JP2015209576A - Reactor, operation method of reactor and reactor system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reactor which is suppressed in damage of a solid electrolyte due to a pressure change in the passage.SOLUTION: A reactor includes a solid electrolyte having a first surface and a second surface, a first electrode formed on the first surface, a second electrode formed on the second surface, a first substrate having a first concave part in one principal surface, a second substrate having a second concave part in one principal surface and a heat generator having a plurality of heating parts. The first and second electrodes each have first and second catalysts. The reactor has a first passage formed by arranging the first substrate on the first surface so that the first concave part opposes the first electrode and a second passage formed by arranging the second substrate on the second surface so that the second concave part opposes the second electrode. The heat generation density in the peripheral part of the reactor is higher than the heat generation density in the central part of the reactor.

Description

  The present application relates to a reactor comprising a solid electrolyte. The present application also relates to a method of operating a reactor comprising a solid electrolyte.

  In recent years, hydrogen has attracted attention as a clean energy source. As a device using hydrogen, a fuel cell that generates power using hydrogen is known. As is well known, a fuel cell includes an anode and a cathode and an electrolyte sandwiched therebetween. As the electrolyte, for example, a solid electrolyte capable of conducting protons (hydrogen ions) can be used. As such a solid electrolyte, a solid polymer film such as Nafion (registered trademark), a perovskite oxide, and the like are known. Yes.

  In addition, a fuel cell including a heater is known. Patent document 1 is disclosing the fuel cell which has a heater formed by sintering a metal oxide (refer FIG. 1). The fuel cell disclosed in Patent Document 1 has a solid polymer membrane as an electrolyte membrane. In the fuel cell disclosed in Patent Document 1, the occurrence of so-called flooding is suppressed by heating the inside of the flow path to which oxygen is supplied with a heater.

JP 2009-146591 A

  In a device having a solid electrolyte, such as a fuel cell, it is required to suppress the damage of the solid electrolyte and improve the reliability of the device.

  The following are provided as exemplary embodiments of the present disclosure.

  A reactor having a first channel and a second channel, wherein the reactor comprises a solid electrolyte having a first surface and a second surface, and a first electrode provided on the first surface. A first electrode having a first catalyst; a second electrode provided on the second surface, the second electrode having a second catalyst; and a first substrate having a first recess on one main surface. And a second substrate having a second recess on one main surface, and a heating element having a plurality of heating portions, wherein the first flow path is arranged such that the first recess faces the first electrode. A flow path formed by disposing the first substrate on the first surface, wherein the second flow path is configured so that the second recess faces the second electrode so that the second recess faces the second electrode. A flow path formed by disposing on the second surface, and the heat generation density at the periphery of the reactor is at the center of the reactor. Greater than kicking heat density, reactor.

  Other exemplary embodiments of the present disclosure are provided as follows.

  A method of operating a reactor having a first channel and a second channel, the step of introducing a first medium and a second medium into the first channel and the second channel, respectively, And a step of sequentially heating the peripheral portion of the reactor and the central portion of the reactor after the introduction of the first medium and the second medium is started.

  The following are provided as still other exemplary embodiments of the present disclosure.

  A method of operating a reactor having a first flow path and a second flow path, the step of heating a peripheral portion and a central portion of the reactor, introduction of a first medium into the first flow path, and After stopping the introduction of the second medium into the second flow path, and after stopping the introduction of the first medium and the second medium, heating of the central part of the reactor and heating of the peripheral part of the reactor are performed. A method of operating the reactor, including a step of sequentially stopping.

  According to the present disclosure, it is possible to provide a reactor that can suppress damage to a solid electrolyte.

Typical sectional drawing of the reactor in Embodiment 1 of this invention Typical sectional drawing of the reactor in Embodiment 1 of this invention Schematic top view of reactor 100 Schematic top view showing an example of the configuration of a reactor 100A having a plurality of independent first flow paths Schematic top view of a reactor 100B having a single heating element 105B provided on the upper substrate 102a Schematic top view of a reactor 100C having a single heating element 105C provided on the upper substrate 102a Typical sectional drawing which shows other examples of arrangement of a heating element Schematic sectional view showing still another example of the arrangement of the heating elements Typical sectional drawing which shows an example of a structure of the reactor 100F which has several heat-emitting parts from which an electrical resistivity differs Schematic cross-sectional view of a reactor 200 according to another exemplary embodiment of the present invention. Schematic sectional view showing another example of a reactor equipped with a sensor FIG. 3 is a block diagram illustrating a configuration of a reactor system 300 according to still another exemplary embodiment of the present invention.

  Before explaining the present disclosure, the knowledge on which the present disclosure is based will be described.

  As is well known, a reactor equipped with a solid electrolyte has a flow path into which a reactant such as water vapor, hydrogen gas, oxygen gas, methanol, and toluene is introduced. For example, a fuel cell has a flow path for introducing hydrogen gas, water vapor, and the like, and a flow path for introducing oxygen gas. These two flow paths are generally arranged so as to face each other with a solid electrolyte interposed therebetween. Further, as described above, a reactor equipped with a heater is known. In such a reactor, in operation, the entire reactor is heated by a heater. Thereby, the reactant in the flow path is also heated.

  However, since the temperature distribution in the reactor is not uniform, there may be a large difference between the pressure in one channel facing through the solid electrolyte and the pressure in the other channel. When the pressure difference between the two flow paths is large, an excessive stress is applied to the solid electrolyte disposed between the flow paths, and the solid electrolyte may be damaged. In particular, when a change in the state of the reactant occurs in any of the flow paths, a rapid change occurs in the pressure in the flow path, so that the solid electrolyte is damaged and the reliability of the reactor is lowered.

  The inventor of the present application studied to suppress the damage of the solid electrolyte due to the pressure change in the flow path. In the process, attention was paid to the temperature difference between the central part and the peripheral part of the reactor.

  In general, the peripheral part of the reactor has a large area in contact with the outside air, and the temperature tends to decrease compared to the central part of the reactor. In addition, a fluid inlet for introducing the reactant and a fluid outlet for discharging the reactant are provided in the peripheral portion of the reactor, so that the reactant is introduced and discharged in the peripheral portion of the reactor. Temperature drop is likely to occur. If the temperature at the periphery of the reactor is low, the temperature at the end of the flow path, that is, near the fluid inlet or near the fluid outlet is lowered. When the temperature at the end of the flow path decreases, the reactants may condense or solidify at the end of the flow path, and the flow path may be blocked. Note that “blocking” in this specification includes not only a state where the flow path is completely blocked, but also a state where the cross-sectional area of the flow path is reduced. When the reactor is heated while the gaseous reactant is confined in the center of the channel due to the blockage of the channel, the pressure in the channel increases due to the expansion of the gaseous reactant. The expansion of the pressure difference between the two flow paths due to such a pressure increase causes damage to the solid electrolyte. In this specification, “the center of the channel” or “near the center of the channel” means a portion excluding the end of the channel.

  Further, the inventor of the present application shows that the damage of the solid electrolyte due to the pressure change in the flow path as described above can occur not only when the reactor is operated, but also when the reactor is started and stopped. I found it.

  At the start of the reactor operation, the entire reactor is heated until the required temperature is reached. At this time, if a reactant in a liquid state or a solid state is present in the flow path, a rapid change may occur in the pressure in the flow path. For example, if the temperature rises faster at the center of the flow path compared to the end of the flow path, the reaction substance present at the end of the flow path remains in a liquid or solid state and remains in the center of the flow path. The substance vaporizes. That is, the pressure inside the channel blocked by the liquid or solid reactant is rapidly increased. Therefore, excessive stress is applied to the solid electrolyte, and the solid electrolyte may be damaged.

