JPH1025102A - Chlorine removal apparatus and oxygen separation by pressure swing adsorption - Google Patents
Chlorine removal apparatus and oxygen separation by pressure swing adsorptionInfo
- Publication number
- JPH1025102A JPH1025102A JP8183542A JP18354296A JPH1025102A JP H1025102 A JPH1025102 A JP H1025102A JP 8183542 A JP8183542 A JP 8183542A JP 18354296 A JP18354296 A JP 18354296A JP H1025102 A JPH1025102 A JP H1025102A
- Authority
- JP
- Japan
- Prior art keywords
- chlorine
- pressure swing
- oxygen
- swing adsorption
- gas
- 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.)
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- 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、例えば塩酸ガスと
酸素を触媒中で反応させて塩素を製造するプロセスから
排出される塩素を含有するプロセス排ガス等、圧力スイ
ング吸着法の障害となる塩素を含んでいるガスの予備処
理装置及び酸素の分離方法に関するものである。BACKGROUND OF THE INVENTION The present invention relates to a process for producing chlorine by reacting hydrochloric acid gas and oxygen in a catalyst to produce chlorine. The present invention relates to a pretreatment device for contained gas and a method for separating oxygen.
【０００２】[0002]
【従来の技術】化学プラントにおいて、各種化学工業プ
ロセスより発生するプロセス排ガスの有効利用は最近の
エネルギー事情から重要性が極めて高くなっている。2. Description of the Related Art In a chemical plant, effective utilization of process exhaust gas generated from various chemical industrial processes has become extremely important due to recent energy situations.
【０００３】プロセス排ガスから有効成分ガスを分離回
収する際、高純度の有効成分ガスを効率よく回収でき、
しかも工程が簡単で設備費が安いプロセスとして選択的
吸着方法を利用した圧力スイング吸着法がある。[0003] When separating and recovering an effective component gas from a process exhaust gas, a high-purity effective component gas can be efficiently recovered.
In addition, there is a pressure swing adsorption method using a selective adsorption method as a process in which the process is simple and the equipment cost is low.
【０００４】従来、ゼオライトなどの吸着剤を用いて空
気より酸素ガスを製造する、いわゆる圧力スイング吸着
法による酸素ガス製造方法はよく知られている。そして
酸素の製造に関してはこの方法の対象ガスは空気に限ら
れてきた。Conventionally, a method of producing oxygen gas from air using an adsorbent such as zeolite, that is, a so-called pressure swing adsorption method, is well known. As for the production of oxygen, the target gas of this method has been limited to air.
【０００５】しかしながら、近年の技術進歩により窒
素、二酸化炭素以外の不純物を含む高濃度の酸素を含有
するガスが化学プラントから排出されるようになってき
た。例えば、塩酸ガスと酸素を触媒中で反応させて塩素
を製造する方法が提案されているが（特開昭６２−２７
５１０４号公報）、このプロセスからはかなり高濃度の
酸素を含有するプロセス排ガスが発生し系外へ排出され
ていた。現在までに、このプロセス排ガスから酸素を圧
力スイング吸着法により回収する方法が提案されている
が（特開平３−２０５３０５号公報）、当該方法の問題
点としてプロセス排ガス中の成分の一つである塩素は、
圧力スイング吸着装置の主体である吸着塔に充填された
ゼオライト等の吸着剤に少量で強く吸着し、脱着再生を
不可能とする物質である。すなわち、プロセス排ガス中
成分の塩素によってゼオライトが劣化して吸着および脱
着の性能が低下し、酸素の分離選択性および分離回収の
効率が低下する。このようなゼオライト等の吸着剤の劣
化を防止するためにプロセス排ガス中の塩素を除去する
必要がある。However, due to recent technological advances, gases containing high concentrations of oxygen containing impurities other than nitrogen and carbon dioxide have been discharged from chemical plants. For example, a method of producing chlorine by reacting hydrochloric acid gas and oxygen in a catalyst has been proposed (Japanese Patent Laid-Open No. 62-27).
