JP2007008750A - Gas pump - Google Patents

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JP2007008750A
JP2007008750A JP2005190435A JP2005190435A JP2007008750A JP 2007008750 A JP2007008750 A JP 2007008750A JP 2005190435 A JP2005190435 A JP 2005190435A JP 2005190435 A JP2005190435 A JP 2005190435A JP 2007008750 A JP2007008750 A JP 2007008750A
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solid electrolyte
gas
flow path
cylindrical body
electrolyte cylindrical
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JP3890070B2 (en
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Ryusuke Iwasaki
隆祐 岩▲崎▼
Haruhiko Matsushita
晴彦 松下
Hiroshi Nishimura
博 西村
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Canon Machinery Inc
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Canon Machinery Inc
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas pump having an increased gas flow capable of being substantially and effectively treated by solid electrolytic cylindrical bodies with proper diameters. <P>SOLUTION: A plurality of circular solid electrolytic cylindrical bodies 10a, 10b having different diameters are concentrically combined so as to make respective center lines almost horizontal and form a double cylindrical structure, and hollow caps are put on at both ends of the cylindrical bodies, respectively. A ring-shaped heater 40 is installed concentrically around the solid electrolytic cylindrical body 10b with a larger diameter. The two pieces solid electrolytic cylindrical bodies, inner and outer, 10a, 10b, have electrodes at both faces, inner and outer, respectively. A gas G1 to be treated is flown in an axial direction in a primary flow path Ma between the solid electrolytic cylindrical bodies 10a, 10b. In secondary spaces Na, Nb, viz. the inner space of the inner solid electrolytic cylindrical body 10a and the outer space of the outer solid electrolytic cylindrical body 10b, a secondary gas G2 based on the treatment of the gas G1 to be treated is flown in an axial direction. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、イオン導電性の固体電解質筒状体を使用した酸素ポンプ、水素ポンプなどの固体電解質型ガスポンプに関する。   The present invention relates to a solid electrolyte gas pump such as an oxygen pump or a hydrogen pump using an ion conductive solid electrolyte cylindrical body.

イオン導電性固体電解質は、高温でイオンを透過させることができる。この現象を利用し、燃料電池、ガス分析の測定、ガス混合物の分離などに実用化されている。酸素ポンプとして使用する場合は、酸素イオンが酸素などの還元により発生し与えられた電位勾配の元で、陰極側から酸素が生成する陽極へ酸素イオン伝導性電解質を通って移動することを利用している。   The ion conductive solid electrolyte can transmit ions at a high temperature. Utilizing this phenomenon, it has been put to practical use in fuel cells, measurement of gas analysis, separation of gas mixtures and the like. When used as an oxygen pump, it is utilized that oxygen ions move through the oxygen ion conductive electrolyte from the cathode side to the anode where oxygen is generated under the potential gradient generated by reduction of oxygen and the like. ing.

上記酸素ポンプを使用した試料育成装置等の設備の概要を図19に、上記酸素ポンプの概要を図20に示す。   FIG. 19 shows an outline of equipment such as a sample growing apparatus using the oxygen pump, and FIG. 20 shows an outline of the oxygen pump.

図19において、1は酸素分圧制御装置で、バルブ2を通してガスボンベ(図示せず)から不活性ガスが供給される。通常、不活性ガス中の酸素分圧は10-4atm程度である。酸素分圧制御装置1は、バルブ2を通った不活性ガスの流量を設定値に制御するマスフローコントローラ(MFC)3と、このマスフローコントローラ3を通った不活性ガスを目的の酸素分圧に制御可能な電気化学的な酸素ポンプ4と、酸素ポンプ4で制御された不活性ガスの酸素分圧をモニタして試料育成装置などの次工程(装置)に供給する供給ガス用の酸素センサ5を有する。 In FIG. 19, reference numeral 1 denotes an oxygen partial pressure control device, through which an inert gas is supplied from a gas cylinder (not shown) through a valve 2. Usually, the oxygen partial pressure in the inert gas is about 10 −4 atm. The oxygen partial pressure control device 1 controls a mass flow controller (MFC) 3 that controls the flow rate of the inert gas that has passed through the valve 2 to a set value, and controls the inert gas that has passed through the mass flow controller 3 to a target oxygen partial pressure. A possible electrochemical oxygen pump 4 and a supply gas oxygen sensor 5 for monitoring the oxygen partial pressure of the inert gas controlled by the oxygen pump 4 and supplying it to the next process (device) such as a sample growing device Have.

酸素分圧制御装置1は、所望の酸素分圧値を設定する酸素分圧設定部6と、酸素センサ5によるモニタ値を酸素分圧設定部6による設定値と比較して酸素ポンプ4から送り出される不活性ガスの酸素分圧を所定値に制御する酸素分圧制御部7と、酸素センサ5によるモニタ値を表示する酸素分圧表示部8を備える。   The oxygen partial pressure control device 1 compares an oxygen partial pressure setting unit 6 for setting a desired oxygen partial pressure value and a monitor value by the oxygen sensor 5 with a set value by the oxygen partial pressure setting unit 6 and sends it out from the oxygen pump 4. An oxygen partial pressure control unit 7 that controls the oxygen partial pressure of the inert gas to be a predetermined value and an oxygen partial pressure display unit 8 that displays a monitor value by the oxygen sensor 5 are provided.

図20の電気化学的な酸素ポンプ4は、酸化物イオン伝導性を有する固体電解質筒状体4aの内外両面に白金よりなる電極4b、4cを形成している。固体電解質筒状体4aは、例えばジルコニア系の固体電解質で、図示しないヒーターで700℃程度に加熱される。固体電解質筒状体4aの一方の開口から他方の開口に向けて軸方向に不活性ガスを供給する。不活性ガスは、例えばAr+O2(10-4atm)である。内外両面の電極4b、4c間に直流電源Eの直流電圧を印加する。外面の電極4cに+極を印加し、内面の電極4bに−極を印加して電流Iを流すと、固体電解質筒状体4a内を流れる不活性ガス中の酸素分子(O2)が固体電解質によって電気的に還元されてイオン(O2-)化され、固体電解質を通して再び酸素分子(O2)として固体電解質筒状体4aの外部に放出される。固体電解質筒状体4aの外部に放出された酸素分子は、空気等の補助ガスと共に排気される。固体電解質筒状体4aに供給されたAr+O2(10-4atm)の不活性ガスは、酸素分子が低減されて目的の酸素分圧に制御された処理済みガスとなり、次工程(装置)に給送される。 In the electrochemical oxygen pump 4 of FIG. 20, electrodes 4b and 4c made of platinum are formed on both inner and outer surfaces of a solid electrolyte cylindrical body 4a having oxide ion conductivity. The solid electrolyte cylindrical body 4a is, for example, a zirconia solid electrolyte, and is heated to about 700 ° C. by a heater (not shown). An inert gas is supplied in the axial direction from one opening of the solid electrolyte cylindrical body 4a toward the other opening. The inert gas is, for example, Ar + O 2 (10 −4 atm). A DC voltage of a DC power source E is applied between the inner and outer electrodes 4b and 4c. When a positive electrode is applied to the outer electrode 4c and a negative electrode is applied to the inner electrode 4b to flow a current I, oxygen molecules (O 2 ) in the inert gas flowing through the solid electrolyte cylindrical body 4a are solid. It is electrically reduced by the electrolyte to be ionized (O 2− ), and is released again as oxygen molecules (O 2 ) through the solid electrolyte to the outside of the solid electrolyte cylindrical body 4a. Oxygen molecules released to the outside of the solid electrolyte cylindrical body 4a are exhausted together with an auxiliary gas such as air. The inert gas of Ar + O 2 (10 −4 atm) supplied to the solid electrolyte cylindrical body 4 a becomes a processed gas whose oxygen molecules are reduced and controlled to the target oxygen partial pressure, and is used in the next process (apparatus). Be fed.

図20の酸素ポンプ4は、固体電解質筒状体4aの内外両面の電極4b、4c間に上記と逆極性の直流電圧を印加してポンプ動作を行わせることも可能である。すなわち、外面の電極4cに−極を印加し、内面の電極4bに+極を印加すると、固体電解質筒状体4aの外面に沿って流れる空気などのガス中の酸素分子(O2)が固体電解質によって電気的に還元されてイオン(O2-)化され、固体電解質を通して再び酸素分子(O2)として固体電解質筒状体4aの内部に放出される。この場合、固体電解質筒状体4aの内部を流れる不活性ガスの酸素分圧が上昇して、外部に給送される。 The oxygen pump 4 shown in FIG. 20 can also perform a pump operation by applying a DC voltage having the opposite polarity between the electrodes 4b and 4c on the inner and outer surfaces of the solid electrolyte cylindrical body 4a. That is, when a negative electrode is applied to the outer electrode 4c and a positive electrode is applied to the inner electrode 4b, oxygen molecules (O 2 ) in a gas such as air flowing along the outer surface of the solid electrolyte cylindrical body 4a are solid. It is electrically reduced by the electrolyte to be ionized (O 2− ), and is released again as oxygen molecules (O 2 ) through the solid electrolyte into the solid electrolyte cylindrical body 4a. In this case, the oxygen partial pressure of the inert gas flowing inside the solid electrolyte cylindrical body 4a is increased and fed to the outside.

このような酸素ポンプにより酸素分圧を制御したガスを供給すれば、結晶育成、合金化、熱処理、半導体製造工程などが酸素分圧を制御した不活性ガスなどの雰囲気下で行うことができる。   If a gas whose oxygen partial pressure is controlled by such an oxygen pump is supplied, crystal growth, alloying, heat treatment, semiconductor manufacturing process, etc. can be performed in an atmosphere such as an inert gas whose oxygen partial pressure is controlled.

イオン導電体の固体電解質筒状体の内部を軸方向に不活性ガスなどのポンプ作用を受ける被処理ガスを流すガスポンプは、図20の酸素ポンプのように、1本の円形パイプ状の固体電解質筒状体を使用する。この1本の固体電解質筒状体の内部空間に軸方向に被処理ガスを流し、固体電解質筒状体内を流れる間に固体電解質隔壁内外でイオン導電のポンプ作用を行う。このようなガスポンプが処理できるガス流量は、被処理ガスと固体電解質筒状体内外面との接触面積に比例する。従って、ガス流量を増大させるためには、被処理ガスと固体電解質筒状体外面との接触面積を増大させる必要がある。   A gas pump for flowing a gas to be processed that receives a pumping action such as an inert gas in the axial direction through the inside of a solid electrolyte cylindrical body of an ionic conductor is a single circular pipe-shaped solid electrolyte like the oxygen pump of FIG. Use a cylindrical body. A gas to be treated is caused to flow in the axial direction in the internal space of the single solid electrolyte cylindrical body, and an ion conductive pumping action is performed inside and outside the solid electrolyte partition wall while flowing through the solid electrolyte cylindrical body. The gas flow rate that can be processed by such a gas pump is proportional to the contact area between the gas to be processed and the outer surface of the solid electrolyte cylindrical body. Therefore, in order to increase the gas flow rate, it is necessary to increase the contact area between the gas to be processed and the outer surface of the solid electrolyte cylindrical body.

そのためには、固体電解質筒状体を長くすることや、パイプ径を大きくすることが考えられる。酸素イオン導電性固体電解質を有効に利用するためには、酸素ポンプの抵抗値をできる限り低くして、酸素ポンプの酸素透過能力を高くすることが必要である。酸素ポンプの抵抗値には、固体電解質の形状(表面積と厚さ)、電極膜、リード端子などが影響する。この中で固体電解質の形状は表面積が大きく、薄いほど抵抗値は小さくなる。すなわち、筒状体を考えると、その直径と長さが大きく、厚みの薄い形状がよい。しかし、固体電解質筒状体を製造する容易さや、加熱・高温保持状態で使用される固体電解質筒状体の強度を考慮すると、直径と長さと厚みには限界がある。また、パイプ径を大きくするほど、固体電解質筒状体の中心部を流れる被処理ガスのイオン伝導反応が急減して、結果的に中心部を流れる被処理ガスが反応なしで素通りすることになり、酸素分圧などの制御精度が低下する。このようなことから、固体電解質筒状体のパイプ径を単純に大きくするには自ずと限界がある。従って、上記の方法で被処理ガスと固体電解質筒状体との接触面積を増大するには限界がある。そのため、ガスポンプが実質的有効に処理できるガス流量が制限され、酸素分圧を制御したガスを供給する用途が制限されていた。   To that end, it is conceivable to lengthen the solid electrolyte cylindrical body or increase the pipe diameter. In order to effectively use the oxygen ion conductive solid electrolyte, it is necessary to reduce the resistance value of the oxygen pump as much as possible and increase the oxygen permeation ability of the oxygen pump. The resistance value of the oxygen pump is affected by the shape (surface area and thickness) of the solid electrolyte, the electrode film, the lead terminal, and the like. Among these, the shape of the solid electrolyte has a large surface area, and the resistance value decreases as the thickness decreases. That is, when considering a cylindrical body, a shape having a large diameter and length and a small thickness is preferable. However, in view of the ease of manufacturing the solid electrolyte cylindrical body and the strength of the solid electrolyte cylindrical body used in a heated and high temperature holding state, there are limits to the diameter, length, and thickness. In addition, as the pipe diameter increases, the ion conduction reaction of the gas to be processed flowing through the center of the solid electrolyte cylindrical body decreases rapidly, and as a result, the gas to be processed flowing through the center passes through without reaction. In addition, control accuracy such as oxygen partial pressure decreases. For this reason, there is a limit to simply increasing the pipe diameter of the solid electrolyte cylindrical body. Therefore, there is a limit in increasing the contact area between the gas to be treated and the solid electrolyte cylindrical body by the above method. For this reason, the gas flow rate that can be processed substantially effectively by the gas pump is limited, and the application of supplying gas with controlled oxygen partial pressure is limited.

