JPH1157375A - Separation of gas - Google Patents
Separation of gasInfo
- Publication number
- JPH1157375A JPH1157375A JP9218761A JP21876197A JPH1157375A JP H1157375 A JPH1157375 A JP H1157375A JP 9218761 A JP9218761 A JP 9218761A JP 21876197 A JP21876197 A JP 21876197A JP H1157375 A JPH1157375 A JP H1157375A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- tower
- pressure
- column
- product
- 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
Landscapes
- Separation Of Gases By Adsorption (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ガス分離方法に関
し、詳しくは、酸素と窒素とを含む原料ガス、特に空気
を原料ガスとして窒素を吸着分離することにより、酸素
に富むガスを製品ガスとして得る方法に好適に適用でき
るガス分離方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas separation method and, more particularly, to a raw material gas containing oxygen and nitrogen, in particular, an oxygen-rich gas as a product gas by adsorbing and separating nitrogen using air as a raw material gas. The present invention relates to a gas separation method suitably applicable to a method for obtaining the gas.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】圧力変
動吸着式ガス分離方法（ＰＳＡ法）による酸素に富むガ
スの製造は、例えば、空気等の酸素含有ガスから、酸素
以外の成分を優先的に吸着する吸着剤を用いて、酸素を
濃縮分離する方法であって、工業的に広く行われてい
る。2. Description of the Related Art In the production of an oxygen-rich gas by a pressure fluctuation adsorption type gas separation method (PSA method), for example, components other than oxygen are preferentially produced from an oxygen-containing gas such as air. This is a method for concentrating and separating oxygen by using an adsorbent that adsorbs on water, and is widely used industrially.
【０００３】ＰＳＡ法は、酸素を含有する原料ガスを相
対的に高い圧力で吸着剤と接触させ、主として酸素以外
の成分を優先的に吸着させて、比較的吸着し難いガスで
ある酸素を製品ガスとして取出す吸着工程と、主として
酸素以外の成分を吸着した吸着剤の雰囲気を吸着圧力よ
り相対的に低い圧力（大気圧あるいは大気圧以下）に減
圧し、酸素以外の成分を吸着剤から脱着させて吸着剤を
再生する再生工程とを主要な工程として繰返す方法であ
る。一般的には、この吸着工程及び再生工程に、低い圧
力にある吸着塔内の圧力を吸着圧力近くまで回復させる
加圧工程が追加される。ＰＳＡ法における操作は、この
ように、２乃至３の主要な工程で成立っているため、複
数の吸着塔を用いて製品ガスを連続的に発生することが
普通である。[0003] In the PSA method, a raw material gas containing oxygen is brought into contact with an adsorbent at a relatively high pressure, and components other than oxygen are mainly adsorbed preferentially. In the adsorption step of extracting as a gas, the atmosphere of the adsorbent that mainly adsorbs components other than oxygen is reduced to a pressure lower than the adsorption pressure (atmospheric pressure or below atmospheric pressure) to desorb components other than oxygen from the adsorbent. And a regeneration step of regenerating the adsorbent as a main step. In general, a pressure step for restoring the pressure in the adsorption tower at a low pressure to near the adsorption pressure is added to the adsorption step and the regeneration step. Since the operation in the PSA method is performed in two or three main steps as described above, it is usual that the product gas is continuously generated using a plurality of adsorption towers.
【０００４】また、ＰＳＡ法により酸素を発生させる場
合は、窒素を優先的に吸着する吸着剤として、Ｃａ−Ａ
型，Ｎａ−Ｘ型，Ｃａ−Ｘ型、あるいはモルデナイト等
のゼオライトが広く使用されている。When oxygen is generated by the PSA method, Ca-A is used as an adsorbent for preferentially adsorbing nitrogen.
Zeolites of the type, Na-X type, Ca-X type, or mordenite are widely used.
【０００５】上述のようなＰＳＡ法の性能を向上させる
ため、従来から様々な提案がなされている。例えば、そ
の一つとして、吸着工程終了時の吸着塔内に残る比較的
濃縮された製品ガスを、再生工程を終了した吸着塔に回
収して製品回収率を向上させる均圧操作がある。特開平
５−１９２５２７号公報には、均圧操作を２段階に分
け、吸着塔の上部同士を連結して行う均圧と、吸着塔の
上部と他の吸着塔の下部とを連結して行う均圧とを連続
的に行う方法が開示されている。しかし、そこで示され
た実施例は、いずれも再生を大気圧で行う、いわゆる大
気圧再生法であって、近年広く行われるようになった、
いわゆる真空再生法については述べられていない。Various proposals have been made in the past to improve the performance of the PSA method as described above. For example, as one of them, there is a pressure equalizing operation for recovering the relatively concentrated product gas remaining in the adsorption tower at the end of the adsorption step to the adsorption tower after the regeneration step and improving the product recovery rate. Japanese Patent Application Laid-Open No. 5-192527 discloses that the equalizing operation is divided into two stages and the equalizing operation is performed by connecting the upper parts of the adsorption towers, and the equalizing operation is performed by connecting the upper part of the adsorption tower and the lower part of another adsorption tower. A method of continuously performing equalization is disclosed. However, the embodiments shown therein are all so-called atmospheric pressure regeneration methods in which regeneration is performed at atmospheric pressure, and have been widely performed in recent years.
No mention is made of the so-called vacuum regeneration method.
【０００６】また、特開平１−２３６９１４号公報は、
真空再生方法に関するものであり、吸着工程終了時に塔
内に残留したガスを、主として他の吸着塔の再生工程時
にパージガスとして用いる方法を開示している。この方
法では、他の吸着塔からのガス回収を短時間行った後、
原料ガスの供給と製品ガスの逆戻しとにより再加圧を行
うようにしている。しかし、製品ガスを再加圧に使用す
る場合は、製品ガスの圧力が変動するので、それを防ぐ
ために製品槽の大型化を招くものと推察される。また、
原料空気による加圧は、比較的低い圧力にある吸着塔に
対して行われるため、空気が急激に流入して不純物成分
である窒素が吸着塔の製品出口端方向に流れ込むおそれ
がある。このような操作は、吸着装置の性能を低下させ
る要因となる。[0006] Japanese Patent Application Laid-Open No. 1-236914 discloses that
It relates to a vacuum regeneration method, and discloses a method in which a gas remaining in a column at the end of an adsorption step is mainly used as a purge gas during a regeneration step of another adsorption column. In this method, after recovering gas from other adsorption towers for a short time,
Re-pressurization is performed by supplying the raw material gas and returning the product gas back. However, when the product gas is used for re-pressurization, the pressure of the product gas fluctuates, and it is presumed that the product tank is enlarged in order to prevent the fluctuation. Also,
Since the pressurization with the raw air is performed on the adsorption tower at a relatively low pressure, there is a possibility that air may rapidly flow in and nitrogen, which is an impurity component, may flow toward the product outlet end of the adsorption tower. Such an operation causes a decrease in the performance of the adsorption device.
