JP2006070282A - High temperature steam electrolyzer and tubular steam electrolytic cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high temperature steam electrolyzer where gas seal parts on a hydrogen side and an oxygen side at the time of a high temperature operation each have a secure and highly reliable structure. <P>SOLUTION: The high temperature steam electrolyzer comprises: a steam feed chamber 52 formed by providing a hydrogen electrode power feed plate 55 at the inside of an upper vessel 65; a steam injection tube 57 sagged from the hydrogen electrode power feed plate 55, feeding steam and performing the feed of power; a cylindrical steam electrolytic cell 51 airtightly fixed to a partition 56; a generated hydrogen discharge chamber 53 formed at the inside of the upper vessel 65 by the partition 56 and discharging generated hydrogen; a generated oxygen discharge chamber 54 formed by providing the partition at the upper end of a lower vessel 54 and discharging generated oxygen; and an oxygen electrode power feed plate 61 of performing the feed of power to an oxygen electrode 73 in the cylindrical steam electrolytic cell 51. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a high-temperature steam electrolysis apparatus and a tubular steam electrolysis cell that modularize a high-temperature steam electrolysis cell.

  This type of high-temperature steam electrolysis method is a method of electrolyzing high-temperature steam to obtain hydrogen gas and oxygen gas, and an electrolysis method based on a reverse reaction of a solid electrolyte fuel cell is known in relation to its operating temperature range ( For example, see Patent Document 1).

 As disclosed in Patent Document 1, FIG. 4 is a schematic longitudinal sectional view showing a configuration of a conventional solid electrolyte fuel cell, and FIG. 5 is a longitudinal sectional view showing a part of the structure of a conventional current collector. FIG.

  In FIG. 4, the solid electrolyte fuel cell includes a cylindrical electrolytic cell 2 and a module housing 3 in which the electrolytic cell 2 is housed. The module housing 3 is divided into a fuel supply chamber 4, a fuel discharge chamber 5 and an air supply chamber 17.

 As shown in FIG. 5, a current collecting metal cap 102 is attached to one end of a cylindrical electrolytic cell 2, and the other end has a completely closed structure by a seal cap 103, so that fuel can be supplied and discharged from the electrolytic cell 2. This is possible only at one end. Further, the electrolysis cell 2 is supported by the seal portion 108 with the tube plate 16 so that the gas can be sealed.

  A power feeding method will be described. The lead part on the hydrogen electrode 106 side is taken out via a taper type sealing 108. The lead portion on the oxygen electrode 105 side is introduced into the electrolysis cell 2 with the cell lead portion 107 at the lower end of the electrolysis cell 2 fixed to the seal cap 103 and taken out from the collecting metal cap 102 through the reducing atmosphere.

In the solid electrolyte fuel cell configured as described above, the gas seal portion on the hydrogen side / oxygen side has two locations above and below the cell, and the gas seal portion includes a cell lead portion 107 in any case. Therefore, it is very difficult to realize a reliable and reliable seal.
Japanese Patent No. 2930326

  In the conventional high-temperature steam electrolysis apparatus described above, the gas seal portions on the hydrogen side and the oxygen side are two places above and below the cell, and the gas seal portion has a seal structure in which the cell lead portion is interposed in any case. Therefore, it is difficult to realize a reliable and reliable seal.

  Moreover, in the conventional high-temperature steam electrolysis apparatus, since the extraction of the cell lead portion of the hydrogen electrode and oxygen electrode is close, when configuring a high-efficiency high-temperature steam electrolysis apparatus that requires a large current supply, disconnection due to heat generation, There was a problem to be solved that would cause failure.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a high-temperature steam electrolyzer having a reliable and reliable structure of the gas seals on the hydrogen side and oxygen side during high-temperature operation. .

