JPH0919621A - Deoxidizing device - Google Patents
Deoxidizing deviceInfo
- Publication number
- JPH0919621A JPH0919621A JP7170750A JP17075095A JPH0919621A JP H0919621 A JPH0919621 A JP H0919621A JP 7170750 A JP7170750 A JP 7170750A JP 17075095 A JP17075095 A JP 17075095A JP H0919621 A JPH0919621 A JP H0919621A
- Authority
- JP
- Japan
- Prior art keywords
- cathode
- cathode side
- anode
- electrolyte
- water
- 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.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Fuel Cell (AREA)
- Cold Air Circulating Systems And Constructional Details In Refrigerators (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、例えば、冷蔵庫庫
内の酸素濃度を低減するのに利用される脱酸素装置に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deoxidizer used for reducing the oxygen concentration in a refrigerator, for example.
【０００２】[0002]
【従来の技術】従来の脱酸素装置は、酸素を化学的に吸
着する物質を用いて酸素濃度を低減させる方法が主に用
いられてきた。また、酸素イオン伝導性の固体電解質と
電解質を挟持する形でガス拡散電極であるアノ−ドとカ
ソ−ドを配し、電気分解によってカソ−ド側の酸素をア
ノ−ド側にポンピングするような酸素ポンプ装置も考案
されている。2. Description of the Related Art A conventional deoxidizing apparatus has mainly used a method of reducing the oxygen concentration by using a substance that chemically adsorbs oxygen. In addition, an anode and a cathode, which are gas diffusion electrodes, are arranged so as to sandwich the oxygen-ion conductive solid electrolyte and the electrolyte, and oxygen on the cathode side is pumped to the anode side by electrolysis. Various oxygen pump devices have also been devised.
【０００３】[0003]
【発明が解決しようとする課題】酸素の化学吸着による
脱酸素法は、吸着剤の酸素の吸着量が飽和に達すると、
それ以上の脱酸素効果がなくなるため、吸着剤の使い捨
てが主流であり、連続的に脱酸素を行うことは困難であ
った。また、酸素イオン伝導性の電解質を用いた酸素ポ
ンプ装置は、電解質として高温で酸素イオン伝導性を有
するジルコニアなどのセラミクス固体電解質などが用い
られている。これらセラミクス固体電解質は、電解質の
酸素イオン伝導度を確保するため少なくとも５００℃程
度以上の高温に保つ必要があった。In the deoxidation method by chemisorption of oxygen, when the adsorbed amount of oxygen of the adsorbent reaches saturation,
Since the deoxidizing effect is further lost, the disposable adsorbent is the mainstream, and it is difficult to continuously perform deoxidizing. Further, in the oxygen pump device using the oxygen ion conductive electrolyte, a ceramic solid electrolyte such as zirconia having oxygen ion conductivity at high temperature is used as the electrolyte. These ceramic solid electrolytes had to be kept at a high temperature of at least about 500 ° C. or more in order to secure the oxygen ion conductivity of the electrolyte.
【０００４】[0004]
【課題を解決するための手段】本発明の脱酸素装置は、
アノ−ド、ガス拡散電極からなるカソ−ド、両電極に挟
持された電解質、電解質に水分を供給する手段、両電極
に直流電圧を印加して水を電気分解するための電圧印加
手段、カソ−ド側空間とアノ−ド側空間を隔離する隔離
手段、およびカソ−ド自身の表面またはカソ−ド近傍に
設けた触媒層を具備し、カソ−ド側から発生した水素と
カソ−ド側空間に存在する酸素とを前記触媒層によって
触媒燃焼し、カソ−ド側空間の酸素濃度を低減させるも
のである。The deoxidizing apparatus of the present invention comprises:
Anode, cathode consisting of gas diffusion electrode, electrolyte sandwiched between both electrodes, means for supplying water to the electrolyte, voltage application means for applying a DC voltage to both electrodes to electrolyze water, cathode -Hydrogen generated from the cathode side and the cathode side, comprising an isolation means for isolating the cathode side space from the anode side space, and a catalyst layer provided on the surface of the cathode itself or in the vicinity of the cathode. Oxygen existing in the space is catalytically burned by the catalyst layer to reduce the oxygen concentration in the cathode side space.
【０００５】また、本発明の脱酸素装置は、アノ−ド、
ガス拡散電極からなるカソ−ド、両電極に挟持された電
解質、電解質に水分を供給する手段、両電極に直流電圧
を印加して水を電気分解するための電圧印加手段、およ
びカソ−ド側空間とアノ−ド側空間を隔離する隔離手段
を具備し、カソード側に生成した水素イオンとカソ−ド
側空間に存在する酸素とを反応させて、カソ−ド側空間
の酸素濃度を低減させるものである。Further, the deoxidizing apparatus of the present invention includes an anode,
A cathode consisting of a gas diffusion electrode, an electrolyte sandwiched between both electrodes, a means for supplying water to the electrolyte, a voltage applying means for applying a DC voltage to both electrodes to electrolyze water, and a cathode side A separation means for separating the space and the anode side space is provided, and hydrogen ions generated on the cathode side are reacted with oxygen existing in the cathode side space to reduce the oxygen concentration in the cathode side space. It is a thing.
【０００６】さらに、本発明の脱酸素装置は、アノ−
ド、ガス拡散電極からなるカソ−ド、両電極に挟持され
た電解質、電解質に水分を供給する手段、両電極に直流
電圧を印加して水を電気分解するための電圧印加手段、
およびカソ−ド側空間とアノ−ド側空間を隔離する隔離
手段を具備する水の電気分解装置と、ガス拡散電極から
なるアノ−ドとカソ−ド、前記両電極に挟持された電解
質、およびアノ−ド側空間とカソ−ド側空間を隔離する
隔離手段を具備する燃料電池とを、水の電気分解装置の
カソ−ド側空間と燃料電池のアノ−ド側空間が連通する
ように組み合わせて構成され、水の電気分解によって発
生した水素を燃料電池のアノ−ド側で燃料として消費
し、燃料電池のカソ−ド側で酸素を消費して燃料電池の
カソ−ド側空間の酸素濃度を低減させるものである。Further, the deoxidizer of the present invention is an anode
A cathode comprising a gas diffusion electrode, an electrolyte sandwiched between both electrodes, a means for supplying water to the electrolyte, a voltage application means for applying a DC voltage to both electrodes to electrolyze water,
And a water electrolyzer having a separating means for separating the cathode side space and the anode side space, an anode and a cathode consisting of gas diffusion electrodes, an electrolyte sandwiched between the electrodes, and A fuel cell having an isolation means for separating the anode side space and the cathode side space is combined so that the cathode side space of the water electrolyzer and the anode side space of the fuel cell communicate with each other. The hydrogen concentration generated by the electrolysis of water is consumed as fuel on the anode side of the fuel cell, and oxygen is consumed on the cathode side of the fuel cell, and the oxygen concentration in the cathode side space of the fuel cell is consumed. Is to reduce.
