JP4386018B2 - Reactor - Google Patents

Description

  The present invention relates to a reaction apparatus that causes reaction of reactants, and more particularly to a reaction apparatus that generates hydrogen from liquid fuel.

  In recent years, development has been progressing in order to mount a fuel cell as a clean power source with high energy conversion efficiency in an automobile or a portable device. A fuel cell is a device that directly extracts electric energy from chemical energy by electrochemically reacting fuel and oxygen in the atmosphere.

  As a fuel used in a fuel cell, hydrogen alone can be mentioned, but there is a problem in handling due to being a gas at normal temperature and normal pressure. In contrast, in a reforming fuel cell that generates hydrogen by reforming a hydrocarbon-based liquid fuel having hydrogen atoms such as alcohols and gasoline, the fuel can be easily stored in a liquid state. In such a fuel cell, a vaporizer that vaporizes liquid fuel and water, a reformer that extracts hydrogen necessary for power generation by reacting the vaporized liquid fuel and high-temperature steam, and a by-product of the reforming reaction A reactor equipped with a reactor such as a carbon monoxide remover that removes carbon monoxide, which is a product, is required (see, for example, Patent Document 1).

In order to reduce the size of such a reforming fuel cell, development of a microreactor in which a vaporizer, a reformer, and a carbon monoxide remover are stacked (see, for example, Patent Document 2). In the configuration described in Patent Document 2, each of the vaporizer, the reformer, and the carbon monoxide remover is formed by joining a metal substrate having a groove serving as a flow path for fuel or the like. .
JP 2002-356310 A JP 2005-132712 A

However, as described above, when a metal substrate in which a groove serving as a flow path is used as a metal substrate forming the reactor, or when the thickness of the metal substrate is reduced to reduce weight, The strength may decrease. In particular, a reactor formed by bonding such metal substrates is housed in a vacuum package in which the periphery of the reactor is kept in a vacuum state in order to maintain a predetermined temperature and reduce the loss of heat energy, and vacuum insulation. In such a case, a force that expands outwardly acts on the reactor due to a pressure difference between inside and around the reactor. If the strength of the metal substrate constituting the reactor is insufficient with respect to such a force, there is a problem that the reactor is deformed or destroyed.
Therefore, an object of the present invention is to provide a reaction apparatus provided with a highly rigid reactor by reinforcing the reactor.

In order to solve the above problems, the invention described in claim 1 is provided with a reactor that causes reaction of a reactant, and in a reaction apparatus that generates hydrogen from liquid fuel , the reactor has a hollow box. And a pair of flat plate-like portions that are accommodated in the box and through which a reactant flows, and that face each other on both sides, and that face the pair of plate-like portions between the pair of plate-like portions. A rectangular wave-like partition plate having at least one partition portion and a plurality of folded portions connected between the adjacent partition portions or between the adjacent partition portions and the plate-like portion. Among the partition plates, at least the pair of plate-like portions are respectively fixed to the inner surface of the box.

  Preferably, the plate-like portion is joined to the inner surface of the box body by either welding or brazing.
  Preferably, the folded portion of the partition plate is in surface contact with the inner surface of the box.
  Preferably, the folded portion is joined to the inner surface of the box body by either welding or brazing.
  Preferably, an edge portion of the partition plate is in contact with an inner surface of the box.
  Preferably, the edge portion of the partition plate is joined to the inner surface of the box body by either welding or brazing.
  Preferably, a through hole for allowing the reactant to flow between the partition portions is formed on one end side of the partition portion in the wave height direction.
  Preferably, the box includes a bottom plate, a rectangular top plate, and four side plates connected in a state of being vertically connected to four sides of the top plate, and accommodates the partition plate and opens. And a box-shaped member closed by being joined to the bottom plate, and the partition plate is accommodated so that the wave height direction is parallel to the top plate.
  Preferably, the apparatus further includes a separate plate that is housed in the box and partitions the space in the box, the partition plate is housed in a space partitioned by the separate plate, and an edge portion of the partition plate is formed on the separate plate. It is in contact.
  Preferably, an edge portion of the partition plate is joined to the separate plate.
  Preferably, the reaction apparatus further includes a heat insulating container that covers the whole of the reactor and has a vacuum pressure inside.
  Preferably, the reaction apparatus is set to a first temperature and is set to a first reaction section that causes a reaction of the reactant, and a second temperature that is lower than the first temperature to cause a reaction of the reactant. A second reaction section; and a connecting pipe for sending a reactant and a product between the first reaction section and the second reaction section, the first reaction section and the second reaction section. At least one of the above comprises the reactor.
  Preferably, the reaction apparatus further includes a heat insulating container that covers the whole of the first reaction part, the second reaction part, and the connection pipe, and that has an internal vacuum pressure.
  Preferably, the first reaction unit is supplied with a first reactant to generate a first product, and the second reaction unit is supplied with the first product to supply a first product. 2, wherein the first reactant is an air-fuel mixture in which water and a hydrocarbon-based liquid fuel are vaporized, and the first reaction section is a reformer of the first reactant. A reformer that causes a reaction, wherein the first product contains hydrogen and carbon monoxide, and the second reaction unit converts the carbon monoxide contained in the first product by selective oxidation. A carbon monoxide remover to be removed.

According to the present invention, the box is reinforced by the partition plate, and the rigidity of the reactor can be increased.

  The best mode for carrying out the present invention will be described below with reference to the drawings. However, although various technically preferable limitations for implementing the present invention are given to the embodiments described below, the scope of the invention is not limited to the following embodiments and illustrated examples.

[First Embodiment]
FIG. 1 is an exploded perspective view showing the reactor 400 in the first embodiment of the reaction apparatus according to the present invention obliquely from below, and FIG. 2 is a two-side view of the reactor 400 in the present embodiment. 3 is a cross-sectional view taken along the line III-III in FIG. 2, and FIG. 4 is a cross-sectional view taken along the line IV-IV in FIG. 2A is a top view, and FIG. 2B is a side view.

  As shown in FIG. 1 to FIG. 4, the reactor 400 has a box-shaped member 410 opened at the lower surface, a partition plate 420 accommodated in the box-shaped member 410, and a lower opening of the box-shaped member 410 closed. And a bottom plate 430.

  The box-shaped member 410, the partition plate 420, and the bottom plate 430 may be made of a plate-like metal material such as stainless steel, may be made of a ceramic material, may be made of a glass material, or is made of a resin material. Things can be used.

  The box-shaped member 410 has a top plate 412 that is square or rectangular, and a pair of side plates 414 that are connected in a state of being vertically connected to the top plate 412 at two opposite sides of the four sides of the top plate 412. , 414 and a pair of side plates 416, 416 connected in a state of being vertically connected to the top plate 412 on two opposite sides of the top plate 412. The side plate 414 is connected to the side plate 416 in a state of being vertically connected, and is provided in a square frame shape or a rectangular frame shape by these four side plates 414, 414, 416, 416.

  The edge of the bottom plate 430 is joined to the lower sides of the side plates 414, 414, 416, 416 so that the bottom plate 430 is parallel to the top plate 412. In this way, the lower surface opening of the box-shaped member 410 is closed by the bottom plate 430, so that a parallel hexahedral reaction vessel having a hollow shape is formed.

  The partition plate 420 has a rectangular wave shape. That is, the partition plate 420 includes a pair of flat plate-like reinforcing portions (plate-like portions) 422 and 422 opposed on both sides, and a plurality of partition portions 424 facing the reinforcing portion 422 between the two reinforcing portions 422 and 422. 424,..., And a plurality of folded portions connected between the partitioning portion 424 and the partitioning portion 424 adjacent on one side among the four sides of the partitioning portion 424 or between the adjacent partitioning portion 424 and the reinforcing portion 422 426, 426,...