No. 5104), a process exhaust gas containing a considerably high concentration of oxygen was generated from this process and discharged out of the system. Until now, a method of recovering oxygen from the process exhaust gas by the pressure swing adsorption method has been proposed (Japanese Patent Laid-Open No. 3-205305). Chlorine is
It is a substance that strongly adsorbs in a small amount to an adsorbent such as zeolite filled in an adsorption tower, which is a main component of the pressure swing adsorption apparatus, and makes desorption regeneration impossible. That is, zeolite is degraded by chlorine in the component of the process exhaust gas, so that adsorption and desorption performance is reduced, and oxygen separation selectivity and separation recovery efficiency are reduced. In order to prevent the deterioration of the adsorbent such as zeolite, it is necessary to remove chlorine in the process exhaust gas.
【０００６】圧力スイング吸着法における成分ガス中の
不純物除去の予備処理装置としては、水素ガスを分離回
収する圧力スイング吸着装置の上流側に酸化鉄を充填し
た塔を設けたことを特徴とする圧力スイング吸着法にお
ける予備処理装置（特開昭６１−６４７８７号公報）が
提案されているが、この場合の不純物としてはコークス
炉ガス中の成分であるＨ2Ｓ、ＣＯＳ等の硫化物、Ｎ
Ｏ、タールミスト等の除去が対象であり、塩素の除去に
ついては記述されていない。また、特開昭５４−１７３
９２号公報においては、不純物として比較的分子量の大
きい炭化水素、ＮＯX、Ｈ2Ｓ、メルカプタン、ＮＨ3、
水蒸気を除去する予備浄化装置を有する水素回収のため
の圧力スイング吸着装置が提案されているが、この場合
でも塩素の除去についての記述はない。[0006] As a pretreatment device for removing impurities in the component gas in the pressure swing adsorption method, a column filled with iron oxide is provided upstream of the pressure swing adsorption device for separating and recovering hydrogen gas. A pretreatment apparatus (Japanese Patent Application Laid-Open No. 61-64787) for the swing adsorption method has been proposed. In this case, impurities such as sulfides such as H 2 S and COS in the coke oven gas and N
It is intended for removal of O, tar mist and the like, and does not describe removal of chlorine. Also, Japanese Patent Application Laid-Open No. 54-173
In 92 JP greater hydrocarbons relatively molecular weight as impurities, NO X, H 2 S, mercaptans, NH 3,
A pressure swing adsorption device for hydrogen recovery having a preliminary purification device for removing water vapor has been proposed, but even in this case, there is no description on the removal of chlorine.
【０００７】現在まで、塩酸ガスと酸素を触媒中で反応
させて塩素を製造する方法におけるプロセス排ガス中の
塩素を経済的および簡易的に除去する方法がなかったの
で、塩素によるゼオライト劣化のため圧力スイング吸着
法による酸素回収は圧力スイング吸着装置の運転時間と
共に回収酸素濃度および酸素回収率が低下する問題があ
るが、もしこのプロセス排ガス中の塩素を除去すること
ができるならば、ゼオライト劣化の問題を解決でき圧力
スイング吸着法による酸素回収は長期に安定した性能が
得られることから、その経済的メリットは大きい。Until now, there has been no method for economically and simply removing chlorine in process exhaust gas in a method for producing chlorine by reacting hydrochloric acid gas and oxygen in a catalyst. Oxygen recovery by the swing adsorption method has the problem that the recovered oxygen concentration and the oxygen recovery rate decrease with the operation time of the pressure swing adsorption device, but if chlorine in this process exhaust gas can be removed, the problem of zeolite deterioration will occur. And oxygen recovery by the pressure swing adsorption method can provide stable performance for a long period of time.
【０００８】[0008]
【発明が解決しようとする課題】本発明の課題は、圧力
スイング吸着法による酸素回収において障害となる塩素
ガスを除去し、塩酸ガスと酸素を触媒中で反応させて塩
素を製造するプロセス排ガスから圧力スイング吸着法に
より酸素を回収することができるプロセスのための塩素
の除去装置及び酸素の分離方法を提供することを目的と
する。SUMMARY OF THE INVENTION An object of the present invention is to remove chlorine gas, which is an obstacle in oxygen recovery by the pressure swing adsorption method, and to react hydrochloric acid gas and oxygen in a catalyst to produce chlorine from a process exhaust gas. An object of the present invention is to provide an apparatus for removing chlorine and a method for separating oxygen for a process capable of recovering oxygen by a pressure swing adsorption method.