【０００７】ここで、電解質としては、水分を含む高分
子電解質または水分を含む酸性電解質で構成されるプロ
トン伝導体からなるものが好ましい。また、水の電気分
解装置および燃料電池のアノ−ドおよびカソ−ドは、カ
−ボン表面に触媒を担持したガス拡散電極によって構成
されるのが好ましい。本発明の冷蔵庫は、上記の脱酸素
装置を庫内の酸素濃度低減手段として備える。The electrolyte is preferably a proton conductor composed of a water-containing polymer electrolyte or a water-containing acidic electrolyte. Further, the anode and cathode of the water electrolyzer and fuel cell are preferably constituted by a gas diffusion electrode having a catalyst supported on the surface of the carbon. The refrigerator of the present invention includes the above deoxidation device as a means for reducing the oxygen concentration in the refrigerator.
【０００８】[0008]
【発明の実施の形態】以下、本発明の実施の形態を具体
例を示す図面を参照しながら説明する。 ［実施例１］図１は、本発明による脱酸素装置の構成を
模式的に示す断面図である。電解質１、および電解質１
を挟持するカソード２とアノード４はホットプレスによ
って一体に接合されている。カソード２とアノード４の
外側には、それぞれカソ−ド集電体３およびアノ−ド集
電体５が密接して設けられている。前記の電気分解用セ
ル本体のより詳細な構成を図５に示している。アノード
４およびカソードを接合した電解質１をアノード集電体
５およびカソード集電体３によって挟み、さらに電解質
および電極と集電体との密着性を保つためステンレス鋼
製の枠体３１および３２によって挟持し、枠体の貫通孔
３３および３４にボルトを通し、ナットで締め付けるこ
とにより電気分解用セルのユニットを構成している。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the drawings showing specific examples. [Embodiment 1] FIG. 1 is a sectional view schematically showing the construction of a deoxidizer according to the present invention. Electrolyte 1 and electrolyte 1
The cathode 2 and the anode 4 sandwiching the are sandwiched together by hot pressing. On the outside of the cathode 2 and the anode 4, a cathode current collector 3 and an anode current collector 5 are provided in close contact with each other. A more detailed structure of the electrolysis cell body is shown in FIG. The electrolyte 1 in which the anode 4 and the cathode are joined is sandwiched by the anode current collector 5 and the cathode current collector 3, and further sandwiched by the stainless steel frames 31 and 32 to maintain the adhesion between the electrolyte and the electrode and the current collector. Then, a bolt is passed through the through holes 33 and 34 of the frame body and tightened with a nut to form a unit of the cell for electrolysis.
【０００９】上記の電気分解用セルのユニットは、電解
質１に水分を供給する水タンク８と、カソ−ド側空間１
１とアノ−ド側空間を隔離する隔離手段１０とを一体と
した容器内に固定されている。カソ−ド集電体３および
アノ−ド集電体５には、直流電圧を印加する電圧印加手
段６が接続されている。９は水を示し、７はアノード４
から電気分解によって発生する酸素を表している。図示
の例では、電解質およびアノードが直接水と接する構成
としているが、アノードが多孔質電極であればアノード
から電解質およびカソードに水分を供給するようにして
もよい。The unit of the above electrolysis cell comprises a water tank 8 for supplying water to the electrolyte 1 and a cathode side space 1.
1 and an isolation means 10 for isolating the space on the anode side are fixed in a container. A voltage applying means 6 for applying a DC voltage is connected to the cathode current collector 3 and the anode current collector 5. 9 indicates water, 7 indicates the anode 4
Represents oxygen generated by electrolysis. In the illustrated example, the electrolyte and the anode are in direct contact with water, but if the anode is a porous electrode, water may be supplied from the anode to the electrolyte and the cathode.
【００１０】この例では、電解質１に、デュポン社から
ナフィオン膜の名で販売されている高分子からなるイオ
ン交換膜を用いた。また、カソード２には、表面に白金
の超微粒子を担持したカ−ボン粉末とフッ素樹脂粉末の
混合物を加圧成形して適度な撥水性を持たせた多孔質ガ
ス拡散電極を用い、アノード４には、同様に表面に白金
の超微粒子を担持したカ−ボン粉末とフッ素樹脂粉末の
混合物を加圧成形して適度な撥水性を持たせた多孔質電
極を用いた。カソード集電体３およびアノード集電体５
には、カ−ボン製のハニカム状の板を用いた。カソ−ド
側空間１１の容積は１リットルとした。また、電気分解
によって発生した水素がカソ−ド表面で酸素と反応して
水分に変換する際、充分に反応が起こらず、未反応の水
素が残存する可能性を想定して、カソ−ド側のカ−ボン
製ハニカム状集電体３には、触媒燃焼用の白金触媒を担
持した。なお、１２はカソ−ド側空間を開閉可能とする
ために取り付けた扉を表し、扉を閉じた状態ではカソー
ド側空間１１は外部とは隔離される。In this example, as the electrolyte 1, an ion exchange membrane made of a polymer sold by DuPont under the name of Nafion membrane was used. Further, as the cathode 2, a porous gas diffusion electrode having an appropriate water repellency by pressure molding a mixture of carbon powder having platinum ultrafine particles on the surface and fluororesin powder is used, and the anode 4 Similarly, a porous electrode having a suitable water repellency was obtained by press-molding a mixture of carbon powder having platinum ultrafine particles on its surface and fluororesin powder. Cathode current collector 3 and anode current collector 5
For this, a honeycomb-shaped plate made of carbon was used. The volume of the cathode side space 11 was 1 liter. Also, assuming that hydrogen generated by electrolysis reacts with oxygen on the surface of the cathode and is converted to water, the reaction may not sufficiently occur and unreacted hydrogen may remain. The carbon-made honeycomb-shaped current collector 3 of No. 1 was loaded with a platinum catalyst for catalytic combustion. Reference numeral 12 represents a door attached to open / close the cathode side space, and the cathode side space 11 is isolated from the outside when the door is closed.