  After shutting down the reactor, the temperature of the entire reactor drops to room temperature. At this time, for example, if the temperature drop at the end of the flow path is faster than that at the center of the flow path, the reaction substance present at the center of the flow path remains in the gaseous state and the reaction present at the end of the flow path. The substance condenses or solidifies. After that, when the reactant at the center of the channel condenses or solidifies due to a decrease in the temperature at the center of the channel, the pressure inside the channel blocked by the liquid or solid reactant rapidly increases. Decrease. Therefore, excessive stress is applied to the solid electrolyte, and the solid electrolyte may be damaged.

  As described above, if the temperature variation in the reactor is large, a large difference occurs between the pressure in one flow path and the pressure in the other flow path, and the solid electrolyte may be damaged. In particular, if the boiling point (or melting point) of the reactant introduced into one main surface side of the solid electrolyte is greatly different from the boiling point (or melting point) of the reactant introduced into the other principal surface side, The solid electrolyte is easily damaged. Further, the temperature change at the start and stop of the reactor can reach several hundred degrees, and it is desirable to suppress damage to the solid electrolyte at the start and stop of the reactor. Note that it has been difficult to reduce the thickness of the solid electrolyte from the above-described circumstances.

  Based on the above findings, the present inventor has intensively studied to suppress damage to the solid electrolyte. As a result, the inventors have found a highly reliable reactor that can suppress damage to the solid electrolyte.

  First, an overview of one embodiment of the present invention will be described.

  A reactor which is one embodiment of the present invention is a reactor having a first flow path and a second flow path, the reactor including a solid electrolyte having a first surface and a second surface, and a first surface on the first surface. A first electrode provided; a second electrode provided on a second surface; a first substrate having a first recess on one main surface; and a second substrate having a second recess on one main surface; And a heating element having a plurality of heating parts. The first electrode has a first catalyst. The second electrode has a second catalyst. The first channel is a channel formed by disposing the first substrate on the first surface so that the first recess faces the first electrode. The second channel is a channel formed by disposing the second substrate on the second surface so that the second recess faces the second electrode. The exothermic density at the periphery of the reactor is greater than the exothermic density at the center of the reactor.

  In one embodiment, the plurality of heat generating portions include first, second, and third heat generating portions arranged so as to be adjacent in order in a plane substantially parallel to the first surface. The distance between the first heat generating part and the second heat generating part may be different from the distance between the second heat generating part and the third heat generating part.

  In a certain aspect, the 1st heat generating part is arrange | positioned in the position nearer the center part than the 2nd heat generating part. Further, the third heat generating part is arranged at a position farther from the center than the second heat generating part. The distance between the third heat generating part and the second heat generating part may be smaller than the distance between the first heat generating part and the second heat generating part.

  In one embodiment, the plurality of heat generating portions include first and second heat generating portions arranged so as to be adjacent to each other in a plane substantially parallel to the first surface. The width of the first heat generating part may be different from the width of the second heat generating part.

  In a certain aspect, the 1st heat generating part is arrange | positioned in the position nearer the center part than the 2nd heat generating part. The width of the second heat generating part may be smaller than the width of the first heat generating part.

  In one embodiment, the plurality of heat generating portions include first and second heat generating portions arranged so as to be adjacent to each other in a plane substantially parallel to the first surface. The electrical resistivity of the first heat generating part may be different from the electrical resistivity of the second heat generating part.

  In a certain aspect, the 1st heat generating part is arrange | positioned in the position nearer the center part than the 2nd heat generating part. The electrical resistivity of the second heat generating part may be larger than the electrical resistivity of the first heat generating part.

  The plurality of heat generating portions may be provided on a main surface opposite to the side facing the first surface of the main surface of the first substrate.

  The plurality of heat generating portions may be provided on the surface of the first recess.

  The plurality of heat generating portions may be provided between the first surface and a portion other than the first concave portion of the main surface having the first concave portion of the first substrate.

  In certain embodiments, the reactor further comprises a sensor disposed in the first flow path. The sensor can be a temperature sensor, a pressure sensor or a deformation sensor.

  The sensor may be disposed on the first surface.

  The sensor may be disposed near the end of the first flow path.

  A reactor operating method according to another aspect of the present invention is a reactor operating method having a first flow path and a second flow path, wherein the first flow path and the second flow path are respectively connected to the first flow path and the second flow path. A step of introducing the first medium and the second medium, and a step of sequentially heating the peripheral portion of the reactor and the central portion of the reactor after the start of introduction of the first medium and the second medium.

  A reactor operating method according to still another aspect of the present invention is a reactor operating method having a first flow path and a second flow path, the step of heating a peripheral portion and a central portion of the reactor; A step of stopping the introduction of the first medium into the first flow path and the introduction of the second medium into the second flow path, and after stopping the introduction of the first medium and the second medium, Heating and heating the periphery of the reactor in turn.

  The operation method of the reactor may include a step of acquiring an output value of the sensor and a step of supplying electric power corresponding to the output value to the heating element.

  The reactor system which is another one aspect | mode of this invention is equipped with the reactor in any one of said, and the control part which controls the electric power supplied to a heat generating body according to the output value of a sensor.

  In certain embodiments, the reactor system further comprises a memory that stores the reference value. The control unit may compare the output value with the reference value and change the magnitude of the power supplied to the heating element based on the comparison result.

  Hereinafter, exemplary embodiments of the present invention will be described with reference to the drawings. In the following description, components having substantially the same function are denoted by common reference numerals, and description thereof may be omitted.

(Embodiment 1)
1 and 2 are schematic cross-sectional views of the reactor according to Embodiment 1 of the present invention. For reference, FIGS. 1 and 2 show an X axis, a Y axis, and a Z axis that are orthogonal to each other. 1 and 2 show a cross section when the reactor is cut along a plane parallel to the ZX plane and a cross section when the reactor is cut along a plane parallel to the XY plane, respectively. 1 is a cross-sectional view taken along line BB ′ of FIG. In other drawings, the X axis, the Y axis, and the Z axis may be shown.

  A reactor 100 shown in FIG. 1 includes a solid electrolyte 101, a first electrode 103a, a second electrode 103b, an upper substrate 102a, a lower substrate 102b, and heating elements 105 and 106. In the configuration illustrated in FIG. 1, the heating element 105 is provided on the main surface Sc on the opposite side of the two main surfaces of the upper substrate 102 a from the side facing the one main surface S <b> 1 of the solid electrolyte 101. Yes. As shown in the figure, typically, the thickness of the heating element 105 (height along the Z direction in the figure) is substantially uniform. The heating element 106 is provided on the main surface Sd opposite to the side facing the other main surface S2 of the solid electrolyte 101 out of the two main surfaces of the lower substrate 102b. Typically, the thickness of the heating element 106 is generally uniform.

  In the configuration illustrated in FIG. 1, the first electrode 103 a is provided on the main surface S <b> 1 of the solid electrolyte 101. The second electrode 103b is provided on the main surface S2 of the solid electrolyte 101. The upper substrate 102a has a concave portion 107a on one main surface, and the upper substrate 102a is disposed on the main surface S1 of the solid electrolyte 101 so that the concave portion 107a faces the first electrode 103a. As a result, the first flow path 104 a is formed inside the reactor 100. That is, the first channel 104a is a channel having the first electrode 103a inside. Similarly, the lower substrate 102b has a recess 107b on one main surface, and the lower substrate 102b is formed on the main surface S2 of the solid electrolyte 101 such that the recess 107b faces the second electrode 103b. Has been placed. Thereby, the 2nd flow path 104b is formed in the inside of the reactor 100. FIG. The second channel 104b is a channel having the second electrode 103b inside. It can be said that each of the first flow path 104a and the second flow path 104b is a space for reaction of a substance introduced into the inside.