本発明の目的とするところは、適切な口径の固体電解質筒状体にて実質的有効に処理できるガス流量を増大させたガスポンプを提供することにある。   An object of the present invention is to provide a gas pump having an increased gas flow rate that can be processed substantially effectively with a solid electrolyte cylindrical body having an appropriate diameter.

本発明は、上記目的を達成するため、同心にして多重に配設された、それぞれが内外両面に電極を有する径の異なる複数の固体電解質筒状体と、この複数の固体電解質筒状体のそれぞれの内外両面の電極に異なる極性となる電圧を印加する直流電源と、複数の固体電解質筒状体の最外側(最大径)の固体電解質筒状体の回りに配置した加熱装置を有する構造を特徴とする。加熱装置は、複数の固体電解質筒状体を均一的に加熱する共通のリング状ヒーターが適用できる。   In order to achieve the above object, the present invention provides a plurality of solid electrolyte cylinders having concentric and multiple electrodes, each having electrodes on both the inner and outer surfaces and having different diameters, and the plurality of solid electrolyte cylinders. A structure having a DC power source that applies voltages having different polarities to the electrodes on both the inner and outer surfaces, and a heating device disposed around the outermost (maximum diameter) solid electrolyte cylinder of the plurality of solid electrolyte cylinders Features. As the heating device, a common ring heater that uniformly heats a plurality of solid electrolyte cylindrical bodies can be applied.

ここで、固体電解質筒状体は、酸化物イオン導電体であるYSZ(イットリウム安定化ジルコニア)のジルコニア系や、プロトン導電体の固体電解質が適用できる。前者ジルコニア系固体電解質筒状体を使用したガスポンプは、所謂酸素ポンプである。後者プロトン導電体の固体電解質筒状体を使用したガスポンプは、所謂水素ポンプであり、燃料電池製造装置などに適用できる。また、複数の固体電解質筒状体は内径が大小異なる円形パイプが強度的、品質的に望ましいが、用途によっては楕円パイプや多角形パイプも適用可能である。径が大小異なる複数の固体電解質筒状体の各々の内外両面に、白金などのネット状の電極を形成する。1つの固体電解質筒状体の外面側電極と内面側電極に極性の異なる直流電圧を印加して、イオン導電のポンプ作用を行わせる。また、複数の各固体電解質筒状体を同心にして多重に配設し、同心状に隣接する内側と外側の固体電解質筒状体の間に筒状空間を形成し、この筒状空間に所望のガスを固体電解質筒状体軸方向に流す。ここでのガスは、酸素分圧制御などされるポンプ動作対象の被処理ガスと、被処理ガスの処理に基づく二次ガス(被処理ガスを処理することで生成された酸素分子などを含む排ガス、または、被処理ガスの処理のために被処理ガスに供与される高酸素分圧の大気ガスなど)である。これらのガスが同心かつ多重に配置された複数の固体電解質筒状体の間の空間や、最大径の固体電解質筒状体の外周と加熱装置の間に形成した流路に流れる。   Here, as the solid electrolyte cylindrical body, a YSZ (yttrium-stabilized zirconia) zirconia-based oxide ion conductor or a proton conductor solid electrolyte can be applied. The former gas pump using a zirconia solid electrolyte cylindrical body is a so-called oxygen pump. The gas pump using the solid electrolyte cylindrical body of the latter proton conductor is a so-called hydrogen pump and can be applied to a fuel cell manufacturing apparatus or the like. In addition, although a plurality of solid electrolyte cylindrical bodies are desirably circular pipes having different inner diameters in terms of strength and quality, elliptical pipes and polygonal pipes can also be applied depending on applications. A net-like electrode such as platinum is formed on both the inner and outer surfaces of each of the plurality of solid electrolyte cylindrical bodies having different diameters. A DC voltage having a different polarity is applied to the outer surface side electrode and the inner surface side electrode of one solid electrolyte cylindrical body to perform an ion conductive pumping action. Also, a plurality of solid electrolyte cylindrical bodies are concentrically arranged in a multiple manner, and a cylindrical space is formed between the inner and outer solid electrolyte cylindrical bodies adjacent to each other in a concentric manner. The gas is flowed in the axial direction of the solid electrolyte cylindrical body. The gas used here is a gas to be processed for pump operation that is subjected to oxygen partial pressure control, etc., and a secondary gas based on the processing of the gas to be processed (exhaust gas including oxygen molecules generated by processing the gas to be processed) Or high oxygen partial pressure atmospheric gas provided to the gas to be processed for the processing of the gas to be processed). These gases flow in a space formed between a plurality of solid electrolyte cylindrical bodies arranged concentrically and multiply, or a flow path formed between the outer periphery of the solid electrolyte cylindrical body having the maximum diameter and the heating device.

本発明においては、複数の固体電解質筒状体間の筒状空間で、最小径の固体電解質筒状体の内部空間から数えて奇数番目の空間をポンプ動作対象の被処理ガスの処理に基づく二次ガスを固体電解質筒状体軸方向に流す二次流路とし、残りの偶数番目の空間を二次流路と区分けされた一次流路として、この一次流路に被処理ガスを固体電解質筒状体軸方向に流すと共に、一次流路に接する固体電解質筒状体面と二次流路に接する固体電解質筒状体面に異なる極性となる電圧を印加する構造とすることができる。   In the present invention, in the cylindrical space between the plurality of solid electrolyte cylindrical bodies, the odd-numbered space counted from the internal space of the solid electrolyte cylindrical body having the smallest diameter is treated based on the processing of the gas to be pumped. The secondary gas flows in the axial direction of the solid electrolyte cylindrical body, and the remaining even-numbered space is defined as the primary flow path separated from the secondary flow path. In addition to flowing in the axial direction of the body, a voltage having different polarities can be applied to the surface of the solid electrolyte cylindrical body in contact with the primary flow path and the surface of the solid electrolyte cylindrical body in contact with the secondary flow path.

さらに、本発明においては、複数の固体電解質筒状体間の筒状空間で、最小径の固体電解質筒状体の内部空間から数えて奇数番目の空間をポンプ動作対象の被処理ガスを固体電解質筒状体軸方向に流す一次流路とし、残りの偶数番目の空間を一次流路と区分けされた二次流路として、この二次流路に被処理ガスの処理に基づく二次ガスを流すと共に、一次流路に接する固体電解質筒状体面と二次流路に接する固体電解質筒状体面に異なる極性となる電圧を印加する構造とすることができる。   Further, in the present invention, in the cylindrical space between the plurality of solid electrolyte cylindrical bodies, the odd-numbered space counted from the internal space of the solid electrolyte cylindrical body having the smallest diameter is treated gas to be pumped as the solid electrolyte. As a primary flow path that flows in the direction of the cylindrical body axis, and the remaining even-numbered space as a secondary flow path that is separated from the primary flow path, a secondary gas based on the processing of the gas to be processed is passed through the secondary flow path. In addition, it is possible to adopt a structure in which voltages having different polarities are applied to the surface of the solid electrolyte cylindrical body in contact with the primary flow path and the surface of the solid electrolyte cylindrical body in contact with the secondary flow path.

ここでの一次流路と二次流路は、交互に多重に配設される。ぼほ同一長さで径が異なる複数の固体電解質筒状体を同心にして多重に配設して、各固体電解質筒状体の両端部に中空のキャップを被嵌し、このキャップで一次流路同士を連通させ、二次流路同士を連通させることができる。複数の各固体電解質筒状体をその中心線を水平にして横置き仕様で配設した場合、各固体電解質筒状体の左右両端にキャップが被嵌される。複数の各固体電解質筒状体をその中心線を鉛直にして縦置き仕様で配設した場合、各固体電解質筒状体の上下両端にキャップが被嵌される。これらキャップを使用することで、複数の一次流路を直列に連通させて被処理ガスを各一次流路に連続的に流すことや、複数の一次流路を並列に連通させて各一次流路に被処理ガスを同方向に流すことができる。同様にして、複数の二次流路を直列に連通させることや、並列に連通させることができる。   Here, the primary flow path and the secondary flow path are alternately arranged in multiple. A plurality of solid electrolyte cylinders having the same length and different diameters are concentrically arranged in multiple layers, and hollow caps are fitted to both ends of each solid electrolyte cylinder, and the primary flow is achieved with these caps. The paths can be communicated with each other, and the secondary flow paths can be communicated with each other. When the plurality of solid electrolyte cylindrical bodies are arranged in a horizontal specification with the center line thereof being horizontal, caps are fitted to the left and right ends of each solid electrolyte cylindrical body. When the plurality of solid electrolyte cylindrical bodies are arranged in a vertical orientation with the center line thereof being vertical, caps are fitted to the upper and lower ends of each solid electrolyte cylindrical body. By using these caps, a plurality of primary flow paths are connected in series so that the gas to be treated flows continuously to each primary flow path, or a plurality of primary flow paths are connected in parallel to each primary flow path. The gas to be treated can flow in the same direction. Similarly, a plurality of secondary flow paths can be communicated in series or in parallel.

また、本発明においては、複数の固体電解質筒状体間の筒状空間に、この空間を内側空間と外側空間に区分けする流路仕切筒体を固体電解質筒状体と同心に配設して、区分けされた内側空間と外側空間の一方をポンプ動作対象の被処理ガスを固体電解質筒状体軸方向に流す一次流路とし、他方を被処理ガスの処理に基づく二次ガスを流す二次流路とすると共に、一次流路に接する固体電解質筒状体面と二次流路に接する固体電解質筒状体面に異なる極性となる電圧を印加する構造とすることができる。   Further, in the present invention, in the cylindrical space between the plurality of solid electrolyte cylindrical bodies, a flow path partitioning cylinder that divides this space into an inner space and an outer space is disposed concentrically with the solid electrolyte cylindrical body. One of the divided inner space and outer space is used as a primary flow path for flowing the gas to be pumped in the axial direction of the solid electrolyte cylindrical body, and the other is a secondary flow for flowing a secondary gas based on the processing of the gas to be processed. In addition to the flow path, it is possible to adopt a structure in which voltages having different polarities are applied to the solid electrolyte cylindrical body surface in contact with the primary flow path and the solid electrolyte cylindrical body surface in contact with the secondary flow path.

ここでの流路仕切筒体は、固体電解質筒状体と異質(非電解質)の耐熱筒である。例えば、径が大小異なる2本の固体電解質筒状体を使用した場合、この2本一対の固体電解質筒状体の中間に1本の流路仕切筒体を配置する。また、径が大中小と異なる3本の固体電解質筒状体を使用した場合、小径と中径の固体電解質筒状体の中間に1本の流路仕切筒体を配置し、中径と大径の固体電解質筒状体の中間にも別の1本の流路仕切筒体を配置する。隣接する固体電解質筒状体の間の空間を流路仕切筒体で内側空間と外側空間に二分して、外側空間を被処理ガスを流す一次流路とし、内側空間を二次ガスを流す二次流路とすることができる。非電解質の流路仕切筒体は固体電解質筒状体に比べ硬質な材料を選択すれば、複数の固体電解質筒状体を補強することもできる。   The channel partition cylinder here is a heat-resistant cylinder that is different from the solid electrolyte cylindrical body (non-electrolyte). For example, when two solid electrolyte cylinders having different diameters are used, one channel partition cylinder is arranged between the two pairs of solid electrolyte cylinders. In addition, when three solid electrolyte cylinders having a diameter different from large, medium, and small are used, a single channel partition cylinder is arranged between the small and medium diameter solid electrolyte cylinders, and the medium diameter and the large Another single channel partition cylinder is also arranged in the middle of the solid electrolyte cylindrical body having a diameter. A space between adjacent solid electrolyte cylindrical bodies is divided into an inner space and an outer space by a flow path partitioning cylinder, and the outer space is used as a primary flow path for flowing a gas to be processed, and the inner space is supplied with a secondary gas. It can be a next flow path. If a non-electrolyte channel partition cylinder is selected from a material that is harder than the solid electrolyte cylinder, a plurality of solid electrolyte cylinders can be reinforced.