【００１１】上記構成の脱酸素装置において、電圧印加
手段６によりアノ−ド４とカソ−ド２の間に電気分解の
ための電圧を印加すると、通常は水が電気分解すること
によってアノ−ド４側から酸素が、カソ−ド２側から水
素がそれぞれ発生する。この時カソ−ド側から発生した
水素とカソ−ド側空間１１に存在する酸素とをカソ−ド
表面の触媒能により触媒燃焼させることによって、また
はカソ−ド近傍に設けた触媒層、上例では集電体３に担
持した触媒層により触媒燃焼させることによって、カソ
−ド側空間の酸素濃度を低減させることが可能である。In the deoxidizing apparatus having the above structure, when a voltage for electrolysis is applied between the anode 4 and the cathode 2 by the voltage applying means 6, usually the water is electrolyzed to cause the anode. Oxygen is generated from the 4 side and hydrogen is generated from the cathode 2 side. At this time, the hydrogen generated from the cathode side and the oxygen existing in the cathode side space 11 are catalytically burned by the catalytic ability of the cathode surface, or a catalyst layer provided in the vicinity of the cathode, the above example. Then, it is possible to reduce the oxygen concentration in the cathode side space by catalytically burning with the catalyst layer carried on the current collector 3.
【００１２】本実施例では、室温下において前記電気分
解用セルに１００ｍＡ／ｃｍ2の定電流を印加し、１時
間電解を連続的に行ったところ、当初２１％であったカ
ソ−ド側空間中の酸素濃度が約１５％に減少した。ま
た、さらに連続して電解を行ったところ、少なくとも酸
素濃度が約５％に減少するまでは、経過時間に対して直
線的に酸素濃度が低下し、本発明の有効性が確認され
た。また、この時カソ−ド側空間の湿度を測定したとこ
ろ、当初３０％であった湿度が７０％まで増加してい
た。従って、カソード側に生成する水分によって、カソ
ード側空間を加湿することができる。このように加湿で
きることは冷蔵庫の特に野菜質の脱酸素装置として好ま
しい。In this example, when a constant current of 100 mA / cm 2 was applied to the electrolysis cell at room temperature and electrolysis was continuously performed for 1 hour, the cathode side space was initially 21%. The oxygen concentration inside was reduced to about 15%. Further, when the electrolysis was further continuously performed, the oxygen concentration decreased linearly with the passage of time until at least the oxygen concentration decreased to about 5%, confirming the effectiveness of the present invention. Further, when the humidity in the cathode side space was measured at this time, the humidity which was initially 30% increased to 70%. Therefore, the space on the cathode side can be humidified by the water generated on the cathode side. Being able to humidify in this manner is preferable as a deoxidizer for vegetables, especially in a refrigerator.
【００１３】［実施例２］図２は、本実施例の脱酸素装
置の構成を模式的に示す断面図である。図１と同一の要
素には同一の番号を付している。本実施例では、電解質
１としてイオン交換膜（旭硝子製）を用い、電圧印加手
段６として印加電圧可変の低電圧直流電源を用いた。ま
た、電解質およびアノードに水を供給する手段として、
カソード側空間１１に集電体３と密接して設けた水分を
凝縮する手段あるいはトラップする手段１３と、凝縮あ
るいはトラップした水分をカソ−ド側空間とアノ−ド側
空間を隔離する隔離手段１０の側面から電解質へ戻すウ
イック１４を有する。水分を凝縮する手段あるいはトラ
ップする手段１３は、不織布からなる多孔質シ−トに、
ガスの透過性を良くするために直径２ｍｍの多数の孔を
あけたものである。[Embodiment 2] FIG. 2 is a sectional view schematically showing the construction of the deoxidizer of this embodiment. The same elements as those in FIG. 1 are denoted by the same numbers. In this example, an ion exchange membrane (made by Asahi Glass) was used as the electrolyte 1, and a low-voltage DC power source with a variable applied voltage was used as the voltage applying means 6. In addition, as a means for supplying water to the electrolyte and the anode,
A means 13 for condensing or trapping water, which is provided in close contact with the current collector 3 in the cathode side space 11, and an isolating means 10 for isolating the condensed or trapped water from the cathode side space and the anode side space. It has a wick 14 for returning to the electrolyte from the side surface of. Means 13 for condensing or trapping water is a porous sheet made of non-woven fabric,
A large number of holes having a diameter of 2 mm are formed in order to improve the gas permeability.
【００１４】上記の構成によると、カソード側で発生し
た水分は、手段１３により凝縮あるいはトラップされ、
ウイック１４により電解質に戻されるので、外部からの
水の補給を極力少なくすることができる。また、アノ−
ドとカソ−ドの間に印加する電圧を、通常の水の電気分
解が起こる電位より低く設定しても、カソ−ド側空間の
酸素濃度を低減させることが可能である。すなわち、カ
ソ−ド側ではカソ−ド側空間に存在する酸素の還元反応
が起こり、アノ−ド側では水の酸化反応によって酸素が
発生する。このような反応が起こった場合、カソ−ド側
では酸素還元反応によって生成した酸素イオンは、直ち
に電解質中の水素イオンと反応して水になるため、カソ
−ド自身の表面で水を生成することが可能で、水素を発
生することなく、安全にカソ−ド側空間の脱酸素を行う
ことが可能である。According to the above construction, the water generated on the cathode side is condensed or trapped by the means 13,
Since it is returned to the electrolyte by the wick 14, replenishment of water from the outside can be minimized. Also,
Even if the voltage applied between the cathode and the cathode is set lower than the potential at which normal electrolysis of water occurs, the oxygen concentration in the cathode side space can be reduced. That is, on the cathode side, a reduction reaction of oxygen existing in the cathode side space occurs, and on the anode side, oxygen is generated by the oxidation reaction of water. When such a reaction occurs, oxygen ions generated by the oxygen reduction reaction on the cathode side immediately react with hydrogen ions in the electrolyte to become water, and thus water is generated on the surface of the cathode itself. It is possible to safely deoxidize the cathode side space without generating hydrogen.
