressure control device for a supercritical fluid that can reduce the average retention amount of the fluid in the valve and that is difficult for substances contained in the fluid to adhere to the inner wall of the valve. .
［問題点を解決するための手段］ 本発明を、実施例図中の対応する構成要素の符号を用
いて説明する。[Means for Solving Problems] The present invention will be described using reference numerals of corresponding components in the embodiment drawings.
本第１発明に係る超臨界流体用圧力制御装置では、例
えば第１図及び第２図に示す如く、 超臨界流体が通る管路P4〜P6と、 管路P4〜P6に介装され、電気的に操作されて全開／全
閉し、全閉のときに入口流路84と出口流路86との間の空
間73に弁棒先端部が嵌合されるように形成された弁17
と、 弁17の上流側又は下流側の管路内超臨界流体圧力を検
出する圧力検出器18と、目標圧力PSが設定される圧力設
定手段20と、 圧力検出器18により検出された圧力PDと該目標圧力PS
との差の符号に応じ該弁を全開又は全閉にして該検出圧
力PDが該目標圧力PSになるようにすることにより該弁を
連続的に開閉させる制御手段22と、 を有することを特徴としている。In the pressure control device for a supercritical fluid according to the first aspect of the present invention, for example, as shown in FIG. 1 and FIG. 2, the pipes P4 to P6 through which the supercritical fluid passes and the pipes P4 to P6 are electrically connected. Operated to be fully opened / closed, and a valve 17 formed so that the valve rod tip portion is fitted in the space 73 between the inlet flow path 84 and the outlet flow path 86 when fully closed.
A pressure detector 18 for detecting the supercritical fluid pressure in the upstream or downstream side of the valve 17, a pressure setting means 20 for setting a target pressure P S, and a pressure detected by the pressure detector 18. P D and the target pressure P S
A control means 22 for continuously opening and closing the valve by fully opening or closing the valve so that the detected pressure P D becomes the target pressure P S according to the sign of the difference between Is characterized by.
ここに、「連続的に」とは、安定状態においても自動
的に、弁開閉が連続的に行われることを意味し、その自
励発信周波数は、例えば１〜20Hz程度である。Here, "continuously" means that the valve opening / closing is continuously performed automatically even in a stable state, and the self-excited transmission frequency is, for example, about 1 to 20 Hz.
本第２発明に係る超臨界流体圧力制御装置では、例え
ば第１、２、４及び５図に示す如く、 超臨界流体が通る管路P4〜P6と、 該管路に介装され、電気的に操作されて全開／全閉
し、全閉のときに入口流路84と出口流路86との間の空間
73に弁棒先端部が嵌合されるように形成された弁17と、 弁開時間TOと弁閉時間TCのデューティ比の目標値が設
定されるデューティ比設定手段20と、 弁17を連続的に全開／全閉させて弁開閉のデューティ
比を該目標値にする制御手段22Bと、 を有することを特徴とする。In the supercritical fluid pressure control device according to the second aspect of the present invention, for example, as shown in FIGS. 1, 2, 4 and 5, the pipelines P4 to P6 through which the supercritical fluid passes, and the electrical pathways provided in the pipelines are provided. Operated to fully open / fully close, and the space between the inlet flow path 84 and the outlet flow path 86 when fully closed.
A valve 17 formed so that the valve rod tip portion is fitted to 73, a duty ratio setting means 20 for setting a target value of the duty ratio of the valve opening time T O and the valve closing time T C , and the valve 17 Is continuously and fully closed to control the duty ratio of valve opening / closing to the target value.
本第２発明の第１態様では、制御手段22Bによる弁開
閉は、１〜20Hzの範囲内の周波数で行われることを特徴
としている。The first aspect of the second aspect of the present invention is characterized in that the valve opening / closing by the control means 22B is performed at a frequency within the range of 1 to 20 Hz.
［実施例］ 最初に、本第１発明の実施例を図面に基づいて説明す
る。[First Embodiment] First, a first embodiment of the present invention will be described with reference to the drawings.
第１図は超臨界流体クロマトグラフの１部を示す模式
図である。FIG. 1 is a schematic diagram showing a part of a supercritical fluid chromatograph.