  The partition plate 420 is accommodated in the box-shaped member 410 so that the wave height direction is parallel to the top plate 412. That is, the reinforcing portions 422 and 422 are plate-like portions on both sides of the partition plate 420, the reinforcing portion 422 is in surface contact with the side plate 414, and preferably the reinforcing portion 422 is joined to the side plate 414 by welding or brazing. Thereby, the side plate 414 can be reinforced and the rigidity of the reaction vessel of the reactor 400 is increased.

  The folded portion 426 of the partition plate 420 is in surface contact with the side plate 416, and preferably the folded portion 426 is joined to the side plate 416 by welding or brazing. Thereby, the side plate 416 can be reinforced and the rigidity of the reaction vessel of the reactor 400 is increased.

  The upper side portion of the folded portion 426, the upper side portion of the reinforcing portion 422, and the upper side portion of the partition portion 424 become the upper edge portion of the partition plate 420, and the upper edge portion of the partition plate 420 abuts on the top plate 412 of the box-shaped member 410. Are preferably joined by welding or brazing. Thereby, the top plate 412 can be reinforced and the rigidity of the reaction vessel of the reactor 400 is increased.

  The lower side portion of the folded portion 426, the lower side portion of the reinforcing portion 422, and the lower side portion of the partition portion 424 serve as the lower side edge portion of the partition plate 420, and the lower side edge portion of the partition plate 420 abuts the bottom plate 430, preferably welding. Or it is joined by brazing. Thereby, the bottom plate 430 can be reinforced and the rigidity of the reaction vessel of the reactor 400 is increased.

  Thus, since the partition plate 420 is accommodated in the box-shaped member 410, the hollow by the box-shaped member 410 and the bottom plate 430 is divided into a plurality of spaces 418, 418,. Among the plurality of spaces 418, 418,..., An introduction port 432 communicating with the space 418 between one reinforcing portion 422 and the partitioning portion 424 is formed in the bottom plate 430, and the other reinforcing portion 422 and the partitioning portion 424 are connected to each other. A discharge port 434 that communicates with the space 418 is formed in the bottom plate 430.

  In addition, a pair of upper and lower through holes 428 and 428 are formed in the vicinity of one end of the partition portion 424 in the wave height direction, and adjacent spaces 418 and 418 communicate with each other through the through holes 428 and 428. Therefore, a hollow formed by the box-shaped member 410 and the bottom plate 430 is provided in a flow path shape from the introduction port 432 to the discharge port 434, and the flow path is formed in a twisted shape.

  In this reactor 400, when the reactant is poured into the inlet 432 by a pump or the like, the reactant flows in the spaces 418, 418,. As the reactant flows through the spaces 418, 418,..., A product is produced from the reactant. And a product is discharged | emitted from the discharge port 434 outside. In each space 418, the reactant flows in the wave height direction of the partition plate 420.

  Here, “reaction from reactant to product” means not only “chemical reaction” but also “state change”.

  Depending on the use of the reactor 400, a heater (for example, a heating wire, a combustor, etc.) may be provided on the outer surface of at least one of the box-shaped member 410 and the bottom plate 430, or a partition plate 420 (mainly, The catalyst may be supported on the surface of the partition portion 424, or the catalyst may be supported on the inner surface of at least one of the box-shaped member 410 and the bottom plate 430.

  For example, when the reactor 400 is used as a vaporizer, a heating wire or a combustor is provided on the outer surface of at least one of the box-shaped member 410 and the bottom plate 430. In this way, the liquid as the reactant is heated while flowing from the inlet 432 to the outlet 434, and the liquid is vaporized. Thereby, the gas as a product flows out from the discharge port 434.

  When the reactor 400 is used as a reformer, a heating wire or a combustor is provided on the outer surface of at least one of the box-shaped member 410 and the bottom plate 430, and a reforming catalyst (for example, Cu / ZnO-based catalyst, Pd / ZnO-based catalyst) are supported. In this way, a mixture of fuel and water as a reactant (for example, a mixture of methanol and water) is heated while flowing from the inlet 432 to the outlet 434, and is hydrogenated from the mixture by the reforming catalyst. Gas etc. are generated. Thereby, the mixed gas containing hydrogen gas etc. flows out from the discharge port 434 as a product.

  When the reactor 400 is used as a carbon monoxide remover, a heating wire or a combustor is provided on the outer surface of at least one of the box-shaped member 410 and the bottom plate 430, and a carbon monoxide selective oxidation catalyst is provided on the surface of the partition portion 424. (For example, platinum) is supported. In this way, the mixture of hydrogen gas, oxygen gas, and carbon monoxide gas as a reactant is heated while flowing from the inlet 432 to the outlet 434, and the carbon monoxide gas is selected by the carbon monoxide selective oxidation catalyst. Is selectively oxidized. As a result, the gas from which the carbon monoxide gas has been removed flows out from the outlet 434 as a product.

  When the reactor 400 is used as a combustor, a combustion catalyst (for example, platinum) is supported on the surface of the partition portion 424. In this way, the hydrogen gas is combusted while the gas mixture of hydrogen gas and oxygen gas as the reactant flows from the inlet 432 to the outlet 434. Thereby, water flows out from the discharge port 434 as a product.

  Next, the heat insulation structure for suppressing the heat loss of the reactor 400 will be described. FIG. 5 is a transparent side view of the reactor 400 in a state in which the heat insulation package 440 (heat insulation container) in the present embodiment is provided. The heat insulation package 440 is made of a metal material such as stainless steel or ceramic, and houses the box-shaped member 410 and the bottom plate 430 in the heat insulation package 440. In this case, the two pipe materials 442 and 444 are passed through the wall surface of the heat insulation package 440, the end portion of one pipe material 442 is connected to the introduction port 432 in the heat insulation package 440, and the end portion of the other tube material 444 is connected to the discharge port 434. Connect to. Here, when the box-shaped member 410 and the bottom plate 430 are supported by the two pipe members 442 and 444 and the box-shaped member 410 and the bottom plate 430 are separated from the inner surface of the heat-insulating package 440, the box-shaped member 410 and the bottom plate 430 are thermally insulated. Direct heat conduction to the package 440 can be suppressed, and heat insulation is further improved. In addition, a vacuum insulation structure is formed by evacuating the inside of the heat insulation package 440 and setting the internal space to a vacuum pressure. When the internal space of the heat insulation package 440 is at a vacuum pressure, the inside of the reaction vessel of the reactor 400 is at a normal pressure, so that stress is applied in the direction in which the box-shaped member 410 and the bottom plate 430 expand. However, the reinforcing portion 422 is joined to the side plate 414 of the box-shaped member 410, the side plate 414 is reinforced, the folded portion 426 is joined to the side plate 416, the side plate 416 is reinforced, and the lower side portion of the partition portion 424 is the bottom plate 430. The top plate 412 is joined to the top plate 412 and the top plate 412 is reinforced by these, thereby reinforcing the entire reaction vessel and breaking or deforming due to stress. It is prevented.

  Next, FIG. 6 is an exploded perspective view of a modified reactor 400A in the present embodiment. In the reactor 400 </ b> A, four triangular openings 423, 423, 423, and 423 are formed in the reinforcing portion 422. Since the reactor 400A is provided in the same manner as the reactor 400 of FIG. 1 except that the opening 423 is formed, the reactor 400 shown in FIG. 1 and the reactor 400A shown in FIG. Then, the same code | symbol is attached | subjected to the part which mutually respond | corresponds, and description of a mutually corresponding part is abbreviate | omitted.

  By forming the opening 423 in the reinforcing portion 422 in this manner, the volume of the reinforcing portion 422 is reduced, and the heat capacity of the reinforcing portion 422 can be reduced. Therefore, heat loss in the reinforcing portion 422 can be reduced, and heat can be effectively used for reaction. In particular, even when four triangular openings 423, 423, 423, and 423 are formed in the reinforcing portion 422, the strength of the reinforcing portion 422 is minimized since the shape of the reinforcing portion 422 is a slash shape. To the limit.