上記本発明においては、筒状一次流路と二次流路を交互に多重に配設して、径方向で隣接する一次流路を直列に連通させて、この隣接する一次流路の一方からの流出する被処理ガスを180°反対方向にリターンさせて他方に流入させることができる。また、筒状一次流路と二次流路を交互に多重に配設して、径方向で隣接する一次流路を並列に連通させて、両一次流路に処理ガスを同方向に流すことができる。   In the present invention, the cylindrical primary flow paths and the secondary flow paths are alternately arranged in multiples, and the primary flow paths adjacent in the radial direction are connected in series, and one of the adjacent primary flow paths is connected. Gas to be treated can be returned in the opposite direction by 180 ° and allowed to flow into the other. In addition, the cylindrical primary flow paths and the secondary flow paths are alternately arranged in multiple layers, the primary flow paths adjacent in the radial direction are connected in parallel, and the processing gas flows in both primary flow paths in the same direction. Can do.

また、本発明においては、同心にして多重に配設された複数の固体電解質筒状体からなる固体電解質筒状体ユニットを、各々の中心線が略鉛直となる縦置き仕様で同心円上に等間隔で複数配設し、この複数の固体電解質筒状体ユニットを囲むリング状の加熱装置で各固体電解質筒状体ユニットを加熱する構成とすることができる。この場合、複数の固体電解質筒状体ユニットで囲まれる空間に加熱装置で加熱されて蓄熱する蓄熱部材を配置することができる。   Further, in the present invention, the solid electrolyte cylindrical unit composed of a plurality of solid electrolyte cylindrical bodies arranged concentrically and in a concentric manner in a vertically placed specification in which each center line is substantially vertical, etc. A plurality of the solid electrolyte cylindrical body units may be heated by a ring-shaped heating device that is disposed at intervals and surrounds the plurality of solid electrolyte cylindrical body units. In this case, a heat storage member that stores heat by being heated by the heating device can be disposed in a space surrounded by the plurality of solid electrolyte cylindrical units.

このように同心円上に配置された複数の固体電解質筒状体ユニットのそれぞれの内部に被処理ガスを流すことで、被処理ガスと固体電解質筒状体との接触面積が増大し、ポンプ処理するガス量が増大する。また、複数の固体電解質筒状体ユニットに対して等距離にあるリング状加熱装置が各個体電解質筒状体ユニットを均一的に加熱して、ユニット間での温度差が少なくなり、この温度差によって生じる固体電解質筒状体ユニットの酸素透過能力差が解消される。さらに、中心線が略鉛直に配置された各個体電解質筒状体ユニットを外側からは加熱装置で加熱し、内側からは蓄熱部材で加熱することで、各ユニットの固体電解質筒状体を周方向に温度差少なくして均一的に加熱することができ、各ユニット内部を流れる被処理ガスの制御精度を高めることができる。これにより、複数の固体電解質筒状体ユニットで個体差なく同質な被処理ガスの処理が行われて、酸素分圧などの制御精度の向上が図れる。   By flowing the gas to be processed into each of the plurality of solid electrolyte cylindrical units arranged concentrically in this way, the contact area between the gas to be processed and the solid electrolyte cylindrical body is increased, and the pump processing is performed. The amount of gas increases. In addition, a ring-shaped heating device equidistant to a plurality of solid electrolyte cylindrical units uniformly heats each solid electrolyte cylindrical unit, and the temperature difference between the units is reduced. This eliminates the difference in oxygen permeation ability of the solid electrolyte cylindrical unit. Furthermore, each solid electrolyte tubular body unit whose center line is arranged substantially vertically is heated from the outside by a heating device, and from the inside by a heat storage member, so that the solid electrolyte tubular body of each unit is circumferentially Thus, the temperature difference can be reduced and the heating can be performed uniformly, and the control accuracy of the gas to be processed flowing inside each unit can be increased. Thereby, the processing of the same gas to be processed is performed in a plurality of solid electrolyte cylindrical units without individual differences, and control accuracy such as oxygen partial pressure can be improved.

また、本発明においては、複数の各固体電解質筒状体を酸化物イオン導電体で構成することができる。この酸化物イオン導電体の固体電解質筒状体は、所定温度で加熱された条件下で被処理ガス中の酸素分子を二次ガスに移動させるポンプ動作、あるいは、二次ガス中の酸素分子を被処理ガスに移動させる逆のポンプ動作をして、安定した動作をする酸素ポンプを構成する。   In the present invention, each of the plurality of solid electrolyte cylindrical bodies can be composed of an oxide ion conductor. This oxide ion conductor solid electrolyte cylinder is operated by a pump that moves oxygen molecules in the gas to be treated to the secondary gas under the condition of being heated at a predetermined temperature, or oxygen molecules in the secondary gas. An oxygen pump that performs a stable operation by performing a reverse pump operation to move to the gas to be processed is configured.

本発明のガスポンプによれば、同心で多重に配置された複数の固体電解質筒状体の間に被処理ガスを流して固体電解質筒状体の隔壁でイオン伝導させるので、被処理ガスは1つの流路(一次流路)で接近した二面からイオン透過が行われて、被処理ガスと固体電解質筒状体との接触面積を増大させることができ、ポンプ処理するガス量の増大が図れるという優れた効果を奏し得る。また、同心円上に配置された複数の固体電解質筒状体ユニットのそれぞれの内部を被処理ガスが通過することによっても、被処理ガスと固体電解質筒状体との接触面積を増大させることができ、ポンプ処理するガス量の増大が図れる。ガスポンプが処理できるガス量の増大で、極低酸素分圧ガスを使用する材料生成装置や高酸素分圧ガスを使用する熱処理装置などの製造設備に処理量の大きな高能力大型設備を適用できる有利さがある。   According to the gas pump of the present invention, the gas to be treated is caused to flow between the plurality of concentrically arranged solid electrolyte cylinders to conduct ions through the partition walls of the solid electrolyte cylinder. Ion permeation is performed from two surfaces approaching in the flow path (primary flow path), the contact area between the gas to be processed and the solid electrolyte cylindrical body can be increased, and the amount of gas to be pumped can be increased. An excellent effect can be achieved. Further, the contact area between the gas to be processed and the solid electrolyte cylindrical body can also be increased by passing the gas to be processed through each of the plurality of solid electrolyte cylindrical units arranged concentrically. The amount of gas to be pumped can be increased. The increased gas volume that can be processed by the gas pump is advantageous in that large-capacity large-capacity facilities with large throughput can be applied to manufacturing facilities such as material generation equipment that uses extremely low oxygen partial pressure gas and heat treatment equipment that uses high oxygen partial pressure gas. There is.

以下、各種の実施の形態の概要を図1(A)〜(C)と図2(A)(B)を参照し、各種の具体例を図3〜図16を参照して説明する。   Hereinafter, an outline of various embodiments will be described with reference to FIGS. 1A to 1C and FIGS. 2A and 2B, and various specific examples will be described with reference to FIGS.

図1(A)は、ほぼ同一長さで直径が大小異なる2本の円形の固体電解質筒状体10a、10bを、それぞれの中心線を略水平にして同心に組み付けて、横置き仕様の二重筒構造体を構成する。最外側である大径の固体電解質筒状体10bの回りに加熱装置であるリング状ヒーター40を同心に配設する。内外2本の固体電解質筒状体10a、10bは、それぞれに内外両面に白金よりなるネット状の電極(図示せず)を有する。この内外両面の電極には、直流電源Eから異なる極性の直流電圧が印加される。内外2本の固体電解質筒状体10a、10bの間の筒状空間が被処理ガスG1の流れる一次流路Maであり、小径の内側固体電解質筒状体10aの内部空間と大径の外側固体電解質筒状体10bの外部空間が二次ガスG2が流れる二次空間Na、Nbである。被処理ガスG1と二次ガスG2は、図1(A)の実線矢印と破線矢印で示すように、固体電解質筒状体軸方向に流れる。図1(A)のガスポンプを酸素ポンプに適用した具体例を図3及び図4に示し、詳細は後述する。   In FIG. 1A, two circular solid electrolyte cylindrical bodies 10a and 10b having substantially the same length and different diameters are assembled concentrically with their respective centerlines being substantially horizontal, A heavy cylinder structure is formed. Around the outermost large-diameter solid electrolyte cylindrical body 10b, a ring heater 40 as a heating device is disposed concentrically. The inner and outer two solid electrolyte cylindrical bodies 10a and 10b each have net-like electrodes (not shown) made of platinum on both the inner and outer surfaces. A DC voltage having a different polarity is applied from the DC power source E to both the inner and outer electrodes. The cylindrical space between the inner and outer solid electrolyte cylinders 10a and 10b is the primary flow path Ma through which the gas G1 to be treated flows, and the inner space of the small-diameter inner solid electrolyte cylinder 10a and the large-diameter outer solid. The external space of the electrolyte cylindrical body 10b is secondary spaces Na and Nb through which the secondary gas G2 flows. The gas to be treated G1 and the secondary gas G2 flow in the solid electrolyte cylindrical body axial direction as indicated by solid line arrows and broken line arrows in FIG. Specific examples in which the gas pump of FIG. 1A is applied to an oxygen pump are shown in FIGS. 3 and 4 and will be described in detail later.

図1(B)は、ほぼ同一長さで直径が異なる4本の円形の固体電解質筒状体10a〜10dを同心に組み付けて、横置き仕様の四重筒構造体を構成している。最大径の固体電解質筒状体10dの回りにリング状ヒーター40を同心に配設する。4本の各固体電解質筒状体10a〜10dはそれぞれの内外両面に電極(図示せず)を有する。最小径の固体電解質筒状体10aの内部空間と、最小径から2番目と3番目に小さい径の固体電解質筒状体10b、10cの間の筒状空間と、最大径の固体電解質筒状体10dの外部空間が、二次ガスG2の流れる二次流路Na、Nb、Ncである。隣接する固体電解質筒状体10a、10bの間の筒状空間と、隣接する固体電解質筒状体10c、10dの間の筒状空間が、被処理ガスG1の流れる一次流路Ma、Mbである。この二つの一次流路Ma、Mbは、図1(B)で右端の開口が直列に連通されて、内側の一次流路Maを図1(B)で右方に流れた被処理ガスG1は180°リターンして外側一次流路Mbに入り、図1(B)で左方に流れる。図1(B)のガスポンプを酸素ポンプに適用した具体例が、図5及び図6に示される。   In FIG. 1 (B), four circular solid electrolyte cylindrical bodies 10a to 10d having substantially the same length and different diameters are assembled concentrically to form a horizontally mounted quadruple cylinder structure. A ring heater 40 is concentrically disposed around the solid electrolyte cylindrical body 10d having the maximum diameter. Each of the four solid electrolyte cylindrical bodies 10a to 10d has electrodes (not shown) on both inner and outer surfaces. The inner space of the solid electrolyte cylindrical body 10a with the smallest diameter, the cylindrical space between the solid electrolyte cylindrical bodies 10b and 10c with the second and third smallest diameters from the smallest diameter, and the solid electrolyte cylindrical body with the largest diameter The external space 10d is secondary flow paths Na, Nb, and Nc through which the secondary gas G2 flows. The cylindrical spaces between the adjacent solid electrolyte cylindrical bodies 10a and 10b and the cylindrical spaces between the adjacent solid electrolyte cylindrical bodies 10c and 10d are primary flow paths Ma and Mb through which the gas to be processed G1 flows. . The two primary flow paths Ma and Mb are connected to the opening at the right end in series in FIG. 1B, and the gas to be treated G1 flowing to the right in the inner primary flow path Ma in FIG. It returns 180 ° and enters the outer primary flow path Mb, and flows to the left in FIG. 1 (B). Specific examples in which the gas pump of FIG. 1B is applied to an oxygen pump are shown in FIGS.

図1(C)は、図1(B)と同様な4本の円形の固体電解質筒状体10a〜10dで四重筒を構成し、図1(B)と同様な一次流路Ma、Mbと二次空間Na、Nb、Ncを備える。最大径の固体電解質筒状体10dの回りにリング状ヒーター40を同心に配設する。図1(C)のガスポンプの場合は、二つの一次流路Ma、Mbが図1(C)で左端の開口が並列に連通されて、被処理ガスG1は各一次流路Ma、Mbに同時に流入して同方向に流れる。   In FIG. 1C, a quadruple cylinder is configured by four circular solid electrolyte cylindrical bodies 10a to 10d similar to FIG. 1B, and primary flow paths Ma and Mb similar to FIG. And secondary spaces Na, Nb, and Nc. A ring heater 40 is concentrically disposed around the solid electrolyte cylindrical body 10d having the maximum diameter. In the case of the gas pump of FIG. 1C, the two primary flow paths Ma and Mb are connected in parallel at the left end opening in FIG. 1C, and the gas G1 to be treated is simultaneously supplied to the primary flow paths Ma and Mb. Inflow and flow in the same direction.