液体CO2ボンベ10とポンプ12とが管P1により接続さ
れ、ポンプ12と試料注入器13とが管P2により接続され、
試料注入器13と分離カラム14とが管P3により接続されて
おり、液体CO2ボンベ10からCO2がポンプ12に流入され、
分離カラム14へ加圧供給される。この試料注入器13及び
分離カラム14は恒温槽15内に備えられており、分離カラ
ム14内のCO2が臨界温度より高い温度に保持される。試
料は試料注入器により流路中に注入され、分離カラム14
内に流入し、分離が行われる。The liquid CO 2 cylinder 10 and the pump 12 are connected by a pipe P1, the pump 12 and the sample injector 13 are connected by a pipe P2,
The sample injector 13 and a separation column 14 Togakan P3 is connected, CO 2 is flowed into the pump 12 from a liquid CO 2 cylinder 10,
Pressure is supplied to the separation column 14. The sample injector 13 and the separation column 14 are provided in a constant temperature bath 15, and CO 2 in the separation column 14 is maintained at a temperature higher than the critical temperature. The sample is injected into the flow path by the sample injector, and the separation column 14
It flows in and is separated.
また、分離カラム14と検出器16とが管P4により接続さ
れ、検出器16と電磁弁17とが管P5により接続されてい
る。この管P4には圧力センサ18が取り付けられ、圧力セ
ンサ18からの圧力検出値及びプログラム設定器20からの
圧力設定値が制御回路22へ供給される。制御回路22は、
これらの値に応じて電磁弁17のソレノイド24をオン・オ
フし、検出圧力PDが設定圧力PSになるよう制御する。こ
れにより、分離カラム14内の圧力が臨界圧力より少し高
い設定値にされる。The separation column 14 and the detector 16 are connected by a pipe P4, and the detector 16 and the solenoid valve 17 are connected by a pipe P5. A pressure sensor 18 is attached to the pipe P4, and the pressure detection value from the pressure sensor 18 and the pressure set value from the program setter 20 are supplied to the control circuit 22. The control circuit 22 is
Depending on these values, the solenoid 24 of the solenoid valve 17 is turned on / off to control the detected pressure P D to the set pressure P S. As a result, the pressure inside the separation column 14 is set to a value slightly higher than the critical pressure.
分離カラム14から流出された溶出物は検出器16により
検出され、次いで管P5、電磁弁17、管P6を通って図示し
ない装置により分取される。The eluate that has flowed out of the separation column 14 is detected by the detector 16, and then is collected by a device (not shown) through the pipe P5, the solenoid valve 17, and the pipe P6.
なお、流量はポンプ12を駆動するモータの回転速度を
調整することにより制御される。The flow rate is controlled by adjusting the rotation speed of the motor that drives the pump 12.
次に、開閉弁としての電磁弁17の構成の一例を第２図
に基づいて説明する。Next, an example of the configuration of the solenoid valve 17 as an opening / closing valve will be described with reference to FIG.
電磁弁17はブラケット28に固定され、弁棒30がその軸
方向へ移動することにより入口32と出口34との間の流路
が全開または全閉されるようになっている。The solenoid valve 17 is fixed to a bracket 28, and the valve rod 30 moves in the axial direction so that the flow path between the inlet 32 and the outlet 34 is fully opened or closed.
弁棒30の基端部には軸継手36が形成されており、この
軸継手36内にプランジャ38の基端部が嵌入され、軸継手
36の内面に螺入されたねじ40により軸継手36とプランジ
ャ38が連結されている。プランジャ38はカバーで覆われ
たソレノイド24の中央部を貫通しており、ソレノイド24
を励磁すると、プランジャ38の先端部に固着された鉄板
44がソレノイド24に吸引されてプランジャ38、鉄板44、
弁棒30が第２図下方へ移動する。軸継手36の先端部には
つば46が形成されており、この軸受36にはリターンスプ
リング48が外嵌され、次にスプリング受50が外嵌され、
リターンスプリング48がつば46とスプリング受50との間
に介在している。軸継手36はハウジング51の軸心部に穿
設された穴52に挿入されており、穴52に形成された段部
53にスプリング受50が圧接係止されている。ソレノイド
24と軸継手36との間のプランジャ38にはストップリング
54が外嵌され、ストップリング54の周面に螺入されたね
じ56によりストップリング54がプランジャ38に固着され
ている。このストップリング54は、ソレノイド24を消磁
するとリターンスプリング48が復帰してソレノイド24に
弾接する。したがって、ストップリング54の取付位置に
より弁棒30の全ストローク長が設定される。A shaft joint 36 is formed at the base end portion of the valve rod 30, and the base end portion of a plunger 38 is fitted into the shaft joint 36 to form a shaft joint.