【０００９】[0009]
【課題を解決するための手段】前述の目的は、本発明に
よれば、塩素と酸素を含有する混合ガスから圧力スイン
グ吸着法によって酸素ガスを分離回収する圧力スイング
吸着装置の入口側に活性炭を充填したカラムを設けるこ
とにより、圧力スイング吸着法における塩素の除去を可
能にし、酸素ガスを効率良く分離回収することを見出し
本発明を完成するに至った。According to the present invention, there is provided, according to the present invention, activated carbon at an inlet side of a pressure swing adsorption apparatus for separating and recovering oxygen gas from a mixed gas containing chlorine and oxygen by a pressure swing adsorption method. By providing a packed column, it was possible to remove chlorine in the pressure swing adsorption method, and it was found that oxygen gas was efficiently separated and recovered, and the present invention was completed.
【００１０】即ち、本発明は、塩素と酸素を含有する混
合ガスから圧力スイング吸着法によって酸素ガスを分離
回収する圧力スイング吸着装置の入口側に活性炭を充填
したカラムを設けたことを特徴とする圧力スイング吸着
法における塩素の除去装置及び、塩素と酸素を含有する
混合ガスから圧力スイング吸着法によって酸素ガスを分
離回収する圧力スイング吸着装置の入口側に活性炭を充
填したカラムを設け、圧力スイング吸着法により酸素ガ
スを分離する方法である。That is, the present invention is characterized in that a column filled with activated carbon is provided at the inlet side of a pressure swing adsorption apparatus for separating and recovering oxygen gas from a mixed gas containing chlorine and oxygen by a pressure swing adsorption method. A pressure swing adsorption column is provided on the inlet side of the pressure swing adsorption device that removes chlorine in the pressure swing adsorption method and a pressure swing adsorption device that separates and recovers oxygen gas from the mixed gas containing chlorine and oxygen by the pressure swing adsorption method. This is a method of separating oxygen gas by a method.
【００１１】[0011]
【発明の実施の形態】本発明に係る塩素の除去装置に使
用する活性炭は、一般にヤシ殻系活性炭と石炭系活性炭
に分類されるが、好ましくはヤシ殻系活性炭が望まし
い。ヤシ殻系活性炭を使用した場合、例えばプロセス排
ガス中の塩素０．１容量％は塩素の除去装置により完全
には除去され、また活性炭の触媒作用による塩酸ガスの
発生もないことから、ヤシ殻系活性炭を使用することで
塩素の除去は達成される。BEST MODE FOR CARRYING OUT THE INVENTION Activated carbon used in the chlorine removing apparatus according to the present invention is generally classified into coconut shell activated carbon and coal activated carbon, and preferably coconut shell activated carbon. When coconut shell activated carbon is used, for example, 0.1% by volume of chlorine in the process exhaust gas is completely removed by a chlorine removing device, and there is no generation of hydrochloric acid gas due to the catalytic action of activated carbon. Removal of chlorine is achieved by using activated carbon.
【００１２】以下に実施態様の例を示す。第１図に本発
明に係る塩素の除去装置を設置した酸素回収圧力スイン
グ吸着装置のフローチャート図を示す。以下、同図に従
って説明する。An example of the embodiment will be described below. FIG. 1 shows a flow chart of an oxygen recovery pressure swing adsorption apparatus provided with a chlorine removal apparatus according to the present invention. Hereinafter, description will be given with reference to FIG.