【０００７】ＰＳＡ法の性能を向上させるために、様々
な工夫がなされており、それなりの効果はあるが、それ
らは必ずしも十分に満足できるものではなく、なお一層
の改善が強く望まれている。Various attempts have been made to improve the performance of the PSA method, and although there are some effects, they are not always sufficiently satisfactory, and further improvement is strongly desired.
【０００８】そこで本発明は、上記事情に鑑み、ＰＳＡ
法のプロセスを改善し、ガス分離の効率を向上させるこ
と、なかでも、空気を分離して酸素に富むガスを効率よ
く発生させるのに好適なガス分離方法を提供することを
目的としている。In view of the above circumstances, the present invention provides a PSA
It is an object of the present invention to improve the process of the method and improve the efficiency of gas separation, and in particular, to provide a gas separation method suitable for separating air to efficiently generate an oxygen-rich gas.
【０００９】[0009]
【課題を解決するための手段】上記目的を達成するた
め、本発明のガス分離方法における第１の構成は、酸素
と窒素とを含む原料ガス中の窒素を優先的に吸着する吸
着剤を充填した２塔の吸着塔を用いて圧力変動吸着分離
法により酸素富化ガスを製品ガスとして回収するガス分
離方法であって、原料供給端から原料ガスが供給されて
吸着工程を行っている第１の塔の製品出口端から製品ガ
スを導出して製品ガス貯槽に供給しながら、該製品ガス
の一部を第２の塔の製品出口端から塔内に導入しつつ原
料供給端から塔内のガスを放出するパージ排気を行うこ
とにより吸着剤の再生工程を行う工程と、上記工程終了
後の第１の塔と第２の塔とを製品出口端で連通させ、吸
着工程を終了して塔内に圧力を保持した第１の塔から再
生工程を終了して低い圧力にある第２の塔へガスを回収
するとともに、第１の塔の原料供給端から系外へガスを
放出する工程と、上記工程終了後の第１の塔から引続き
ガスを系外に放出して塔内の圧力を下げることにより、
窒素を吸着した吸着剤から窒素ガスを脱着させるととも
に、第２の塔においては、製品ガス貯槽に貯えられた製
品ガスを第２の塔の製品出口端から導入しながら、同時
に原料供給端から原料ガスを供給して塔内の圧力を上昇
させる工程と、上記工程終了後の第１の塔から引続きガ
スを系外に放出して塔内の圧力を更に下げることによ
り、窒素を吸着した吸着剤から窒素ガスを脱着させると
ともに、第２の塔においては、原料供給端から原料ガス
を供給して塔内の圧力を上昇させる工程と、の各工程
を、第１及び第２の吸着塔を順次切換えて連続的に行う
ことにより、製品ガスを継続して発生することを特徴と
している。Means for Solving the Problems To achieve the above object, a first configuration of the gas separation method of the present invention is a method of charging an adsorbent which preferentially adsorbs nitrogen in a source gas containing oxygen and nitrogen. A gas separation method for recovering an oxygen-enriched gas as a product gas by a pressure fluctuation adsorption separation method using the two adsorption towers described above, wherein a raw material gas is supplied from a raw material supply end to perform an adsorption step. While the product gas is led out from the product outlet end of the second tower and supplied to the product gas storage tank, a part of the product gas is introduced into the tower from the product outlet end of the second tower while the product gas is introduced into the tower from the raw material supply end. A step of performing a regeneration step of the adsorbent by performing a purge evacuation for releasing gas, and communicating the first tower and the second tower after the above-mentioned step at the product outlet end. When the regeneration step is completed from the first tower with the pressure Recovering the gas into the second column at a pressure and releasing the gas from the raw material supply end of the first column to the outside of the system, and continuously releasing the gas from the first column after the above process to the outside of the system By lowering the pressure inside the tower
In the second tower, the product gas stored in the product gas storage tank is introduced from the product outlet end of the second tower while the nitrogen gas is desorbed from the adsorbent that has adsorbed nitrogen. A step of supplying gas to increase the pressure in the column, and further releasing gas from the first column after the above step to further lower the pressure in the column, thereby adsorbing the nitrogen. In the second tower, a step of supplying a raw material gas from the raw material supply end to increase the pressure in the tower is performed in the second column, and the first and second adsorption towers are sequentially performed. It is characterized in that the product gas is continuously generated by performing the switching continuously.