【００１５】従って、電極が充分な触媒能を有していれ
ば、アノ−ド側とカソ−ド側の酸素濃度差に起因する電
圧に過電圧を加算した電圧を印加することで脱酸素が可
能であり、水の電気分解を行う電圧より、より低い電圧
で脱酸素が可能であるため、消費電力を低減することが
可能である。さらに、電位を制御することで、前記の水
の電気分解によって発生した水素を触媒燃焼させること
による脱酸素と、カソ−ド側空間に存在する酸素を直接
還元して、電解質中に存在する水素イオンとの反応によ
る脱酸素を同時に起こすことも可能である。Therefore, if the electrode has sufficient catalytic ability, deoxidation can be performed by applying a voltage obtained by adding an overvoltage to the voltage caused by the difference in oxygen concentration between the anode side and the cathode side. Therefore, deoxidation can be performed at a voltage lower than the voltage at which water is electrolyzed, and thus power consumption can be reduced. Further, by controlling the electric potential, deoxygenation by catalytic combustion of hydrogen generated by the electrolysis of the water and oxygen directly present in the cathode side space are directly reduced, and hydrogen present in the electrolyte is reduced. It is also possible to cause deoxidation by reaction with ions at the same time.
【００１６】本実施例では、室温下において前記電気分
解用セルに０．８５Ｖの定電圧を連続的に印加した。
０．８５Ｖの印加電圧は、水の電気分解が起こる電圧よ
り低い電圧である。カソ−ド側空間の酸素濃度を測定し
たところ、電圧印加前には２１％であったカソ−ド側空
間中の酸素濃度が、１時間後には約１８％に減少した。
また、さらに連続して電解を行ったところ、少なくとも
酸素濃度が約５％に減少するまでは、徐々に酸素濃度が
低下し、本発明の有効性が確認された。また、本実施例
では、カソ−ド側のハニカム状集電体に、実施例１で設
けたような触媒燃焼用の触媒層を設けなかったが、カソ
−ド側空間の水素濃度を測定したところ、検出できなか
った。In this example, a constant voltage of 0.85 V was continuously applied to the electrolysis cell at room temperature.
The applied voltage of 0.85 V is lower than the voltage at which electrolysis of water occurs. When the oxygen concentration in the cathode side space was measured, the oxygen concentration in the cathode side space, which was 21% before the voltage application, decreased to about 18% after 1 hour.
Further, when electrolysis was further continuously performed, the oxygen concentration gradually decreased at least until the oxygen concentration decreased to about 5%, and the effectiveness of the present invention was confirmed. Further, in this example, the honeycomb-shaped current collector on the cathode side was not provided with the catalyst layer for catalytic combustion as provided in Example 1, but the hydrogen concentration in the cathode side space was measured. However, it could not be detected.
【００１７】［実施例３］図３は、本実施例の脱酸素装
置の構成を模式的に示す断面図である。本実施例の脱酸
素装置は、前記のような水の電気分解装置と燃料電池と
を、水の電気分解装置のカソ−ド側空間と燃料電池のア
ノ−ド側空間が連通するように組み合わせて構成されて
いる。すなわち、水の電気分解装置は、電解質１、これ
を挟持するアノ−ド４とガス拡散電極からなるカソ−ド
２、電解質に水分を供給するタンク８、両電極に直流電
圧を印加して水を電気分解するための電圧印加手段６、
およびカソ−ド側空間とアノ−ド側空間を隔離する隔離
手段１０から構成されている。また、燃料電池は、ガス
拡散電極からなるアノ−ド１８とカソ−ド１６、両電極
に挟持された電解質１５、および集電体１７、１９から
なり、さらに前記の隔離手段１０が燃料電池のアノ−ド
側空間とカソ−ド側空間を隔離する役割を果たしてい
る。なお、２０は燃料電池を放電するための手段、２１
は燃料電池の放電電流を制御する手段あるいは燃料電池
の起電圧をモニタ−する手段、２２は燃料電池のカソ−
ド側空間であり、燃料電池のアノード側空間は水の電気
分解装置のカソード側空間１１と共通となっている。[Embodiment 3] FIG. 3 is a sectional view schematically showing the construction of the deoxidizer of this embodiment. In the deoxidizer of this embodiment, the water electrolyzer and the fuel cell as described above are combined so that the cathode side space of the water electrolyzer and the anode side space of the fuel cell communicate with each other. Is configured. That is, the electrolyzer of water comprises an electrolyte 1, a cathode 2 holding the anode 4 and a cathode 2 composed of a gas diffusion electrode, a tank 8 for supplying water to the electrolyte, and a DC voltage applied to both electrodes of the water. Voltage applying means 6 for electrolyzing
It is also composed of an isolation means 10 for isolating the cathode side space and the anode side space. The fuel cell comprises an anode 18 and a cathode 16 which are gas diffusion electrodes, an electrolyte 15 sandwiched between the electrodes, and current collectors 17 and 19, and the isolation means 10 is a fuel cell. It plays a role of separating the space on the anode side and the space on the cathode side. In addition, 20 is a means for discharging the fuel cell, 21
Is a means for controlling the discharge current of the fuel cell or a means for monitoring the electromotive voltage of the fuel cell, and 22 is a cathode of the fuel cell.
The anode side space of the fuel cell is common with the cathode side space 11 of the water electrolyzer.
【００１８】この例では、電解質１および１５には、デ
ュポン社からナフィオン膜の名で販売されているイオン
交換膜を用いた。また、電極２、４、１６および１８に
は、表面に白金の超微粒子を担持したカ−ボン粉末とフ
ッ素樹脂粉末の混合物を加圧成形して適度な撥水性を持
たせた多孔質電極を用い、集電体３、５、１７および１
９には、金属製の穴あき板を用いた。さらに、電圧印加
手段６には印加電流可変の直流電源を用いた。In this example, the electrolytes 1 and 15 used were ion exchange membranes sold by DuPont under the name of Nafion membrane. Further, as the electrodes 2, 4, 16 and 18, a porous electrode having a suitable water repellency by press-molding a mixture of carbon powder carrying platinum ultrafine particles on its surface and fluororesin powder. Used, current collectors 3, 5, 17 and 1
For 9, a perforated plate made of metal was used. Further, the voltage applying means 6 uses a DC power supply whose applied current is variable.