図2(A)は、ほぼ同一長さで直径が大中小と異なる3本の円形の固体電解質筒状体10a〜10cを同心に組み付けて、横置き仕様の三重筒構造体を構成している。最大径の固体電解質筒状体10cの回りにリング状ヒーター40を同心に配設する。3本の各固体電解質筒状体10a〜10cはそれぞれの内外両面に電極を有する。最小径の固体電解質筒状体10aの内部空間と、中径と最大径の固体電解質筒状体10b、10cの筒状空間が被処理ガスG1の流れる一次流路Ma、Mbである。最小径と中径の固体電解質筒状体10a、10bの間の筒状空間と、最大径の固体電解質筒状体10cの外部空間が二次ガスG2の流れる二次流路Na、Nbである。二つの一次流路Ma、Mbは、図2(A)で右端の開口が直列に連通されて、内側の一次流路Maを図2(A)で右方に流れた被処理ガスG1は180°リターンして外側一次流路Mbに入り、図2(A)で左方に流れる。   In FIG. 2 (A), three circular solid electrolyte cylindrical bodies 10a to 10c having substantially the same length and different diameters from large, medium, and small are assembled concentrically to form a horizontal cylinder triple cylinder structure. . A ring heater 40 is concentrically disposed around the solid electrolyte cylindrical body 10c having the maximum diameter. Each of the three solid electrolyte cylindrical bodies 10a to 10c has electrodes on both inner and outer surfaces. The internal space of the solid electrolyte cylindrical body 10a having the minimum diameter and the cylindrical spaces of the solid electrolyte cylindrical bodies 10b and 10c having the medium diameter and the maximum diameter are the primary flow paths Ma and Mb through which the gas to be processed G1 flows. The cylindrical space between the solid electrolyte cylinders 10a and 10b having the minimum diameter and the medium diameter and the external space of the solid electrolyte cylinder 10c having the maximum diameter are the secondary flow paths Na and Nb through which the secondary gas G2 flows. . The two primary flow paths Ma and Mb are connected in series at the right end opening in FIG. 2A, and the gas to be processed G1 flowing to the right in the inner primary flow path Ma in FIG. 2A is 180. ° Return to enter the outer primary flow path Mb and flow leftward in FIG.

図2(B)は、図2(A)の中径の固体電解質筒状体10bの代わりに同様な寸法形状の流路仕切構体20aを配置して、横置き仕様の三重筒構造体を構成している。流路仕切筒体20aは非固体電解質の円筒で、内外2本の固体電解質筒状体10a、10bの間の空間を円筒状の内側空間と外側空間に二分する。この場合、小径の固体電解質筒状体10aの内部空間と、流路仕切構体20aと大径の固体電解質筒状体10bの間の筒状空間が被処理ガスG1が流れる一次流路Ma、Mbである。小径の固体電解質筒状体10aと流路仕切構体20aの間の筒状空間と、大径の固体電解質筒状体10bの外部空間が二次ガスG2の流れる二次流路Na、Nbである。二つの一次流路Ma、Mbは、図2(B)で右端の開口が直列に連通されて、内側の一次流路Maを図2(B)で右方に流れた被処理ガスG1は180°リターンして外側一次流路Mbに入り、図2(B)で左方に流れる。図2(B)のガスポンプを酸素ポンプに適用した具体例が、図7〜図10に示される。また、図2(B)の応用例が図11及び図12に示される。これらの具体例は後述する。   FIG. 2B shows a horizontally installed triple-cylinder structure in which a channel partition structure 20a having the same size and shape is arranged instead of the medium-diameter solid electrolyte cylindrical body 10b shown in FIG. is doing. The flow partition cylinder 20a is a non-solid electrolyte cylinder, and divides the space between the inner and outer two solid electrolyte cylinders 10a and 10b into a cylindrical inner space and an outer space. In this case, the primary flow paths Ma and Mb in which the gas G1 flows in the internal space of the small diameter solid electrolyte cylindrical body 10a and the cylindrical space between the flow path partitioning structure 20a and the large diameter solid electrolyte cylindrical body 10b. It is. The cylindrical space between the small-diameter solid electrolyte cylindrical body 10a and the channel partition structure 20a and the external space of the large-diameter solid electrolyte cylindrical body 10b are the secondary flow paths Na and Nb through which the secondary gas G2 flows. . The two primary flow paths Ma, Mb are connected in series at the right end opening in FIG. 2B, and the gas G1 to be treated that flows to the right in the inner primary flow path Ma in FIG. 2B is 180. ° Return to enter the outer primary flow path Mb and flow to the left in FIG. 2 (B). Specific examples in which the gas pump of FIG. 2B is applied to an oxygen pump are shown in FIGS. An application example of FIG. 2B is shown in FIGS. Specific examples of these will be described later.

次に、図3及び図4で図1(A)のガスポンプを酸素ポンプに応用した具体例を説明する。この酸素ポンプは、二重筒構造体の両端部に中空の耐熱性キャップ31、32を被嵌している。内側固体電解質筒状体10aの内部空間と、外側固体電解質筒状体10bとヒーター40の間の空間が、軸方向に二次ガスG2を流す二次流路Na、Nbであり、内外で隣接する各固体電解質筒状体10a、10bの間の空間が軸方向に被処理ガスG1を流す一次流路Maである。図3で左側のキャップ31に一次流路Maに外部から被処理ガスG1を給送するガス入口流路35が形成され、図3で右側のキャップ32に一次流路Maから処理済みガスを排気するガス出口流路35’が形成される。また、左右の各キャップ31、32の中央部には、二次流路Naから二次ガスG2を排気する排気口36が形成される。   Next, a specific example in which the gas pump of FIG. 1A is applied to an oxygen pump will be described with reference to FIGS. This oxygen pump is fitted with hollow heat-resistant caps 31 and 32 at both ends of a double cylinder structure. The internal space of the inner solid electrolyte cylindrical body 10a and the space between the outer solid electrolyte cylindrical body 10b and the heater 40 are secondary flow paths Na and Nb through which the secondary gas G2 flows in the axial direction and are adjacent inside and outside. A space between the solid electrolyte cylindrical bodies 10a and 10b is a primary flow path Ma through which the gas to be processed G1 flows in the axial direction. In FIG. 3, a gas inlet channel 35 is formed in the left cap 31 to feed the gas G1 to be processed from the outside to the primary channel Ma. In FIG. 3, the processed gas is exhausted from the primary channel Ma to the right cap 32. A gas outlet channel 35 ′ is formed. Further, an exhaust port 36 for exhausting the secondary gas G2 from the secondary flow path Na is formed at the center of each of the left and right caps 31 and 32.

内外2本の固体電解質筒状体10a、10bは、それぞれに内外両面に白金よりなるネット状の電極(図面の+記号、−記号)を形成している。この電極には、図示しない直流電源から直流電圧が印加される。図3においては、内側固体電解質筒状体10aの外面の電極にマイナス電圧が印加され、内面の電極にプラス電圧が印加され、外側固体電解質筒状体10bの外面の電極にプラス電圧が印加され、内面の電極にマイナス電圧が印加される。この内外両面の電極を、図3において+記号と−記号で表示する。このような電極の+、−の表示は、図5以降の他の実施の形態においても同様である。被処理ガスG1は、図18のAr+O2(10-4atm)の被処理ガス(一次ガス)である。また、二次ガスG2は、図18で説明した不活性ガスの処理に基づくガスである。つまり、不活性ガス中の酸素分子(O2)が固体電解質によって電気的に還元されてイオン(O2-)化され、固体電解質を通して再び酸素分子(O2)として固体電解質の外部に放出された酸素分子(O2)と、キャリアガスとしての空気との混合ガスである。 The inner and outer two solid electrolyte cylindrical bodies 10a and 10b respectively form net-like electrodes (+ and-symbols in the drawing) made of platinum on both the inner and outer surfaces. A DC voltage is applied to this electrode from a DC power source (not shown). In FIG. 3, a negative voltage is applied to the outer electrode of the inner solid electrolyte cylindrical body 10a, a positive voltage is applied to the inner electrode, and a positive voltage is applied to the outer electrode of the outer solid electrolyte cylindrical body 10b. A negative voltage is applied to the inner electrode. The electrodes on both the inside and outside are indicated by + and-symbols in FIG. Such display of + and − on the electrode is the same in other embodiments shown in FIG. The gas to be processed G1 is a gas to be processed (primary gas) of Ar + O 2 (10 −4 atm) in FIG. The secondary gas G2 is a gas based on the treatment of the inert gas described with reference to FIG. In other words, oxygen molecules (O 2 ) in the inert gas are electrically reduced and ionized (O 2− ) by the solid electrolyte, and are released again outside the solid electrolyte as oxygen molecules (O 2 ) through the solid electrolyte. A mixed gas of oxygen molecules (O 2 ) and air as a carrier gas.

図3の酸素ポンプの動作を説明する。ヒーター40に通電して内外の固体電解質筒状体10a、10bを共に700℃程度に加熱し、加熱温度を維持する。各固体電解質筒状体10a、10bの内外両面の電極に直流電圧を印加して、キャップ31を介して一次流路Maに被処理ガスG1を流す。被処理ガスG1が一次流路Maを流れる間に内側固体電解質筒状体10aの外面と外側固体電解質筒状体10bの内面に沿って流れるガス中の酸素分子(O2)の一部が固体電解質によって電気的に還元されてイオン(O2-)化され、固体電解質筒状体10a、10bをイオン伝導して二次流路Na、Nbに放出される。被処理ガスG1が一次流路Maを通過する間に酸素分圧が目的値まで下がり、処理済みガスとして一次流路Maからキャップ32を介して排気される。 The operation of the oxygen pump in FIG. 3 will be described. The heater 40 is energized to heat the inner and outer solid electrolyte cylindrical bodies 10a, 10b to about 700 ° C., and the heating temperature is maintained. A direct current voltage is applied to the inner and outer electrodes of each solid electrolyte cylindrical body 10a, 10b, and the gas G1 to be treated is caused to flow through the cap 31 to the primary flow path Ma. A part of oxygen molecules (O 2 ) in the gas flowing along the outer surface of the inner solid electrolyte cylindrical body 10a and the inner surface of the outer solid electrolyte cylindrical body 10b while the gas to be treated G1 flows through the primary flow path Ma is solid. It is electrically reduced by the electrolyte to be ionized (O 2− ), and is ionically conducted through the solid electrolyte cylindrical bodies 10a and 10b to be discharged into the secondary flow paths Na and Nb. While the gas to be treated G1 passes through the primary flow path Ma, the oxygen partial pressure decreases to the target value and is exhausted from the primary flow path Ma through the cap 32 as a processed gas.

図3の酸素ポンプの場合、一次流路Maを流れる被処理ガスG1は、内側固体電解質筒状体10aの外面と外側固体電解質筒状体10bの内面に共に接触して、この外面と内面の両方で酸素分子のイオン化反応によるポンプ動作が同時に行われる。一次流路Maは円筒状で、半径方向の幅が小さいため、内側固体電解質筒状体10aの外面および外側固体電解質筒状体10bの内面の近くを被処理ガスG1が流れることになり、酸素分子のイオン化反応が効率よく行われる。   In the case of the oxygen pump of FIG. 3, the gas to be treated G1 flowing through the primary flow path Ma is in contact with the outer surface of the inner solid electrolyte cylindrical body 10a and the inner surface of the outer solid electrolyte cylindrical body 10b. In both cases, the pumping operation by the ionization reaction of oxygen molecules is performed simultaneously. Since the primary flow path Ma is cylindrical and has a small radial width, the gas to be treated G1 flows near the outer surface of the inner solid electrolyte cylindrical body 10a and the inner surface of the outer solid electrolyte cylindrical body 10b. The ionization reaction of molecules is performed efficiently.