  FIG. 2 schematically shows exemplary shapes of the first flow path 104a and the first electrode 103a when viewed from the Z-axis direction shown in the drawing. In the illustrated example, in the reactor 100, the first flow path 104a is formed in a meander shape. Further, the first electrode 103a is formed in a meander shape like the first flow path 104a. Openings 108a and 108b communicating with the first flow path 104a are formed at both ends of the first flow path 104a. The openings 108a and 108b function as a fluid inlet and a fluid outlet, respectively. That is, a fluid such as hydrogen gas or water vapor is introduced into the first flow path 104a (here, the space formed between the upper substrate 102a and the main surface S1 of the solid electrolyte 101) through the opening 108a. can do. Further, the fluid in the first flow path 104a can be discharged to the outside of the reactor 100 through the opening 108b. The arrangement of the fluid inlet and the fluid outlet is not limited to the above example. For example, the openings 108a and 108b may function as the fluid outlet and the fluid inlet, respectively.

  In the reactor 100, the second flow path 104b is formed so as to face the first flow path 104a with the solid electrolyte 101 interposed therebetween (see FIG. 1). That is, here, the second flow path 104b is formed in a meander shape similar to the first flow path 104a, and has openings (not shown) at both ends thereof. The second electrode 103b is also formed in a meander shape like the second channel 104b.

  As will be described in detail later, the first electrode 103a is an electrode having a catalyst. The second electrode 103b is also an electrode having a catalyst. The reactor 100 can function as a fuel cell, for example. When the reactor 100 functions as, for example, a fuel cell, the first electrode 103a and the second electrode 103b function as, for example, a cathode and an anode, respectively. Hereinafter, the first electrode 103a and the second electrode 103b may be referred to as a cathode 103a and an anode 103b, respectively.

  FIG. 3 is a schematic top view of the reactor 100. 3 is the same as the cross section shown in FIG. As described above, the reactor 100 includes the heating element 105. Note that the heating element 106 (not shown in FIG. 3) illustrated in FIG. 1 may have a configuration similar to that of the heating element 105. In order to avoid duplication, description of the heating element 106 may be omitted below.

  In the configuration illustrated in FIG. 3, the heating element 105 includes a plurality of heating portions (here, heating portions 105 a, 105 b, and 105 c) extending along the Y direction in the drawing. As shown in FIG. 3, here, the intervals between the heat generating portions when viewed from the upper surface of the upper substrate 102 are unequal intervals. In the configuration shown in the drawing, the plurality of heat generating parts are arranged more densely in the peripheral part of the reactor 100 than in the central part. In other words, the heat generation density in the periphery of the reactor 100 is larger than the heat generation density in the center of the reactor 100. The “heat generation density” in the present specification means the amount of heat generated per unit time per unit area when the reactor is viewed from a direction perpendicular to the main surface of the solid electrolyte. The region where the “heat generation density” is defined in the present specification is not limited to the region on the heating element, but may be a region including the heating element and the outer peripheral portion.

  In the present disclosure, the heat generation density in the peripheral part of the reactor is set to be larger than the heat generation density in the central part of the reactor. As will be described in detail later, according to the present disclosure, it is possible to suppress the temperature variation in the reactor and to suppress the damage of the solid electrolyte accompanying the pressure change in the flow path.

  Hereinafter, the structure of each part and operation | movement of a reactor in exemplary embodiment of this invention are demonstrated in detail.

<Solid electrolyte>
An example of the solid electrolyte 101 is an organic membrane or a solid oxide having proton conductivity. For example, a perovskite oxide having proton conductivity (generally expressed by a chemical formula of ABO ₃ ) can be used as the solid electrolyte. At the A site located at the apex of the cubic crystal, at least one alkaline earth metal selected from the group consisting of Ba, Sr and Ca, and at the B site located at the body center of the cubic crystal, Zr, Hf, Y, La, By arranging O (oxygen) at least one element selected from the group consisting of Ce, Gd, In, Ga, Al and Ru, at a site located at the center of the cubic crystal, a good proton conductor can be obtained. Can be obtained. A perovskite oxide in which BaZrO ₃ is used as a skeleton and part of the B site is substituted with Y (yttrium) or the like may be used. Here, as the solid electrolyte 101, a perovskite oxide having proton conductivity is exemplified. However, the solid electrolyte 101 is not limited to a proton conductor, and may be an oxygen ion conductor formed from a solid oxide or the like. For example, a solid oxide such as yttrium stabilized zirconia (YSZ) may be used. The carrier in the solid electrolyte is not limited to protons, and may be oxygen ions.

  For example, a sputtering method can be used to form the solid electrolyte 101. The formation method of the solid electrolyte 101 is not limited to the sputtering method, but a PLD (Pulsed Laser Deposition) method, a vacuum deposition method, an ion plating method, a CVD (Chemical Vapor Deposition) method, or MBE (Molecular Beam Epitaxy) is used. be able to.

  The solid electrolyte 101 has a range of 0.5 μm or more and 2 μm or less, for example. By setting the thickness of the solid electrolyte 101 to about 0.5 μm or more, the occurrence of defects in the solid electrolyte can be suppressed. Therefore, it is possible to obtain sufficient ionic conductivity while suppressing the occurrence of leakage of the reactant. Further, by setting the thickness of the solid electrolyte 101 to about 2 μm or less, it is possible to suppress the occurrence of cracks and the like due to stress during film formation as compared with the case where the film thickness is extremely large.

  According to the present disclosure, it is possible to suppress the damage of the solid electrolyte accompanying the pressure change in the flow path, and therefore it is relatively easy to use the solid electrolyte having the thickness in the above range. By reducing the thickness of the solid electrolyte, proton conductivity can be improved. For example, power generation efficiency can be improved when the reactor 100 is used as a fuel cell.

<First electrode and second electrode>
Each of the first electrode 103a and the second electrode 103b has a catalyst. For example, when the reactor 100 is operated as a fuel cell, the first electrode 103a has a catalyst for reducing oxygen and functions as a cathode. The second electrode 103b has a catalyst that oxidizes hydrogen and functions as an anode.

The first electrode 103a is made of, for example, a material having proton permeability (conductivity), electron conductivity, and a catalytic function. Examples of such materials are metals such as platinum (Pt) and solid oxides such as SrRuO ₃ . Here, a 20 nm thick Pt film patterned in a meander shape is illustrated. The width of the first electrode 103a (the width indicated by the arrow “w1” in FIGS. 1 and 2) is, for example, 150 μm. The first electrode 103a may have a stacked structure of a metal and a solid oxide. Note that the first electrode 103a may not be formed of a single material having all of proton permeability, electron conductivity, and catalytic function. For example, the first electrode 103a may have a laminated structure of an electrode having electron conductivity and a catalyst. It may be formed. The second electrode 103b can also be formed using a material similar to that of the first electrode 103a. The materials used for the first electrode 103 a and the second electrode 103 b can be changed as appropriate depending on the application of the reactor 100. The second electrode 103b need not have the same configuration as the first electrode 103a.

<Upper board and lower board>
Examples of the material of the upper substrate 102a are silicon (Si), glass, quartz, and the like. The upper substrate 102a is formed on the main surface of the solid electrolyte 101 by PVD (Physical Vapor Deposition), CVD, electroforming, or the like, oxide (for example, SiO ₂ ), nitride (for example, SiN), or metal (for example, It may be a layer made of nickel (Ni). The lower substrate 102b can be formed using the same material as the upper substrate 102a. The shape of the upper substrate 102a and the lower substrate 102b is not limited to the plate shape illustrated in FIG. 1, and may be a shape having a step, a bend, or the like.