【００１９】水の電気分解装置のアノ−ドとカソ−ドの
間に電気分解のための電圧を印加すると、通常は水が電
気分解することによって水の電気分解装置のアノ−ド４
側から酸素が、カソ−ド２側から水素がそれぞれ発生す
る。この時水の電気分解装置のカソ−ド側から発生した
水素は、燃料電池の燃料として燃料電池のアノ−ド１８
に供給される。燃料電池のカソ−ド１６では、燃料電池
のカソ−ド側空間に存在する酸素の還元反応が起こり、
燃料電池のアノ−ド側からイオン伝導してきた水素イオ
ンと反応して燃料電池のカソ−ド側空間の酸素濃度を低
減させると同時に水分を発生する。When a voltage for electrolysis is applied between the anode and cathode of the water electrolyzer, water is usually electrolyzed to cause the anode 4 of the water electrolyzer.
Side to generate oxygen, and the cathode 2 side to generate hydrogen. At this time, hydrogen generated from the cathode side of the electrolyzer of water is used as fuel for the fuel cell, and is used as an anode of the fuel cell.
Is supplied to. In the cathode 16 of the fuel cell, a reduction reaction of oxygen existing in the cathode side space of the fuel cell occurs,
It reacts with hydrogen ions that have been ion-conducted from the anode side of the fuel cell to reduce the oxygen concentration in the cathode side space of the fuel cell, and at the same time generate water.
【００２０】また、燃料電池のアノ−ドとカソ−ドの間
の起電力をモニタ−すると、燃料電池のカソ−ド側空間
２２の酸素濃度が低下し、これによって燃料電池の起電
力が低下する。このため、充分に燃料電池のカソ−ド側
空間の脱酸素を達成した後には、水の電気分解装置に電
圧を印加する装置を制御して余分な電解を抑制し、省電
力化を図ると同時に、余分な水素の発生を抑制し、安全
に燃料電池のカソ−ド側空間２２の脱酸素を行うことが
可能である。When the electromotive force between the anode and cathode of the fuel cell is monitored, the oxygen concentration in the space 22 on the cathode side of the fuel cell decreases, which reduces the electromotive force of the fuel cell. To do. For this reason, after sufficiently achieving deoxidation of the cathode side space of the fuel cell, it is possible to control the device that applies a voltage to the water electrolyzer to suppress excessive electrolysis and save power. At the same time, it is possible to suppress the generation of excess hydrogen and safely deoxidize the cathode side space 22 of the fuel cell.
【００２１】本実施例では、室温下において前記電気分
解用セルに３００ｍＡ／ｃｍ2の定電流を印加し、３時
間電解を連続的に行ったところ、当初２０％であった燃
料電池のカソ−ド側空間（容積１リットル）中の酸素濃
度が約１９％に減少した。また、さらに連続して電解を
行ったところ、少なくとも酸素濃度が約５％に減少する
までは、経過時間に対して直線的に酸素濃度が低下し、
本発明の有効性が確認された。また、この時燃料電池の
カソ−ド側空間の湿度を測定したところ、当初３０％で
あった湿度が７０％まで増加していた。In this example, a constant current of 300 mA / cm 2 was applied to the electrolysis cell at room temperature and electrolysis was continuously performed for 3 hours. The oxygen concentration in the side space (volume 1 liter) was reduced to about 19%. Further, when the electrolysis was further continuously performed, the oxygen concentration decreased linearly with time until at least the oxygen concentration decreased to about 5%,
The effectiveness of the present invention has been confirmed. Further, when the humidity in the cathode side space of the fuel cell was measured at this time, the humidity which was initially 30% increased to 70%.
【００２２】［実施例４］図４は、本実施例の脱酸素装
置を模式的に示す断面図である。本実施例では、電解質
に水を供給する手段として、燃料電池のカソード側空間
２２に集電体１７と密接して設けた水分を凝縮する手段
あるいはトラップする手段１３と、凝縮あるいはトラッ
プした水分を隔離手段１０の側面から水の電気分解装置
の電解質へ戻すウイック１４を有する。水分を凝縮する
手段あるいはトラップする手段１３は、不織布からなる
多孔質シ−トに、ガスの透過性を良くするために直径１
ｍｍの多数の孔をあけたものである。この他の構成は実
施例３と同様である。この構成によると、燃料電池のカ
ソード１６側で発生した水分は、手段１３により凝縮あ
るいはトラップされ、ウイック１４により水の電気分解
装置の電解質に戻されるので、外部からの水の補給を極
力少なくすることができる。[Embodiment 4] FIG. 4 is a cross-sectional view schematically showing the deoxidizer of this embodiment. In this embodiment, as means for supplying water to the electrolyte, means for condensing or trapping water, which is provided in the cathode side space 22 of the fuel cell in close contact with the current collector 17, and means for condensing or trapping water, are used. It has a wick 14 which returns from the side of the isolation means 10 to the electrolyte of the water electrolyzer. The means 13 for condensing or trapping water has a diameter of 1 in order to improve gas permeability in a porous sheet made of a non-woven fabric.
It has a large number of holes of mm. The other structure is the same as that of the third embodiment. According to this configuration, the water generated on the cathode 16 side of the fuel cell is condensed or trapped by the means 13 and returned to the electrolyte of the water electrolyzer by the wick 14, so that replenishment of water from the outside is minimized. be able to.
【００２３】本実施例では、室温下において前記電気分
解用セルに１．４Ｖの定電圧を連続的に印加した。燃料
電池のカソ−ド側空間の酸素濃度を測定したところとこ
ろ、電圧印加前には２１％であったカソ−ド側空間中の
酸素濃度が、１時間後には約１７％に減少した。また、
さらに連続して電解を行ったところ、少なくとも酸素濃
度が約５％に減少するまでは、徐々に酸素濃度が低下
し、本発明の有効性が確認された。In this example, a constant voltage of 1.4 V was continuously applied to the electrolysis cell at room temperature. When the oxygen concentration in the cathode side space of the fuel cell was measured, the oxygen concentration in the cathode side space, which was 21% before the voltage application, decreased to about 17% after 1 hour. Also,
When electrolysis was further continuously performed, the oxygen concentration gradually decreased at least until the oxygen concentration decreased to about 5%, confirming the effectiveness of the present invention.