【００１０】また、第２の構成は、酸素と窒素とを含む
原料ガス中の窒素を優先的に吸着する吸着剤を充填した
２塔の吸着塔を用いて圧力変動吸着分離法により酸素富
化ガスを製品ガスとして回収するガス分離方法であっ
て、原料供給端から原料ガスが供給されて吸着工程を行
っている第１の塔の製品出口端から製品ガスを導出して
製品ガス貯槽に供給しながら、該製品ガスの一部を第２
の塔の製品出口端から塔内に導入しつつ原料供給端から
塔内のガスを放出するパージ排気を行うことにより吸着
剤の再生工程を行う工程と、上記工程終了後の第１の塔
と第２の塔とを製品出口端で連通させ、吸着工程を終了
して塔内に圧力を保持した第１の塔から再生工程を終了
して低い圧力にある第２の塔へガスを回収した後、第１
の塔の原料供給端から系外へガスを放出する工程と、上
記工程終了後の第１の塔から引続きガスを系外に放出し
て塔内の圧力を下げることにより、窒素を吸着した吸着
剤から窒素ガスを脱着させるとともに、第２の塔におい
ては、製品ガス貯槽に貯えられた製品ガスを第２の塔の
製品出口端から導入しながら、同時に原料供給端から原
料ガスを供給して塔内の圧力を上昇させる工程と、上記
工程終了後の第１の塔から引続きガスを系外に放出して
塔内の圧力を更に下げることにより、窒素を吸着した吸
着剤から窒素ガスを脱着させるとともに、第２の塔にお
いては、原料供給端から原料ガスを供給して塔内の圧力
を上昇させる工程と、の各工程を、第１及び第２の吸着
塔を順次切換えて連続的に行うことにより、製品ガスを
継続して発生することを特徴としている。[0010] The second configuration is to enrich oxygen by a pressure fluctuation adsorption separation method using two adsorption columns packed with an adsorbent that preferentially adsorbs nitrogen in a source gas containing oxygen and nitrogen. A gas separation method for recovering a gas as a product gas, wherein the product gas is supplied from a raw material supply end and the product gas is derived from a product outlet end of a first tower performing an adsorption process and supplied to a product gas storage tank. While a part of the product gas is
A step of performing a regeneration step of the adsorbent by performing a purge exhaust that releases gas in the tower from a raw material supply end while introducing the gas into the tower from a product outlet end of the tower, and a first tower after the above-described step. The second column was communicated with the product outlet end, and the gas was recovered from the first column, in which the adsorption step was completed and the pressure was maintained in the column, to the second column at a low pressure after the regeneration step was completed. Later, the first
A step of releasing gas from the raw material supply end of the column to the outside of the system, and a step of continuously releasing gas from the first column after the above-mentioned step to reduce the pressure in the column, thereby adsorbing nitrogen. While desorbing nitrogen gas from the agent, in the second tower, the product gas stored in the product gas storage tank is introduced from the product outlet end of the second tower, and at the same time, the raw material gas is supplied from the raw material supply end. The step of increasing the pressure in the column, and continuously releasing gas from the first column after the above-mentioned step to further reduce the pressure in the column, thereby desorbing nitrogen gas from the adsorbent that has adsorbed nitrogen. In the second column, the steps of supplying the source gas from the source end and increasing the pressure in the column are continuously performed by sequentially switching the first and second adsorption towers. By doing so, product gas is continuously generated It is characterized by a door.
【００１１】また、第３の構成は、上記第１，第２の構
成において、前記吸着塔への原料ガスの供給量を流量制
御手段により制御することを特徴としている。A third configuration is characterized in that, in the first and second configurations, the supply amount of the raw material gas to the adsorption tower is controlled by a flow control unit.
【００１２】[0012]
【発明の実施の形態】図１は、本発明のガス分離方法を
実施するための圧力変動吸着式ガス分離装置（ＰＳＡ装
置）の一例を示す系統図、図２は、本発明の各工程にお
けるガスの流れを説明するための概念図で、各機器間を
接続する矢印線は、矢印の方向にガスが流れていること
を示している。DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is a system diagram showing an example of a pressure fluctuation adsorption type gas separation apparatus (PSA apparatus) for carrying out the gas separation method of the present invention, and FIG. In the conceptual diagram for explaining the gas flow, an arrow line connecting between the devices indicates that the gas flows in the direction of the arrow.
【００１３】本形態例に示すＰＳＡ装置は、窒素を優先
的に吸着する吸着剤を使用し、酸素を含有する混合ガ
ス、具体的には、空気を原料として酸素に富んだガスを
製品として得るためのものであって、２塔の吸着塔Ａ，
Ｂを所定の工程に従って運転することにより、高い酸素
回収率と酸素発生量とを得るものである。各吸着塔Ａ，
Ｂには、原料空気中の酸素以外の成分、特に窒素を優先
的に吸着する吸着剤として、Ｃａ−Ａ型，Ｎａ−Ｘ型，
Ｃａ−Ｘ型，モルデナイト、あるいはこれらに他のイオ
ンを単独又は複数組み合わせて導入したゼオライトが充
填されている。両吸着塔の原料供給端には、原料空気圧
縮機１から原料空気流量調整弁２を経て供給される原料
空気を導入するための入口弁３ａ，３ｂと、塔内のガス
を排気するための排気弁４ａ，４ｂとが設けられ、製品
出口端には、製品ガスを導出する出口弁５ａ，５ｂと、
均圧及びパージの際に塔内にガスを導入するためのパー
ジガス導入弁６ａ，６ｂとが設けられている。The PSA apparatus shown in this embodiment uses an adsorbent that preferentially adsorbs nitrogen, and obtains a mixed gas containing oxygen, specifically, a gas rich in oxygen from air as a product. And two adsorption towers A,
By operating B according to a predetermined process, a high oxygen recovery rate and a high oxygen generation amount are obtained. Each adsorption tower A,
B has a Ca-A type, a Na-X type, an adsorbent which preferentially adsorbs components other than oxygen in the raw material air, particularly nitrogen.
It is filled with Ca-X type, mordenite, or a zeolite into which other ions are introduced alone or in combination. At the raw material supply ends of both adsorption towers, inlet valves 3a and 3b for introducing raw air supplied from the raw air compressor 1 via the raw air flow regulating valve 2, and for exhausting gas in the tower. Exhaust valves 4a and 4b are provided, and at the product outlet end, outlet valves 5a and 5b for discharging product gas,
Purge gas introduction valves 6a and 6b for introducing gas into the tower at the time of equalizing and purging are provided.
【００１４】さらに、前記排気弁４ａ，４ｂには、真空
ポンプ７と放出弁８とが接続されており、出口弁５ａ，
５ｂには、製品ガス貯槽９が接続されるとともに、吸着
塔にパージガスを供給するためのパージガス供給弁１
０，パージガス流量調整弁１１及び流量計１２を有する
パージライン１３が接続されている。また、原料空気圧
縮機１にバイパス弁１ａが、製品貯槽９には製品供給弁
９ａが設けられており、原料空気流量調整弁２には、制
御器１４との間に弁開度制御信号１４ａが接続されてい
る。Further, a vacuum pump 7 and a discharge valve 8 are connected to the exhaust valves 4a and 4b, and the outlet valves 5a and 4b are connected to the exhaust valves 4a and 4b.