[Second Embodiment]
FIG. 7 is an exploded perspective view showing the reactor 500 in the second embodiment of the reaction apparatus according to the present invention obliquely from below, and FIG. 8 is a two-side view of the reactor 500 in the present embodiment. 9 is a cross-sectional view taken along the line IX-IX in FIG. 8, and FIG. 10 is a cross-sectional view taken along the line XX in FIG. 8A is a top view, and FIG. 8B is a side view.

  The reactor 500 includes a box-shaped member 510 that is open on the lower surface, a separation plate 550 that is housed in the box-shaped member 510 and partitions the space in the box-shaped member 510 up and down, and a lower-side opening of the box-shaped member 510. A bottom plate 530, a partition plate 520 accommodated in the upper space of the two spaces partitioned by the separation plate 550, and a partition plate 540 accommodated in the lower space.

  The box-shaped member 510, the partition plate 520, the bottom plate 530, the partition plate 540, and the bottom plate 530 may be made of a metal material such as stainless steel, may be made of a ceramic material, or may be made of a glass material, It may be made of a resin material.

  The box-shaped member 510 has a square or rectangular top plate 512 and a pair of side plates 514 connected in a state of being vertically connected to the top plate 512 at two opposite sides of the four sides of the top plate 512. 514, and a pair of side plates 516, 516 connected in a state of being vertically connected to the top plate 512 at two opposite sides of the top plate 512. The side plate 514 is connected to the side plate 516 in a state of being connected vertically.

  The edge of the bottom plate 530 is joined to the lower side of the side plates 514, 514, 516, and 516 so that the bottom plate 530 is parallel to the top plate 512, and a parallel tetrahedral reaction vessel having a hollow shape is formed. The separate plate 550 is accommodated in the box-shaped member 510 so as to be parallel to the bottom plate 530 and the top plate 512, and the edges of the separate plate 550 are joined to the upper and lower abdomen portions of the side plates 514, 514, 516 and 516.

  The partition plate 520 has a rectangular wave shape. That is, the partition plate 520 includes a pair of flat plate-like reinforcing portions 522, 522 opposed on both sides, and a plurality of partitioning portions 524, 524,... Facing the reinforcing portion 522 between the two reinforcing portions 522, 522, Among the four sides of the partition part 524, a plurality of folded parts 526, 526,... Connected between the partition part 524 adjacent to each other on one side or the partition part 524 or between the adjacent partition part 524 and the reinforcing part 522. And have.

  Similarly to the partition plate 520, the partition plate 540 also includes a pair of reinforcing portions 542, 542, a plurality of partition portions 544, 544,... And a plurality of folded portions 546, 546,. The partition shape of the partition plate 540 is formed in the same manner as the partition shape of the partition plate 520.

  The partition plate 520 is accommodated in the space between the separate plate 550 and the top plate 512 so that the wave height direction is parallel to the top plate 512. The reinforcing portions 522 and 522 are plate-like portions on both sides of the partition plate 520, the reinforcing portion 522 is in surface contact with the side plate 514, and preferably the reinforcing portion 522 is joined to the side plate 514 by welding or brazing. Further, the folded portion 526 of the partition plate 520 is in surface contact with the side plate 516, and preferably the folded portion 526 is joined to the side plate 516 by welding or brazing.

  The upper side portion of the folded portion 526, the upper side portion of the reinforcing portion 522, and the upper side portion of the partition portion 524 become the upper edge portion of the partition plate 520, and the upper edge portion of the partition plate 520 contacts the top plate 512 of the box-shaped member 510. Are preferably joined by welding or brazing. The lower side portion of the folded portion 526, the lower side portion of the reinforcing portion 522, and the lower side portion of the partition portion 524 become the lower edge portion of the partition plate 520, and the lower edge portion of the partition plate 520 abuts on the separate plate 550, preferably They are joined by welding or brazing.

  A partition plate 520 is accommodated in a space between the top plate 512 and the separation plate 550 in the box-shaped member 510, and the space is partitioned into a plurality of spaces 518, 518,.

  Further, the partition plate 540 is accommodated in a space between the separate plate 550 and the bottom plate 530 so that the wave height direction is parallel to the top plate 512. The reinforcing portions 542 and 542 become plate-like portions on both sides of the partition plate 540, the reinforcing portion 542 is in surface contact with the side plate 514, and preferably the reinforcing portion 542 is joined to the side plate 514 by welding or brazing. Further, the folded portion 546 of the partition plate 540 is in surface contact with the side plate 516, and preferably the folded portion 546 is joined to the side plate 516 by welding or brazing.

The upper side portion of the folded portion 546, the upper side portion of the reinforcing portion 542, and the upper side portion of the partition portion 544 become the upper edge portion of the partition plate 540, and the upper edge portion of the partition plate 540 abuts on the separate plate 550, preferably welded or Joined by brazing. The lower side portion of the folded portion 546, the lower side portion of the reinforcing portion 542, and the lower side portion of the partition portion 544 serve as the lower edge portion of the partition plate 540, and the lower edge portion of the partition plate 540 contacts the bottom plate 530, preferably welding. Or it is joined by brazing.
Thus, the box-shaped member 510 and the bottom plate 530 are reinforced by the partition plates 520 and 540 and the separate plate 550, and the rigidity of the reaction vessel of the reactor 500 is increased.

  A partition plate 540 is accommodated in a space between the bottom plate 530 and the separation plate 550 in the box-shaped member 510, and the space is partitioned into a plurality of spaces 519, 519,. The lower partition plate 540 overlaps the upper partition plate 520 with the separate plate 550 interposed therebetween, and the upper space 518 is partitioned from the lower space 519 by the separate plate 550.

  A through hole 528 is formed in the partition portion 524, and adjacent spaces 518 and 518 communicate with each other through the through hole 528. A through hole 548 is formed in the partition portion 544, and adjacent spaces 519 and 519 communicate with each other through the through hole 548. A plurality of through holes 552, 552,... Are formed in the separation plate 550, and spaces 518 and 519 that are adjacent in the vertical direction communicate with each other through the through holes 552. The spaces 518, 518,... And the spaces 519, 519,... Are formed as a series of twisted flow paths by the through holes 528, the through holes 548, and the through holes 552.

  An inlet 532 that communicates with any one of the plurality of spaces 519, 519,... Is formed in the bottom plate 430, and a discharge port 534 that communicates with another space 519 is formed in the bottom plate 530.

  In this reactor 500, when the reactant is poured into the inlet 532 by a pump or the like, the reactant flows through the spaces 518, 518,... And the spaces 519, 519,. When the reactants flow through the spaces 518, 518,... And the spaces 519, 519,..., Products are generated from the reactants. And a product is discharged | emitted from the discharge port 534 outside. In each space 518, 519, the reactant flows in the wave height direction of the partition plates 520, 540.

  In the reactor 500, similarly to the reactor 400 of the first embodiment, a heater may be provided on the outer surface of at least one of the box-shaped member 510 and the bottom plate 530, depending on the application. The catalyst may be supported on the partition plates 520 and 540, the catalyst may be supported on the inner surface of at least one of the box-shaped member 510 and the bottom plate 530, or the catalyst may be supported on the separate plate 550. .

  Similarly to the case of the first embodiment, heat loss of the reactor 500 can be suppressed by housing the reactor 500 in a heat insulating package (heat insulating container) whose inside is a vacuum pressure. Also in this case, stress is applied in the direction in which the reaction vessel is expanded by the box-shaped member 510 and the bottom plate 530, but the box-shaped member 510 and the bottom plate 530 are also reinforced by the separate plate 550 and the partition plates 520 and 540 in this embodiment. In addition, since the rigidity of the reaction vessel of the reactor 500 is enhanced, it can be prevented from being broken or deformed by stress. One of the two pipes penetrating the heat insulation package is connected to the introduction port 532, the other is connected to the discharge port 534, and the box member 510 and the bottom plate 530 are supported by the two pipe materials. Alternatively, the box-shaped member 510 and the bottom plate 530 may be separated from the inner surface of the heat insulation package, and direct heat conduction to the heat insulation package may be suppressed to improve heat insulation.