【００１３】酸素を含む塩素製造のプロセス排ガス１は
圧力スイング吸着装置の入口側に設置された活性炭を充
填した塩素の除去装置２ａまたは２ｂに導入され、プロ
セス排ガス中の塩素の除去を行う。塩素の除去装置を通
過したプロセス排ガスは塩素濃度計３にて塩素濃度を測
定する。塩素のリークが確認されたら他方の塩素の除去
装置２ａまたは２ｂに切り換えて塩素の除去を行う。塩
素がリークする程度に塩素を吸着した活性炭は加熱再生
することで次の塩素の除去に使用される。塩素が除去さ
れたプロセス排ガスは吸着剤としてゼオライト等を充填
した圧力スイング装置５ａ、５ｂまたは５ｃへ導入され
酸素を分離回収する。The process exhaust gas 1 for the production of chlorine containing oxygen is introduced into a chlorine removal device 2a or 2b filled with activated carbon installed at the inlet side of the pressure swing adsorption device to remove chlorine in the process exhaust gas. The chlorine concentration of the process exhaust gas passing through the chlorine removing device is measured by the chlorine concentration meter 3. When a chlorine leak is confirmed, the chlorine is removed by switching to the other chlorine removing device 2a or 2b. Activated carbon that has adsorbed chlorine to such an extent that chlorine is leaked is heated and regenerated to be used for the next removal of chlorine. The process exhaust gas from which chlorine has been removed is introduced into a pressure swing device 5a, 5b or 5c filled with zeolite or the like as an adsorbent to separate and recover oxygen.
【００１４】圧力スイング吸着法の操作は一般的な酸素
分離の方法に準じる。すなわち１塔以上の吸着塔に、順
次に吸着精製、均圧、減圧、真空脱気逆洗、昇圧の工程
を繰り返すことで酸素と酸素以外の成分ガスを分離し高
濃度の酸素を得ることができる。The operation of the pressure swing adsorption method conforms to a general oxygen separation method. That is, by sequentially repeating the steps of adsorption purification, equalization, decompression, vacuum degassing, backwashing, and pressure increase in one or more adsorption towers, oxygen and a component gas other than oxygen can be separated to obtain high concentration oxygen. it can.
【００１５】[0015]
【実施例】次に、本発明の方法を実施例でさらに詳細に
説明する。％は容量％である。 実施例１ 圧力スイング吸着装置の入口側にヤシ殻系活性炭ＰＣＢ
（東洋カルゴン株式会社製）１５ｋｇをそれぞれ充填し
た塩素の除去装置を設けた酸素の分離回収装置におい
て、圧力スイング吸着剤としてＣａ−Ｘ型ゼオライト
（ユニオン昭和株式会社製）７２ｋｇをそれぞれ充填し
た吸着塔を２．０×１０4Ｐａとした後に１５０秒間塩
素（０．１％）、酸素（５９．０％）、窒素（１６．０
％）、二酸化炭素（１４．０％）、アルゴン（１１．０
％）の組成のガスを８．１×１０5Ｐａとなるように操
作しながら１．１０Ｎｍ3導入し、塩素（不検出）、酸
素（８６．０％）、窒素（０．０％）、二酸化炭素
（０．０％）、アルゴン（１４．０％）の組成のガスを
０．４１Ｎｍ3を得た。続いて大気圧まで減圧しさらに
真空ポンプで２．０×１０4Ｐａまで減圧した。この操
作を１００００回繰り返し行った後にガス組成を分析し
た結果、塩素（不検出）、酸素（８５．０％）、窒素
（２．０％）、二酸化炭素（０．０％）、アルゴン（１
３．０％）の組成のガス０．４０Ｎｍ3を得た。Next, the method of the present invention will be described in more detail with reference to Examples. % Is volume%. Example 1 Coconut shell activated carbon PCB at the inlet side of pressure swing adsorption device
An adsorption tower filled with 72 kg of Ca-X type zeolite (manufactured by Union Showa Co., Ltd.) as a pressure swing adsorbent in an oxygen separation and recovery apparatus provided with a chlorine removing device filled with 15 kg (manufactured by Toyo Calgon Co., Ltd.). Was set to 2.0 × 10 4 Pa, chlorine (0.1%), oxygen (59.0%), nitrogen (16.0%) for 150 seconds.
%), Carbon dioxide (14.0%), argon (11.0%).