5b is connected to a product gas storage tank 9 and a purge gas supply valve 1 for supplying a purge gas to the adsorption tower.
0, a purge line 13 having a purge gas flow control valve 11 and a flow meter 12 is connected. The raw material air compressor 1 is provided with a bypass valve 1a, the product storage tank 9 is provided with a product supply valve 9a, and the raw material air flow regulating valve 2 is provided with a valve opening control signal 14a between the raw material air compressor 1 and the controller 14. Is connected.
【００１５】次に図２を参照しながら、上記ＰＳＡ装置
による本発明方法の第１形態例を説明する。なお、各工
程において、記載の無い弁は基本的に閉じた状態になっ
ており、流量調整弁は、特に説明が無い限り所定の開度
に開いた状態になっているものとする。また、図２では
弁の位置を黒丸で略記する。Next, a first embodiment of the method of the present invention using the PSA apparatus will be described with reference to FIG. In each step, valves not described are basically in a closed state, and the flow control valve is in an open state at a predetermined opening degree unless otherwise specified. In FIG. 2, the position of the valve is abbreviated as a black circle.
【００１６】まず、工程１は、吸着塔Ａ（第１の塔）が
吸着工程を行っており、吸着塔Ｂ（第２の塔）が再生工
程最終段階のパージ操作を行っている工程である。吸着
工程中の吸着塔Ａでは、原料空気圧縮機１で所定圧力に
圧縮された原料空気が原料空気流量調整弁２及び入口弁
３ａを経て原料供給端から吸着塔Ａ内に供給され、塔内
に充填された吸着剤により原料空気中の窒素が優先的に
吸着除去され、製品出口端に向かって酸素が濃縮され
る。濃縮した酸素は、出口弁５ａから製品ガス貯槽９に
供給されて該製品ガス貯槽９を充圧するとともに、その
一部が製品供給弁９ａを経て使用先に送られる。First, step 1 is a step in which the adsorption tower A (first tower) is performing an adsorption step and the adsorption tower B (second tower) is performing a purging operation at the final stage of the regeneration step. . In the adsorption tower A during the adsorption step, the raw air compressed to a predetermined pressure by the raw air compressor 1 is supplied from the raw material supply end into the adsorption tower A via the raw air flow control valve 2 and the inlet valve 3a. Nitrogen in the raw material air is preferentially adsorbed and removed by the adsorbent charged in the, and oxygen is concentrated toward the product outlet end. The concentrated oxygen is supplied from the outlet valve 5a to the product gas storage tank 9 to pressurize the product gas storage tank 9, and a part of the oxygen is sent to the destination through the product supply valve 9a.
【００１７】一方、吸着塔Ｂでは、原料供給端から排気
弁４ｂを介して塔内のガス（脱着ガス）が真空ポンプ７
に吸引されて大気に放出されるとともに、製品ガスの一
部が、パージガス供給弁１０及びパージガス導入弁６ｂ
を経て吸着塔Ｂの製品出口端から塔内に逆方向に導入さ
れる。このように、酸素に富んだガス、すなわち、窒素
分が少ないガスを製品出口端から塔内に導入しつつ原料
供給端から塔内のガスを放出するパージ排気を行うこと
により、吸着剤に吸着されている窒素の脱着が促進さ
れ、この工程を行うことにより吸着塔Ｂ内の吸着剤の再
生が完了する。On the other hand, in the adsorption tower B, the gas (desorption gas) in the tower is supplied from the raw material supply end via the exhaust valve 4b to the vacuum pump 7
And a part of the product gas is supplied to the purge gas supply valve 10 and the purge gas introduction valve 6b.
Through the product outlet end of the adsorption tower B into the tower in the opposite direction. In this way, by performing a purge exhaust in which a gas rich in oxygen, that is, a gas having a low nitrogen content is introduced into the tower from the product outlet end and the gas in the tower is released from the raw material supply end, the gas is adsorbed by the adsorbent. This desorption of nitrogen is promoted, and by performing this step, regeneration of the adsorbent in the adsorption tower B is completed.
【００１８】前記吸着塔Ａの吸着工程において、窒素の
吸着前線が製品出口端に向かって進行し、製品ガス濃度
が決められた値より低下し始めると、工程１から工程２
に切換えられる。この工程２は、吸着塔Ａが減圧操作を
行い、吸着塔Ｂが加圧操作を開始する工程である。この
工程２では、吸着工程を終了して塔内に圧力を保持した
吸着塔Ａの製品出口端と、再生工程を終了して低い圧力
にある吸着塔Ｂの製品出口端とをパージガス導入弁６
ａ，６ｂを介して連通させ、吸着塔Ａ内のガスを吸着塔
Ｂ内に回収していわゆる上部均圧操作を行うとともに、
吸着塔Ａの排気弁４ａから塔内のガスを系外に放出す
る。これにより、吸着塔Ｂは加圧され、吸着塔Ａは減圧
される。このように上部均圧を行うと同時に、吸着塔Ａ
の原料供給端から塔内のガスを放出することにより、原
料供給端側の窒素分に富むガスが、吸着塔Ａから回収側
の吸着塔Ｂに流入することを防止でき、酸素の回収率や
発生量が向上する。In the adsorption step of the adsorption tower A, when the nitrogen adsorption front advances toward the product outlet end and the product gas concentration starts to fall below a predetermined value, the steps 1 to 2 are performed.
Is switched to This step 2 is a step in which the adsorption tower A performs a pressure reduction operation and the adsorption tower B starts a pressure operation. In this step 2, the purge gas introduction valve 6 connects the product outlet end of the adsorption tower A whose pressure has been maintained in the tower after the end of the adsorption step and the product outlet end of the adsorption tower B at a low pressure after the regeneration step.
a and 6b, the gas in the adsorption tower A is recovered in the adsorption tower B, and a so-called upper pressure equalizing operation is performed.
The gas in the tower is discharged out of the system from the exhaust valve 4a of the adsorption tower A. Thereby, the adsorption tower B is pressurized and the adsorption tower A is depressurized. At the same time as the upper pressure equalization is performed, the adsorption tower A
By releasing the gas in the column from the raw material supply end, the nitrogen-rich gas on the raw material supply end side can be prevented from flowing from the adsorption column A to the adsorption column B on the recovery side, and the oxygen recovery rate and The amount of generation is improved.