【００２４】［実施例５］図６は、本発明の脱酸素装置
を野菜室の上部に設置した冷蔵庫を示している。簡単の
ため、扉は除いてある。３５は冷蔵庫の外容器であり、
その内部は隔壁により冷凍室３６、冷蔵室３７、および
野菜室３８に仕切られている。野菜室３８の容量は５０
Ｌである。この野菜室３８を脱酸素するため、その上部
に、図３の脱酸素装置３９を燃料電池のカソ−ド側空間
２２を野菜室と連通させて取り付けている。４０はプラ
スチック製の水タンクで、タンク下部から電気分解用セ
ルのアノ−ドおよび電解質に水を供給できる構造になっ
ている。そして、タンクは冷蔵庫前面からスライドさせ
て着脱可能であり、タンク内の水量が減少すると、パイ
ロットランプで知らせ、その都度タンクに水を補給する
方式を採用した。この構成によると、脱酸素装置によっ
て野菜室の脱酸素を行うと同時に、脱酸素装置のカソー
ド側から発生した水分を野菜室へ供給することができ
る。[Embodiment 5] FIG. 6 shows a refrigerator in which the deoxidizer of the present invention is installed in the upper part of a vegetable compartment. The door is omitted for simplicity. 35 is an outer container of the refrigerator,
The interior is partitioned by a partition into a freezer compartment 36, a refrigerator compartment 37, and a vegetable compartment 38. The capacity of the vegetable compartment 38 is 50
L. In order to deoxygenate the vegetable compartment 38, the deoxidizer 39 shown in FIG. 3 is attached to the upper portion of the vegetable compartment 38 so that the cathodic space 22 of the fuel cell communicates with the vegetable compartment. Reference numeral 40 denotes a plastic water tank having a structure capable of supplying water from the lower portion of the tank to the anode of the electrolysis cell and the electrolyte. The tank is removable by sliding it from the front of the refrigerator, and when the amount of water in the tank has decreased, a pilot lamp is used to notify the tank and water is replenished to the tank each time. According to this configuration, the deoxidizer can deoxidize the vegetable compartment, and at the same time, the water generated from the cathode side of the deoxidizer can be supplied to the vegetable compartment.
【００２５】上記のように脱酸素装置を装備した冷蔵庫
と、脱酸素装置を具備していない同タイプの通常の冷蔵
庫の野菜室に実際にキャベツを５個ずつ入れて冷蔵し、
扉の開閉なしに１週間冷蔵保管した。保管後の野菜の状
態を目視観察したところ、明らかに本発明の脱酸素装置
を装備した冷蔵庫に保管したキャベツは、同タイプの通
常の冷蔵庫の野菜室に保管したキャベツと比べて鮮度を
保っていた。本実施例では、電気分解用の水を供給する
手段として、プラスチック製の水タンクを用いたが、連
続製氷器が付随している冷蔵庫などの場合には、製氷用
の水源を電気分解用の水源としてもよい。As described above, a refrigerator equipped with a deoxidizer and an ordinary refrigerator of the same type not equipped with a deoxidizer are put in a vegetable compartment and each of the cabbage is actually put into a refrigerator for storage in a refrigerator.
It was stored refrigerated for one week without opening and closing the door. Visual observation of the state of the vegetables after storage revealed that the cabbage stored in the refrigerator equipped with the oxygen scavenging device of the present invention clearly retains its freshness as compared to the cabbage stored in the vegetable compartment of a normal refrigerator of the same type. It was In the present embodiment, a plastic water tank was used as a means for supplying water for electrolysis, but in the case of a refrigerator with a continuous ice maker, a water source for ice making is used for electrolysis. It may be used as a water source.
【００２６】[0026]
【発明の効果】以上のように本発明によれば、常温付近
で安定した性能を維持しつつ連続的に脱酸素を行える脱
酸素装置を提供するものである。As described above, according to the present invention, there is provided a deoxidizer capable of continuously performing deoxidation while maintaining stable performance at around room temperature.
【図１】本発明の一実施例における脱酸素装置の構成を
模式的に示す断面図である。FIG. 1 is a cross-sectional view schematically showing the configuration of a deoxidizer in one embodiment of the present invention.
【図２】本発明の他の実施例における脱酸素装置の構成
を模式的に示す断面図である。FIG. 2 is a cross-sectional view schematically showing the configuration of a deoxidizer in another embodiment of the present invention.
【図３】本発明のさらに他の実施例における脱酸素装置
の構成を模式的に示す断面図である。FIG. 3 is a cross-sectional view schematically showing the configuration of a deoxidizer in still another embodiment of the present invention.
【図４】本発明の他の実施例における脱酸素装置の構成
を模式的に示す断面図である。FIG. 4 is a sectional view schematically showing the configuration of a deoxidizer in another embodiment of the present invention.
【図５】本発明の一実施例における脱酸素装置のセル本
体の分解斜視図である。FIG. 5 is an exploded perspective view of a cell body of a deoxidizer in one embodiment of the present invention.
【図６】脱酸素装置を備えた冷蔵庫の扉を除いた正面図
である。FIG. 6 is a front view of a refrigerator equipped with a deoxidizer without a door.