  As described with reference to FIG. 1, the reactor 100 includes the first flow path 104a and the second flow path 104b. The first flow path 104a can be formed, for example, by bonding the upper substrate 102a having the recess 107a and the solid electrolyte 101. Similarly, the second flow path 104b can be formed by joining the lower substrate 102b having the recess 107b and the solid electrolyte 101. For example, when a silicon substrate is used for the upper substrate 102a or the lower substrate 102b, the recess (107a or 107b) can be easily formed by dry etching, wet etching, or the like. A fluid inlet and a fluid outlet may be formed together with the recess.

  Here, as the upper substrate 102a and the lower substrate 102b, single crystal Si substrates (thickness: about 500 μm) on which a thermal oxide film having a thickness of 1 μm is formed are used. The recess 107a on the upper substrate 102a and the recess 107b on the lower substrate 102b can be formed by, for example, deep RIE (Reactive Ion Etching). When the recess 107a and the recess 107b are formed by dry etching, the recesses 107a and 107b have a rectangular cross section as shown in FIG. Wet etching may be used to form the recess 107a and / or the recess 107b, and therefore the cross section of the recess 107a and / or the recess 107b may be tapered.

  The width (width indicated by the arrow “w2” in FIG. 1) and depth (depth indicated by the arrow “t” in FIG. 1) of the recess 107a and the recess 107b are, for example, 200 μm and 50 μm, respectively. That is, in the example shown in FIG. 1, the widths of the first flow path 104a and the second flow path 104b are set to 200 μm. The size of the flow path in the reactor 100 is appropriately selected according to the use of the reactor 100. However, considering the mechanical strength of the laminated body of the first electrode 103a, the solid electrolyte 101, and the second electrode 103b, the width of the flow path in the reactor 100 should be set to about 500 times or less of the total thickness of the laminated body. Is beneficial.

  Anodic bonding can be used for bonding the upper substrate 102a and the solid electrolyte 101. In joining the upper substrate 102a and the solid electrolyte 101, the upper substrate 102a is disposed on the main surface S1 of the solid electrolyte 101 so that the recess 107a faces the first electrode 103a. Further, the upper substrate 102a and the solid electrolyte 101 are pressurized while heating and applying a voltage. This can be a diffusion bond between a solid electrolyte that is an oxide and a thermal oxide film (not shown) that is pre-formed on the surface of the Si substrate. Such direct bonding can be performed when the bonding surface has good cleanliness and flatness. The lower substrate 102b and the solid electrolyte 101 can be joined in the same manner.

  Note that the bonding between the upper substrate 102a and / or the lower substrate 102b and the solid electrolyte 101 is performed through a bonding layer formed of an organic film, an oxide film, a metal layer, a glass layer, a metallized ceramic layer, or the like. You may go. For example, bonding is performed via a bonding layer by applying an epoxy resin, glass powder (glass frit), or the like on the upper substrate 102a (or the lower substrate 102b) or the solid electrolyte 101 before bonding. Can do. By providing the bonding layer, stronger bonding can be performed. By using an insulating material as the material of the bonding layer, the degree of freedom in designing a wiring for connecting the first electrode 103a and the second electrode 103b to an external power source is also improved.

  The shapes of the first flow path 104a and the second flow path 104b are not limited to meander shapes. The first flow path 104a and the second flow path 104b may not be configured as a continuous single flow path as illustrated in FIG.

  FIG. 4 is a schematic top view showing an example of the configuration of a reactor 100A having a plurality of independent first flow paths. A reactor 100A shown in FIG. 4 has a plurality of first flow paths 104A arranged two-dimensionally. The reactor 100A has a plurality of first electrodes 103A. Each of the first electrodes 103A is exposed inside the corresponding first flow path 104A. In the illustrated example, the plurality of first flow paths 104A include a first flow path 104x and a first flow path 104y that are independent of each other. The plurality of first electrodes 103A includes a first electrode 103x and a first electrode 103y. The first flow path 104x has a first electrode 103x inside, and the first flow path 104y has a first electrode 103y inside. The first electrodes 103A are typically connected to each other by a wiring (not shown). Each of the first flow paths 104A is provided with a fluid inlet and a fluid outlet (not shown). Each of the first flow paths 104A is kept airtight and watertight, and is configured so that fluids introduced into the flow paths do not mix with each other. Inside each first flow path, the reaction of the substance introduced inside proceeds independently. 4 may be the same as the cross section shown in FIG.

<Heating element>
Heating elements 105 and 106 shown in FIG. 1 are heaters that heat the reactor 100. The heating element 105 is typically an electric resistance that can generate a relatively large amount of heat by applying a current. An example of the heating element 105 is a wiring formed of polycrystalline silicon, an alloy containing Ni and Cr, or the like. When a conductor such as a Si substrate is used as the upper substrate 102a, for example, an electrical insulator for preventing an electrical short circuit can be disposed between the heating element 105 and the upper substrate 102a. Here, the heating element 105 and the upper substrate 102a are electrically separated by the thermal oxide film of the upper substrate 102a.

  Please refer to FIG. As described above, the heating element 105 has a plurality of heating portions. In the configuration illustrated in FIG. 3, the plurality of heat generating portions include three heat generating portions 105a, 105b, and 105c arranged adjacently in this order in the X direction of the drawing. In the example shown in FIG. 3, each of the heat generating portions 105a, 105b, and 105c is an independent heat generator. The materials, widths, and thicknesses constituting each of the heat generating portions 105a, 105b, and 105c are the same. Here, each of the heat generating portions 105a, 105b, and 105c is electrically connected to an external power source in parallel. In FIG. 3, the illustration of a power source that supplies power to the heating element 105 and a connection line between the power source and the heating element 105 is omitted. Also in other drawings, illustration of a power supply and connection lines is omitted. Each of the plurality of heat generating portions included in the heat generating element 105 can be a part of a single heat generating element, as will be described later with reference to the drawings.

  The heat generating part located in the central part of the reactor 100 and the heat generating part located in the peripheral part of the reactor 100 may be configured to be controllable independently of each other. For example, the heat generating part located in the center of the reactor 100 and the heat generating part located in the peripheral part of the reactor 100 may be connected to separate switching elements. That is, the reactor 100 may have a configuration in which heating of the central portion of the reactor 100 and heating of the peripheral portion of the reactor 100 can be controlled independently.

  Here, the heating element 105 having a plurality of heating portions is provided on the main surface Sc of the upper substrate 102a (see FIG. 1). That is, the plurality of heat generating portions are typically arranged in a plane substantially parallel to the main surface (for example, main surface S1) of solid electrolyte 101. Of the heat generating parts 105 a, 105 b and 105 c, the heat generating part 105 a is closest to the central part of the reactor 100. Here, the distance between the heat generating part 105b and the heat generating part 105c (the distance indicated by the arrow “d23” in FIG. 3) is the distance between the heat generating part 105a and the heat generating part 105b (the arrow “d12” in FIG. 3). Smaller than the distance indicated by “”. That is, the heat generation density in the peripheral part of the reactor 100 is larger than the heat generation density in the central part of the reactor 100. Therefore, for example, it is possible to suppress a relative temperature decrease at the periphery of the reactor 100 due to the inflow and outflow of the reactant.