図3の酸素ポンプは、被処理ガスG1が極低酸素分圧の場合に、この酸素分圧を上げるポンプ動作を次のように行う。内外で隣接する各固体電解質筒状体10a、10bの内面両面の電極に印加される直流電圧の極性を逆にして、被処理ガスG1を前述と同様にして流す。処理ガスG1が一次流路Maを流れる間に、二次流路Na、Nbのガス中の酸素分子(O2)がイオン(O2-)化され、各固体電解質筒状体10a、10bをイオン伝導して一次流路Maに酸素分子(O2)が放出され、一次流路Maを流れる被処理ガスG1の酸素分圧が上がる。一次流路Maで酸素分圧制御された処理済みガスがガス出口35’から排気される。このような酸素分圧を上げるポンプ動作は、図5以降の他の酸素ポンプにおいても同様にして行われる。 The oxygen pump shown in FIG. 3 performs the pump operation for increasing the oxygen partial pressure as follows when the gas to be treated G1 has an extremely low oxygen partial pressure. The gas to be treated G1 is flowed in the same manner as described above with the polarity of the DC voltage applied to the electrodes on both inner surfaces of the solid electrolyte cylinders 10a and 10b adjacent inside and outside being reversed. While the processing gas G1 flows through the primary flow path Ma, oxygen molecules (O 2 ) in the gases of the secondary flow paths Na and Nb are ionized (O 2− ), and the solid electrolyte tubular bodies 10a and 10b are turned on. Ion conduction causes oxygen molecules (O 2 ) to be released into the primary channel Ma, and the oxygen partial pressure of the gas to be processed G1 flowing through the primary channel Ma increases. The treated gas whose oxygen partial pressure is controlled in the primary flow path Ma is exhausted from the gas outlet 35 ′. The pump operation for increasing the oxygen partial pressure is performed in the same manner in other oxygen pumps shown in FIG.

次に、図5の断面図と図6の分解斜視図で、図1(B)のガスポンプを酸素ポンプに応用した具体例を説明する。この酸素ポンプは、直径が異なる4本の円形固体電解質筒状体10a〜10dを同心に組み付けた四重筒構造体を備え、両端部にキャップ31、32が被嵌される。最大径の固体電解質筒状体10dの回りにリング状ヒーター40が設置される。隣接する固体電解質筒状体10a、10bの間の筒状空間と、別の隣接する固体電解質筒状体10c、10dの間の筒状空間が一次流路Ma、Mbである。この両流路Ma、Mbは、図5で右端開口がリターン流路Mgで一連に連接されて、直列に連通する。また、最小径の固体電解質筒状体10aの内部空間と、隣接する固体電解質筒状体10b、10cの間の筒状空間、最大径の固体電解質筒状体10dの外部空間が二次流路Na、Nb、Ncである。   Next, referring to the cross-sectional view of FIG. 5 and the exploded perspective view of FIG. 6, a specific example in which the gas pump of FIG. 1B is applied to an oxygen pump will be described. This oxygen pump includes a quadruple cylinder structure in which four circular solid electrolyte cylinders 10a to 10d having different diameters are assembled concentrically, and caps 31 and 32 are fitted on both ends. A ring heater 40 is installed around the solid electrolyte cylinder 10d having the maximum diameter. A cylindrical space between adjacent solid electrolyte cylindrical bodies 10a and 10b and a cylindrical space between other adjacent solid electrolyte cylindrical bodies 10c and 10d are primary flow paths Ma and Mb. Both the flow paths Ma and Mb are connected in series with the right end opening in FIG. 5 being connected in series by a return flow path Mg. Further, the internal space of the solid electrolyte cylindrical body 10a having the smallest diameter, the cylindrical space between the adjacent solid electrolyte cylindrical bodies 10b and 10c, and the external space of the solid electrolyte cylindrical body 10d having the maximum diameter are secondary flow paths. Na, Nb, and Nc.

図5の酸素ポンプは、被処理ガスG1が一次流路Maを流れて両固体電解質筒状体10a、10bで酸素分子のイオン化反応が行われる。さらに、リターン流路Mgを通過して別の一次流路Mbに流れ、両固体電解質筒状体10c、10dで酸素分子のイオン化反応が行われ、最終的に目的値の酸素分圧となって排気される。この図5の酸素ポンプは、図3の酸素ポンプに比べガスと固体電解質との接触面積が増大し、その分、処理できるガス量が増大する。   In the oxygen pump of FIG. 5, the gas G1 to be processed flows through the primary flow path Ma, and an ionization reaction of oxygen molecules is performed in both solid electrolyte cylindrical bodies 10a and 10b. Further, it passes through the return channel Mg and flows into another primary channel Mb, and the ionization reaction of oxygen molecules is performed in both solid electrolyte cylindrical bodies 10c, 10d, and finally the oxygen partial pressure of the target value is obtained. Exhausted. The oxygen pump of FIG. 5 has a larger contact area between the gas and the solid electrolyte than the oxygen pump of FIG. 3, and the amount of gas that can be processed increases accordingly.

図7〜図10で、図2(B)のガスポンプを酸素ポンプに適用した具体例を説明する。   A specific example in which the gas pump of FIG. 2B is applied to an oxygen pump will be described with reference to FIGS.

内外2本の固体電解質筒状体10a、10bは、1本の流路仕切筒体20aを介し隣接する。内外で隣接する2本の固体電解質筒状体10a、10bの間の空間が、1本の流路仕切筒体20aで円筒状の内側空間と外側空間に二分される。2本の固体電解質筒状体10a、10bと1本の円形の流路仕切筒体20aは長さが同一で、これらを同心にして三重に組み付けた三重筒構造体の両開口端部に耐熱性キャップ31、32が被嵌される。左右のキャップ31、32は、各固体電解質筒状体10a、10bと流路仕切筒体20aを同心に組み付けて固定する。最大径の外側固体電解質筒状体10bの回りに共通のリング状ヒーター40が設置される。ヒーター40と外側固体電解質筒状体10bの間に、ガス流路となる円筒状の空間が形成される。   The inner and outer two solid electrolyte cylinders 10a and 10b are adjacent to each other via one flow path partition cylinder 20a. A space between two solid electrolyte cylindrical bodies 10a and 10b adjacent inside and outside is divided into a cylindrical inner space and an outer space by one flow path partitioning cylinder 20a. The two solid electrolyte cylindrical bodies 10a and 10b and the single circular flow channel partitioning cylinder 20a have the same length, and heat resistance is provided at both open ends of the triple cylinder structure in which these are concentrically assembled. The caps 31 and 32 are fitted. The left and right caps 31 and 32 fix the solid electrolyte cylindrical bodies 10a and 10b and the flow path partitioning cylinder 20a concentrically. A common ring heater 40 is installed around the outermost solid electrolyte cylindrical body 10b having the maximum diameter. A cylindrical space serving as a gas flow path is formed between the heater 40 and the outer solid electrolyte cylindrical body 10b.

最小径の内側固体電解質筒状体10aの内部空間と、流路仕切筒体20aと外側固体電解質筒状体10bの間の空間が一次流路Ma、Mbである。図7で右側のキャップ32の内部に形成したリターン流路Mgで、内外の一次流路Ma、Mbが直列に連接されて一連に連通する。図7で左側のキャップ31の中央部に形成したガス入口33から被処理ガスG1が内側固体電解質筒状体10aの内部の一次流路Maに給送され、図1で右方の軸方向に流れる。この被処理ガスG1は右側キャップ32の内面中央部に形成したガス出口からリターン流路Mgに流出し、リターン流路Mgを上下左右放射状に流れて外側固体電解質筒状体10bと流路仕切筒体20aの間の一次流路Mbに流入する。一次流路Mbに流入した被処理ガスG1は、図7で左方の軸方向に流れ、左側キャップ31の周辺部に形成したガス出口34から処理済みガスとして排気される。被処理ガスG1が一次流路Ma、bを流れる間に、酸素イオン還元によるイオン伝導が行われる。被処理ガスG1が一次流路Maを流れる方向(図7で右方向)と、一次流路Mcを流れる方向(図7で左方向)が180度逆であり、中間のリターン流路Mgでガス流を最短距離で180度リターンさせている。このリターンするガス流路はイオン伝導が行われない部所であるが、この部所を最短距離にすることで、酸素ポンプ全体としてのイオン伝導の効率低下が抑制される。   The inner space of the minimum inner diameter solid electrolyte cylindrical body 10a and the space between the flow path partitioning cylindrical body 20a and the outer solid electrolyte cylindrical body 10b are the primary flow paths Ma and Mb. In FIG. 7, the return flow channel Mg formed inside the right cap 32 connects the inner and outer primary flow channels Ma and Mb in series and communicates in series. The gas G1 to be treated is fed from the gas inlet 33 formed at the center of the left cap 31 in FIG. 7 to the primary flow path Ma inside the inner solid electrolyte cylindrical body 10a. In FIG. Flowing. This gas to be treated G1 flows out from the gas outlet formed at the center of the inner surface of the right cap 32 to the return channel Mg, flows radially through the return channel Mg vertically and horizontally, and flows into the outer solid electrolyte cylindrical body 10b and the channel partition cylinder. It flows into the primary flow path Mb between the bodies 20a. The gas to be processed G1 flowing into the primary flow path Mb flows in the left axial direction in FIG. 7 and is exhausted as a processed gas from the gas outlet 34 formed in the peripheral portion of the left cap 31. While the gas to be processed G1 flows through the primary flow paths Ma, b, ion conduction by oxygen ion reduction is performed. The direction in which the gas to be treated G1 flows through the primary flow path Ma (right direction in FIG. 7) and the direction in which the gas G1 flows through the primary flow path Mc (left direction in FIG. 7) are 180 degrees opposite, and gas flows through the intermediate return flow path Mg. The flow is returned 180 degrees at the shortest distance. This returning gas flow path is a portion where ion conduction is not performed, but by making this portion the shortest distance, a decrease in the efficiency of ion conduction as a whole oxygen pump is suppressed.

内側固体電解質筒状体10aと流路仕切筒体20aの間の筒状空間と、外側固体電解質筒状体10bとヒーター40との間の外部空間が、二次ガスG2を排気する二次流路Na、Nbである。左右のキャップ31、32には、二次流路Naに連通するガス出入口35、36が形成される。二次流路Nbの両端は開口されて、それぞれに対応するガス出入口35、36に連通させてある。   The secondary space in which the cylindrical space between the inner solid electrolyte cylindrical body 10a and the flow path partitioning cylinder 20a and the outer space between the outer solid electrolyte cylindrical body 10b and the heater 40 exhaust the secondary gas G2. Path Na, Nb. In the left and right caps 31 and 32, gas inlets and outlets 35 and 36 communicating with the secondary channel Na are formed. Both ends of the secondary flow path Nb are opened and communicated with gas inlets 35 and 36 corresponding to the respective ends.

図7の酸素ポンプの動作は、図3や図5の酸素ポンプと同様にして行われる。ヒーター40に通電して各固体電解質筒状体10a、10bを共に700℃程度に加熱し、加熱温度を維持する。各固体電解質筒状体10a、10bの内外両面の電極に直流電圧を印加して、一次流路Maに被処理ガスG1を流し、リターン流路Mgでリターンさせて一次流路Mbに流す。被処理ガスG1が一次流路Maを流れる間にガス中の酸素分子(O2)の一部が固体電解質によって電気的に還元されてイオン(O2-)化され、固体電解質筒状体10aをイオン伝導して二次流路Naに放出される。被処理ガスG1が一次流路Maを通過する間に酸素分圧が下がり、一次流路Maから次の一次流路Mbにリターンして流入する。被処理ガスG1が一次流路Mbを流れる間にさらにイオン化反応が行われて外側固体電解質筒状体10bから二次流路Nbに放出される。このようにして二段階式に被処理ガスG1の酸素分圧制御が行われて、最終的にの処理済みガスとして一次流路Mbから排気される。 The operation of the oxygen pump in FIG. 7 is performed in the same manner as the oxygen pump in FIGS. The heater 40 is energized to heat the solid electrolyte cylinders 10a and 10b to about 700 ° C., and the heating temperature is maintained. A DC voltage is applied to the inner and outer electrodes of each solid electrolyte cylindrical body 10a, 10b, the gas to be treated G1 is caused to flow through the primary flow path Ma, and the gas is returned through the return flow path Mg to flow into the primary flow path Mb. While the gas to be treated G1 flows through the primary flow path Ma, a part of oxygen molecules (O 2 ) in the gas is electrically reduced and ionized (O 2− ) by the solid electrolyte, and the solid electrolyte cylindrical body 10a. Are ion-conducted and discharged to the secondary flow path Na. The oxygen partial pressure decreases while the gas to be treated G1 passes through the primary flow path Ma, and returns from the primary flow path Ma to the next primary flow path Mb and flows in. While the gas to be treated G1 flows through the primary flow path Mb, an ionization reaction is further performed and discharged from the outer solid electrolyte cylindrical body 10b to the secondary flow path Nb. In this way, the oxygen partial pressure control of the gas to be processed G1 is performed in a two-stage manner, and the gas is exhausted from the primary flow path Mb as the final processed gas.