The shaft joint 36 and the plunger 38 are connected by a screw 40 screwed into the inner surface of 36. The plunger 38 penetrates the center of the solenoid 24 covered by the cover,
When the magnet is excited, the iron plate fixed to the tip of the plunger 38
44 is attracted to the solenoid 24 and the plunger 38, the iron plate 44,
The valve rod 30 moves downward in FIG. A flange 46 is formed at the tip of the shaft coupling 36, and a return spring 48 is externally fitted to the bearing 36, and then a spring receiver 50 is externally fitted to the bearing 36.
A return spring 48 is interposed between the collar 46 and the spring bridge 50. The shaft coupling 36 is inserted into a hole 52 formed in the shaft center of the housing 51, and a step portion formed in the hole 52.
The spring bridge 50 is pressed and locked to 53. solenoid
Stop ring on plunger 38 between 24 and shaft coupling 36
54 is externally fitted, and the stop ring 54 is fixed to the plunger 38 by a screw 56 screwed into the peripheral surface of the stop ring 54. When the solenoid 24 is demagnetized, the return spring 48 of the stop ring 54 returns to make elastic contact with the solenoid 24. Therefore, the total stroke length of the valve rod 30 is set by the mounting position of the stop ring 54.
ハウジング51の基端部に形成されたフランジ58及びこ
のフランジ58とソレノイド24との間に挟持されたブラケ
ット28にはそれぞれ切欠60、62が形成されており、ドラ
イバ先端部をこれへ挿入してねじ56を回転させることに
よりストップリング54の取付位置を調整可能となってい
る。Notches 60 and 62 are formed in the flange 58 formed at the base end portion of the housing 51 and the bracket 28 sandwiched between the flange 58 and the solenoid 24, respectively. By rotating the screw 56, the mounting position of the stop ring 54 can be adjusted.
ハウジング51の先端部にはブロック64の基端部が螺着
されている。ブロック64の先端部には穴66が穿設され、
これにシール機能をも有する弁座68が嵌入され、ナット
72が螺合された管継手70が穴66へ螺入され、ナット72に
より管継手70がブロック64に締め付けられている。弁棒
30は穴52と穴66連通する穴73に嵌入され、弁棒30とハウ
ジング51及びブロック64との間に形成された隙間にそれ
ぞれシール74、76が装填されている。シール74、76は例
えば強化四弗化エチレン樹脂で形成されており、弁座68
は例えばポリイミド樹脂で形成されている。弁座68の破
損に備えて、ブロック64には穴66と外部とを連通するベ
ントホール78が穿設されている。また、シール74、76の
破損に備えて、ハウジング51には穴52と外部とを連通す
るベントホール80、82が穿設されている。The base end of the block 64 is screwed to the tip of the housing 51. A hole 66 is formed at the tip of the block 64,
A valve seat 68 that also has a sealing function is fitted into this, and the nut
The pipe joint 70 in which 72 is screwed is screwed into the hole 66, and the pipe joint 70 is fastened to the block 64 by the nut 72. Valve rod
The hole 30 is fitted into a hole 73 communicating with the hole 52 and the hole 66, and seals 74 and 76 are loaded in the gaps formed between the valve rod 30 and the housing 51 and the block 64, respectively. The seals 74 and 76 are made of, for example, reinforced tetrafluoroethylene resin, and have a valve seat 68.
Is formed of, for example, a polyimide resin. In case of damage to the valve seat 68, the block 64 is provided with a vent hole 78 that communicates the hole 66 with the outside. Further, in case of damage to the seals 74, 76, the housing 51 is provided with vent holes 80, 82 for communicating the hole 52 with the outside.
上記構成において、ソレノイド24が消磁されている場
合には、リターンスプリング48の弾性力により弁棒30が
上昇して入口32と出口34との間の流路が全開になり、ソ
レノイド24を励磁すると、リターンスプリング48の弾性
力に抗して弁棒30が下降しその先端面が弁座68に当接し
て入口32と出口34の間の流路が全閉になる。In the above configuration, when the solenoid 24 is demagnetized, the elastic force of the return spring 48 raises the valve rod 30 so that the flow path between the inlet 32 and the outlet 34 is fully opened and the solenoid 24 is excited. The valve rod 30 descends against the elastic force of the return spring 48, and its tip end surface abuts against the valve seat 68 to fully close the flow path between the inlet 32 and the outlet 34.
穴73と入口32とを連通する流路84及び穴73と出口34と
を連通する流路86の内径は、それぞれ第１図に示す管P3
及び管P4の内径に略等しくなっている。また、ソレノイ
ド24が連続的にオン・オフされるので、流路84と流路86
との間の穴73の流体滞留時間の平均値は極めて短い。し
たがって、実質的に弁内流体滞留量が極めて少なく、抽
出物質が弁内部で再混合することがない。The inner diameters of the flow passage 84 that communicates the hole 73 and the inlet 32 and the flow passage 86 that communicates the hole 73 and the outlet 34 are respectively the pipe P3 shown in FIG.