  As described above, by making the heat generation density in the peripheral portion of the reactor 100 larger than the heat generation density in the central portion of the reactor 100, temperature variations in the reactor 100 can be reduced. Therefore, according to the present disclosure, even when a gaseous reactant is introduced into at least one of the first channel 104a and the second channel 104b, the reaction in the liquid state or the solid state is performed. Blockage of the flow path by the substance can be suppressed, and occurrence of damage due to application of local stress to the solid electrolyte can be suppressed. Moreover, by reducing the temperature variation in the reactor, the variation in reaction efficiency due to the position in the flow path is reduced, and a more efficient reaction can be realized.

<Reactor operation>
Here, an example of the operation and operation method of the reactor 100 will be described.

  The reactor 100 can be used for various applications depending on the combination of the cathode 103a and the anode 103b to be used. The reactor 100 can be used for a hydrogenation device, a dehydrogenation device, a hydrogen sensor, etc. in addition to a fuel cell. Here, an example in which the reactor 100 is used for electrolysis of water vapor and hydrogenation of a hydride will be described. Hereinafter, an apparatus used for electrolysis of steam and hydrogenation of a hydride is sometimes referred to as “steam electrolysis hydrogenation apparatus” or simply “electrolysis hydrogenation apparatus”.

  When the reactor 100 is used as an electrolytic hydrogenation apparatus, an anode including a catalyst that oxidizes hydrogen in a gas containing water and a cathode including a hydrogenation catalyst are used. An example of a catalyst for oxidizing hydrogen in a gas containing water, and a hydrogenation catalyst is a metal or alloy containing Pt.

Here, an example of hydrogenating toluene (C ₆ H ₅ CH ₃ ) using hydrogen obtained by electrolysis of steam will be described. Note that one opening (fluid inlet) of the first flow path 104 a is connected to a storage container for a reactant (here, toluene) outside the reactor 100. Further, one opening (fluid inlet) of the second flow path 104b is connected to a storage container for the reactant (here, water) outside the reactor 100.

  First, for example, water vapor is introduced as a reactant into the second channel 104b. Further, for example, toluene is introduced into the first flow path 104a. Further, an external power source is connected to the cathode 103a and the anode 103b, and a potential difference (for example, 1.5 V) is applied between the anode and the cathode. By applying a potential difference between the anode and the cathode, the solid electrolyte 101 conducts carriers such as protons more efficiently.

Protons are extracted from water vapor (water) by bringing water vapor into contact with the anode 103b in the second flow path 104b. Protons generated at the anode 103 b move in the solid electrolyte 101. The proton in the solid electrolyte 101 is a concentration gradient, a partial pressure difference (of hydrogen) between the second channel 104b and the first channel 104a facing the second channel 104b, or between the anode 103b and the cathode 103a. The cathode 103a is reached by at least one of the voltage differences applied therebetween. By bringing toluene into contact with the cathode 103a, toluene is hydrogenated. Thereby, methylcyclohexane (C ₆ H ₁₁ CH ₃ ) can be obtained in the first flow path 104a.

  After the introduction of water vapor and toluene, the electrolytic hydrogenation apparatus is heated. During operation of the electrolytic hydrogenation apparatus, the entire electrolytic hydrogenation apparatus is maintained at approximately 300 ° C. In the heating of the electrolytic hydrogenation apparatus, the peripheral part and the central part of the electrolytic hydrogenation apparatus are heated in this order. The reason is as follows.

  Toluene (and methylcyclohexane) is a liquid at room temperature. For example, when the operation of the electrolytic hydrogenation apparatus is stopped for inspection or the like and then restarted, liquid toluene (or methylcyclohexane) may remain in the first flow path 104a. When the central portion of the electrolytic hydrogenation apparatus is heated first, toluene (and methylcyclohexane) near the center of the first flow path 104a is vaporized first. That is, when the toluene (and methylcyclohexane) confined in the central portion of the first flow path 104a is vaporized by the liquid toluene (or methylcyclohexane), the pressure inside the first flow path 104a rapidly increases. If it does so, there exists a possibility that the solid electrolyte 101 may be damaged by the rapid pressure change inside the 1st flow path 104a.

  In the present disclosure, the peripheral part and the central part of the electrolytic hydrogenation apparatus are heated in order. As a result, gaseous toluene (or methylcyclohexane) is not confined in the central portion of the first flow path 104a, and damage to the solid electrolyte 101 can be prevented.

  When stopping the electrolytic hydrogenation apparatus, first, the introduction of toluene into the first flow path 104a and the introduction of water vapor into the second flow path 104b are stopped. Thereafter, the heating of the central part of the electrolytic hydrogenation apparatus and the heating of the peripheral part of the electrolytic hydrogenation apparatus are stopped in this order. As the temperature of the electrolytic hydrogenation apparatus decreases, methylcyclohexane (and toluene) present in the first flow path 104a condenses. At this time, if the heating of the peripheral portion of the electrolytic hydrogenation apparatus is stopped first, methylcyclohexane (and toluene) may condense at the end of the first flow path 104a, and the first flow path 104a may be blocked. If the gaseous methylcyclohexane (and toluene) present in the center of the first flow path 104a condenses in a state where the first flow path 104a is closed, the solid electrolyte 101 may be damaged due to negative pressure. There is. By sequentially stopping the heating of the central portion of the electrolytic hydrogenation device and the peripheral portion of the electrolytic hydrogenation device, gaseous methylcyclohexane (or toluene) is not confined in the central portion of the first flow path 104a. Thus, damage to the solid electrolyte 101 can be prevented.

  By applying the above operation method, it is possible to prevent a sudden change in the pressure inside the second flow path 104b when the operation of the electrolytic hydrogenation apparatus is started and / or when the operation is stopped. Thus, according to the present disclosure, it is possible to prevent liquid or solid and gas from being mixed in the flow path in the process of heating or cooling the reactor. Therefore, it is possible to prevent the gaseous reactants or reaction products from being trapped in the flow path at the start or stop of the reactor, and to prevent damage to the solid electrolyte at the start or stop of the reactor. Can be suppressed.

  The hydrogenation reaction as described above is generally an exothermic reaction. In a configuration in which a reaction product (here, methylcyclohexane) is obtained by flowing a reactant (here, toluene) through the channel, the temperature rises near the center of the channel compared to the end of the channel. It tends to be easy. For example, the ratio of unreacted substances is low near the fluid outlet, and the amount of reaction heat generated by hydrogenation is small compared to the vicinity of the center of the flow path. In other words, it can be said that the temperature at the end of the flow path is likely to decrease, and the flow path is likely to be blocked. According to the present disclosure, since the exothermic density in the peripheral part of the reactor is set to be larger than the exothermic density in the central part of the reactor, when the reaction occurring in the flow path is an exothermic reaction, A more advantageous effect can be obtained. Of course, even if the reaction occurring in the flow path is an endothermic reaction, damage to the solid electrolyte can be suppressed.

  In a reactor using a solid oxide as a solid electrolyte, toluene hydrogenation is usually achieved in a temperature range of 400 ° C to 800 ° C. In contrast, according to an exemplary embodiment of the present invention, a so-called organic hydride such as methylcyclohexane can be obtained by operating the reactor at a temperature of about 300 ° C., for example. As described above, according to the exemplary embodiment of the present invention, the temperature variation in the reactor can be reduced, and the blockage of the flow path due to the liquid or solid can be effectively suppressed. Therefore, damage to the solid electrolyte 101 due to a sudden pressure change in the flow path is suppressed, so that a solid electrolyte thin film having a thickness of, for example, about several μm can be used. By using a solid electrolyte having a thickness of about several μm, higher ionic conductivity can be obtained. Therefore, it is possible to set the operating temperature of the reactor to be lower than before.