%) Of the gas was 1.10 nm 3 introduced with engineered to be 8.1 × 10 5 Pa to composition, chlorine (not detected), oxygen (86.0%), nitrogen (0.0%), 0.41 Nm 3 of a gas having a composition of carbon dioxide (0.0%) and argon (14.0%) was obtained. Subsequently, the pressure was reduced to atmospheric pressure and further reduced to 2.0 × 10 4 Pa with a vacuum pump. After repeating this operation 10,000 times, the gas composition was analyzed. As a result, chlorine (not detected), oxygen (85.0%), nitrogen (2.0%), carbon dioxide (0.0%), argon (1%) were used.
0.40 Nm 3 of a gas composition of (3.0%).
【００１６】比較例１ 圧力スイング吸着装置の入口側に塩素の除去装置を設け
ていない酸素の分離回収装置において、圧力スイング吸
着剤としてＣａ−Ｘ型ゼオライトを７２ｋｇ充填した吸
着塔を２．０×１０4Ｐａとした後に１５０秒間塩素
（０．１％）、酸素（５９．０％）、窒素（１６．０
％）、二酸化炭素（１４．０％）、アルゴン（１１．０
％）の組成のガスを８．１×１０5Ｐａとなるように操
作しながら１．１０Ｎｍ3導入し、塩素（不検出）、酸
素（８６．０％）、窒素（０．０％）、二酸化炭素
（０．０％）、アルゴン（１４．０％）の組成のガスを
０．４１Ｎｍ3を得た。続いて大気圧まで減圧しさらに
真空ポンプで２．０×１０4Ｐａまで減圧した。この操
作を１００００回繰り返し行った後にガス組成を分析し
た結果、塩素（不検出）、酸素（６９．０％）、窒素
（１６．０％）、二酸化炭素（４．０％）、アルゴン
（１１．０％）の組成のガス０．４０Ｎｍ3を得た。COMPARATIVE EXAMPLE 1 In an oxygen separation / recovery apparatus in which a chlorine removing apparatus was not provided on the inlet side of a pressure swing adsorption apparatus, an adsorption column filled with 72 kg of Ca-X type zeolite as a pressure swing adsorbent was 2.0 × After setting to 10 4 Pa, chlorine (0.1%), oxygen (59.0%), nitrogen (16.0)
%), Carbon dioxide (14.0%), argon (11.0%).
%) Of the gas was 1.10 nm 3 introduced with engineered to be 8.1 × 10 5 Pa to composition, chlorine (not detected), oxygen (86.0%), nitrogen (0.0%), 0.41 Nm 3 of a gas having a composition of carbon dioxide (0.0%) and argon (14.0%) was obtained. Subsequently, the pressure was reduced to atmospheric pressure and further reduced to 2.0 × 10 4 Pa with a vacuum pump. After repeating this operation 10,000 times, the gas composition was analyzed. As a result, chlorine (not detected), oxygen (69.0%), nitrogen (16.0%), carbon dioxide (4.0%), and argon (11%) were used. to obtain a gas 0.40 nm 3 in the composition of 2.0%).
【００１７】[0017]
【発明の効果】本発明の方法によれば、塩素と酸素を含
有した混合ガスから圧力スイング吸着法によって酸素ガ
スを分離回収する圧力スイング吸着装置の入口側に活性
炭を充填した塩素の除去装置を設置することにより、塩
素の影響を受けずに酸素を分離回収することのできる方
法を提供するもので、その工業的価値は非常に大きい。According to the method of the present invention, there is provided a chlorine removing apparatus in which activated carbon is filled at the inlet side of a pressure swing adsorption apparatus for separating and recovering oxygen gas from a mixed gas containing chlorine and oxygen by a pressure swing adsorption method. By providing the method, a method capable of separating and recovering oxygen without being affected by chlorine is provided, and its industrial value is very large.
【図１】本発明に係る圧力スイング吸着法における塩素
の除去装置を含むフローチャート図である。FIG. 1 is a flowchart including a chlorine removing device in a pressure swing adsorption method according to the present invention.