And is substantially equal to the inner diameter of the pipe P4. Further, since the solenoid 24 is continuously turned on / off, the flow path 84 and the flow path 86 are
The average value of the fluid residence time of the holes 73 between and is extremely short. Therefore, the amount of fluid retained in the valve is substantially extremely small, and the extracted substance does not remix inside the valve.
しかも、弁棒30が連続的に往復運動するので、弁内壁
へ抽出物質が殆ど付着しない。Moreover, since the valve rod 30 continuously reciprocates, the extracted substance hardly adheres to the inner wall of the valve.
次に、制御回路22の一例を第３図に基づいて説明す
る。Next, an example of the control circuit 22 will be described with reference to FIG.
圧力センサ18の出力電圧は、アンプ100を介して比較
器102の反転入力端子に供給される。また、プログラム
設定器20の出力電圧は、抵抗器104を介して比較器102の
非反転入力端子に供給される。この非反転入力端子には
また、手動設定器106の出力電圧が抵抗器108を介して供
給される。The output voltage of the pressure sensor 18 is supplied to the inverting input terminal of the comparator 102 via the amplifier 100. Further, the output voltage of the program setter 20 is supplied to the non-inverting input terminal of the comparator 102 via the resistor 104. The output voltage of the manual setting device 106 is also supplied to the non-inverting input terminal via the resistor 108.
比較器102の出力電圧によりスイッチ回路110がオン・
オフされ、比較器102の出力電圧がハイレベルのときの
みソレノイド24が通電される。The switch circuit 110 is turned on by the output voltage of the comparator 102.
The solenoid 24 is energized only when the comparator 102 is turned off and the output voltage of the comparator 102 is at a high level.
上記構成において、手動設定の場合には、プログラム
設定器20の出力電圧を０にし、手動設定器106の可変抵
抗器を調整して圧力を設定する。自動設定の場合には、
手動設定器106の出力電圧を０にしておき、プラグラム
設定器20から設定電圧を出力させる。In the above configuration, in the case of manual setting, the output voltage of the program setting device 20 is set to 0, and the variable resistor of the manual setting device 106 is adjusted to set the pressure. In case of automatic setting,
The output voltage of the manual setting device 106 is set to 0, and the set voltage is output from the program setting device 20.
検出圧力PDが設定圧力PSよりも小さい場合には、比較
器102の出力がハイレベルになり、ソレノイド24が通電
されて電磁弁17が全閉になる。これにより、分離カラム
14内の圧力が上昇し検出圧力PDが設定圧力PSよりも大き
くなると、比較器102の出力電圧がロウレベルになり、
ソレノイド24への通電が遮断されて電磁弁17が全開とな
り、分離カラム14内の圧力が減少する。そしてPD＜PSと
なり、前記動作が繰り返されて電磁弁17が連続的に開閉
する。換言すれば、本圧力制御装置は自励式発振器を構
成する。When the detected pressure P D is lower than the set pressure P S , the output of the comparator 102 becomes high level, the solenoid 24 is energized, and the solenoid valve 17 is fully closed. This allows the separation column
When the pressure in 14 rises and the detected pressure P D becomes larger than the set pressure P S , the output voltage of the comparator 102 becomes low level,
The energization of the solenoid 24 is cut off, the solenoid valve 17 is fully opened, and the pressure in the separation column 14 is reduced. Then, P D <P S , and the above operation is repeated, so that the solenoid valve 17 is continuously opened and closed. In other words, the pressure control device constitutes a self-excited oscillator.
この開閉周波数は、設定圧力PS、流体の圧縮率、ポン
プ12の流体吐出量、電磁弁17を通過する流体の流量、分
離カラム14の容器弾性係数 ソレノイド24のインダクタ
ンス及び弁開閉の応答速度等により定まる系全体の等価
的キャパシタンス、インダクタンス及び抵抗により自動
的に定まる。This opening / closing frequency is set pressure P S , fluid compressibility, fluid discharge amount of pump 12, flow rate of fluid passing through solenoid valve 17, container elastic coefficient of separation column 14, inductance of solenoid 24, response speed of valve opening / closing, etc. It is automatically determined by the equivalent capacitance, inductance and resistance of the entire system determined by.