図7の酸素ポンプの場合も、最小径の内側固体電解質筒状体10a内に軸方向に設けた一次流路Maは、小径の円形穴であり、この穴中心部と固体電解質筒状体10a内面との距離は短くて、酸素分子のイオン化反応が効率よく行われる。また、最大径の外側固体電解質筒状体10b内に軸方向に設けた一次流路Mbは、大径の円形穴であるが、この穴の中心部は流路仕切筒体20aが占めている。そのため、一次流路Mbを流れる被処理ガスG1と固体電解質筒状体10bの内面との最大距離は十分に短く、一次流路Mbにおいても酸素分子のイオン化反応が効率よく行われる。内外で隣接する各固体電解質筒状体10a、10bの長さを図20の場合と同一とすると、被処理ガスG1は内側固体電解質筒状体10aの外面に接触し、さらに、外側固体電解質筒状体10bの内面に接触するため、ガスと固体電解質との接触面積が図18と比較して増大する。その結果、被処理ガスG1の流速を上げて、酸素ポンプで処理されるガス流量を増大させることができる。   Also in the case of the oxygen pump of FIG. 7, the primary flow path Ma provided in the axial direction in the inner diameter solid electrolyte tubular body 10a having the smallest diameter is a small-diameter circular hole, and the hole central portion and the solid electrolyte tubular body 10a. The distance from the inner surface is short, and the ionization reaction of oxygen molecules is performed efficiently. Further, the primary flow path Mb provided in the axial direction in the outermost solid electrolyte cylindrical body 10b having the maximum diameter is a large-diameter circular hole, and the central portion of this hole is occupied by the flow path partitioning cylinder 20a. . Therefore, the maximum distance between the gas to be treated G1 flowing through the primary flow path Mb and the inner surface of the solid electrolyte cylindrical body 10b is sufficiently short, and the ionization reaction of oxygen molecules is efficiently performed also in the primary flow path Mb. If the lengths of the solid electrolyte cylindrical bodies 10a and 10b adjacent inside and outside are the same as those in FIG. 20, the gas G1 to be treated contacts the outer surface of the inner solid electrolyte cylindrical body 10a, and further, the outer solid electrolyte cylinders. Since it contacts the inner surface of the body 10b, the contact area between the gas and the solid electrolyte increases as compared with FIG. As a result, it is possible to increase the flow rate of the gas to be processed G1 and increase the flow rate of gas processed by the oxygen pump.

図7の酸素ポンプは、被処理ガスG1を内側の一次流路Maからリターン流路Mgでリターンさせて外側の一次流路Mcに流しているが、逆方向に流すことも可能である。すなわち、被処理ガスG1を外側の一次流路Mbに給送して軸方向に流し、リターン流路Mgで一次流路Maにリターンさせて排気することも可能である。   In the oxygen pump of FIG. 7, the gas G1 to be treated is returned from the inner primary flow path Ma through the return flow path Mg and flows to the outer primary flow path Mc, but can also flow in the reverse direction. That is, the gas G1 to be treated can be fed to the outer primary flow path Mb and flowed in the axial direction, and returned to the primary flow path Ma through the return flow path Mg to be exhausted.

図7の酸素ポンプを応用した他の実施の形態を、図11と図12を参照して説明する。図11の酸素ポンプは、図7の酸素ポンプの固体電解質筒状体と流路仕切筒体を1本ずつ追加したものに相当する。図11の酸素ポンプは、図12に示すような直径が大中小の3段階で異なる3本の円形固体電解質筒状体10a、10b、10cと、直径が大小2段階で異なる2本の流路仕切筒体20a、20bを軸方向水平にして同心に組み付けた五重筒構造体を備える。この場合、最小径の固体電解質筒状体10aと中径の固体電解質筒状体10bの中間に1本の流路仕切筒体20aが設置され、中径の固体電解質筒状体10bと最大径の固体電解質筒状体10cの中間に1本の流路仕切筒体20bが設置される。   Another embodiment to which the oxygen pump of FIG. 7 is applied will be described with reference to FIGS. 11 and 12. The oxygen pump of FIG. 11 corresponds to the oxygen pump of FIG. 7 with one solid electrolyte cylinder and one channel partition cylinder added. The oxygen pump of FIG. 11 has three circular solid electrolyte cylindrical bodies 10a, 10b, and 10c having different diameters in three stages of large, medium, and small as shown in FIG. A quintuple cylinder structure is provided in which the partition cylinders 20a and 20b are axially horizontal and assembled concentrically. In this case, a single channel partition cylinder 20a is installed between the minimum diameter solid electrolyte cylinder 10a and the medium diameter solid electrolyte cylinder 10b, and the medium diameter solid electrolyte cylinder 10b and the maximum diameter One channel partition cylinder 20b is installed in the middle of the solid electrolyte cylinder 10c.

最小径の固体電解質筒状体10aの内部空間が、被処理ガスG1を軸方向に流す一次流路Maとなる。中径の固体電解質筒状体10bと流路仕切筒体20aの間の空間が、一次流路Maとリターン流路Mgで直列に連通された一次流路Mbとなる。中径の固体電解質筒状体10bと流路仕切筒体20bの間の空間が、一次流路Mbとリターン流路Mhで直列に連通された一次流路Mcとなる。最小径の固体電解質筒状体10aと流路仕切筒体20aの間の空間が、二次ガスG2を軸方向に流して排気する二次流路Naとなる。中径の固体電解質筒状体10bと流路仕切筒体20bの間の空間と、最大径の固体電解質筒状体10cの外部空間が、二次ガスG2を軸方向に流して排気する二次流路Nb、Ncとなる。   The internal space of the solid electrolyte cylindrical body 10a having the minimum diameter becomes the primary flow path Ma that allows the gas to be processed G1 to flow in the axial direction. A space between the medium-diameter solid electrolyte cylindrical body 10b and the flow path partitioning cylinder body 20a becomes a primary flow path Mb communicated in series with the primary flow path Ma and the return flow path Mg. A space between the medium-diameter solid electrolyte cylindrical body 10b and the flow path partitioning cylindrical body 20b becomes a primary flow path Mc connected in series by the primary flow path Mb and the return flow path Mh. The space between the solid electrolyte cylindrical body 10a having the minimum diameter and the flow path partitioning cylinder 20a becomes the secondary flow path Na that exhausts the secondary gas G2 in the axial direction. The space between the medium-diameter solid electrolyte cylindrical body 10b and the channel partitioning cylinder 20b and the external space of the maximum-diameter solid electrolyte cylindrical body 10c flow secondary gas G2 in the axial direction and exhaust the secondary gas. The flow paths become Nb and Nc.

図11の酸素ポンプの酸素分圧制御のためのポンプ動作は、図7の酸素ポンプと同様に行われることから詳細説明は省略する。図11の酸素ポンプの場合、被処理ガスG1が3本の固体電解質筒状体10a〜10cの内外面に沿って流れるため、ガスと固体電解質との有効接触面積が尚一層に増大し、その分、処理できるガス量が増大する。   The pump operation for oxygen partial pressure control of the oxygen pump in FIG. 11 is performed in the same manner as the oxygen pump in FIG. In the case of the oxygen pump of FIG. 11, the gas G1 to be treated flows along the inner and outer surfaces of the three solid electrolyte cylindrical bodies 10a to 10c, so that the effective contact area between the gas and the solid electrolyte is further increased. This increases the amount of gas that can be processed.

以上の各実施の形態は、固体電解質筒状体の中心線を水平にした横置き仕様の酸素ポンプである。次に、固体電解質筒状体の中心線を略鉛直にした縦置き仕様の酸素ポンプの具体例を図13〜図18を参照して説明する。   Each of the above-described embodiments is a laterally-positioned oxygen pump in which the center line of the solid electrolyte cylindrical body is horizontal. Next, a specific example of a vertically installed oxygen pump in which the center line of the solid electrolyte cylindrical body is substantially vertical will be described with reference to FIGS.

図13及び図14に示す酸素ポンプは、図3の酸素ポンプを縦置き仕様にしたものに相当する。つまり、直径が大小異なる2本の円形固体電解質筒状体10a、10bを同心に組み合わせ、各固体電解質筒状体10a、10bの中心線を略鉛直に配置する。鉛直に縦配置された2本の固体電解質筒状体10a、10bの下端部が中空の下部キャップ12に連結され、各固体電解質筒状体10a、10bの上端部が中空の上部キャップ13に連結される。大径の固体電解質筒状体10bの回りにリング状ヒーター40が設置される。   The oxygen pump shown in FIGS. 13 and 14 corresponds to a vertical installation of the oxygen pump shown in FIG. That is, two circular solid electrolyte cylindrical bodies 10a and 10b having different diameters are concentrically combined, and the center lines of the solid electrolyte cylindrical bodies 10a and 10b are arranged substantially vertically. The lower ends of two vertically disposed solid electrolyte cylinders 10a and 10b are connected to a hollow lower cap 12, and the upper ends of the solid electrolyte cylinders 10a and 10b are connected to a hollow upper cap 13. Is done. A ring heater 40 is installed around the large-diameter solid electrolyte cylindrical body 10b.

ヒーター40で各固体電解質筒状体10a、10bを700℃程度に加熱した状態で、下部キャップ12の中の流路穴14に被処理ガスG1を給送する。下部キャップ12の流路穴14と各固体電解質筒状体10a、10bの間の筒状空間である一次流路Maが連通させてあり、流路穴14に外部から給送された被処理ガスG1は、一次通路Maに流入して上昇する。被処理ガスG1が鉛直な一次流路Maを上昇する間に、酸素分子のイオン化反応が行われて、処理済みガスが中空の上部キャップ13に入り、最終的に排気される。また、固体電解質筒状体10aの内部空間である二次流路Naと、固体電解質筒状体10bの外部空間である二次流路Nbに放出された酸素分子が周囲のキャリアガス(空気)と共に排気される。図13の酸素ポンプも図3の酸素ポンプと同様に、ガスと固体電解質の接触面積が増大して、処理されるガス量が増大する。図13の酸素ポンプの場合、被処理ガスG1が上昇する筒状一次流路Maは周方向に温度差がなく、周方向での酸素透過能力差が解消されて、被処理ガスG1が一次流路Maの全周で均一的に酸素分圧制御される。その結果、酸素分圧の制御精度を向上させることができる。このような筒状一次流路における周方向温度差低減による効果は、図15および図16の酸素ポンプにおいても同様である。   In a state where the solid electrolyte cylindrical bodies 10 a and 10 b are heated to about 700 ° C. by the heater 40, the gas G <b> 1 to be processed is fed to the flow path hole 14 in the lower cap 12. A primary flow path Ma, which is a cylindrical space between the flow path hole 14 of the lower cap 12 and each of the solid electrolyte cylindrical bodies 10a and 10b, communicates, and the gas to be processed fed from the outside to the flow path hole 14 G1 flows into the primary passage Ma and rises. While the gas to be treated G1 moves up the vertical primary flow path Ma, an ionization reaction of oxygen molecules is performed, and the treated gas enters the hollow upper cap 13 and is finally exhausted. Also, oxygen molecules released into the secondary flow path Na, which is the internal space of the solid electrolyte cylindrical body 10a, and the secondary flow path Nb, which is the external space of the solid electrolyte cylindrical body 10b, are the surrounding carrier gas (air). It is exhausted with. Similarly to the oxygen pump of FIG. 3, the oxygen pump of FIG. 13 increases the contact area between the gas and the solid electrolyte, and the amount of gas to be processed increases. In the case of the oxygen pump of FIG. 13, the cylindrical primary flow path Ma in which the gas to be processed G1 rises has no temperature difference in the circumferential direction, and the difference in oxygen transmission capacity in the circumferential direction is eliminated, so that the gas to be processed G1 flows as a primary flow. The oxygen partial pressure is uniformly controlled over the entire circumference of the path Ma. As a result, it is possible to improve the control accuracy of the oxygen partial pressure. The effect obtained by reducing the circumferential temperature difference in the cylindrical primary flow path is the same in the oxygen pumps of FIGS. 15 and 16.