<Modification of reactor>
Hereinafter, modified examples of the reactor will be described with reference to FIGS.

  As described above, each of the plurality of heat generating parts included in the heat generating element 105 may be a part of a single heat generating element. FIG. 5 is a schematic top view of a reactor 100B having a single heating element 105B provided on the upper substrate 102a.

  In the configuration shown in FIG. 5, the heating element 105B is formed in a meander shape, and has a plurality of portions extending in the Y direction in the figure. More specifically, the heating element 105B has three heating portions 105d, 105e, and 105f arranged adjacent to each other in the X direction in the figure. The exothermic part 105d is disposed at a position closer to the central part of the reactor 100B than the exothermic part 105e. The exothermic part 105f is arranged at a position farther from the central part of the reactor 100B than the exothermic part 105e. Here, the distance between the heat generating part 105e and the heat generating part 105f is smaller than the distance between the heat generating part 105d and the heat generating part 105e. 5 is the same as the cross section shown in FIG. 1, and the heat generation density in the periphery of the reactor 100B is larger than the heat generation density in the center of the reactor 100B. Even with such a configuration, the effect of suppressing damage to the solid electrolyte 101 can be obtained.

  FIG. 6 is a schematic top view of a reactor 100C having a single heating element 105C provided on the upper substrate 102a. In the configuration shown in FIG. 6, the heating element 105C is formed in a spiral shape. As shown in the figure, the spiral shape of the heating element 105C is formed of a plurality of portions extending in the X direction in the drawing and a plurality of portions extending in the Y direction in the drawing. Here, the plurality of portions extending in the X direction in the figure are arranged more densely in the peripheral portion than in the central portion of the reactor 100C. Similarly, the plurality of portions extending in the Y direction in the figure are arranged more densely in the peripheral portion than in the central portion of the reactor 100C. Therefore, the heat generation density in the periphery of the reactor 100C is larger than the heat generation density in the center of the reactor 100C. As shown in FIG. 6, the interval between the arrangement of the plurality of heat generating portions may be changed two-dimensionally.

  Next, an example of the arrangement of the heating elements 105 will be described. In the configuration described with reference to FIGS. 1 to 3, the heating element 105 is provided on the main surface Sc (outer surface) of the upper substrate 102a. The arrangement of the heating element 105 with respect to the upper substrate 102a is not limited to this example, and various arrangements are possible.

  FIG. 7 is a schematic cross-sectional view showing another example of the arrangement of the heating elements. In the reactor 100D shown in FIG. 7, the heating element 105 having a plurality of heating portions is disposed inside the first flow path 104a. As illustrated, the plurality of heat generating portions are disposed on the surface of the recess 107a. In the illustrated example, the heating element 106 is also disposed inside the second flow path 104b, like the heating element 105.

  By disposing the plurality of heat generating portions on the surface of the recess, the fluid in the flow channel can be directly heated, and blockage of the flow channel can be more effectively suppressed. However, forming the heating element on the outer surface of the upper substrate 102a does not complicate the formation process of the plurality of heating portions, and thus the degree of freedom of the shape and arrangement of the first flow path 104a is high.

  FIG. 8 is a schematic cross-sectional view showing still another example of the arrangement of the heating elements. In the reactor 100E shown in FIG. 8, a heating element 105E having a plurality of heating portions is provided at a joint portion between the solid electrolyte 101 and the upper substrate 102a. More specifically, as shown in FIG. 8, the heating element 105E is provided between the main surface S1 of the solid electrolyte 101 and a portion other than the recess 107a in the main surface Sa having the recess 107a of the upper substrate 102a. Yes. In the example shown in the figure, the heating element 106E on the main surface S2 side of the solid electrolyte 101 is also provided at the junction between the solid electrolyte 101 and the lower substrate 102b, similarly to the heating element 105E.

  As shown in FIG. 8, a bonding layer for bonding the upper substrate 102a and / or the lower substrate 102b and the solid electrolyte 101 may be used as a heating element. In this case, as shown in the drawing, by arranging the flow paths in the cross section perpendicular to the main surface S1 (or the main surface S2) of the solid electrolyte 101 to be unequally spaced, it is possible to dispose a plurality of heat generating portions at unequally spaced intervals. .

  In the illustrated example, the heating element 105E has heating portions 105g and 105h adjacent to each other. The heat generating portions 105g and 105h are typically formed from the same material. Here, the width of the heat generating portion 105g is different from the width of the heat generating portion 105h. More specifically, the width of the heat generating part 105h (the width indicated by the arrow “w4” in FIG. 7) is the width of the heat generating part 105g (in FIG. 7) located closer to the center of the reactor 100E than the heat generating part 105h. , The width indicated by the arrow “w3”). Therefore, the heat generation density in the peripheral part of the reactor 100E is larger than the heat generation density in the central part of the reactor 100E.

  By disposing a plurality of heat generating portions at the junction between the upper substrate 102a (or the lower substrate 102b) and the solid electrolyte 101, the fluid in the flow path can be effectively heated. As in the configuration illustrated in FIG. 8, the heat generation density in the reactor may be controlled by controlling the width of the plurality of heat generating units. The widths of the plurality of heat generating portions can be appropriately set in consideration of the electrical resistivity of the material.

  In the configuration described above, by changing the density (may be referred to as an interval) or the width (may be referred to as a shape) of a plurality of exothermic parts, the exothermic density in the central part of the reactor and the reaction The heat generation density in the peripheral part of the vessel is different. In other words, when viewed from the upper surface of the upper substrate 102a (or the lower substrate 102b), the ratio of the area occupied by the plurality of heat generating parts to the upper substrate 102a (or the lower substrate 102b) is the central portion of the reactor. And the periphery. As will be described below, the heat generation density in the central portion of the reactor and the heat generation density in the peripheral portion of the reactor may be made different by changing the electrical resistivity of the plurality of heat generation portions.

  FIG. 9 is a schematic cross-sectional view showing an example of the configuration of a reactor 100F having a plurality of heat generating portions having different electrical resistivity. In the configuration illustrated in FIG. 9, the reactor 100F includes a heating element 105F provided on the main surface Sc of the upper substrate 102a. The heating element 105F has, for example, a plurality of heating portions extending along the Y direction in the figure. As shown in the drawing, the plurality of heat generating portions are equally spaced along the X direction in the drawing. Here, the heating element 106F provided on the main surface Sd of the lower substrate 102b also has the same configuration as the heating element 105F.

  Heating element 105F includes heat generating portions 105m and 105n arranged adjacent to each other. As shown in the figure, the heat generating portion 105m is disposed closer to the center of the reactor 100F than the heat generating portion 105n. Here, the electrical resistivity of the heat generating portion 105m is different from the electrical resistivity of the heat generating portion 105n. In the configuration illustrated in FIG. 9, the electric resistivity of the heat generating portion 105n is larger than the electric resistivity of the heat generating portion 105m. Thus, the heat generation density in the reactor can also be set by setting the electrical resistivity of the heat generating part located in the periphery of the reactor to be larger than the electric resistivity of the heat generating part located near the center of the reactor. Can be controlled.

  As described with reference to FIG. 9, the amount of heat generated in the heat generating portion can also be controlled by changing the electrical resistivity of the plurality of heat generating portions in the plane where the heat generating element is disposed. That is, by appropriately adjusting at least one of the density, width, thickness, and electrical resistivity of the plurality of heat generating portions, it is possible to adjust the heat generation density in the reactor to achieve a desired temperature distribution. .