 In order to achieve the above object, the high temperature steam electrolysis apparatus of the present invention is formed by providing a module housing divided into an upper container and a lower container through a partition wall, and a hydrogen electrode power supply plate inside the upper container. A water vapor supply chamber for storing water vapor; a water vapor injection pipe that is suspended from the hydrogen electrode power supply plate and supplies water vapor and supplies power to the hydrogen electrode of the cylindrical water vapor electrolysis cell; The cylindrical steam electrolysis cell into which the steam injection pipe is inserted, and the generated hydrogen discharge chamber for discharging the hydrogen generated from the cylindrical steam electrolysis cell formed by the hydrogen electrode power supply plate and the partition in the upper container. And a generated oxygen discharge chamber formed by providing the partition at the upper end of the lower container and discharging oxygen generated from the cylindrical steam electrolysis cell, and the circle It is characterized in that it has a, and the oxygen electrode power supply means provided in the lower vessel for supplying power to the oxygen electrode type steam electrolytic cell.

 In order to achieve the above object, the present invention provides a tubular steam electrolysis cell that electrolyzes water vapor to produce hydrogen gas and oxygen gas, and is formed on an inner wall that forms a hydrogen electrode and an outer peripheral surface of the inner wall. An electrolyte layer comprising an electrolyte, an oxygen electrode layer comprising an oxygen electrode formed on the outer peripheral surface of the electrolyte layer, an outer wall formed as a porous current collector on the outer peripheral surface of the oxygen electrode layer, and the inner wall A water vapor injection pipe which is inserted from one end to inject the water vapor and supplies power to the hydrogen electrode; a seal lid for storing the water vapor by closing the other end of the inner wall; and an oxygen electrode provided on the outer periphery of the outer wall. And an oxygen electrode power supply means for supplying power to the battery.

 According to the present invention, since the tubular steam electrolysis cell is stably and airtightly fixed to the partition wall, the setting of the tubular steam electrolysis cell and the improvement of the gas seal reliability between the product hydrogen side and the product oxygen side are achieved. Can be achieved.

 In addition, since power can be supplied to the high-temperature steam electrolysis apparatus between the upper container and the lower container, easy and large power supply is possible, and a highly efficient and highly reliable apparatus can be obtained.

 Hereinafter, an embodiment of a high-temperature steam electrolysis apparatus according to the present invention will be described with reference to FIGS. 1 to 3. Here, the same reference numerals are assigned to the conventional technology, or the same or similar parts to each other, and a duplicate description is omitted.

 FIG. 1 is a schematic longitudinal sectional view showing a configuration of a high temperature steam electrolyzer according to an embodiment of the present invention.

As shown in FIG. 1, the high-temperature steam electrolysis apparatus includes, as an example, a plurality of cylindrical steam electrolysis cells 51 and a module housing 80 that houses the cylindrical steam electrolysis cells 51. In the cylindrical steam electrolysis cell 51, the water vapor (H ₂ O) is electrolyzed to generate hydrogen gas (H ₂ ) and oxygen gas (O ₂ ). The module housing 80 is divided into an upper container 65 and a lower container 66 through a partition wall 56.

 The water vapor supply chamber 52 is formed by providing the hydrogen electrode power supply plate 55 inside the upper container 65. In the water vapor supply chamber 52, a hydrogen electrode side gas inlet 67 for injecting water vapor is provided. Further, the hydrogen electrode side power supply plate 55 provided in the water vapor supply chamber 52 performs gas shielding between the water vapor supply chamber 52 and the generated hydrogen discharge chamber 53.

 A water vapor injection pipe 57 is suspended from the hydrogen electrode side power supply plate 55 via a water vapor supply port 55a. A plurality of hydrogen electrode power supply terminals 58 are attached to the outer surface of the water vapor injection pipe 57 and have a function of a current collecting terminal for supplying power to the hydrogen electrode 71 of the cylindrical water vapor electrolysis cell 51.

 A partition wall 56 is provided between the generated hydrogen discharge chamber 53 and the oxygen generation chamber 54 in order to shut off the gas. Further, the partition wall 56 is provided with a through hole 56a, and a cell seal metal connector 62 is placed on the side of the generated hydrogen discharge chamber 53.

 The plurality of cylindrical steam electrolysis cells 51 are fixed to the partition wall 56 by the cell seal metal connector 62 through the through hole 56a with the steam injection pipe 57 suspended from the hydrogen electrode side power supply plate 55 inserted.

In addition, a cell seal 63 is interposed between the metal connector 62 and the cylindrical steam electrolysis cell 51 to maintain airtightness. Here, as the material of the cell seal 63, a glass sealing material for high temperature or the like is used.