本発明者は、弁棒の直径3.2mmで流体の滞留量役10μ
ｌの弁部を備えた電磁弁を製作し、ポンプ12の吐出量を
１〜10ml/minとして、液化二酸化炭素を１〜50mlの容積
をもつ分離カラム14に圧送し、分離カラム14を二酸化炭
素の臨界温度（31.3℃）以上に加温して超臨界流体二酸
化炭素とし、その圧力を100〜300kg/cm2に制御したとこ
ろ、自励発振周波数、すなわち弁の開閉周波数は、ポン
プ12の吐出量並びに設定圧力に応じて自動的に変化し、
１〜20Hz程度となった。この周波数は、ストップリング
54の取付位置を調整することにより変化させることも可
能である。The inventor has found that the valve rod diameter is 3.2 mm and the fluid retention amount is 10 μm.
A solenoid valve having a valve portion of 1 was manufactured, and the discharge amount of the pump 12 was set to 1 to 10 ml / min, and liquefied carbon dioxide was pressure-fed to the separation column 14 having a volume of 1 to 50 ml, and the separation column 14 was changed to carbon dioxide. When the carbon dioxide was heated to a temperature above the critical temperature (31.3 ° C) to become a supercritical fluid carbon dioxide and its pressure was controlled to 100 to 300 kg / cm 2 , the self-excited oscillation frequency, that is, the valve opening / closing frequency, Automatically changes according to the amount and set pressure,
It became about 1 to 20 Hz. This frequency is the stop ring
It is also possible to change it by adjusting the mounting position of 54.
また、設定圧力に対する該開閉に基づく圧力変動の振
幅、すなわち圧力制御の精密さは、ポンプ12が発生する
脈動に対し充分小さく、ペンレコーダで記録（横軸の目
盛20kg/cm）することができなかった。Further, the amplitude of pressure fluctuation based on the opening and closing with respect to the set pressure, that is, the precision of pressure control is sufficiently small with respect to the pulsation generated by the pump 12, and can be recorded by a pen recorder (scale of horizontal axis 20 kg / cm). There wasn't.
前記周波数範囲は、超臨界流体抽出、超臨界流体クロ
マトグラフィにおいて、最適なものと言えよう。何故な
ら、光学的検出器、或いは水素イオン化検出器（水素イ
オン化検出器の場合には、これが電磁弁17の下流側に配
設される。）を検出器16として使用した場合、検出器16
に大きな雑音を与えて検出を困難にする程周波数が低く
ないからである。It can be said that the above frequency range is optimum for supercritical fluid extraction and supercritical fluid chromatography. Because an optical detector or a hydrogen ionization detector (in the case of a hydrogen ionization detector, this is arranged on the downstream side of the solenoid valve 17) is used as the detector 16, the detector 16
This is because the frequency is not low enough to give a large amount of noise to and make detection difficult.
本実施例によれば、弁開度を調整する従来の機械的平
衡制御型圧力調整弁、或は、それに油圧、空圧平衡回路
を組み合わせた圧力調整弁の流体滞留量の数100〜１、0
00分の１も小さい滞留量を実現することが可能である。According to the present embodiment, the conventional mechanical balance control type pressure adjusting valve for adjusting the valve opening degree, or the number of fluid retention amount of the pressure adjusting valve in which the hydraulic pressure and the air pressure balancing circuit are combined is 100 to 1, 0
It is possible to realize a retention amount as small as 1/00.
これにより、１〜10mlという小さな抽出容器をもつ小
型の超臨界流体抽出装置や超臨界流体クロマトグラフに
おける分取が可能となった。This enabled fractionation in a small supercritical fluid extractor or supercritical fluid chromatograph with a small extraction container of 1 to 10 ml.
次に、、本第２発明の実施例を説明する。 Next, an example of the second invention will be described.
この実施例では、電磁弁17の開閉周波数を所定値に調
整できるようになっている。第４図には制御回路22Bの
構成が示されており、圧力センサ18の出力電圧が差動ラ
ンプ112の反転入力端子に供給され、プログラム設定器2
0の出力電圧が差動アンプ112の非反転入力端子に供給さ
れ、差動アンプ112の出力電圧が比較器102の非反転入力
端子に供給される。比較器102の反転入力端子には、の
こぎり波発生器112の出力電圧が供給される。他の点に
ついては第３図に示す構成と同一になっている。In this embodiment, the opening / closing frequency of the solenoid valve 17 can be adjusted to a predetermined value. The configuration of the control circuit 22B is shown in FIG. 4, in which the output voltage of the pressure sensor 18 is supplied to the inverting input terminal of the differential lamp 112, and the program setter 2
The output voltage of 0 is supplied to the non-inverting input terminal of the differential amplifier 112, and the output voltage of the differential amplifier 112 is supplied to the non-inverting input terminal of the comparator 102. The output voltage of the sawtooth wave generator 112 is supplied to the inverting input terminal of the comparator 102. The other points are the same as the configuration shown in FIG.