図15及び図16に示す酸素ポンプは、図13の酸素ポンプを応用したものである。図15の酸素ポンプは、直径が大小異なる2本の円形固体電解質筒状体10a、10bを同心に組み合わせてユニット化した円形固体電解質筒状体ユニット10’を複数ユニット使用する。同一サイズの複数の個体電解質筒状体10’を、各々の中心軸を鉛直にして等間隔で同心円上に設置する。鉛直に縦配置された複数の円形固体電解質筒状体ユニット10’の下端部が中空の下部キャップ12に連結され、各固体電解質筒状体ユニット10’の上端部が中空の上部キャップ13に連結される。同心円上の複数の固体電解質筒状体ユニット10’で囲まれる空間に蓄熱部材例えばダミーパイプ15が設置される。ダミーパイプ15の上下端部が各キャップ12、13に固定される。同心円上の複数の固体電解質筒状体ユニット10’の回りにリング状ヒーター40が設置される。   The oxygen pump shown in FIGS. 15 and 16 is an application of the oxygen pump shown in FIG. The oxygen pump of FIG. 15 uses a plurality of circular solid electrolyte cylindrical units 10 'that are unitized by concentrically combining two circular solid electrolyte cylindrical bodies 10a and 10b having different diameters. A plurality of solid electrolyte cylinders 10 ′ having the same size are placed on concentric circles at equal intervals with each central axis being vertical. The lower ends of a plurality of circular solid electrolyte cylindrical units 10 ′ vertically arranged are connected to a hollow lower cap 12, and the upper ends of each solid electrolyte cylindrical unit 10 ′ are connected to a hollow upper cap 13. Is done. A heat storage member such as a dummy pipe 15 is installed in a space surrounded by a plurality of solid electrolyte cylindrical units 10 ′ on concentric circles. The upper and lower ends of the dummy pipe 15 are fixed to the caps 12 and 13. A ring-shaped heater 40 is installed around a plurality of concentric solid electrolyte cylinder units 10 '.

図15の酸素ポンプの場合、複数の各固体電解質筒状体ユニット10’の内側固体電解質筒状体10aと外側固体電解質筒状体10bの間の筒状空間が被処理ガスG1を流す一次流路Mpであり、内側固体電解質筒状体10aの内部空間と各固体電解質筒状体ユニット10’の間の空間が二次流路Npである。下部キャップ12を下にして各固体電解質筒状体ユニット10’を縦置きした状態にして、周囲からヒーター40で加熱する。各固体電解質筒状体ユニット10’はヒーター40から等距離にあるので加熱斑少なくして均一的に加熱される。また、各固体電解質筒状体ユニット10’で囲まれる内部空間にあるダミーパイプ15もヒーター40で加熱される。このダミーパイプ15の蓄熱で、ダミーパイプ15の回りの各固体電解質筒状体ユニット10’が加熱される。つまり、複数の各固体電解質筒状体ユニット107は、内外双方から加熱されるので、周方向に温度差少なくして均一的に加熱され、かつ、加熱効率が良くなり、ヒーター40の消費電力量を抑えることができる。   In the case of the oxygen pump of FIG. 15, the primary flow in which the cylindrical space between the inner solid electrolyte cylindrical body 10a and the outer solid electrolyte cylindrical body 10b of each of the plurality of solid electrolyte cylindrical units 10 ′ flows the gas G1 to be processed. The path Mp, and the space between the internal space of the inner solid electrolyte cylindrical body 10a and each solid electrolyte cylindrical body unit 10 'is the secondary flow path Np. Each solid electrolyte cylindrical body unit 10 ′ is placed vertically with the lower cap 12 facing down, and heated by the heater 40 from the surroundings. Since each solid electrolyte cylindrical unit 10 'is equidistant from the heater 40, it is heated uniformly with less heating spots. Further, the dummy pipe 15 in the internal space surrounded by each solid electrolyte cylindrical unit 10 ′ is also heated by the heater 40. The solid electrolyte cylindrical unit 10 ′ around the dummy pipe 15 is heated by the heat storage of the dummy pipe 15. That is, since each of the plurality of solid electrolyte tubular units 107 is heated from both inside and outside, it is heated uniformly with a small temperature difference in the circumferential direction, and the heating efficiency is improved. Can be suppressed.

各固体電解質筒状体ユニット10’を700℃程度に加熱した状態で、下部キャップ12の流路穴14に被処理ガスG1を給送する。流路穴14と各固体電解質筒状体ユニット10’の一次流路Mpが連通させてあり、下部キャップ12に外部から給送された被処理ガスG1は、各固体電解質筒状体ユニット10’の一次通路Mpにほぼ同時にほぼ同量で流入し、上昇する。被処理ガスG1が鉛直な一次流路Mpを上昇する間に、周方向で均一的に酸素分子のイオン化反応が行われて、酸素分圧の制御精度を上げることができる。最終的に処理済みガスが中空の上部キャップ13に入り、排気される。また、各固体電解質筒状体ユニット10’の外部空間である二次流路Npに放出された酸素分子が周囲のキャリアガス(空気)と共に排気される。下部キャップ12に給送された被処理ガスG1が複数本の固体電解質筒状体ユニット10’内を通過するため、ガスと固体電解質の接触面積が増大して、処理されるガス量が増大する。   In a state where each solid electrolyte cylindrical body unit 10 ′ is heated to about 700 ° C., the gas G <b> 1 to be processed is fed to the flow path hole 14 of the lower cap 12. The flow path hole 14 and the primary flow path Mp of each solid electrolyte cylindrical body unit 10 ′ are communicated with each other, and the gas to be processed G1 fed from the outside to the lower cap 12 is supplied to each solid electrolyte cylindrical body unit 10 ′. Into the primary passage Mp at substantially the same amount and rise. While the gas to be treated G1 moves up the vertical primary flow path Mp, the ionization reaction of oxygen molecules is uniformly performed in the circumferential direction, and the control accuracy of the oxygen partial pressure can be increased. Finally, the treated gas enters the hollow upper cap 13 and is exhausted. In addition, oxygen molecules released into the secondary flow path Np, which is the external space of each solid electrolyte cylindrical unit 10 ', are exhausted together with the surrounding carrier gas (air). Since the gas to be processed G1 fed to the lower cap 12 passes through the plurality of solid electrolyte cylindrical units 10 ′, the contact area between the gas and the solid electrolyte increases, and the amount of gas to be processed increases. .

図15に示す酸素ポンプの固体電解質筒状体ユニット10’は、二重筒構造体としたが、二重以上の多重筒構造体にしてもよく、また、単一の固体電解質筒状体のみでユニット化しない構造体も可能である。その具体例を図17及び図18に示す。   Although the solid electrolyte cylindrical unit 10 ′ of the oxygen pump shown in FIG. 15 is a double cylindrical structure, it may be a double or more multiple cylindrical structure, or only a single solid electrolyte cylindrical body. Structures that are not unitized are also possible. Specific examples thereof are shown in FIGS.

図17及び図18に示す酸素ポンプは、図13の酸素ポンプを応用したもので、同一径で同一長さの複数の円形固体電解質筒状体11を、各々の中心軸を鉛直にして同心円上に設置している。鉛直に縦配置された複数の円形固体電解質筒状体11の下端部が中空の下部キャップ12に連結され、上端部が中空の上部キャップ13に連結される。同心円上の複数の固体電解質筒状体11で囲まれる空間に蓄熱部材のダミーパイプ15が設置される。ダミーパイプ15の上下端部が各キャップ12、13に固定される。同心円上の複数の固体電解質筒状体11の回りにリング状ヒーター40が設置される。   The oxygen pump shown in FIG. 17 and FIG. 18 is an application of the oxygen pump of FIG. 13, and a plurality of circular solid electrolyte cylinders 11 having the same diameter and the same length are arranged concentrically with their central axes vertical. It is installed in. The lower ends of the plurality of circular solid electrolyte cylinders 11 vertically arranged vertically are connected to the hollow lower cap 12, and the upper ends are connected to the hollow upper cap 13. A dummy pipe 15 as a heat storage member is installed in a space surrounded by a plurality of solid electrolyte cylindrical bodies 11 on concentric circles. The upper and lower ends of the dummy pipe 15 are fixed to the caps 12 and 13. A ring heater 40 is installed around the plurality of concentric solid electrolyte cylinders 11.

図17の酸素ポンプの場合、複数の各固体電解質筒状体11の内部空間が被処理ガスG1を流す一次流路Mpであり、各固体電解質筒状体11の間の空間が二次流路Npである。下部キャップ12を下にして各固体電解質筒状体11を縦置きした状態にして、周囲からヒーター40で加熱する。各固体電解質筒状体11はヒーター40から等距離にあるので加熱斑少なくして均一的に加熱され、ダミーパイプ15もヒーター40で加熱される。ダミーパイプ15の蓄熱で、ダミーパイプ15の回りの各固体電解質筒状体11が加熱される。この場合も、複数の各固体電解質筒状体11は、内外双方から加熱されるので、加熱効率が良くなり、ヒーター40の消費電力量を抑えることができる。   In the case of the oxygen pump of FIG. 17, the internal space of each of the plurality of solid electrolyte cylindrical bodies 11 is a primary flow path Mp through which the gas to be processed G1 flows, and the space between the solid electrolyte cylindrical bodies 11 is a secondary flow path. Np. Each solid electrolyte cylindrical body 11 is placed vertically with the lower cap 12 facing down, and heated by the heater 40 from the surroundings. Since each solid electrolyte cylindrical body 11 is equidistant from the heater 40, it is heated uniformly with less heating spots, and the dummy pipe 15 is also heated by the heater 40. Each solid electrolyte cylindrical body 11 around the dummy pipe 15 is heated by the heat storage of the dummy pipe 15. Also in this case, since each of the plurality of solid electrolyte cylindrical bodies 11 is heated from both inside and outside, the heating efficiency is improved and the power consumption of the heater 40 can be suppressed.

各固体電解質筒状体11を700℃程度に加熱した状態で、下部キャップ12の流路穴14に被処理ガスG1を給送する。流路穴14と各固体電解質筒状体11の一次流路Mpが連通させてあり、下部キャップ12に外部から給送された被処理ガスG1は、各固体電解質筒状体11の一次通路Mpにほぼ同時にほぼ同量で流入し、上昇する。被処理ガスG1が鉛直な一次流路Mpを上昇する間に、酸素分子のイオン化反応が行われて、処理済みガスが中空の上部キャップ13に入り、最終的に排気される。また、各固体電解質筒状体11の外部空間である二次流路Npに放出された酸素分子が周囲のキャリアガスと共に排気される。下部キャップ12に給送された被処理ガスG1が複数本の固体電解質筒状体11内を通過するため、ガスと固体電解質の接触面積が増大して、処理されるガス量が増大する。また、複数本の固体電解質筒状体11が均一的に加熱されて固体間の酸素透過能力差が解消されるため、酸素分圧の制御精度を向上させることができる。   In a state where each solid electrolyte cylindrical body 11 is heated to about 700 ° C., the gas G1 to be treated is fed to the flow path hole 14 of the lower cap 12. The flow path hole 14 and the primary flow path Mp of each solid electrolyte cylindrical body 11 communicate with each other, and the gas G1 to be treated fed from the outside to the lower cap 12 flows into the primary passage Mp of each solid electrolyte cylindrical body 11. At the same time, it flows in almost the same amount and rises. While the gas to be processed G1 moves up the vertical primary flow path Mp, an ionization reaction of oxygen molecules is performed, and the processed gas enters the hollow upper cap 13 and is finally exhausted. Further, oxygen molecules released into the secondary flow path Np, which is the external space of each solid electrolyte cylindrical body 11, are exhausted together with the surrounding carrier gas. Since the gas to be processed G1 fed to the lower cap 12 passes through the plurality of solid electrolyte cylindrical bodies 11, the contact area between the gas and the solid electrolyte increases, and the amount of gas to be processed increases. In addition, since the plurality of solid electrolyte cylindrical bodies 11 are uniformly heated and the difference in oxygen permeability between solids is eliminated, the control accuracy of the oxygen partial pressure can be improved.

なお、本発明のガスポンプは、上記した実施の形態に限定されるものではなく、特許請求の範囲に記載の要旨を逸脱しない範囲内において種々変更を加え得ることは勿論である。   The gas pump of the present invention is not limited to the above-described embodiment, and various changes can be made without departing from the scope of the claims.