 A generated hydrogen discharge chamber 53 that discharges hydrogen generated by the cylindrical steam electrolysis cell 51 formed by the partition wall 56 is provided in the upper container 65. The hydrogen produced by electrolyzing water vapor in the cylindrical water vapor electrolysis cell 51 is generated at the hydrogen electrode side gas outlet 69 for discharging through the gap between the metal connector 62 and the water vapor injection pipe 57. Is provided.

 Further, the product oxygen discharge chamber 54 is formed by providing the partition wall 56 at the upper end of the lower container 66. That is, an oxygen generation chamber 54 is provided in which generated oxygen generated by electrolyzing water vapor in the cylindrical steam electrolysis cell 51 is primarily stored. In order to discharge the generated oxygen that is primarily stored, the oxygen generation chamber 54 is provided with an oxygen electrode side gas inlet 68 for supplying a flow gas, and an oxygen electrode side gas outlet 70 is provided.

 An insulating seal 64 made of an insulating material is interposed between the lower container 66 forming the oxygen generation chamber 54 and the partition wall 56.

 Further, an oxygen electrode power supply plate 61, which is an oxygen electrode power supply means for supplying power to the oxygen electrode of the cylindrical steam electrolysis cell 51, is provided in the oxygen generation chamber 54. The oxygen electrode power supply plate 61 supplies the oxygen electrode 73 of the cylindrical steam electrolysis cell 51 through the oxygen electrode power supply terminal 60 and the porous current collector 74.

 The power supply to the high-temperature steam electrolysis apparatus is performed between the upper container 65 that forms the steam supply chamber 52 and the generated hydrogen discharge chamber 53 and the lower container 66 that forms the oxygen generation chamber 54.

 FIG. 2 is a longitudinal sectional view showing the configuration of the cylindrical steam electrolysis cell according to the embodiment of the present invention.

 As shown in FIG. 2, the inner side of the cylindrical steam electrolysis cell 51 is formed by an inner wall made of a hydrogen electrode 71. An electrolyte layer made of the electrolyte 72 is formed on the outer peripheral surface of the inner wall made of the hydrogen electrode 71. On the outer peripheral surface of the electrolyte layer made of the electrolyte 72, an oxygen electrode layer made of the oxygen electrode 73 is further formed. An outer wall functioning as a porous current collector 74 is formed on the outer peripheral surface of the oxygen electrode layer formed of the oxygen electrode 73. Thus, the cylindrical steam electrolysis cell 51 has a layer composed of the hydrogen electrode 71, the electrolyte 72, the oxygen electrode 73, and the porous current collector 74 formed from the inside with good adhesion.

 In the upper part of the cylindrical steam electrolysis cell 51, a steam injection pipe 57 suspended from the hydrogen electrode power supply plate 55 is inserted. A plurality of hydrogen electrode power supply terminals 58 are attached to the outer surface of the water vapor injection pipe 57 to supply power to the hydrogen electrode 71 of the cylindrical water vapor electrolysis cell 51. The lower end of the cylindrical water vapor electrolysis cell 51 is closed with a seal lid 81, and water vapor is stored therein.

 In the present embodiment configured as described above, the hydrogen gas containing water vapor is supplied from the hydrogen electrode side gas inlet 67 to the water vapor supply chamber 52. The water vapor containing hydrogen gas is introduced into the inside of the inner wall made of the hydrogen electrode 71 of the cylindrical water vapor electrolysis cell 1 via the water vapor injection pipe 57.

 Electric power is supplied to the high temperature steam electrolyzer between the upper container 65 and the lower container 66.

 The electric power supplied to the upper container 65 passes through the hydrogen electrode side power supply plate 55 provided in the upper container 65, and the outer surfaces of the water vapor injection pipe 57 and the water vapor injection pipe 7 depending from the hydrogen electrode side power supply plate 55. Is supplied to the hydrogen electrode 71 of the cylindrical steam electrolysis cell 51 via a plurality of hydrogen electrode power supply terminals 58 attached to.

 The electric power supplied to the lower container 66 passes through the oxygen electrode side power supply plate 61 provided in the oxygen generation chamber 54, passes through the oxygen electrode power supply terminal 60 and the porous current collector 74, and the cylindrical steam electrolysis cell 51. The oxygen electrode 73 is supplied.