上記構成において、設定圧力を上昇させると、すなわ
ち差動アンプ112の出力電圧を上昇させると、第５図に
示す如く、電磁弁17の開時間TOと閉時間TCの比、すなわ
ち弁開のデューティ比が小さくなり、分離カラム14内の
圧力が上昇する。In the above configuration, when the set pressure is raised, that is, the output voltage of the differential amplifier 112 is raised, as shown in FIG. 5, the ratio of the opening time T O to the closing time T C of the solenoid valve 17, that is, the valve opening time. The duty ratio becomes smaller and the pressure in the separation column 14 rises.
この実施例では、弁開閉の周波数がのこぎり波の周波数
に一致するので、圧力制御における微少圧力変動の周波
数を所定範囲内にしたい場合に特に有効である。In this embodiment, the frequency of opening and closing the valve matches the frequency of the sawtooth wave, so that it is particularly effective when it is desired to set the frequency of the minute pressure fluctuation in the pressure control within a predetermined range.
次に、本第２発明の他の実施例を説明する。この実施
例では、第１図に示す制御回路22がマイクロコンピュー
タにより構成されている。また、プログラム設定器20は
圧力のみならず弁開閉の周波数ｆをも設定可能となって
いる。Next, another embodiment of the second invention will be described. In this embodiment, the control circuit 22 shown in FIG. 1 is composed of a microcomputer. Further, the program setter 20 can set not only the pressure but also the frequency f of opening and closing the valve.
このマイクロコンピュータのソフトウェア構成を第６
図に基づいて説明する。The software configuration of this microcomputer
It will be described with reference to the drawings.
ステップ200で、設定周波数ｆを読み込む。次にステ
ップ202で弁開閉の周期Ｔを1/fとし、この周期Ｔにおけ
る弁開時間TOを半周期に初期設定する。In step 200, the set frequency f is read. Then the cycle T of the valve as a 1 / f in step 202, initializes the valve open time T O in the period T in the half period.
次にステップ204で設定圧力PS及び検出圧力PDを読み
込む。次にステップ206でTOにＫ（PD−PS）を加えた値
を新たな弁開時間TOとし（Ｔ−TO）を１周期における弁
閉時間TCとする。次にステップ208で時間TOが経過する
のを待ち、すなわち時間TO電磁弁17を開にし、次にステ
ップ210でソレノイド24を励磁して時間TC電磁弁17を閉
にする。次にステップ204へ戻り上記処理を繰り返す。Next, at step 204, the set pressure P S and the detected pressure P D are read. Then the T O and K (P D -P S) the value obtained by adding a new valve opening time T O (T-T O) between a valve closed in the one period T C at step 206. Next, in step 208, the time T O is awaited, that is, the time T O solenoid valve 17 is opened, and then the solenoid 24 is excited in step 210 to close the time T C solenoid valve 17. Then, the process returns to step 204 and the above process is repeated.
このようにして、弁開時間のデューティ比が調整さ
れ、検出圧力PDが目標圧力PSになるようフィードバック
制御される。In this way, the duty ratio of the valve opening time is adjusted, and feedback control is performed so that the detected pressure P D becomes the target pressure P S.
なお、上記実施例では、圧力センサ18が電磁弁17の上
流側に配設された圧力制御装置、すなわち背圧制御装置
を説明したが、圧力センサ18を電磁弁17の下流側に配設
すれば減圧調整装置として作動する。In the above embodiment, the pressure sensor 18 has been described as the pressure control device provided upstream of the solenoid valve 17, that is, the back pressure control device, but the pressure sensor 18 may be provided downstream of the solenoid valve 17. For example, it works as a decompression adjusting device.
また、上記実施例では閉ループ制御の場合を説明した
が、本発明は開ループ制御の場合であってもよい。Further, although the case of the closed loop control has been described in the above embodiment, the present invention may be the case of the open loop control.