(A)〜(C)はガスポンプ(酸素ポンプ)の各種の実施の形態を説明するための断面図である。(A)-(C) are sectional drawings for demonstrating various embodiment of a gas pump (oxygen pump). (A)(B)は他の実施の形態を説明するための断面図である。(A) (B) is sectional drawing for demonstrating other embodiment. 図1(A)のガスポンプの具体例を示す断面図である。It is sectional drawing which shows the specific example of the gas pump of FIG. 1 (A). 図3のT1−T1線に沿う断面図である。It is sectional drawing which follows the T1-T1 line | wire of FIG. 他の実施の形態を示すガスポンプの概要を示す断面図である。It is sectional drawing which shows the outline | summary of the gas pump which shows other embodiment. 図5のガスポンプの要部の分解斜視図である。It is a disassembled perspective view of the principal part of the gas pump of FIG. 他の実施の形態を示すガスポンプの概要を示す断面図である。It is sectional drawing which shows the outline | summary of the gas pump which shows other embodiment. 図7のT2−T2線に沿う断面図である。It is sectional drawing which follows the T2-T2 line | wire of FIG. 図7のガスポンプの要部の左側面図である。It is a left view of the principal part of the gas pump of FIG. 図7のT3−T3線に沿う断面図である。It is sectional drawing which follows the T3-T3 line | wire of FIG. 他の実施の形態を示すガスポンプの概要を示す断面図である。It is sectional drawing which shows the outline | summary of the gas pump which shows other embodiment. 図11のガスポンプの要部の分解斜視図である。It is a disassembled perspective view of the principal part of the gas pump of FIG. 他の実施の形態を示すガスポンプの概要を示す部分断面を含む側面図である。It is a side view including the partial cross section which shows the outline | summary of the gas pump which shows other embodiment. 図13のT4−T4線に沿う断面図である。It is sectional drawing which follows the T4-T4 line | wire of FIG. 他の実施の形態を示すガスポンプの概要を示す部分断面を含む側面図である。It is a side view including the partial cross section which shows the outline | summary of the gas pump which shows other embodiment. 図15のT5−T5線に沿う断面図である。It is sectional drawing which follows the T5-T5 line | wire of FIG. 他の実施の形態を示すガスポンプの概要を示す部分断面を含む側面図である。It is a side view including the partial cross section which shows the outline | summary of the gas pump which shows other embodiment. 図16のT6−T6線に沿う断面図である。It is sectional drawing which follows the T6-T6 line | wire of FIG. 酸素ポンプを使用した設備のブロック図である。It is a block diagram of the installation using an oxygen pump. 酸素ポンプの概要を示す断面図である。It is sectional drawing which shows the outline | summary of an oxygen pump.

符号の説明Explanation of symbols

10a〜10d 固体電解質筒状体
10’ 固体電解質筒状体ユニット
11 固体電解質筒状体
12 下部キャップ
13 上部キャップ
15 ダミーパイプ
20a、20b 流路仕切筒体
31 キャップ
32 キャップ
40 加熱装置、リング状ヒーター
G1 被処理ガス
G2 二次ガス
E 直流電源
+、− 電極
M 一次流路
N 二次流路
10a to 10d Solid electrolyte cylindrical body 10 'Solid electrolyte cylindrical body unit 11 Solid electrolyte cylindrical body 12 Lower cap 13 Upper cap 15 Dummy pipe 20a, 20b Channel partition cylindrical body 31 Cap 32 Cap 40 Heating device, ring-shaped heater G1 Gas to be treated G2 Secondary gas E DC power source +,-Electrode M Primary flow path N Secondary flow path

Claims (11)

同心にして多重に配設された、それぞれが内外両面に電極を有する、径の異なる複数の固体電解質筒状体と、
前記複数の固体電解質筒状体のそれぞれの前記内外両面の電極に、異なる極性となる電圧を印加する直流電源と、
最外側の前記固体電解質筒状体の回りに配置した加熱装置と、
を有することを特徴とするガスポンプ。
A plurality of concentrically arranged, each having electrodes on both the inner and outer surfaces, a plurality of solid electrolyte cylindrical bodies having different diameters;
A direct current power source that applies voltages having different polarities to the electrodes on both the inner and outer surfaces of each of the plurality of solid electrolyte cylindrical bodies;
A heating device disposed around the outermost solid electrolyte tubular body;
A gas pump comprising:
前記複数の固体電解質筒状体間の筒状空間で、最小径の固体電解質筒状体の内部空間から数えて奇数番目の空間をポンプ動作対象の被処理ガスの処理に基づく二次ガスを固体電解質筒状体軸方向に流す二次流路とし、残りの偶数番目の空間を前記二次流路と区分けされた一次流路として、この一次流路に前記被処理ガスを固体電解質筒状体軸方向に流すと共に、前記一次流路に接する固体電解質筒状体面と前記二次流路に接する固体電解質筒状体面に異なる極性となる電圧を印加することを特徴とする請求項1に記載のガスポンプ。   In the cylindrical space between the plurality of solid electrolyte cylinders, an odd-numbered space counted from the internal space of the solid electrolyte cylinder with the smallest diameter is a solid secondary gas based on the processing of the gas to be pumped. As a secondary flow path that flows in the axial direction of the electrolyte cylindrical body, and the remaining even-numbered space as a primary flow path that is separated from the secondary flow path, the gas to be treated is supplied to the primary flow path as a solid electrolyte cylindrical body. The voltage having different polarities is applied to the surface of the solid electrolyte cylindrical body in contact with the primary flow path and the surface of the solid electrolyte cylindrical body in contact with the secondary flow path while flowing in the axial direction. Gas pump. 前記複数の固体電解質筒状体間の筒状空間で、最小径の固体電解質筒状体の内部空間から数えて奇数番目の空間をポンプ動作対象の被処理ガスを固体電解質筒状体軸方向に流す一次流路とし、残りの偶数番目の空間を前記一次流路と区分けされた二次流路として、この二次流路に前記被処理ガスの処理に基づく二次ガスを流すと共に、前記一次流路に接する固体電解質筒状体面と前記二次流路に接する固体電解質筒状体面に異なる極性となる電圧を印加することを特徴とする請求項1に記載のガスポンプ。   In the cylindrical space between the plurality of solid electrolyte cylindrical bodies, the odd-numbered space counted from the internal space of the solid electrolyte cylindrical body with the smallest diameter is the target gas to be pumped in the axial direction of the solid electrolyte cylindrical body. As a primary flow path to flow, the remaining even-numbered space as a secondary flow path that is separated from the primary flow path, a secondary gas based on the processing of the gas to be processed is flowed to the secondary flow path, and the primary flow 2. The gas pump according to claim 1, wherein voltages having different polarities are applied to the surface of the solid electrolyte cylindrical body in contact with the flow path and the surface of the solid electrolyte cylindrical body in contact with the secondary flow path. 前記複数の固体電解質筒状体間の筒状空間に、この空間を内側空間と外側空間に区分けする流路仕切筒体を、前記固体電解質筒状体と同心に配設して、前記区分けされた内側空間と外側空間の一方をポンプ動作対象の被処理ガスを固体電解質筒状体軸方向に流す一次流路とし、他方を前記被処理ガスの処理に基づく二次ガスを流す二次流路とすると共に、前記一次流路に接する固体電解質筒状体面と前記二次流路に接する固体電解質筒状体面に異なる極性となる電圧を印加することを特徴とする請求項1に記載のガスポンプ。   In the cylindrical space between the plurality of solid electrolyte cylindrical bodies, a flow path partitioning cylinder that divides this space into an inner space and an outer space is disposed concentrically with the solid electrolyte cylindrical body, and is divided. One of the inner space and the outer space is used as a primary flow path for flowing the gas to be pumped in the direction of the solid electrolyte cylindrical body, and the other is a secondary flow path for flowing a secondary gas based on the processing of the gas to be processed. The gas pump according to claim 1, wherein voltages having different polarities are applied to the surface of the solid electrolyte cylindrical body in contact with the primary flow path and the surface of the solid electrolyte cylindrical body in contact with the secondary flow path. 前記一次流路と二次流路を交互に多重に配設し、径方向で隣接する一次流路を直列に連通させて、この隣接する一次流路の一方から流出する前記被処理ガスを反対方向にリターンさせて他方に流入させるようにしたことを特徴とする請求項2〜4のいずれかに記載のガスポンプ。   The primary flow path and the secondary flow path are alternately arranged in multiple layers, the primary flow paths that are adjacent in the radial direction are connected in series, and the gas to be processed flowing out from one of the adjacent primary flow paths is opposed. The gas pump according to any one of claims 2 to 4, wherein the gas pump is returned in the direction and allowed to flow into the other. 前記一次流路と二次流路を交互に多重に配設して、径方向で隣接する一次流路を並列に連通させて、この隣接する一次流路に前記処理ガスを同方向に流すようにしたことを特徴とする請求項2〜4のいずれかに記載のガスポンプ。   The primary flow paths and the secondary flow paths are alternately arranged in multiple layers, and the primary flow paths adjacent in the radial direction are connected in parallel so that the processing gas flows through the adjacent primary flow paths in the same direction. The gas pump according to any one of claims 2 to 4, wherein the gas pump is configured as described above. 前記複数の固体電解質筒状体を、各々の中心線が略鉛直な縦置き仕様で多重に配設したことを特徴とする請求項1〜6のいずれかに記載のガスポンプ。   The gas pump according to any one of claims 1 to 6, wherein the plurality of solid electrolyte cylindrical bodies are arranged in multiples in a vertically placed specification in which each center line is substantially vertical. 前記複数の固体電解質筒状体の下端部に前記一次流路に連通する流路穴を有する中空のキャップを被嵌したことを特徴とする請求項7に記載のガスポンプ。   The gas pump according to claim 7, wherein a hollow cap having a flow path hole communicating with the primary flow path is fitted to lower end portions of the plurality of solid electrolyte cylindrical bodies. 同心にして多重に配設された前記複数の固体電解質筒状体からなる固体電解質筒状体ユニットを、各々の中心線が略鉛直となる縦置き仕様で同心円上に等間隔で複数配設し、この複数の固体電解質筒状体ユニットを囲むリング状の加熱装置で各固体電解質筒状体ユニットを加熱することを特徴とする請求項7または8に記載のガスポンプ。   A plurality of solid electrolyte cylinder units composed of the plurality of solid electrolyte cylinders arranged concentrically and in a plurality are arranged at equal intervals on concentric circles in a vertically placed specification in which each center line is substantially vertical. The gas pump according to claim 7 or 8, wherein each solid electrolyte cylindrical body unit is heated by a ring-shaped heating device surrounding the plurality of solid electrolyte cylindrical body units. 前記複数の固体電解質筒状体ユニットで囲まれる空間に前記加熱装置で加熱されて蓄熱する蓄熱部材を配置したことを特徴とする請求項9に記載のガスポンプ。   The gas pump according to claim 9, wherein a heat storage member that stores heat by being heated by the heating device is disposed in a space surrounded by the plurality of solid electrolyte cylindrical units. 前記固体電解質筒状体が酸化物イオン導電体であることを特徴とする請求項1〜10のいずれかに記載のガスポンプ。   The gas pump according to any one of claims 1 to 10, wherein the solid electrolyte cylindrical body is an oxide ion conductor.
JP2005190435A 2005-06-29 2005-06-29 Gas pump Expired - Fee Related JP3890070B2 (en)

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WO2008114740A1 (en) * 2007-03-16 2008-09-25 National Institute Of Advanced Industrial Science And Technology Apparatus for generating gas having extremely low oxygen concentration, processing system, thin film deposition method and inert gas
JP2008231466A (en) * 2007-03-16 2008-10-02 National Institute Of Advanced Industrial & Technology Very-low oxygen concentration gas generating apparatus
JP2008272609A (en) * 2007-04-25 2008-11-13 National Institute Of Advanced Industrial & Technology Treating system and method for treating article to be treated
WO2012011489A1 (en) * 2010-07-21 2012-01-26 シャープ株式会社 Carbon dioxide separator and method of use therefor
JP2012166112A (en) * 2011-02-10 2012-09-06 Sumitomo Electric Ind Ltd Apparatus and system for gas decomposition
US9364913B2 (en) 2013-05-01 2016-06-14 Denso Corporation Method for brazing sheet material and heat exchanger
JPWO2014084284A1 (en) * 2012-11-30 2017-01-05 三菱化学株式会社 Organic EL light emitting module manufacturing system and organic EL light emitting module manufacturing method

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008114740A1 (en) * 2007-03-16 2008-09-25 National Institute Of Advanced Industrial Science And Technology Apparatus for generating gas having extremely low oxygen concentration, processing system, thin film deposition method and inert gas
JP2008231466A (en) * 2007-03-16 2008-10-02 National Institute Of Advanced Industrial & Technology Very-low oxygen concentration gas generating apparatus
US8597732B2 (en) 2007-03-16 2013-12-03 National Institute Of Advanced Industrial Science And Technology Thin film depositing method
JP2008272609A (en) * 2007-04-25 2008-11-13 National Institute Of Advanced Industrial & Technology Treating system and method for treating article to be treated
WO2012011489A1 (en) * 2010-07-21 2012-01-26 シャープ株式会社 Carbon dioxide separator and method of use therefor
CN103003199A (en) * 2010-07-21 2013-03-27 夏普株式会社 Carbon dioxide separator and method of use therefor
JP2012166112A (en) * 2011-02-10 2012-09-06 Sumitomo Electric Ind Ltd Apparatus and system for gas decomposition
JPWO2014084284A1 (en) * 2012-11-30 2017-01-05 三菱化学株式会社 Organic EL light emitting module manufacturing system and organic EL light emitting module manufacturing method
US9364913B2 (en) 2013-05-01 2016-06-14 Denso Corporation Method for brazing sheet material and heat exchanger

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