【００１９】なお、排気弁４ａから吸着塔Ａ内のガスを
排気する際、排気の初期においては、塔内の圧力が大気
圧以上であるから、そのまま真空ポンプ７に吸引させる
ことは、真空ポンプ７に過大な負荷を与えることとなる
ため、弁８を開いてガスを大気へ直接放出する。この工
程２において、製品ガスは製品ガス貯槽９から製品供給
弁９ａを経て供給される。また、原料空気圧縮機１で
は、バイパス弁１ａが開いた状態となる。When the gas in the adsorption tower A is exhausted from the exhaust valve 4a, the pressure in the tower is equal to or higher than the atmospheric pressure in the initial stage of the evacuation. Since an excessive load is applied to the valve 7, the valve 8 is opened and the gas is directly discharged to the atmosphere. In this step 2, the product gas is supplied from the product gas storage tank 9 via the product supply valve 9a. In the raw material air compressor 1, the bypass valve 1a is in an open state.
【００２０】前記上部均圧操作におけるガスの回収が所
定量となると、工程２から工程３に切換えられる。この
工程３では、吸着塔Ａは、排気弁４ａから真空ポンプ７
を経て塔内の排気が継続され、圧力の低下とともに吸着
剤に吸着されていた窒素が脱着し、吸着剤が再生される
（減圧再生操作）。吸着塔Ｂにおいては、製品ガスと原
料空気とによる再加圧が開始される。製品ガスは、製品
ガス貯槽９からパージガス供給弁１０，パージガス導入
弁６ｂを経て製品出口端から吸着塔Ｂ内へ供給され、原
料空気は、原料空気圧縮機１から入口弁３ｂを経て原料
供給端から吸着塔Ｂ内へ供給される。この原料空気の供
給の初期において、吸着塔Ｂ内の圧力が大気圧より低い
間は、原料空気圧縮機１のバイパス弁１ａが開かれ、原
料空気圧縮機１の吐出圧力が吸入圧力より低くならない
ようにして原料空気圧縮機１を保護する。また、製品ガ
スは、前記同様に製品ガス貯槽９から製品供給弁９ａを
経て供給される。When the gas recovery in the upper equalizing operation reaches a predetermined amount, the process is switched from step 2 to step 3. In this step 3, the adsorption tower A is connected to the vacuum pump 7 by the exhaust valve 4a.
Then, the exhaust in the tower is continued, and the nitrogen adsorbed by the adsorbent is desorbed as the pressure decreases, and the adsorbent is regenerated (reduced pressure regeneration operation). In the adsorption tower B, re-pressurization with the product gas and the raw material air is started. The product gas is supplied from the product gas storage tank 9 through the purge gas supply valve 10 and the purge gas introduction valve 6b to the adsorption tower B from the product outlet end, and the raw material air is supplied from the raw material air compressor 1 through the inlet valve 3b. To the adsorption tower B. In the initial stage of the supply of the raw air, while the pressure in the adsorption tower B is lower than the atmospheric pressure, the bypass valve 1a of the raw air compressor 1 is opened, and the discharge pressure of the raw air compressor 1 does not become lower than the suction pressure. Thus, the raw material air compressor 1 is protected. Further, the product gas is supplied from the product gas storage tank 9 through the product supply valve 9a in the same manner as described above.
【００２１】吸着塔Ｂの圧力が所定圧力に高まると、工
程３から工程４に切換えられる。この工程４では、吸着
塔Ａは、排気弁４ａからの真空ポンプ７による排気が継
続して行われ、吸着剤の再生が進む。吸着塔Ｂは、製品
出口端からの製品ガスの供給が停止し、原料空気圧縮機
１で圧縮された原料空気が入口弁３ｂから吸着塔Ｂ内に
供給され，吸着塔Ｂの最終的な加圧が行われる。また、
製品ガスは、前記同様に製品ガス貯槽９から製品供給弁
９ａを経て供給される。When the pressure in the adsorption tower B increases to a predetermined pressure, the process is switched from step 3 to step 4. In this step 4, in the adsorption tower A, the exhaust from the exhaust valve 4a by the vacuum pump 7 is continuously performed, and the regeneration of the adsorbent proceeds. In the adsorption tower B, the supply of the product gas from the product outlet end is stopped, and the raw material air compressed by the raw material air compressor 1 is supplied into the adsorption tower B from the inlet valve 3b. Pressure is applied. Also,
The product gas is supplied from the product gas storage tank 9 through the product supply valve 9a as described above.
【００２２】吸着塔Ｂの圧力が吸着工程の圧力まで高ま
ると工程４が終了し、吸着塔Ｂが吸着工程、吸着塔Ａが
パージ操作となる。すなわち、前記工程１における吸着
塔Ａと吸着塔Ｂとが入換った状態となり、以後、前記各
工程における吸着塔Ａが吸着塔Ｂの状態、吸着塔Ｂが吸
着塔Ａの状態となって工程４まで行われ、以降、吸着塔
Ａ，Ｂを切換えて、工程１から工程４を繰返し行うこと
で、連続して製品ガスである酸素富化ガスが得られる。When the pressure in the adsorption tower B increases to the pressure in the adsorption step, the step 4 is completed, the adsorption step in the adsorption tower B is performed and the purge operation in the adsorption tower A is performed. That is, the adsorption tower A and the adsorption tower B in the step 1 are interchanged, and thereafter, the adsorption tower A in each step is in the state of the adsorption tower B, and the adsorption tower B is in the state of the adsorption tower A. The process is performed up to the step 4. Thereafter, the adsorption towers A and B are switched, and the steps 1 to 4 are repeated, whereby an oxygen-enriched gas as a product gas is continuously obtained.