また、弁棒30の駆動装置としてソレノイド24を用いた
場合を説明したが、電気信号を機械的変位に変換する素
子ならばソレノイドに限られず、例えば、圧電素子を駆
動源として用いたり、或いは弁棒そのものを圧電素子で
構成してもよい。Further, although the case where the solenoid 24 is used as the drive device of the valve rod 30 has been described, the element is not limited to the solenoid as long as it is an element that converts an electric signal into a mechanical displacement, and for example, a piezoelectric element is used as a drive source or a valve. The rod itself may be composed of a piezoelectric element.
［発明の効果］ 本発明に係る超臨界流体用圧力制御装置では、電気的
に操作されて全開全閉する弁が、全閉のときに入口流路
と出口流路との間の空間に弁棒先端部が嵌合されるよう
に形成されており、この弁を連続的に全開／全閉して圧
力を制御しているので、流体に含まれている物質が弁内
壁に付着し難く、かつ、弁開閉部における弁内流体の平
均滞留量を低減でき、異なる物質が順次弁内を流れた場
合に弁内でこれら物質が混合するのを防止することがで
きるという優れた効果を奏する。このような効果によ
り、従来では実現できなかった、１〜10mlという小さな
抽出容器をもつ小型の超臨界抽出装置が実現可能とな
り、かつ、超臨界流体クロマトグラフにおける物質分離
度の高い分取が可能となった。[Effects of the Invention] In the pressure control device for a supercritical fluid according to the present invention, a valve that is electrically operated to be fully opened and fully closed is a valve in a space between the inlet passage and the outlet passage when fully closed. The rod tip is formed so that it fits, and the valve is continuously fully opened / closed to control the pressure, so that the substance contained in the fluid does not easily adhere to the inner wall of the valve. Moreover, it is possible to reduce the average retention amount of the in-valve fluid in the valve opening / closing portion, and it is possible to prevent mixing of these substances in the valve when different substances sequentially flow in the valve. Due to these effects, it is possible to realize a compact supercritical extraction device with a small extraction container of 1 to 10 ml, which was not possible in the past, and it is also possible to perform fractionation with a high degree of substance separation in supercritical fluid chromatography. Became.
第１図乃至第３図は本第１発明の実施例に係り、第１図
は超臨界流体抽出装置の１部を示す模式図、第２図は電
磁弁17の構成の一例を示す一部縦断面図、第３図は制御
回路22の構成の一例を示す回路図である。第４図及び第
５図は本第２発明の実施例に係り、第４図は制御回路
図、第５図は弁開閉動作を説明するタイミングチャート
である。第６図は本第２発明の他の実施例に係り、マイ
クロコンピュータで制御回路を構成した場合のソフトウ
エア構成を示すフローチャートである。 17:電磁弁、18:圧力センサ 24:ソレノイド、30:弁棒 32:入口、34:出口 54:ストップリング 68:弁座1 to 3 relate to an embodiment of the present invention, FIG. 1 is a schematic view showing a part of a supercritical fluid extraction device, and FIG. 2 is a part showing an example of the configuration of a solenoid valve 17. FIG. 3 is a longitudinal sectional view, and FIG. 3 is a circuit diagram showing an example of the configuration of the control circuit 22. 4 and 5 relate to the embodiment of the present invention, FIG. 4 is a control circuit diagram, and FIG. 5 is a timing chart for explaining the valve opening / closing operation. FIG. 6 is a flow chart showing a software configuration when a control circuit is configured by a microcomputer according to another embodiment of the second invention. 17: Solenoid valve, 18: Pressure sensor 24: Solenoid, 30: Valve rod 32: Inlet, 34: Outlet 54: Stop ring 68: Valve seat
フロントページの続き (72)発明者 菅原 道明 東京都八王子市石川町2967番地の５ 日本 分光工業株式会社内 (56)参考文献 特開 昭60−8747（ＪＰ，Ａ) 特開 昭61−176851（ＪＰ，Ａ) 実開 昭57−106014（ＪＰ，Ｕ) 実開 昭58−40671（ＪＰ，Ｕ)Front page continuation (72) Inventor Michiaki Sugawara 529-2967 Ishikawa-cho, Hachioji-shi, Tokyo Within Japan Spectroscopy Co., Ltd. (56) Reference JP-A-60-8747 (JP, A) JP-A-61-176851 ( JP, A) Actually opened 57-106014 (JP, U) Actually opened 58-40671 (JP, U)
Claims (3)
全閉のときに入口流路（84）と出口流路（86）との間の
空間（73）に弁棒先端部が嵌合されるように形成された
弁（17）と、 該弁の上流側又は下流側の管路内超臨界流体圧力を検出
する圧力検出器（18）と、 目標圧力PSが設定される圧力設定手段（20）と、 該圧力検出器により検出された圧力PDと該目標圧力PSと
の差の符号に応じ該弁を全開又は全閉にして該検出圧力
PDが該目標圧力PSになるようにすることにより該弁を連
続的に開閉させる制御手段（22）と、 を有することを特徴とする超臨界流体用圧力制御装置。1. A pipe line (P4 to P6) through which a supercritical fluid passes, and a full-open / full-closed line which is interposed in the pipe line and electrically operated.