[Third Embodiment]
FIG. 11 is a side view of a microreactor module 600 (reaction apparatus) in the third embodiment of the reaction apparatus according to the present invention. The microreactor module 600 is built in an electronic device such as a notebook personal computer, a PDA, an electronic notebook, a digital camera, a mobile phone, a wristwatch, a register, or a projector, and generates hydrogen gas used for a fuel cell.

  As shown in FIG. 11, the microreactor module 600 includes a supply / exhaust unit 602 that supplies reactants and discharges products, and a high-temperature reaction unit 604 that generates a reforming reaction at a relatively high temperature (first Between the high-temperature reaction unit 604 and the low-temperature reaction unit 606, the low-temperature reaction unit 606 (second reaction unit) in which the selective oxidation reaction is set to a temperature lower than the set temperature of the high-temperature reaction unit 604. And a connecting pipe 608 for feeding the reactants and products.

  FIG. 12 is a schematic side view when the microreactor module 600 according to the present embodiment is divided for each function. As shown in FIG. 12, the supply / discharge section 602 is mainly provided with a carburetor 610 and a first combustor 612. Air and gaseous fuel (for example, hydrogen gas, methanol gas, etc.) are supplied to the first combustor 612 separately or as an air-fuel mixture, and heat is generated by the catalytic combustion. The vaporizer 610 is supplied with water and liquid fuel (for example, methanol, ethanol, dimethyl ether, butane, gasoline) from the fuel container separately or in a mixed state, and water and liquid are generated by the combustion heat in the first combustor 612. The fuel is vaporized in the vaporizer 610.

  The high temperature reaction section 604 is mainly provided with a second combustor 614 and a reformer 400B provided on the second combustor 614. Air and gaseous fuel (for example, hydrogen gas, methanol gas, etc.) are supplied to the second combustor 614 separately or as an air-fuel mixture, and heat is generated by the catalytic combustion. In the fuel cell, electricity is generated by the electrochemical reaction of hydrogen gas, and the unreacted hydrogen gas contained in the off-gas discharged from the fuel cell is mixed with air in the first combustor 612 and the second combustor 614. May be supplied. Of course, the liquid fuel (for example, methanol, ethanol, dimethyl ether, butane, gasoline) stored in the fuel container is vaporized by another vaporizer, and the vaporized fuel / air mixture becomes the first combustor 612 and It may be supplied to the second combustor 614.

The reformer 400B is supplied with a gas mixture (first reactant) obtained by vaporizing water and liquid fuel from the vaporizer 610, and the reformer 400B is heated by the second combustor 614. In the reformer 400B, hydrogen gas or the like (first product) is generated from water vapor and the vaporized liquid fuel by a catalytic reaction, and a carbon monoxide gas is further generated in a small amount. When the fuel is methanol, chemical reactions such as the following formulas (1) and (2) occur. Note that the reaction in which hydrogen is generated is an endothermic reaction, and the combustion heat of the second combustor 614 is used.
CH ₃ OH + H ₂ O → 3H ₂ + CO ₂ (1)
2CH ₃ OH + H ₂ O → 5H ₂ + CO + CO ₂ (2)

  The low temperature reaction unit 606 is mainly provided with a carbon monoxide remover 500B. The carbon monoxide remover 500B is heated by the first combustor 612, and includes a gas mixture (second gas) containing hydrogen gas and a small amount of carbon monoxide gas generated by the chemical reaction of (2) above from the reformer 400B. The reaction product is supplied with oxygen (or air). The carbon monoxide remover 500B selectively oxidizes carbon monoxide from the air-fuel mixture, thereby removing the carbon monoxide. An air-fuel mixture (second product; hydrogen-rich gas) from which carbon monoxide has been removed is supplied to the fuel electrode of the fuel cell.

  A specific configuration of the microreactor module 600 will be described with reference to FIGS. 11 and 13 to 17. 13 is an exploded perspective view of the microreactor module 600 in the present embodiment, FIG. 14 is a cross-sectional view taken along the line XIV-XIV in FIG. 11, and FIG. 15 is a cross-sectional view in FIG. 16 is a cross-sectional view taken along the line XV-XV, FIG. 16 is a cross-sectional view taken along the line XVI-XVI in FIG. 11, and FIG. 17 is a cross-sectional view taken along the line XVII in FIG. It is arrow sectional drawing of the surface along -XVII.

  As shown in FIGS. 11, 13, and 14, the supply / exhaust unit 602 includes a liquid fuel introduction pipe 622 and a combustor plate provided to surround the liquid fuel introduction pipe 622 at the upper end of the liquid fuel introduction pipe 622. 624 and five pipe members 626, 628, 630, 632, and 634 arranged around the liquid fuel introduction pipe 622.

  The liquid fuel introduction pipe 622 is made of, for example, a tubular metal material such as stainless steel, and the liquid fuel introduction pipe 622 is filled with a liquid absorbing material 623. The liquid-absorbing material 623 absorbs liquid, and the liquid-absorbing material 623 is, for example, an inorganic fiber or organic fiber solidified with a binder, an inorganic powder sintered, or an inorganic powder solidified with a binder. , And a mixture of graphite and glassy carbon. Specifically, a felt material, a ceramic porous material, a fiber material, a carbon porous material, or the like is used as the liquid absorbing material 623.

  The pipe materials 626, 628, 630, 632, and 634 are made of a tubular metal material such as stainless steel.

  The combustor plate 624 is also made of a plate-like metal material such as stainless steel. A through hole is formed at the center of the combustor plate 624, and the liquid fuel introduction pipe 622 is fitted into the through hole, and the liquid fuel introduction pipe 622 and the combustor plate 624 are joined. Here, the liquid fuel introduction pipe 622 is joined to the combustor plate 624 by brazing, for example. As the brazing agent, the melting point is higher than the highest temperature of the fluid flowing through the liquid fuel introduction pipe 622 and the combustor plate 624, and silver, copper, zinc, cadmium is added to gold having a melting point of 700 degrees or more. Particularly preferred are gold waxes contained, waxes based on gold, silver, zinc and nickel, or waxes based on gold, palladium and silver. In addition, a partition wall is provided on one surface of the combustor plate 624 so as to protrude. A part of the partition wall is provided over the entire outer periphery of the combustor plate 624, the other part is provided over the radial direction, and the combustor plate 624 is joined to the lower surface of the low temperature reaction unit 606, A combustion channel 625 is formed on the joint surface, and the liquid fuel introduction pipe 622 is surrounded by the combustion channel 625. A combustion catalyst for burning the combustion mixture is carried on the wall surface of the combustion channel 625. An example of the combustion catalyst is platinum. The liquid absorbing material 623 in the liquid fuel introduction pipe 622 is filled up to the position of the combustor plate 624.

  As shown in FIGS. 11 and 13, the high-temperature reaction unit 604, the low-temperature reaction unit 606, and the connection pipe 608 use the laminated insulating plate 640 and base plate 642 as a common base. Therefore, the insulating plate 640 becomes a lower surface common to the high temperature reaction unit 604, the low temperature reaction unit 606, and the connection pipe 608, but the lower surface of the connection pipe 608 is flush with the lower surface of the high temperature reaction unit 604, Furthermore, it is flush with the lower surface of the low temperature reaction part 606.

  The base plate 642 includes a base portion 652 serving as a base for the low temperature reaction portion 606, a base portion 654 serving as a base for the high temperature reaction portion 604, and a connection base portion 656 serving as a base for the connection pipe 608. The base plate 642 is formed by integrally forming a base portion 652, a base portion 654, and a connection base portion 656, and is in a state of being constricted at the connection base portion 656. The base plate 642 is made of a plate-like metal material such as stainless steel.