  As illustrated in FIG. 2, when the flow path in the reactor is a single continuous flow path, the flow path from the center of the reactor to the heating element 105B shown in FIG. You may gradually narrow the space | interval of several heat-emitting parts toward an edge part (fluid inlet, fluid outlet). In addition, as illustrated in FIG. 4, when a plurality of independent flow paths are two-dimensionally arranged, the intervals between the plurality of heat generating portions are gradually increased from the central portion to the peripheral portion of the reactor. It may be narrowed. For example, a heating element 105C as shown in FIG. 6 may be used. At this time, when viewed from the top surface of the reactor, it is beneficial that the heating portions overlapping the flow paths are equidistant, because the temperature distribution in each flow path can be made constant.

  With the various configurations described above, the heat generation density in the peripheral portion of the reactor can be made larger than that in the central portion of the reactor. That is, according to the present disclosure, the reliability of the reactor can be improved with a simple configuration.

(Embodiment 2)
FIG. 10 is a schematic cross-sectional view of a reactor 200 according to another exemplary embodiment of the present invention. A reactor 200 shown in FIG. 10 is similar to the reactor 100 shown in FIG. 1 in that a solid electrolyte 101, a first electrode 103a, a second electrode 103b, an upper substrate 102a, a lower substrate 102b, and a heating element. 105 and 106. The reactor 200 further includes a sensor 109a in the first flow path 104a. In the illustrated example, the sensor 109a is installed on the main surface S1 of the solid electrolyte 101.

  The sensor 109a is, for example, a pressure sensor using a piezoresistance effect. By installing a pressure sensor in the first flow path 104a, a pressure change in the first flow path 104a can be detected. For example, when the central portion of the reactor 200 is heated in a state where both ends of the first flow path 104a are closed, the fluid in the first flow path 104a expands and the pressure in the first flow path 104a increases. . Therefore, it is possible to detect whether or not a blockage has occurred in the first flow path 104a by monitoring an increase in pressure in the first flow path 104a. When it is determined that the blockage has occurred in the first flow path 104a, for example, by heating the peripheral portion of the reactor 200 to remove the blockage, the solid electrolyte caused by the pressure increase in the first flow path 104a is obtained. 101 can be prevented from being damaged.

  The sensor 109a is not limited to a pressure sensor, and may be a temperature sensor. For example, the sensor 109a is arranged in the vicinity of the end portion (fluid inlet and / or fluid outlet) of the first flow path 104a, and the temperature drop in the peripheral portion of the reactor 200 is monitored, thereby blocking the first flow path 104a. It is possible to detect the occurrence. When the temperature of the periphery of the reactor 200 is lowered to such an extent that the occurrence of the blockage in the first flow path 104a is expected, the occurrence of the blockage is prevented by heating the periphery of the reactor 200. be able to. Alternatively, a temperature difference between the central portion and the peripheral portion of the reactor 200 may be monitored by installing a sensor near the center of the first flow path 104a.

  In the illustrated example, the sensor 109b is also disposed in the second flow path 104b. The sensor 109b is installed on the main surface S2 of the solid electrolyte 101. By installing sensors on both main surfaces of the solid electrolyte 101, information on the pressure distribution and / or temperature distribution on the first flow path 104a side and information on the pressure distribution and / or temperature distribution on the second flow path 104b side. And you can get Thereby, for example, the power supplied to the heating element 105 on the upper substrate 102a side and the power supplied to the heating element 106 on the lower substrate 102b side can be individually adjusted. According to such an aspect, finer temperature adjustment is possible. That is, even if the melting point (or boiling point) of the fluid introduced into the first channel 104a and the melting point (or boiling point) of the fluid introduced into the second channel 104b are greatly different, The difference between the pressure in 104a and the pressure in the second flow path 104b can be reduced. Therefore, it is possible to suppress an excessive stress from being applied to the solid electrolyte 101 due to an extreme pressure difference between the first channel 104a and the second channel 104b.

  The pressure sensor is not limited to a sensor using the piezoresistance effect, and the detection method of the temperature sensor is not limited to a specific method. As long as the pressure distribution and / or temperature distribution in the flow path can be estimated, the installation location of the sensor is not limited to the example described with reference to FIG. For example, the sensor 109a may be disposed on the surface of the recess 107a of the upper substrate 102a. A slot communicating with the first flow path 104a may be formed in the upper substrate 102a, and a sensor may be inserted from the outside of the reactor through the slot.

  FIG. 11 is a schematic cross-sectional view showing another example of a reactor including a sensor. A reactor 200A shown in FIG. 11 has a sensor 110a in the first flow path 104a, similarly to the reactor 200 shown in FIG. Here, the sensor 110a is a deformation sensor that detects deformation of the solid electrolyte 101, such as a strain gauge. In the configuration illustrated in FIG. 11, the sensor 110 a is installed on the main surface S <b> 1 of the solid electrolyte 101. As shown in the figure, when the sensor 110a is disposed on the main surface S1 of the solid electrolyte 101 and in the center of the flow channel width direction (X direction in the configuration illustrated in FIG. 11), the deformation of the solid electrolyte 101 is performed. Easy to detect.

  As in the configuration illustrated in FIG. 11, by installing a deformation sensor on the main surface of the solid electrolyte 101, it is possible to detect whether or not the solid electrolyte 101 has undergone extreme deformation. When extreme deformation of the solid electrolyte 101 is detected, for example, the first flow path 104a is clogged, and it is considered that an unintended pressure increase occurs in the first flow path 104a. In such a case, the solid electrolyte 101 can be prevented from being damaged, for example, by heating the periphery of the reactor 200A to remove the blockage. As shown in FIG. 11, the sensor 110 b may be installed on the main surface S <b> 2 of the solid electrolyte 101 so as to face the sensor 110 a through the solid electrolyte 101. By installing the sensors so as to face both main surfaces of the solid electrolyte 101, the deformation of the solid electrolyte 101 can be detected more reliably.

  As described with reference to FIGS. 10 and 11, an output value of a sensor included in the reactor may be acquired, and power corresponding to the output value may be supplied to the heating element. Such an operation method may be executed by being controlled based on an instruction from the control unit as described below.

  With reference to FIG. 12, a reactor system according to an exemplary embodiment of the present invention will be described. FIG. 12 is a block diagram illustrating a configuration of a reactor system 300 according to an exemplary embodiment of the present invention. In FIG. 12, arrows r1, r2, p1, and p2 respectively indicate the flow of the reactant introduced into the first channel, the flow of the reactant introduced into the second channel, and the exhaust from the first channel. The flow of the reaction product and the flow of the reaction product discharged from the second flow path are schematically shown.

  The reactor system 300 includes a reactor having a sensor in a flow path (here, the reactor 200 described with reference to FIG. 10) and a control unit 150. The control unit 150 includes a computer or the like. The controller 150 controls the power supplied to the heating element (here, the heating element 105) in accordance with the output value of the sensor (here, the sensor 109a) included in the reactor 200. Note that the control unit 150 may be connected to the sensor and the heating element of the reactor 200 by a wired or wireless method, and may not be arranged integrally with the reactor 200.

  Here, an example of control in the reactor system 300 will be described. As schematically illustrated in FIG. 12, the control unit 150 acquires an output value from the sensor 109a. The output from the sensor 109a may include information regarding the pressure distribution or temperature distribution in the flow path of the reactor 200 (here, the first flow path 104a). Next, the control part 150 controls the magnitude | size of the electric current or voltage supplied to the heat generating body 105 from a power supply not shown based on the output value acquired from the sensor 109a. More specifically, the control unit 150 compares the output value from the sensor 109a with a preset reference value. The reference value is stored in a memory 160 such as a RAM or a ROM connected to the control unit 150, for example.