 In this way, by supplying power to the hydrogen electrode 71 and the oxygen electrode 73 of the cylindrical steam electrolysis cell 51, in the intermediate layer made of the electrolyte 72 in the cylindrical steam electrolysis cell 51, electrolytic reaction with water vapor causes hydrogen and oxygen to react. Generated.

 The generated hydrogen is discharged from the hydrogen electrode side gas outlet 69 via the generated hydrogen discharge chamber 53.

 On the other hand, the produced oxygen is discharged from the oxygen electrode side gas outlet 70 together with the flow gas supplied from the oxygen side gas inlet 68 via the oxygen generation chamber 54.

 Further, the gas sealing on the hydrogen side and the oxygen side is carried out by attaching a cell seal metal connector 62 to the upper part of the cylindrical steam electrolysis cell 51 and fixing it to the partition wall 56 via the cell seal 63. For this reason, the gas seal of the cylindrical steam electrolysis cell 51 is only required at one place, and since it does not have a seal structure including the lead portion, a reliable and reliable sealing property can be secured.

 According to the present embodiment, the cylindrical steam electrolysis cell 51 is stably and airtightly fixed to the partition wall 56 via the sealing material 63 formed from a high temperature glass sealing material or the like by the cell sealing metal connector 62. In addition, it is possible to improve the reliability of the setting of the cylindrical steam electrolysis cell 51 and the gas seal between the hydrogen side and the oxygen side.

 In addition, since power can be supplied to the high-temperature steam electrolysis apparatus between the upper container 65 and the lower container 66, it is possible to easily supply large power, and to obtain a highly efficient and highly reliable apparatus. it can.

 Further, in the cylindrical steam electrolysis cell 51, one end opposite to the partition wall 56 is formed of a porous current collector 74 and is held by a flexible oxygen electrode power supply terminal 60. The porous current collector 74 is made of, for example, conductive ceramics.

  According to the present embodiment, the cylindrical steam electrolysis cell 51 is held by the flexible oxygen electrode power supply terminal 60, so the difference in thermal expansion coefficient between the module housing 80 and the cylindrical steam electrolysis cell 51. It is possible to prevent the cylindrical steam electrolysis cell 51 from being broken due to the difference in thermal elongation due to the above.

 In FIG. 3, in a cylindrical steam electrolysis cell 51, a nickel felt 75 is incorporated between an inner wall made of a hydrogen electrode 71 and a steam injection pipe 57 that hangs down from a hydrogen electrode power supply plate 55.

 In the present embodiment, a plurality of hydrogen electrode power supply terminals 58 are provided on the outer surface of the water vapor injection pipe 57 suspended from the hydrogen electrode power supply plate 55 on the outer surface of the water vapor injection pipe 57 depending from the hydrogen electrode power supply plate 55. It may be attached to supply power to the hydrogen electrode 71.

 According to the present embodiment, since the power supply to the hydrogen electrode 71 side of the cylindrical steam electrolysis cell 51 is efficiently performed and a large current can be supplied, a high-efficiency high-temperature steam electrolysis apparatus can be obtained.

 Needless to say, the high-temperature steam electrolysis apparatus according to the present embodiment can also be applied to the module structure of a solid electrolyte fuel cell.

The schematic longitudinal cross-sectional view which shows the structure of the high temperature steam electrolysis apparatus of embodiment of this invention. The longitudinal cross-sectional view which shows the structure of the cylindrical steam electrolysis cell of embodiment of this invention. The longitudinal cross-sectional view which shows the structure of the cylindrical steam electrolysis cell incorporating the nickel felt of embodiment of this invention. The schematic longitudinal cross-sectional view which shows the structure of the conventional solid electrolyte fuel cell. The longitudinal cross-sectional view which cuts and shows the conventional current collection part structure partially.