  The insulating plate 640 includes a base portion 662 serving as a base for the low temperature reaction portion 606, a base portion 664 serving as a base for the high temperature reaction portion 604, and a connection base portion 666 serving as a base for the connection pipe 608. The insulating plate 640 is formed by integrally forming a base portion 662, a base portion 664, and a connection base portion 666, and is in a state of being constricted at the connection base portion 666. The insulating plate 640 is made of an electrical insulator such as ceramic.

  As shown in FIGS. 13 and 15, the through holes 671 to 678 penetrate the base portion 652 of the base plate 642 and the base portion 662 of the insulating plate 640 in a state where the insulating plate 640 is joined to the base plate 642. As shown in FIGS. 11 and 13, the base portion 662 of the insulating plate 640 becomes the lower surface of the low temperature reaction portion 606, and pipes 626, 628, 630, 632, 634 and a liquid fuel introduction pipe are formed on the lower surface of the low temperature reaction portion 606. 622 is joined by brazing or the like. Here, the tube material 626 communicates with the through hole 671, the tube material 628 communicates with the through hole 672, the tube material 630 communicates with the through hole 673, the tube material 632 communicates with the through hole 674, the tube material 634 communicates with the through hole 675, and liquid fuel An introduction pipe 622 communicates with the through hole 678. As shown in FIGS. 13, 14, and 15, the combustor plate 624 is joined to the lower surface of the low temperature reaction section 606, but one end of the combustion flow path 625 of the combustor plate 624 is a through hole 676. And the other end of the combustion channel 625 communicates with the through hole 677.

  As shown in FIG. 15, the base plate 642 includes a reformed fuel supply channel 702, a communication channel 704, an air supply channel 706, a mixing chamber 708, a combustion fuel supply channel 710, and a combustion chamber 712. An exhaust gas channel 714, a combustion fuel supply channel 716, and an exhaust chamber 718 are formed.

  The reformed fuel supply channel 702 is formed so as to extend from the through hole 678 through the connection base portion 656 to the corner portion of the base portion 654. The mixing chamber 708 is formed in a square shape in the base portion 652. The communication channel 704 is formed so as to extend from the corner of the base portion 654 to the mixing chamber 708 through the connection base portion 656. The air supply channel 706 is formed so as to extend from the through hole 675 to the mixing chamber 708.

  The combustion chamber 712 is formed in a C shape at the center of the base portion 654. A combustion catalyst for burning the combustion mixture is carried on the wall surface of the combustion chamber 712.

  The combustion fuel supply channel 710 is formed so as to extend from the through hole 672 to the combustion chamber 712 through the connection base portion 656. The exhaust gas flow channel 714 is formed so as to reach the through hole 673 from the through hole 677, and is formed so as to reach the through hole 673 from the combustion chamber 712 through the connection base portion 656. The combustion fuel supply channel 716 is formed so as to reach the through hole 676 from the through hole 674 in the base portion 652. The exhaust chamber 718 is formed in a rectangular shape in the base portion 652, and a through hole 671 communicates with a corner portion of the exhaust chamber 718.

  A carbon monoxide remover 500 </ b> B is provided on the base portion 652. This carbon monoxide remover 500B is an application of the reactor 500 in the second embodiment, and the carbon monoxide remover 500B is provided in the same manner as the reactor 500 shown in FIGS. The cross section of the carbon monoxide remover 500B shown in FIG. 16 corresponds to the cross section of the reactor 500 shown in FIG. 9, and the cross section of the carbon monoxide remover 500B shown in FIG. This corresponds to the cross section of the reactor 500 shown. In addition, the same code | symbol is attached | subjected to the part which mutually respond | corresponds between the carbon monoxide remover 500B and the reactor 500, and description of a part corresponding to each other is abbreviate | omitted.

  As shown in FIGS. 11 and 13, the bottom plate 530 of the carbon monoxide remover 500 </ b> B is joined to the upper surface of the base portion 652. By the bottom plate 530, a part of the reformed fuel supply channel 702, a part of the exhaust gas channel 714, a part of the combustion fuel supply channel 710, a part of the communication channel 704, and the air supply channel 706 Then, the mixing chamber 708, the combustion fuel supply channel 716, and the exhaust chamber 718 are covered. The introduction port 532 formed in the bottom plate 530 is located above the corner portion 709 of the mixing chamber 708, and the discharge port 534 formed in the bottom plate 530 is located above the corner portion 719 of the exhaust chamber 718.

  In the carbon monoxide remover 500B, a carbon monoxide selective oxidation catalyst (for example, platinum) is supported on the inner surface of the box-shaped member 510 and the bottom plate 530, the partition plate 520, the partition plate 540, and the separate plate 550.

  Next, the reformer 400 </ b> B is provided on the base portion 654. The reformer 400B is an application of the reactor 400 in the first embodiment, and the reformer 400B is provided in the same manner as the reactor 400 shown in FIGS. The cross section of the reformer 400B shown in FIG. 17 corresponds to the cross section of the reactor 400 shown in FIG. In addition, the same code | symbol is attached | subjected to the part which mutually respond | corresponds between the reformer 400B and the reactor 400, and description of a part corresponding to each other is abbreviate | omitted.

  As shown in FIGS. 11 and 13, the bottom plate 430 of the reformer 400 </ b> B is joined to the upper surface of the base portion 654. By the bottom plate 430, a part of the reformed fuel supply channel 702, a part of the exhaust gas channel 714, a part of the combustion fuel supply channel 710, a part of the communication channel 704, and the combustion chamber 712 are formed. Covered. The inlet 432 formed in the bottom plate 430 is positioned above the end 703 of the reformed fuel supply channel 702, and the discharge port 434 formed in the bottom plate 430 is positioned above the end 705 of the communication channel 704. ing.

  In the reformer 400B, a reforming catalyst (for example, a Cu / ZnO-based catalyst or a Pd / ZnO-based catalyst) is supported on the inner surface of the box-shaped member 410 and the bottom plate 430 and the partition plate 420.

  As shown in FIG. 13, the bottom plate 430 of the reformer 400 </ b> B and the bottom plate 530 of the carbon monoxide remover 500 </ b> B are integrally formed in a state of being connected by a connecting lid 680. A plate material 690 in which the bottom plate 430, the bottom plate 530, and the connection lid 680 are integrated is confined in the connection lid 680. The plate member 690 is joined to the base plate 642, but the connection lid 680 of the plate member 690 is joined to the connection base portion 656 of the base plate 642, thereby forming the connection pipe 608. In this connection pipe 608, a part of the reformed fuel supply flow path 702, a part of the exhaust gas flow path 714, a part of the combustion fuel supply flow path 710, and a part of the communication flow path 704 are connected to the connection lid. Covered by 680.

As shown in FIG. 11 and the like, the outer shape of the connection pipe 608 is a prismatic shape, the width of the connection pipe 608 is narrower than the width of the high temperature reaction part 604 and the low temperature reaction part 606, and the height of the connection pipe 608 is also high temperature reaction. It is lower than the height of the part 604 and the low temperature reaction part 606. The connecting pipe 608 is installed between the high temperature reaction part 604 and the low temperature reaction part 606. The connecting pipe 608 is connected to the high temperature reaction part 604 at the center in the width direction of the high temperature reaction part 604 and at low temperature. The reaction unit 606 is connected to the low temperature reaction unit 606 at the center in the width direction.
As described above, the connecting pipe 608 is provided with the reformed fuel supply channel 702, the communication channel 704, the combustion fuel supply channel 710, and the exhaust gas channel 714.

  Next, the path of the flow path provided inside the supply / discharge section 602, the high temperature reaction section 604, the low temperature reaction section 606, and the connecting pipe 608 will be described. FIG. 18 is a diagram showing a path from the supply of a combustion mixture consisting of gaseous fuel and air to the discharge of water or the like as a product in the microreactor module 600 of the present embodiment. It is the figure in the micro reactor module 600 of this embodiment which showed the path | route after supplying liquid fuel and water until the hydrogen gas which is a product is discharged | emitted. Here, the correspondence between FIG. 18, FIG. 19 and FIG. 12 will be described. The liquid fuel introduction pipe 622 corresponds to the vaporizer 610, the combustion channel 625 corresponds to the first combustor 612, and the combustion chamber 712 corresponds to the first. Corresponds to two combustors.