１ 電解質 ２ カソ−ド ３ カソ−ド集電体 ４ アノ−ド ５ アノ−ド集電体 ６ 電気分解のための電圧印加装置 ７ 発生酸素 ８ 水供給手段 ９ 水 １０ 隔離手段 １１ カソ−ド側空間 １２ カソ−ド側空間の開閉手段 １３ 水分を凝縮あるいはトラップする手段 １４ ウイック １５ 電解質 １６ 燃料電池のカソ−ド １７ カソ−ド集電体 １８ 燃料電池のアノ−ド １９ アノ−ド集電体 ２０ 燃料電池の放電手段 ２１ 燃料電池の放電電流を制御する手段 ２２ 燃料電池のカソ−ド側空間 ３１、３２ ステンレス鋼製の枠体 ３３、３４ 貫通孔 ３５ 冷蔵庫の外容器 ３６ 冷凍室 ３７ 冷蔵室 ３８ 野菜室 ３９ 脱酸素装置 ４０ 水タンク 1 Electrolyte 2 Cathode 3 Cathode Current Collector 4 Anode 5 Anode Current Collector 6 Voltage Application Device for Electrolysis 7 Oxygen Generation 8 Water Supply Means 9 Water 10 Isolation Means 11 Cathode Side Space 12 Opening / closing means for the cathode side space 13 Means for condensing or trapping moisture 14 Wick 15 Electrolyte 16 Fuel cell cathode 17 Cathode current collector 18 Fuel cell anode 19 Anod current collector 20 Fuel Cell Discharging Means 21 Fuel Cell Discharge Current Controlling Means 22 Fuel Cell Cathode Side Space 31, 32 Stainless Steel Frame 33, 34 Through Hole 35 Refrigerator Outer Container 36 Freezing Chamber 37 Refrigerating Chamber 38 Vegetable room 39 Deoxidizer 40 Water tank
───────────────────────────────────────────────────── フロントページの続き (72)発明者 行天 久朗 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kuro Gyoten 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.
Claims (8)
ド、前記両電極に挟持された電解質、前記電解質に水分
を供給する手段、前記両電極に直流電圧を印加して水を
電気分解するための電圧印加手段、カソ−ド側空間とア
ノ−ド側空間を隔離する隔離手段、およびカソ−ド自身
の表面またはカソ−ド近傍に設けた触媒層を具備し、カ
ソ−ド側から発生した水素とカソ−ド側空間に存在する
酸素とを前記触媒層によって触媒燃焼し、カソ−ド側空
間の酸素濃度を低減させることを特徴とする脱酸素装
置。1. A personal computer comprising an anode and a gas diffusion electrode.
An electrolyte sandwiched between the electrodes, means for supplying water to the electrolyte, voltage application means for electrolyzing water by applying a DC voltage to the electrodes, cathode side space and anode It comprises a separating means for isolating the side space, and a catalyst layer provided on the surface of the cathode itself or in the vicinity of the cathode, and hydrogen generated from the cathode side and oxygen existing in the cathode side space are described above. A deoxidizing device characterized by catalytically burning by a catalyst layer to reduce the oxygen concentration in the cathode side space.
ド、前記両電極に挟持された電解質、前記電解質に水分
を供給する手段、前記両電極に直流電圧を印加して水を
電気分解するための電圧印加手段、およびカソ−ド側空
間とアノ−ド側空間を隔離する隔離手段を具備し、カソ
ード側に生成した水素イオンとカソ−ド側空間に存在す
る酸素とを反応させて、カソ−ド側空間の酸素濃度を低
減させることを特徴とする脱酸素装置。2. A cathode comprising an anode and a gas diffusion electrode.
, An electrolyte sandwiched between the electrodes, a means for supplying water to the electrolyte, a voltage application means for applying a DC voltage to the electrodes to electrolyze water, and a cathode side space and an anode. The present invention is characterized by comprising an isolation means for isolating the space on the cathode side, and reacting hydrogen ions generated on the cathode side with oxygen existing in the cathode side space to reduce the oxygen concentration in the cathode side space. Deoxidizer.
ド、前記両電極に挟持された電解質、前記電解質に水分
を供給する手段、前記両電極に直流電圧を印加して水を
電気分解するための電圧印加手段、およびカソ−ド側空
間とアノ−ド側空間を隔離する隔離手段を具備する水の
電気分解装置と、ガス拡散電極からなるアノ−ドとカソ
−ド、前記両電極に挟持された電解質、およびアノ−ド
側空間とカソ−ド側空間を隔離する隔離手段を具備する
燃料電池とを、水の電気分解装置のカソ−ド側空間と燃
料電池のアノ−ド側空間が連通するように組み合わせて
構成され、水の電気分解によって発生した水素を燃料電
池のアノ−ド側で燃料として消費し、燃料電池のカソ−
ド側で酸素を消費して燃料電池のカソ−ド側空間の酸素
濃度を低減させることを特徴とする脱酸素装置。3. A cathode comprising an anode and a gas diffusion electrode.
, An electrolyte sandwiched between the electrodes, a means for supplying water to the electrolyte, a voltage application means for applying a DC voltage to the electrodes to electrolyze water, and a cathode side space and an anode. Water electrolyzer having isolation means for isolating the space on the cathode side, the anode and cathode consisting of gas diffusion electrodes, the electrolyte sandwiched between the electrodes, and the anode side space and cathode A fuel cell having an isolation means for isolating a side space is combined with the cathode side space of the water electrolyzer and the anode side space of the fuel cell so as to communicate with each other. The hydrogen generated is consumed as fuel on the anode side of the fuel cell, and the
A deoxidizing device characterized by consuming oxygen on the cathode side to reduce the oxygen concentration in the cathode side space of the fuel cell.
せると同時に発生する水分により加湿することを特徴と
する請求項１〜３のいずれかに記載の脱酸素装置。4. The oxygen scavenging apparatus according to claim 1, wherein the oxygen concentration in the cathode side space is reduced and the oxygen is simultaneously humidified by the generated moisture.
は水分を含む酸性電解質で構成されるプロトン伝導体か
らなるなる請求項１〜４のいずれかに記載の脱酸素装
置。5. The deoxidizing apparatus according to claim 1, wherein the electrolyte comprises a proton conductor composed of a polymer electrolyte containing water or an acidic electrolyte containing water.
給する手段を有する請求項１または２に記載の脱酸素装
置。6. The deoxidizing apparatus according to claim 1, further comprising means for supplying water generated on the cathode side to the electrolyte.
水の電気分解装置の電解質へ供給する手段を有する請求
項３に記載の脱酸素装置。7. The deoxidizer according to claim 3, further comprising means for supplying water generated on the cathode side of the fuel cell to an electrolyte of a water electrolyzer.