【００２３】また、前記工程２を二つの工程に分割して
行うこともできる。すなわち、工程２の初期では、吸着
塔Ａ及び吸着塔Ｂの製品出口端同士をパージガス導入弁
６ａ，６ｂを介して連通させることによる上部均圧操作
のみを行い、この上部均圧操作を行った後、吸着塔Ａの
排気弁４ａを開いて塔内ガスの排気を開始する。これに
より、吸着塔Ａの製品出口側に濃縮されている酸素の回
収量を多くすることができ、酸素の回収率や発生量が向
上する。Further, the step 2 can be performed by dividing the step into two steps. That is, in the early stage of the process 2, only the upper pressure equalization operation was performed by connecting the product outlet ends of the adsorption tower A and the adsorption tower B via the purge gas introduction valves 6a and 6b, and the upper pressure equalization operation was performed. Thereafter, the exhaust valve 4a of the adsorption tower A is opened to start exhausting gas in the tower. As a result, the amount of oxygen that is concentrated on the product outlet side of the adsorption tower A can be increased, and the oxygen recovery rate and the amount of generated oxygen can be improved.
【００２４】さらに、各吸着塔Ａ，Ｂに原料空気を供給
する際には、塔内の窒素の吸着帯（物質移動帯、ＭＴ
Ｚ）が、吸着塔の製品出口端に向かって延びることを防
止するため、原料空気の供給速度を調整することが好ま
しい。例えば、前記工程３が始まる段階で、加圧工程に
ある吸着塔Ｂは、工程２の均圧操作による加圧を行った
状態にあるので、その圧力は大気圧よりも低いから、何
らの制限もなく大気圧以上の原料空気を供給すると、同
時に行う製品ガスによる加圧のガス量に比較して大幅に
多い原料空気が流入するので、窒素の吸着帯はすぐに製
品出口端に延びてしまう。また、吸着塔に成り行きで空
気を供給すると、受入側の吸着塔の圧力次第で好ましく
ない過大な流速になることがある。窒素吸着に好ましい
条件は、適切な流速で空気が流れることであり、その条
件は、吸着塔の空気流入速度を調整することにより達成
される。Further, when supplying the raw material air to each of the adsorption towers A and B, the nitrogen adsorption zone (mass transfer zone, MT
In order to prevent Z) from extending toward the product outlet end of the adsorption tower, it is preferable to adjust the supply speed of the raw material air. For example, at the stage where the step 3 is started, the adsorption tower B in the pressurizing step is in a state where the pressure is applied by the pressure equalizing operation in the step 2, and the pressure is lower than the atmospheric pressure. If the raw material air is supplied at a pressure higher than the atmospheric pressure, a large amount of the raw material air flows in compared with the amount of gas pressurized by the product gas at the same time, so that the nitrogen adsorption zone immediately extends to the product outlet end. . In addition, if air is supplied to the adsorption tower, the flow rate may become undesirably excessive depending on the pressure of the adsorption tower on the receiving side. A preferable condition for nitrogen adsorption is that air flows at an appropriate flow rate, and this condition is achieved by adjusting the air inflow speed of the adsorption tower.
【００２５】空気流入速度の調整は、ＰＳＡ装置全体の
制御を行う操作の制御器１４からの弁開度制御信号１４
ａにより、原料空気ラインに設置した原料空気流量調整
弁２の開度を調整することにより行うことができる。こ
の開度調整は、例えば、工程の切換えを制御する制御器
１４からの信号により、調整弁２に送られる制御空気圧
を変えて弁開度を変えることで行える。最も流速が大き
くなると思われる工程３においては、最も小さい弁開度
とし、次の工程４では弁開度を大きくする。また、特に
流れを制御する必要のない工程１においては調整弁２は
全開とする。この空気流入速度の調整の方法は、調整弁
による方法以外、原料空気圧縮機１の回転数を制御する
方法等によっても行うことができる。このように空気流
入速度を制御することにより、分離性能の向上ととも
に、吸着剤の流動化を防ぎ、吸着剤の粉化を防止すると
いう効果も得られる。The adjustment of the air inflow speed is performed by controlling the valve opening control signal 14 from the controller 14 for controlling the entire PSA apparatus.
According to a, it can be performed by adjusting the opening degree of the raw material air flow control valve 2 installed in the raw material air line. This opening adjustment can be performed, for example, by changing the valve opening by changing the control air pressure sent to the adjustment valve 2 based on a signal from the controller 14 that controls the switching of the process. In step 3 where the flow velocity is considered to be the largest, the valve opening is set to the smallest, and in the next step 4, the valve opening is increased. Further, in the step 1 where there is no particular need to control the flow, the regulating valve 2 is fully opened. The method of adjusting the air inflow speed can be performed by a method of controlling the number of revolutions of the raw material air compressor 1 other than the method using the adjusting valve. By controlling the air inflow speed in this way, it is possible to obtain the effect of improving the separation performance, preventing fluidization of the adsorbent, and preventing powdering of the adsorbent.
【００２６】上述のように、真空再生を行った吸着塔の
再加圧を、均圧操作によって回収されるガス、すなわ
ち、酸素分に富むガスを用いて原料空気の流れに対して
向流方向に加圧することにより、原料空気による加圧を
実施する時点での塔内圧力をある程度まで上昇させてお
くことができるので、原料空気による加圧の際の空気の
流速が過大になることを防ぐことができる。As described above, the re-pressurization of the adsorption tower subjected to the vacuum regeneration is performed by using the gas recovered by the equalizing operation, that is, the gas rich in oxygen, in the countercurrent direction to the flow of the raw material air. , The pressure in the tower at the time of pressurizing with the raw material air can be increased to a certain extent, so that the flow velocity of the air at the time of pressurizing with the raw material air is prevented from becoming excessive. be able to.
【００２７】また、工程２の均圧操作で酸素分に富むガ
スで加圧した後、工程３において、製品出口端からは製
品ガスを、原料供給端からは原料空気を同時に送って加
圧することにより、空気中の窒素が製品出口端に向かっ
て前進することを防ぐことができる。さらに、工程４で
は、工程２及び工程３で既に塔内の圧力がかなり上昇し
ているため、原料空気のみを供給して最終的な加圧を行
えるので、製品ガスを用いることなく、吸着工程に移行
するための準備を終了することができる。Further, after pressurizing with a gas rich in oxygen in the pressure equalizing operation in step 2, in step 3, the product gas is simultaneously sent from the product outlet end and the raw material air is sent from the raw material supply end to be pressurized. Thereby, it is possible to prevent nitrogen in the air from advancing toward the product outlet end. Further, in the step 4, since the pressure in the tower has already been considerably increased in the steps 2 and 3, the final pressurization can be performed by supplying only the raw material air. Preparations for shifting to can be completed.