  As shown in FIG. 13, on the lower surface of the low temperature reaction part 606, that is, the lower surface of the insulating plate 640, the heating wire 720 is patterned in a meandering manner, and these are passed from the low temperature reaction part 606 through the connecting pipe 608 to the high temperature reaction part 604. The heating wire 722 is patterned in a meandering state on the lower surface. A heating wire 724 is patterned from the lower surface of the low temperature reaction part 606 through the surface of the combustor plate 624 to the side surface of the liquid fuel introduction pipe 622. Here, an insulating film such as silicon nitride or silicon oxide is formed on the side surface of the liquid fuel introduction pipe 622 and the surface of the combustor plate 624, and a heating wire 724 is formed on the surface of the insulating film. By patterning the heating wires 720, 722, 724 on the insulating film or insulating plate 640, the voltage to be applied is not applied to the base plate 642 made of metal material, the liquid fuel introduction pipe 622, the combustor plate 624, etc. The heat generation efficiency of the heating wires 720, 722, 724 can be improved.

  The heating wires 720, 722, and 724 are formed by laminating an insulating film or insulating plate 640, a diffusion prevention layer, and a heat generation layer in this order. The heat generating layer is a material having the lowest resistivity among the three layers (for example, Au). When a voltage is applied to the heating wires 720, 722, and 724, a current flows intensively and generates heat. The diffusion prevention layer is a material in which even if the heating wires 720, 722, and 724 generate heat, the material of the heat generation layer is not easily diffused into the diffusion prevention layer, and the material of the diffusion prevention layer is difficult to thermally diffuse into the heat generation layer. It is preferable to use a substance (for example, W) having a high target melting point and low reactivity. Further, when the diffusion preventing layer has low adhesion to the insulating film and is easily peeled off, an adhesion layer may be further provided between the insulating film and the diffusion preventing layer. And an insulating film or an insulating plate 640 are made of a material having excellent adhesion (for example, Ta, Mo, Ti, Cr). The heating wire 720 heats the low-temperature reaction unit 606 at startup, the heating wire 722 heats the high-temperature reaction unit 604 and the connecting pipe 608 at startup, and the heating wire 724 includes the vaporizer 610 and the first in the supply / discharge unit 602. The combustor 612 is heated. Thereafter, when the second combustor 614 is burned with off-gas containing hydrogen from the fuel cell, the heating wire 722 heats the high-temperature reaction unit 604 and the connecting pipe 608 as an auxiliary to the second combustor 612. Similarly, when the first combustor 612 is burned with off-gas containing hydrogen from the fuel cell, the heating wire 720 heats the low-temperature reaction unit 606 as an auxiliary to the first combustor 612.

  Further, the heating wires 720, 722, and 724 change in electrical resistance depending on the temperature, and also function as a temperature sensor that reads a change in temperature from a change in resistance value. Specifically, the temperature of the heating wires 720, 722, 724 is proportional to the electrical resistance.

  Any end portions of the heating wires 720, 722, 724 are located on the lower surface of the low temperature reaction portion 606, and these end portions are arranged so as to surround the combustor plate 624. Lead wires 731 and 732 are connected to both ends of the heating wire 720, lead wires 733 and 734 are connected to both ends of the heating wire 722, and lead wires 735 and 736 are connected to both ends of the heating wire 724, respectively. Is connected. In FIG. 11, the heating wires 720, 722, and 724 and the lead wires 731 to 736 are not shown for easy viewing of the drawing.

  Further, as shown in FIG. 13, a getter material 728 may be provided on the surface of the connecting pipe 608. The getter material 728 is provided with a heater such as an electric heating material, and lead wires 737 and 738 are connected to the getter material 728, respectively. The getter material 728 is activated by being heated and has an adsorption action, such as a gas remaining in the internal space of the heat insulation package 791 described later, a gas leaked from the microreactor module 600 to the internal space of the heat insulation package 791, By adsorbing the gas that has entered the heat insulation package 791 from the outside, the degree of vacuum in the internal space of the heat insulation package 791 is deteriorated and the heat insulation effect is prevented from being lowered. Examples of the material of the getter material 728 include an alloy containing zirconium, barium, titanium, or vanadium as a main component. In FIG. 11, the lead wires 737 and 738 are not shown in order to make the drawing easy to see.

  Next, FIG. 20 is an exploded perspective view of a heat insulating package 791 (heat insulating container) covering the microreactor module 600 of the present embodiment. As shown in FIG. 20, the heat insulation package 791 is configured to cover the entire microreactor module 600, and the high temperature reaction unit 604, the low temperature reaction unit 606, and the connecting pipe 608 are accommodated in the heat insulation package 791. The heat insulation package 791 is composed of a parallelepiped case 792 whose bottom surface is open, and a plate 793 that closes the bottom surface opening of the case 792, and the plate 793 is joined to the case 792. Both the case 792 and the plate 793 are made of a heat insulating material such as glass or a metal material. Further, a metal reflection film such as aluminum or gold may be formed on the inner surface. When such a metal reflective film is formed, heat loss due to radiation from the supply / discharge unit 602, the high temperature reaction unit 604, the low temperature reaction unit 606, and the connection pipe 608 can be suppressed.

  A plurality of through holes penetrate through the plate 793, and the pipe materials 626, 628, 630, 632, 634, the liquid fuel introduction pipe 622, and the lead wires 731 to 738 are inserted into the respective through holes, and heat is insulated from the through holes. The pipe materials 626, 628, 630, 632, and 634, the liquid fuel introduction pipe and the lead wires 731 to 738, and the through holes of the plate 793 are made of, for example, a glass material or an insulating seal so that outside air and moisture do not enter the package 791. Bonded and sealed with a material. In addition, the internal space of the heat insulation package 791 is sealed and evacuated, and the internal space is vacuumed to form a vacuum heat insulation structure. As a result, heat of each part of the microreactor module 600 can be prevented from propagating to the outside, and heat loss can be reduced.

  The pipe materials 626, 628, 630, 632, 634 and the liquid fuel introduction pipe 622 are partially exposed to the outside of the heat insulating package 791. Therefore, inside the heat insulation package 791, the pipe materials 626, 628, 630, 632, 634 and the liquid fuel introduction pipe 622 are made to stand with respect to the plate 793 as columns, and the high temperature reaction unit 604, the low temperature reaction unit 606 and the connection are made. The pipe 608 is supported by the pipe materials 626, 628, 630, 632, 634 and the liquid fuel introduction pipe 622, and the high temperature reaction part 604, the low temperature reaction part 606 and the connection pipe 608 are separated from the inner surface of the heat insulation package 791.

  The liquid fuel introduction pipe 622 is preferably connected to the lower surface of the low temperature reaction section 606 at the center of gravity of the high temperature reaction section 604, the low temperature reaction section 606, and the connection pipe 608 in plan view.

  Note that the getter material 728 is provided, for example, on the surface of the connection pipe 608, but the getter material 728 is not particularly limited as long as the getter material 728 is provided inside the heat insulating package 791.

Next, the operation of the microreactor module 600 will be described.
First, when a voltage is applied between the lead wires 737 and 738, the getter material 728 is heated by the heater, and the getter material 728 is activated. Thereby, the gas in the heat insulation package 791 is adsorbed by the getter material 728, the degree of vacuum in the heat insulation package 791 is increased, and the heat insulation efficiency is increased.