１ プロセス排ガス ２ａ，２ｂ 塩素の除去装置 ３ 塩素濃度計 ４ 圧縮機 ５ａ，５ｂ，５ｃ 圧力スイング吸着装置 ６〜２７ 切替弁 １６ 真空ポンプ ２３ 弁 ２４ ブロワー ２５ 流量調節機構 DESCRIPTION OF SYMBOLS 1 Process exhaust gas 2a, 2b Chlorine removal device 3 Chlorine concentration meter 4 Compressor 5a, 5b, 5c Pressure swing adsorption device 6-27 Switching valve 16 Vacuum pump 23 Valve 24 Blower 25 Flow rate adjustment mechanism
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山田 国博 福岡県大牟田市浅牟田町30番地 三井東圧 化学株式会社内 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Kunihiro Yamada, Inventor: 30 Asamuta-cho, Omuta-shi, Fukuoka Prefecture Mitsui Toatsu Chemical Co., Ltd.
Claims (4)
イング吸着法によって酸素ガスを分離回収する圧力スイ
ング吸着装置の入口側に活性炭を充填したカラムを設け
たことを特徴とする圧力スイング吸着法における塩素の
除去装置。1. A pressure swing adsorption method characterized in that a column filled with activated carbon is provided at the inlet side of a pressure swing adsorption apparatus for separating and recovering oxygen gas from a mixed gas containing chlorine and oxygen by a pressure swing adsorption method. Equipment for chlorine removal in
イング吸着法によって酸素ガスを分離回収する圧力スイ
ング吸着装置の入口側に活性炭を充填したカラムを設
け、圧力スイング吸着法により酸素ガスを分離する方
法。2. A column filled with activated carbon is provided at the inlet side of a pressure swing adsorption apparatus for separating and recovering oxygen gas from a mixed gas containing chlorine and oxygen by a pressure swing adsorption method, and the oxygen gas is separated by the pressure swing adsorption method. how to.
素、アルゴンよりなる請求項２記載の方法。3. The method according to claim 2, wherein the mixed gas comprises chlorine, oxygen, nitrogen, carbon dioxide, and argon.
装置のカラムに充填した活性炭がヤシ殻系活性炭である
請求項２記載の方法。4. The process according to claim 2, wherein the activated carbon packed in the column of the chlorine removal device on the inlet side of the pressure swing adsorption device is coconut shell activated carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8183542A JPH1025102A (en) | 1996-07-12 | 1996-07-12 | Chlorine removal apparatus and oxygen separation by pressure swing adsorption |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8183542A JPH1025102A (en) | 1996-07-12 | 1996-07-12 | Chlorine removal apparatus and oxygen separation by pressure swing adsorption |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1025102A true JPH1025102A (en) | 1998-01-27 |
Family
ID=16137645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8183542A Pending JPH1025102A (en) | 1996-07-12 | 1996-07-12 | Chlorine removal apparatus and oxygen separation by pressure swing adsorption |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1025102A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008029940A1 (en) | 2006-09-06 | 2008-03-13 | Sumitomo Chemical Company, Limited | Start-up method |
| WO2010067751A1 (en) | 2008-12-09 | 2010-06-17 | 住友化学株式会社 | Method for manufacturing chlorine |
| WO2010073888A1 (en) | 2008-12-22 | 2010-07-01 | 住友化学株式会社 | Chlorine manufacturing method |
| JP2020018977A (en) * | 2018-08-02 | 2020-02-06 | ダイキン工業株式会社 | Oxygen concentrator |
-
1996
- 1996-07-12 JP JP8183542A patent/JPH1025102A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008029940A1 (en) | 2006-09-06 | 2008-03-13 | Sumitomo Chemical Company, Limited | Start-up method |
| US8168154B2 (en) | 2006-09-06 | 2012-05-01 | Sumitomo Chemical Company, Limited | Start-up method for producing chlorine |
| WO2010067751A1 (en) | 2008-12-09 | 2010-06-17 | 住友化学株式会社 | Method for manufacturing chlorine |
| WO2010073888A1 (en) | 2008-12-22 | 2010-07-01 | 住友化学株式会社 | Chlorine manufacturing method |
| JP2020018977A (en) * | 2018-08-02 | 2020-02-06 | ダイキン工業株式会社 | Oxygen concentrator |
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