  For example, it is assumed that the output value from the sensor 109a indicates the magnitude of the pressure in the flow path. At this time, if the output value exceeds the reference value, it can be determined that the pressure in the flow channel has increased unintentionally and the solid electrolyte 101 is likely to be damaged. Therefore, when it is determined that the output value exceeds the reference value, the control unit 150 increases the power supplied to the heating element 105. In the reactor 200, the heating element 105 is configured such that the heat generation density at the periphery of the reactor 200 is larger than the heat generation density at the center of the reactor 200. Therefore, the peripheral part of the reactor 200 can be effectively heated by increasing the power supplied to the heating element 105. Thereby, blockage | blocking of a flow path can be eliminated. When it is determined that the output value does not exceed the reference value, the control unit 150 maintains the power supplied to the heating element 105 or decreases it as necessary.

  Depending on the setting of the reference value, the power supplied to the heating element 105 may be increased when it is determined that the output value does not exceed the reference value. For example, assume that the output value from the sensor 109a indicates the temperature at the end of the flow path. At this time, if the output value does not exceed the reference value, it can be determined that there is a high possibility that the solid electrolyte 101 is damaged due to blockage occurring at the end of the flow path. Therefore, in this case, the control unit 150 increases the power supplied to the heating element 105.

  As described above, for example, by controlling the current or voltage applied to the heating element based on the signal of the sensor installed in the flow path, it is possible to prevent the solid electrolyte 101 from being damaged. In addition, when the heat generating part located in the central part of the reactor and the heat generating part located in the peripheral part of the reactor are configured to be controllable independently of each other, the reaction is started at the start of operation of the reactor. You may make a control part perform the driving | running method which heats the peripheral part and center part of a container in order. When the operation of the reactor is stopped, the control unit may be caused to execute an operation method in which heating of the central portion of the reactor and heating of the peripheral portion are sequentially stopped.

  The various aspects described above can be combined with each other as long as no contradiction occurs. In addition, the arrangement of the heating elements, and the density, width, thickness, electrical resistivity, and the like of the plurality of heating parts included in the heating elements can be appropriately set according to the type of reaction in the reactor. The configuration of the heating element on the main surface S1 side of the solid electrolyte 101 and the configuration of the heating element on the main surface S2 side may not be the same. The reactor may further include a heater for heating the entire reactor in addition to the above-described heating element. In addition, the reactor may further include an auxiliary heater that is configured to be controllable independently of the above-described heating element at the periphery of the reactor. By using the auxiliary heater, finer temperature control can be realized. The solid electrolyte 101 may be stored in a storage container in which the upper substrate and the lower substrate are integrated.

  As described above, according to the present disclosure, it is possible to suppress the damage of the solid electrolyte due to the pressure change in the flow path, and to improve the reliability of the reactor. Moreover, according to this indication, since damage to a solid electrolyte is suppressed, it is relatively easy to reduce the thickness of the solid electrolyte. Therefore, by reducing the thickness of the solid electrolyte, the ion conductivity can be improved, and the operating temperature of the reactor can be lowered as compared with the conventional case.

  The reactor according to the present disclosure can be used for a fuel cell, a hydrogenation device, a dehydrogenation device, a steam electrolysis device, a steam electrolysis hydrogenation device, and the like.

100, 200 Reactor 101 Solid electrolyte 102a Upper substrate (first substrate)
102b Lower substrate (second substrate)
103a 1st electrode 103b 2nd electrode 104a 1st flow path 104b 2nd flow path 105,106 Heating body 109,110 Sensor 150 Control part 160 Memory 300 Reactor system

Claims (18)

A reactor having a first flow path and a second flow path,
The reactor is
A solid electrolyte having a first surface and a second surface;
A first electrode provided on the first surface, the first electrode having a first catalyst;
A second electrode provided on the second surface, the second electrode having a second catalyst;
A first substrate having a first recess on one main surface;
A second substrate having a second recess on one main surface;
A heating element having a plurality of heating parts,
The first flow path is a flow path formed by disposing the first substrate on the first surface so that the first recess faces the first electrode.
The second channel is a channel formed by disposing the second substrate on the second surface so that the second recess faces the second electrode,
The reactor, wherein the exothermic density at the periphery of the reactor is greater than the exothermic density at the center of the reactor. The plurality of heat generating portions include first, second, and third heat generating portions arranged in order to be adjacent to each other in a plane substantially parallel to the first surface,
2. The reactor according to claim 1, wherein an interval between the first heat generating unit and the second heat generating unit is different from an interval between the second heat generating unit and the third heat generating unit. The first heat generating part is disposed at a position closer to the central part than the second heat generating part,
The third heat generating part is disposed at a position farther from the central part than the second heat generating part,
The reactor according to claim 2, wherein an interval between the third heat generating unit and the second heat generating unit is smaller than an interval between the first heat generating unit and the second heat generating unit. The plurality of heat generating portions include first and second heat generating portions arranged to be adjacent to each other in a plane substantially parallel to the first surface,
The reactor according to claim 1, wherein a width of the first heat generating part is different from a width of the second heat generating part. The first heat generating part is disposed at a position closer to the central part than the second heat generating part,
The reactor according to claim 4, wherein a width of the second heat generating part is smaller than a width of the first heat generating part. The plurality of heat generating portions include first and second heat generating portions arranged to be adjacent to each other in a plane substantially parallel to the first surface,
The reactor according to claim 1, wherein an electrical resistivity of the first heat generating part is different from an electric resistivity of the second heat generating part. The first heat generating part is disposed at a position closer to the central part than the second heat generating part,
The reactor according to claim 6, wherein an electrical resistivity of the second heat generating part is larger than an electric resistivity of the first heat generating part.   The reaction according to any one of claims 1 to 7, wherein the plurality of heat generating portions are provided on a main surface of the main surface of the first substrate opposite to a side facing the first surface. vessel.   The reactor according to any one of claims 1 to 7, wherein the plurality of heating portions are provided on a surface of the first recess.   The plurality of heat generating portions are provided between the first surface and a portion other than the first concave portion of the main surface having the first concave portion of the first substrate. A reactor according to the above. A sensor disposed in the first flow path;
The reactor according to any one of claims 1 to 10, wherein the sensor is a temperature sensor, a pressure sensor, or a deformation sensor.   The reactor according to claim 11, wherein the sensor is disposed on the first surface.   The reactor according to claim 11 or 12, wherein the sensor is disposed in the vicinity of an end of the first flow path. A method of operating a reactor having a first channel and a second channel,
Introducing the first medium and the second medium into the first flow path and the second flow path, respectively;
And a step of sequentially heating a peripheral portion of the reactor and a central portion of the reactor after the introduction of the first medium and the second medium is started. A method of operating a reactor having a first channel and a second channel,
Heating the periphery and center of the reactor;
Stopping the introduction of the first medium into the first flow path and the introduction of the second medium into the second flow path;
And a step of sequentially stopping heating of the central portion of the reactor and heating of the peripheral portion of the reactor after the introduction of the first medium and the second medium is stopped. A method for operating a reactor according to any one of claims 11 to 13, comprising:
Obtaining an output value of the sensor;
And supplying the electric power corresponding to the output value to the heating element. A reactor according to any of claims 11 to 13,
And a control unit that controls electric power supplied to the heating element according to an output value of the sensor. A memory for storing a reference value;
The reactor system according to claim 17, wherein the control unit compares the output value with the reference value, and changes a magnitude of electric power supplied to the heating element based on a comparison result.

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