  Further, when a voltage is applied between the lead wires 731 and 732, the heating wire 720 generates heat and the low temperature reaction unit 606 is heated. When a voltage is applied between the lead wires 733 and 734, the heating wire 722 generates heat, and the high temperature reaction unit 604 is heated. When a voltage is applied between the lead wires 735 and 736, the heating wire 724 generates heat and the upper portion of the liquid fuel introduction pipe 622 is heated. Since the liquid fuel introduction pipe 622, the high temperature reaction section 604, the low temperature reaction section 606, and the connection pipe 608 are made of a metal material, heat conduction among them is easy. Note that the current and voltage of the heating wires 720, 722, and 724 are measured by the control device, whereby the temperatures of the liquid fuel introduction pipe 622, the high-temperature reaction unit 604, and the low-temperature reaction unit 606 are measured, and the measured temperatures are transferred to the control device. The voltage of the heating wires 720, 722, and 724 is controlled by the control device, and thereby the temperatures of the liquid fuel introduction pipe 622, the high temperature reaction unit 604, and the low temperature reaction unit 606 are controlled.

  In a state where the liquid fuel introduction pipe 622, the high temperature reaction section 604, and the low temperature reaction section 606 are heated by the heating wires 720, 722, 724, the liquid fuel and water mixed liquid is continuously supplied to the liquid fuel introduction pipe 622 by a pump or the like. When intermittently supplied, the liquid mixture is absorbed by the liquid absorbing material 623, and the liquid mixture permeates upward in the liquid fuel introduction pipe 622 by capillary action. Then, the liquid mixture in the liquid absorbing material 623 is vaporized, and the mixture of fuel and water evaporates from the liquid absorbing material. Since the liquid mixture is vaporized in the liquid absorbing material 623, bumping can be suppressed and vaporization can be stably performed.

  Then, the air-fuel mixture evaporated from the liquid absorbing material 623 flows into the reformer 400B through the through hole 678, the reformed fuel supply channel 702, and the inlet 432. Thereafter, when the air-fuel mixture flows through the reformer 400B, the air-fuel mixture is heated and undergoes a catalytic reaction to generate hydrogen gas or the like (when the fuel is methanol, the above chemical reaction formula) (See (1) and (2).)

  The air-fuel mixture (including hydrogen gas, carbon dioxide gas, carbon monoxide gas, etc.) generated by the reformer 400B flows into the mixing chamber 708 through the discharge port 434 and the communication channel 704. On the other hand, air is supplied to the pipe material 634 by a pump or the like, flows into the mixing chamber 708 through the through-hole 675 and the air supply flow path 706, and the air-fuel mixture such as hydrogen gas is mixed with air.

  Then, an air-fuel mixture containing air, hydrogen gas, carbon monoxide gas, carbon dioxide gas, or the like flows from the mixing chamber 708 through the inlet 532 into the carbon monoxide remover 500B. When the air-fuel mixture flows in the carbon monoxide remover 500B, the carbon monoxide gas in the air-fuel mixture is selectively oxidized and the carbon monoxide gas is removed.

  Then, the air-fuel mixture from which carbon monoxide has been removed is supplied from the exhaust port 534 to the fuel electrode of the fuel cell via the exhaust chamber 718, the through hole 671, and the tube material 626. In the fuel cell, electricity is generated by an electrochemical reaction of hydrogen gas, and off-gas containing unreacted hydrogen gas and the like is discharged from the fuel cell.

  The above operation is an initial operation, and the mixed liquid continues to be supplied to the liquid fuel introduction pipe 622 during the subsequent power generation operation. Then, air is mixed with the off-gas discharged from the fuel cell, and the mixture (hereinafter referred to as combustion mixture) is supplied to the pipe 632 and the pipe 628. The combustion mixture supplied to the pipe 632 flows into the combustion channel 625 through the through hole 674, the combustion fuel supply channel 716, and the through hole 676, and the combustion mixture undergoes catalytic combustion in the combustion channel 625, and combustion Heat is generated. Since the combustion channel 625 circulates around the liquid fuel introduction pipe 622 below the low temperature reaction section 606, the liquid fuel introduction pipe 622 is heated by the combustion heat and the low temperature reaction section 606 is heated. Therefore, the electric power supplied to the heating wires 720 and 724 can be reduced, and the energy use efficiency is increased.

On the other hand, the combustion mixture supplied to the pipe 628 flows into the combustion chamber 712 through the through-hole 672 and the combustion fuel supply flow path 710, and the combustion mixture is catalytically combusted in the combustion chamber 712. As a result, combustion heat is generated. The reformer 400B is heated by this combustion heat. Therefore, the power supplied to the heating wire 722 can be reduced, and the energy use efficiency is increased.
Note that the liquid fuel stored in the fuel container may be vaporized, and the vaporized fuel and air combustion mixture may be supplied to the pipe members 628 and 632.

  In the state where the mixed liquid is supplied to the liquid fuel introduction pipe 622 and the combustion air-fuel mixture is supplied to the pipe materials 628 and 632, the control device measures the temperature based on the resistance values of the heating wires 720, 722 and 724. While controlling the applied voltage of the heating wires 720, 722, 724, the pump and the like are controlled. When the pump is controlled by the control device, the flow rate of the combustion air-fuel mixture supplied to the pipe materials 628 and 632 is controlled, whereby the amount of combustion heat of the combustors 612 and 614 is controlled. As described above, the control device controls the heating wires 720, 722, 724 and the pump, thereby controlling the temperatures of the liquid fuel introduction pipe 622, the high temperature reaction unit 604, and the low temperature reaction unit 606, respectively. Here, the high temperature reaction part 604 is 250 ° C. to 400 ° C., preferably 300 ° C. to 380 ° C., and the low temperature reaction part 606 is lower than the high temperature reaction part 4, specifically 120 ° C. to 200 ° C., more preferably 140 ° C. Temperature control is performed so as to be ˜180 ° C.

  Next, a schematic configuration of the power generation unit 801 including the microreactor module 600 in the present embodiment will be described. FIG. 21 is a perspective view showing an example of a power generation unit 801 including the microreactor module 600 in the present embodiment. As shown in FIG. 21, the microreactor module 600 as described above can be used by being assembled in the power generation unit 801. The power generation unit 801 is housed in, for example, a frame 802, a fuel container 804 that can be attached to and detached from the frame 802, a flow rate control unit 806 having a flow path, a pump, a flow rate sensor, a valve, and the like, and a heat insulation package 791. The microreactor module 600 in a state, a power generation module 808 having a fuel cell, a humidifier that humidifies the fuel cell, a recovery unit that recovers a byproduct generated in the fuel cell, and the like, and the microreactor module 600 and the power generation module 808 include air ( An air pump 810 for supplying oxygen), and a power supply unit 812 having an external interface and the like for electrical connection with a secondary battery, a DC-DC converter and an external device driven by the output of the power generation unit 801. Composed. By supplying the mixture of water and liquid fuel in the fuel container 804 to the microreactor module 600 by the flow rate control unit 806, the hydrogen rich gas is generated as described above, and the hydrogen rich gas is supplied to the fuel cell of the power generation module 808. The generated electricity is stored in the secondary battery of the power supply unit 812.

  FIG. 22 is a perspective view illustrating an example of an electronic device 851 that uses the power generation unit 801 as a power source. As shown in FIG. 22, the electronic device 851 is a portable electronic device, for example, a notebook personal computer. The electronic device 851 includes a lower housing 854 having a built-in arithmetic processing circuit composed of a CPU, RAM, ROM, and other electronic components and having a keyboard 852, and an upper housing 858 having a liquid crystal display 856. Prepare. The lower casing 854 and the upper casing 858 are coupled by a hinge, and the upper casing 858 is overlapped with the lower casing 854 and can be folded with the liquid crystal display 856 facing the keyboard 852. Yes. A mounting portion 860 for mounting the power generation unit 801 is formed from the right side surface to the bottom surface of the lower housing 854. When the power generation unit 801 is mounted on the mounting portion 860, the electronic device 851 is operated by electricity of the power generation unit 801.