装置を庫内の酸素濃度低減手段として備える冷蔵庫。8. A refrigerator provided with the deoxidizing device according to claim 1 as a means for reducing oxygen concentration in a refrigerator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7170750A JPH0919621A (en) | 1995-07-06 | 1995-07-06 | Deoxidizing device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7170750A JPH0919621A (en) | 1995-07-06 | 1995-07-06 | Deoxidizing device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0919621A true JPH0919621A (en) | 1997-01-21 |
Family
ID=15910700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7170750A Pending JPH0919621A (en) | 1995-07-06 | 1995-07-06 | Deoxidizing device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0919621A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1025584A (en) * | 1996-07-12 | 1998-01-27 | Opt D D Melco Lab:Kk | Electrochemical device |
| JP2004350929A (en) * | 2003-05-29 | 2004-12-16 | Matsushita Electric Ind Co Ltd | Cooked rice temperature keeping device |
| JP2005016875A (en) * | 2003-06-27 | 2005-01-20 | Matsushita Electric Ind Co Ltd | Preservation box |
| JP2005221216A (en) * | 2004-02-09 | 2005-08-18 | Ogata:Kk | Refrigerator with hydrogen reduction sterilization and antisepsis, moisture retention, and deodorization function |
| CN1293353C (en) * | 2003-03-25 | 2007-01-03 | 株式会社东芝 | Refrigerator |
| WO2010041396A1 (en) * | 2008-10-06 | 2010-04-15 | パナソニック株式会社 | Oxygen pump, method for manufacturing oxygen pump, and storing warehouse comprising oxygen pump |
| JP2013067850A (en) * | 2011-09-26 | 2013-04-18 | Toshiba Corp | Oxygen reduction apparatus and refrigerator |
| JP2014009860A (en) * | 2012-06-28 | 2014-01-20 | Toshiba Corp | Refrigerator |
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| JP2014059075A (en) * | 2012-09-14 | 2014-04-03 | Toshiba Corp | Oxygen-reduced device and refrigerator |
| JP2014094334A (en) * | 2012-11-08 | 2014-05-22 | Toshiba Corp | Oxygen decreasing device and refrigerator |
| JP2015029978A (en) * | 2013-08-06 | 2015-02-16 | 株式会社東芝 | Oxygen reduction device |
| KR101505721B1 (en) * | 2012-07-17 | 2015-03-24 | 가부시끼가이샤 도시바 | Refrigerator |
| JP2016003803A (en) * | 2014-06-16 | 2016-01-12 | 株式会社東芝 | Oxygen reduction device and refrigerator |
| DE102014213810A1 (en) * | 2014-07-16 | 2016-01-21 | BSH Hausgeräte GmbH | Domestic refrigerating appliance with an oxygen device with a removable container |
| CN105276902A (en) * | 2014-07-16 | 2016-01-27 | Bsh家用电器有限公司 | Household appliance with oxygen device and filter device |
| JP2019002061A (en) * | 2017-06-20 | 2019-01-10 | 日立アプライアンス株式会社 | Storage house, and refrigerator using the same |
| CN109850386A (en) * | 2017-11-30 | 2019-06-07 | 青岛海尔股份有限公司 | Refrigerating device and its container for storing |
| CN110559842A (en) * | 2018-06-06 | 2019-12-13 | 中国石油化工股份有限公司 | propylene gas catalytic deoxidation device and method with temperature and tail oxygen concentration control |
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-
1995
- 1995-07-06 JP JP7170750A patent/JPH0919621A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1025584A (en) * | 1996-07-12 | 1998-01-27 | Opt D D Melco Lab:Kk | Electrochemical device |
| CN1293353C (en) * | 2003-03-25 | 2007-01-03 | 株式会社东芝 | Refrigerator |
| JP2004350929A (en) * | 2003-05-29 | 2004-12-16 | Matsushita Electric Ind Co Ltd | Cooked rice temperature keeping device |
| JP2005016875A (en) * | 2003-06-27 | 2005-01-20 | Matsushita Electric Ind Co Ltd | Preservation box |
| JP2005221216A (en) * | 2004-02-09 | 2005-08-18 | Ogata:Kk | Refrigerator with hydrogen reduction sterilization and antisepsis, moisture retention, and deodorization function |
| WO2010041396A1 (en) * | 2008-10-06 | 2010-04-15 | パナソニック株式会社 | Oxygen pump, method for manufacturing oxygen pump, and storing warehouse comprising oxygen pump |
| JP2013067850A (en) * | 2011-09-26 | 2013-04-18 | Toshiba Corp | Oxygen reduction apparatus and refrigerator |
| JP2014009860A (en) * | 2012-06-28 | 2014-01-20 | Toshiba Corp | Refrigerator |
| JP2014037620A (en) * | 2012-06-29 | 2014-02-27 | Toshiba Corp | Device for reducing oxygen, chamber for reducing oxygen and refrigerator |
| KR101505721B1 (en) * | 2012-07-17 | 2015-03-24 | 가부시끼가이샤 도시바 | Refrigerator |
| JP2014059075A (en) * | 2012-09-14 | 2014-04-03 | Toshiba Corp | Oxygen-reduced device and refrigerator |
| JP2014094334A (en) * | 2012-11-08 | 2014-05-22 | Toshiba Corp | Oxygen decreasing device and refrigerator |
| JP2015029978A (en) * | 2013-08-06 | 2015-02-16 | 株式会社東芝 | Oxygen reduction device |
| JP2016003803A (en) * | 2014-06-16 | 2016-01-12 | 株式会社東芝 | Oxygen reduction device and refrigerator |
| DE102014213810A1 (en) * | 2014-07-16 | 2016-01-21 | BSH Hausgeräte GmbH | Domestic refrigerating appliance with an oxygen device with a removable container |
| CN105276902A (en) * | 2014-07-16 | 2016-01-27 | Bsh家用电器有限公司 | Household appliance with oxygen device and filter device |
| JP2019002061A (en) * | 2017-06-20 | 2019-01-10 | 日立アプライアンス株式会社 | Storage house, and refrigerator using the same |
| CN109850386A (en) * | 2017-11-30 | 2019-06-07 | 青岛海尔股份有限公司 | Refrigerating device and its container for storing |
| CN110559842A (en) * | 2018-06-06 | 2019-12-13 | 中国石油化工股份有限公司 | propylene gas catalytic deoxidation device and method with temperature and tail oxygen concentration control |
| WO2022050397A1 (en) * | 2020-09-04 | 2022-03-10 | 国立大学法人九州大学 | Water electrolysis device and water electrolysis method using same |
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