A valve (17) formed so that the valve rod tip portion is fitted into the space (73) between the inlet flow path (84) and the outlet flow path (86) when fully closed; A pressure detector (18) for detecting the upstream or downstream side supercritical fluid pressure in the pipeline, a pressure setting means (20) for setting a target pressure P S, and a pressure P detected by the pressure detector. Depending on the sign of the difference between D and the target pressure P S , the valve is fully opened or fully closed and the detected pressure is
A pressure control device for a supercritical fluid, comprising: a control means (22) for continuously opening and closing the valve by setting P D to the target pressure P S.
全閉のときに入口流路（84）と出口流路（86）との間の
空間（73）に弁棒先端部が嵌合されるように形成された
弁（17）と、 弁開時間と弁閉時間のデューティ比の目標値が設定され
るデューティ比設定手段（20）と、 該弁を連続的に全開／全閉させて弁開閉のデューティ比
を該目標値にする制御手段（22）と、 を有することを特徴とする超臨界流体用圧力制御装置。2. A pipe line (P4 to P6) through which a supercritical fluid passes, and a fully opened / fully closed pipe which is interposed in the pipe line and electrically operated.
A valve (17) formed so that the tip of the valve rod is fitted in the space (73) between the inlet flow path (84) and the outlet flow path (86) when fully closed, and the valve opening time And a duty ratio setting means (20) for setting a target value of the duty ratio of the valve closing time, and a control means (22) for continuously fully opening / closing the valve to set the duty ratio of the valve opening / closing to the target value. ), And a pressure control device for supercritical fluids.
20Hzの範囲内の周波数で行われることを特徴とする請求
項２記載の超臨界流体用圧力制御装置。3. The valve opening and closing by the control means (22) is 1 to
The pressure control device for a supercritical fluid according to claim 2, wherein the pressure control device is operated at a frequency within a range of 20 Hz.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62008652A JPH0830989B2 (en) | 1987-01-17 | 1987-01-17 | Pressure control device for supercritical fluid |
| DE3851763T DE3851763T2 (en) | 1987-01-17 | 1988-01-15 | Extraction device. |
| DE3850786T DE3850786T2 (en) | 1987-01-17 | 1988-01-15 | Pressure regulator. |
| EP19910104018 EP0438184B1 (en) | 1987-01-17 | 1988-01-15 | Apparatus for effecting extraction |
| EP19880100485 EP0275933B1 (en) | 1987-01-17 | 1988-01-15 | Pressure control apparatus |
| US07/455,804 US4984602A (en) | 1987-01-17 | 1989-12-22 | Pressure control apparatus and apparatus for effecting extraction chromatographic separation, and fractionation by employing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62008652A JPH0830989B2 (en) | 1987-01-17 | 1987-01-17 | Pressure control device for supercritical fluid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63177209A JPS63177209A (en) | 1988-07-21 |
| JPH0830989B2 true JPH0830989B2 (en) | 1996-03-27 |
Family
ID=11698864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62008652A Expired - Lifetime JPH0830989B2 (en) | 1987-01-17 | 1987-01-17 | Pressure control device for supercritical fluid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0830989B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011118880A (en) * | 2009-10-28 | 2011-06-16 | Jasco Corp | Pressure control apparatus for supercritical fluid |
| JP2012078210A (en) * | 2010-10-01 | 2012-04-19 | Jasco Corp | Minute capacity pressure gauge |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2825878A4 (en) * | 2012-03-08 | 2016-07-20 | Waters Technologies Corp | COUNTER-PRESSURE CONTROL |
| CN113906363B (en) * | 2019-06-11 | 2025-01-14 | 株式会社岛津制作所 | Supercritical fluid device and pressure control method of supercritical fluid device |
-
1987
- 1987-01-17 JP JP62008652A patent/JPH0830989B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011118880A (en) * | 2009-10-28 | 2011-06-16 | Jasco Corp | Pressure control apparatus for supercritical fluid |
| JP2012078210A (en) * | 2010-10-01 | 2012-04-19 | Jasco Corp | Minute capacity pressure gauge |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63177209A (en) | 1988-07-21 |
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