Explanation of symbols

 DESCRIPTION OF SYMBOLS 51 ... Cylindrical steam electrolysis cell (cylindrical steam electrolysis cell), 52 ... Steam supply chamber, 53 ... Product hydrogen discharge chamber, 54 ... Product oxygen discharge chamber, 55 ... Hydrogen electrode feeding Plate, 56 ... partition wall, 57 ... steam inlet tube (current collector terminal), 58 ... hydrogen electrode power supply terminal, 60 ... oxygen electrode power supply terminal, 61 ... oxygen electrode power supply plate, 62 ..Metal connector for cell seal, 63 ... Cell seal, 64 ... Insulating seal, 65 ... Upper container, 66 ... Lower container, 67 ... Hydrogen electrode side gas inlet, 68 ... Oxygen electrode Side gas inlet, 69 ... Hydrogen electrode side gas outlet, 70 ... Oxygen electrode side gas outlet, 71 ... Hydrogen electrode, 72 ... Electrolyte, 73 ... Oxygen electrode, 74 ... Porous Current collector, 75 ... nickel felt, 80 ... module housing, 81 ... sea Lid

Claims (11)

A module housing divided into an upper container and a lower container via a partition;
A water vapor supply chamber that is formed by providing a hydrogen electrode power supply plate inside the upper container and stores water vapor;
A steam injection pipe that is suspended from the hydrogen electrode power supply plate and supplies steam to the hydrogen electrode of the cylindrical steam electrolysis cell; and
The cylindrical steam electrolysis cell, which is airtightly fixed to the partition wall and into which the steam injection pipe is inserted,
A generated hydrogen discharge chamber that discharges hydrogen generated from the cylindrical steam electrolysis cell formed by the hydrogen electrode power supply plate and the partition in the upper container;
A generated oxygen discharge chamber formed by providing the partition at the upper end of the lower container and discharging oxygen generated from the cylindrical steam electrolysis cell;
An oxygen electrode power supply means provided in the lower container for supplying power to the oxygen electrode of the cylindrical steam electrolysis cell;
A high temperature steam electrolyzer characterized by comprising:  2. The high-temperature steam electrolysis apparatus according to claim 1, wherein an upper end of the cylindrical steam electrolysis cell is fixed to the partition via a cell seal by a cell seal metal connector.  The high temperature steam electrolysis apparatus according to claim 1, wherein an insulating seal made of an insulating material is provided over the entire circumference of the side wall forming the lower container.  2. The high-temperature steam electrolysis apparatus according to claim 1, wherein a plurality of hydrogen electrode power supply terminals for supplying power to the hydrogen electrode are provided on an outer peripheral surface of the water vapor injection pipe.  The high temperature steam electrolysis apparatus according to claim 1, wherein the oxygen electrode power feeding means is formed from an oxygen electrode power feeding plate provided in the product oxygen discharge chamber.  The high temperature steam electrolysis apparatus according to claim 1, wherein a lower part of the cylindrical steam electrolysis cell is held by a flexible oxygen electrode power supply terminal.  2. The high-temperature steam electrolysis apparatus according to claim 1, wherein power supply to the cylindrical steam electrolysis cell is performed through the upper container and the lower container. In a cylindrical steam electrolysis cell that electrolyzes water vapor to produce hydrogen gas and oxygen gas,
An inner wall forming a hydrogen electrode;
An electrolyte layer made of an electrolyte formed on the outer peripheral surface of the inner wall;
An oxygen electrode layer composed of an oxygen electrode formed on the outer peripheral surface of the electrolyte layer;
An outer wall formed as a porous current collector on the outer peripheral surface of the oxygen electrode layer;
A water vapor injection tube that is inserted from one end of the inner wall to inject the water vapor and to feed the hydrogen electrode;
A seal lid for storing the water vapor by closing the other end of the inner wall;
An oxygen electrode power supply means provided on the outer periphery of the outer wall to supply power to the oxygen electrode layer;
A cylindrical steam electrolysis cell characterized by comprising:  The cylindrical water vapor electrolysis cell according to claim 8, wherein the water vapor injection pipe is provided with a plurality of hydrogen electrode power supply terminals for supplying power to the hydrogen electrode on an outer peripheral surface of the water vapor injection pipe.  The cylindrical steam electrolysis cell according to claim 8 or 9, wherein nickel felt is incorporated between the inner wall and the steam injection pipe.  The cylindrical water vapor electrolysis cell according to claim 8, wherein the porous current collector is formed of conductive ceramics.

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