【００２８】以上の各工程を組合わせることにより、極
めて高い酸素回収率と、吸着剤当たりの高い酸素発生量
を達成することができる。By combining the above steps, an extremely high oxygen recovery rate and a high oxygen generation amount per adsorbent can be achieved.
【００２９】[0029]
【実施例】図１に示す系統のＰＳＡ装置を使用して、
図２に示す工程１〜４を行った場合（第１の構成に相
当）、工程２を分割した場合（第２の構成に相当）、
工程２を分割するとともに原料空気の流入速度を調整
した場合（第２の構成に相当）の３通りの実験を行っ
た。主な操作条件は、次の通りである。 吸着圧力 ８００Ｔｏｒｒ 再生圧力 ２００Ｔｏｒｒ 原料空気温度 ２５℃ サイクルタイム ６０秒 窒素吸着剤 Ｃａ−Ａ型ゼオライトDESCRIPTION OF THE PREFERRED EMBODIMENTS Using a PSA system of the system shown in FIG.
When steps 1 to 4 shown in FIG. 2 are performed (corresponding to the first configuration), when step 2 is divided (corresponding to the second configuration),
Three experiments were performed in which the process 2 was divided and the flow rate of the raw material air was adjusted (corresponding to the second configuration). The main operating conditions are as follows. Adsorption pressure 800 Torr Regeneration pressure 200 Torr Raw material air temperature 25 ° C Cycle time 60 seconds Nitrogen adsorbent Ca-A type zeolite
【００３０】その結果、では酸素回収率が４３％、吸
着剤１トン当たりの酸素発生量が２４Ｎｍ３／ｈであっ
た。では酸素回収率が４５％、吸着剤１トン当たりの
酸素発生量が２５Ｎｍ３／ｈに向上し、では酸素回収
率が４６％、吸着剤１トン当たりの酸素発生量が２７Ｎ
ｍ３／ｈに更に向上した。なお、酸素発生量は２塔合計
の吸着剤を基準にした値である。As a result, the oxygen recovery rate was 43%, and the amount of oxygen generated per ton of the adsorbent was 24 Nm 3 / h. In, the oxygen recovery rate was improved to 45%, and the amount of oxygen generated per ton of adsorbent was improved to 25 Nm 3 / h. In, the oxygen recovery rate was improved to 46%, and the amount of oxygen generated per ton of adsorbent was increased to 27 Nm
m 3 / h was further improved. Note that the oxygen generation amount is a value based on the total amount of the adsorbents in the two columns.
【００３１】[0031]
【発明の効果】以上説明したように、本発明のガス分離
方法によれば、製品回収率、吸着剤当たりの製品発生量
を共に向上させることができる。これに加えて、吸着剤
の流動による粉化も防止することができる。As described above, according to the gas separation method of the present invention, it is possible to improve both the product recovery rate and the product generation amount per adsorbent. In addition, powdering due to the flow of the adsorbent can be prevented.
【図１】 ＰＳＡ装置の一例を示す系統図である。FIG. 1 is a system diagram showing an example of a PSA device.
【図２】 各工程におけるガスの流れを説明する概念図
である。FIG. 2 is a conceptual diagram illustrating a gas flow in each process.
Ａ，Ｂ…吸着塔、１…原料空気圧縮機、１ａ…バイパス
弁、２…原料空気流量調整弁、３ａ，３ｂ…入口弁、４
ａ，４ｂ…排気弁、５ａ，５ｂ…出口弁、６ａ，６ｂ…
パージガス導入弁、７…真空ポンプ、８…放出弁、９…
製品ガス貯槽、９ａ…製品供給弁、１０…パージガス供
給弁、１１…パージガス流量調整弁、１２…流量計、１
３…パージライン、１４…制御器、１４ａ…弁開度制御
信号A, B: adsorption tower, 1: raw material air compressor, 1a: bypass valve, 2: raw material air flow control valve, 3a, 3b: inlet valve, 4
a, 4b ... exhaust valve, 5a, 5b ... outlet valve, 6a, 6b ...
Purge gas introduction valve, 7: vacuum pump, 8: release valve, 9 ...
Product gas storage tank, 9a: product supply valve, 10: purge gas supply valve, 11: purge gas flow control valve, 12: flow meter, 1
3 ... Purge line, 14 ... Controller, 14a ... Valve opening control signal
Claims (3)
優先的に吸着する吸着剤を充填した２塔の吸着塔を用い
て圧力変動吸着分離法により酸素富化ガスを製品ガスと
して回収するガス分離方法であって、 原料供給端から原料ガスが供給されて吸着工程を行って
いる第１の塔の製品出口端から製品ガスを導出して製品
ガス貯槽に供給しながら、該製品ガスの一部を第２の塔
の製品出口端から塔内に導入しつつ原料供給端から塔内
のガスを放出するパージ排気を行うことにより吸着剤の
再生工程を行う工程と、 上記工程終了後の第１の塔と第２の塔とを製品出口端で
連通させ、吸着工程を終了して塔内に圧力を保持した第
１の塔から再生工程を終了して低い圧力にある第２の塔
へガスを回収するとともに、第１の塔の原料供給端から
系外へガスを放出する工程と、 上記工程終了後の第１の塔から引続きガスを系外に放出
して塔内の圧力を下げることにより、窒素を吸着した吸
着剤から窒素ガスを脱着させるとともに、第２の塔にお
いては、製品ガス貯槽に貯えられた製品ガスを第２の塔
の製品出口端から導入しながら、同時に原料供給端から
原料ガスを供給して塔内の圧力を上昇させる工程と、 上記工程終了後の第１の塔から引続きガスを系外に放出
して塔内の圧力を更に下げることにより、窒素を吸着し
た吸着剤から窒素ガスを脱着させるとともに、第２の塔
においては、原料供給端から原料ガスを供給して塔内の
圧力を上昇させる工程と、の各工程を、第１及び第２の
吸着塔を順次切換えて連続的に行うことにより、製品ガ
スを継続して発生することを特徴とするガス分離方法。1. An oxygen-enriched gas is recovered as a product gas by a pressure fluctuation adsorption separation method using two adsorption columns packed with an adsorbent that preferentially adsorbs nitrogen in a source gas containing oxygen and nitrogen. A source gas is supplied from a source supply end, and a product gas is derived from a product outlet end of a first tower performing an adsorption step and supplied to a product gas storage tank. Performing a regenerating step of the adsorbent by performing a purge exhaust that releases gas in the tower from a raw material supply end while introducing a part of the gas into the tower from a product outlet end of the second tower; The first column and the second column are communicated at the product outlet end, and the regeneration process is completed from the first column, which has completed the adsorption process and maintained the pressure in the column, and has a second pressure at a low pressure. While collecting the gas in the tower, the gas was discharged from the raw material supply end of the first tower to the outside of the system. Releasing the gas from the first tower after the above-mentioned step, and continuously desorbing the nitrogen gas from the adsorbent having adsorbed nitrogen by releasing the gas to the outside of the system to reduce the pressure in the tower. In the tower, while introducing the product gas stored in the product gas storage tank from the product outlet end of the second tower, simultaneously supplying the raw material gas from the raw material supply end to increase the pressure in the column; After the completion, the gas is continuously discharged from the first column to the outside of the system to further reduce the pressure in the column, thereby desorbing the nitrogen gas from the adsorbent having adsorbed nitrogen, and supplying the raw material in the second column. The step of supplying the raw material gas from the end to increase the pressure in the tower is continuously performed by sequentially switching the first and second adsorption towers, thereby continuously generating the product gas. A gas separation method comprising:
優先的に吸着する吸着剤を充填した２塔の吸着塔を用い
て圧力変動吸着分離法により酸素富化ガスを製品ガスと
して回収するガス分離方法であって、 原料供給端から原料ガスが供給されて吸着工程を行って
いる第１の塔の製品出口端から製品ガスを導出して製品
ガス貯槽に供給しながら、該製品ガスの一部を第２の塔
の製品出口端から塔内に導入しつつ原料供給端から塔内
のガスを放出するパージ排気を行うことにより吸着剤の
再生工程を行う工程と、 上記工程終了後の第１の塔と第２の塔とを製品出口端で
連通させ、吸着工程を終了して塔内に圧力を保持した第
１の塔から再生工程を終了して低い圧力にある第２の塔
へガスを回収した後、第１の塔の原料供給端から系外へ
ガスを放出する工程と、 上記工程終了後の第１の塔から引続きガスを系外に放出
して塔内の圧力を下げることにより、窒素を吸着した吸
着剤から窒素ガスを脱着させるとともに、第２の塔にお
いては、製品ガス貯槽に貯えられた製品ガスを第２の塔
の製品出口端から導入しながら、同時に原料供給端から
原料ガスを供給して塔内の圧力を上昇させる工程と、 上記工程終了後の第１の塔から引続きガスを系外に放出
して塔内の圧力を更に下げることにより、窒素を吸着し
た吸着剤から窒素ガスを脱着させるとともに、第２の塔
においては、原料供給端から原料ガスを供給して塔内の
圧力を上昇させる工程と、の各工程を、第１及び第２の
吸着塔を順次切換えて連続的に行うことにより、製品ガ
スを継続して発生することを特徴とするガス分離方法。2. An oxygen-enriched gas is recovered as a product gas by a pressure fluctuation adsorption separation method using two adsorption columns packed with an adsorbent that preferentially adsorbs nitrogen in a source gas containing oxygen and nitrogen. A source gas is supplied from a source supply end, and a product gas is derived from a product outlet end of a first tower performing an adsorption step and supplied to a product gas storage tank. Performing a regenerating step of the adsorbent by performing a purge exhaust that releases gas in the tower from a raw material supply end while introducing a part of the gas into the tower from a product outlet end of the second tower; The first column and the second column are communicated at the product outlet end, and the regeneration process is completed from the first column, which has completed the adsorption process and maintained the pressure in the column, and has a second pressure at a low pressure. After recovering the gas to the tower, release the gas from the raw material supply end of the first tower to the outside of the system And a step of continuously releasing gas from the first tower after the above step to reduce the pressure in the tower, thereby desorbing nitrogen gas from the adsorbent that has adsorbed nitrogen, In the method, while introducing the product gas stored in the product gas storage tank from the product outlet end of the second column, simultaneously supplying the source gas from the raw material supply end to increase the pressure in the column; Subsequently, the gas is continuously discharged from the first column to the outside of the system to further reduce the pressure in the column, thereby desorbing the nitrogen gas from the adsorbent that has adsorbed nitrogen. Continuously increasing the pressure in the tower by supplying the raw material gas from the first and second adsorption towers in order to continuously generate the product gas. A gas separation method comprising:
制御手段により制御することを特徴とする請求項１又は
２記載のガス分離方法。3. The gas separation method according to claim 1, wherein the supply amount of the raw material gas to the adsorption tower is controlled by a flow rate control means.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21876197A JP3889125B2 (en) | 1997-08-13 | 1997-08-13 | Gas separation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21876197A JP3889125B2 (en) | 1997-08-13 | 1997-08-13 | Gas separation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1157375A true JPH1157375A (en) | 1999-03-02 |
| JP3889125B2 JP3889125B2 (en) | 2007-03-07 |
Family
ID=16724996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21876197A Expired - Fee Related JP3889125B2 (en) | 1997-08-13 | 1997-08-13 | Gas separation method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3889125B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008173284A (en) * | 2007-01-18 | 2008-07-31 | Teijin Pharma Ltd | Adsorption oxygen concentrator |
| JP2008214151A (en) * | 2007-03-06 | 2008-09-18 | Teijin Pharma Ltd | Oxygen concentrator |
| JP2019058299A (en) * | 2017-09-26 | 2019-04-18 | 株式会社メトラン | Oxygen concentrator |
-
1997
- 1997-08-13 JP JP21876197A patent/JP3889125B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008173284A (en) * | 2007-01-18 | 2008-07-31 | Teijin Pharma Ltd | Adsorption oxygen concentrator |
| JP2008214151A (en) * | 2007-03-06 | 2008-09-18 | Teijin Pharma Ltd | Oxygen concentrator |
| JP2019058299A (en) * | 2017-09-26 | 2019-04-18 | 株式会社メトラン | Oxygen concentrator |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3889125B2 (en) | 2007-03-07 |
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