  As described above, according to the present embodiment, the reformer 400B of the high temperature reaction unit 604 is reinforced by the partition plate 420 to increase the rigidity, and the carbon monoxide remover 500B of the low temperature reaction unit 606 is formed by the partition plates 520 and 540. Is reinforced to increase rigidity. In particular, since the reformer 400B and the carbon monoxide remover 500B are accommodated in a vacuum heat insulation package 791, stress that causes the reformer 400B and the carbon monoxide remover 500B to expand acts. Since the partition plate 420 is joined in the reformer 400B and the partition plates 520 and 540 are joined in the carbon monoxide remover 500B, the reformer 400B and the carbon monoxide remover 500B expand. Thus, deformation can be suppressed.

  Further, the internal space of the heat insulation package 791 is a heat insulation space, the high temperature reaction part 604 is separated from the low temperature reaction part 606, and the distance from the high temperature reaction part 604 to the low temperature reaction part 606 is the length of the connecting pipe 608. ing. Accordingly, the heat transfer path from the high temperature reaction unit 604 to the low temperature reaction unit 606 is limited to the connection pipe 608, and heat transfer to the low temperature reaction unit 606 that does not require high temperature is limited. In particular, since the height and width of the connection pipe 608 are smaller than the height and width of the high temperature reaction part 604 and the low temperature reaction part 606, heat conduction through the connection pipe 608 is suppressed as much as possible. Therefore, the heat loss of the high temperature reaction part 604 can be suppressed, and the temperature increase of the low temperature reaction part 606 above the set temperature can be suppressed. That is, even when the high temperature reaction unit 604 and the low temperature reaction unit 606 are accommodated in one heat insulating package 791, a temperature difference can be generated between the high temperature reaction unit 604 and the low temperature reaction unit 606.

  In addition, since the flow paths 702, 704, 710, and 714 passing between the low temperature reaction unit 606 and the high temperature reaction unit 604 are combined into one connection pipe 608, stress generated in the connection pipe 608 and the like. Can be reduced. That is, since there is a temperature difference between the high temperature reaction unit 604 and the low temperature reaction unit 606, the high temperature reaction unit 604 expands more than the low temperature reaction unit 606, but the high temperature reaction unit 604 is connected to the connection pipe 608. Since the portion other than the portion is a free end, the stress generated in the connecting pipe 608 and the like can be suppressed. In particular, the connection pipe 608 is smaller in height and width than the high temperature reaction part 604 and the low temperature reaction part 606, and the connection pipe 608 further includes the high temperature reaction part 604 and the low temperature reaction at the center in the width direction of the high temperature reaction part 604 and the low temperature reaction part 606. Since it is connected to the part 606, it is possible to suppress the generation of stress in the connecting pipe 608, the high temperature reaction part 604, and the low temperature reaction part 606.

  The pipe materials 626, 628, 630, 632, 634 and the liquid fuel introduction pipe 622 extend to the outside of the heat insulation package 791, and these are all connected to the low temperature reaction part 606. Therefore, direct heat transfer from the high temperature reaction part 604 to the outside of the heat insulation package 791 can be suppressed, and heat loss of the high temperature reaction part 604 can be suppressed. Therefore, even when the high temperature reaction unit 604 and the low temperature reaction unit 606 are accommodated in one heat insulating package 791, a temperature difference can be generated between the high temperature reaction unit 604 and the low temperature reaction unit 606.

  Since the lower surface of the connecting pipe 608, the lower surface of the high temperature reaction unit 604, and the lower surface of the low temperature reaction unit 606 are flush with each other, the heating wire 722 can be patterned relatively easily and the disconnection of the heating wire 722 can be suppressed. Can do.

  Further, since the liquid fuel introduction pipe 622 is filled with the liquid absorbing material 623 and the liquid fuel introduction pipe 622 is used as the vaporizer 610, it is necessary to vaporize the mixed liquid while reducing the size and simplification of the microreactor module 600. Temperature state (state in which the upper portion of the liquid fuel introduction pipe 622 becomes 120 ° C.).

  The combustor plate 624 is provided around the liquid fuel introduction pipe 622 at the upper end portion of the liquid fuel introduction pipe 622, and the liquid absorbing material 623 in the liquid fuel introduction pipe 622 is positioned at the height of the combustor plate 624. Therefore, the combustion heat in the first combustor 612 can be efficiently used for vaporization of the mixed liquid.

  The present invention is not limited to the above-described embodiment, and various improvements and design changes may be made without departing from the spirit of the present invention.

  For example, a single connection pipe 608 is installed between the low temperature reaction section 606 and the high temperature reaction section 604, but a plurality of connection pipes are installed between the low temperature reaction section 606 and the high temperature reaction section 604. May be.

  Further, in the reactor 500 and the carbon monoxide remover 500B, one separate plate is accommodated in the box-shaped member 510 and divided into two spaces, but a plurality of separate plates are divided into the box-shaped member 510. And may be partitioned into more spaces. In this case, the partition plate is accommodated in each space in the same manner as the partition plates 520 and 540.

It is a disassembled perspective view of the reactor in 1st Embodiment of the reaction apparatus concerning this invention. It is the upper side figure and side view of the reactor in this embodiment. It is arrow sectional drawing of the surface along the cutting line III-III of FIG. FIG. 4 is a cross-sectional view taken along the line IV-IV in FIG. It is a permeation | transmission side view of the reactor of the state which provided the heat insulation package in this embodiment. It is a disassembled perspective view of the modification of the reactor in this embodiment. It is a disassembled perspective view of the reactor in 2nd Embodiment of the reaction apparatus concerning this invention. It is the upper side figure and side view of the reactor in this embodiment. It is arrow sectional drawing of the surface along the cutting line IX-IX of FIG. It is arrow sectional drawing of the surface along the cutting line XX of FIG. It is a side view of the micro reactor module in 3rd Embodiment of the reaction apparatus concerning this invention. It is a schematic side view at the time of dividing the micro reactor module in this embodiment for every function. It is a disassembled perspective view of the micro reactor module in this embodiment. It is arrow sectional drawing of the surface along the cutting line XIV-XIV of FIG. It is arrow sectional drawing of the surface along the cutting line XV-XV of FIG. It is arrow sectional drawing of the surface along the cutting line XVI-XVI of FIG. It is arrow sectional drawing of the surface along the cutting line XVII-XVII of FIG. It is drawing which showed the path | route until the water etc. which are a product are discharged | emitted in the micro reactor module of this embodiment after a combustion mixture is supplied. It is drawing which showed the path | route after liquid fuel and water are supplied in the micro reactor module of this embodiment until hydrogen rich gas which is a product is discharged | emitted. It is a disassembled perspective view of the heat insulation package which covers the micro reactor module of this embodiment. It is a perspective view which shows an example of an electric power generation unit provided with the micro reactor module in this embodiment. It is a perspective view which shows an example of the electronic device which uses a power generation unit as a power supply.

Explanation of symbols

400, 400A, 500 Reactor 400B Reformer 500B Carbon monoxide remover 410, 510 Box-shaped member 420, 520, 540 Partition plate 422, 522, 542 Reinforcement part 424, 524, 544 Partition part 426, 526, 546 Folding 430, 530 Bottom plate 550 Separate plate 600 Microreactor module 604 High temperature reaction unit 606 Low temperature reaction unit 608 Connecting tube

Claims (14)

In a reactor equipped with a reactor for reacting reactants and generating hydrogen from liquid fuel ,
The reactor is
A box having a hollow;
A pair of flat plate-like portions accommodated in the box and forming a flow path through which reactants flow, opposite at both sides, and at least opposed to the pair of plate-like portions between the pair of plate-like portions; A rectangular wave-like partition plate having one partition portion and a plurality of folded portions connected between the adjacent partition portions or between the adjacent partition portion and the plate-like portion;
Among the partition plates, at least the pair of plate-like portions are fixed in surface contact with the inner surface of the box, respectively.   The reaction apparatus according to claim 1, wherein the plate-like portion is joined to the inner surface of the box body by either welding or brazing. The reaction apparatus according to claim 1 or 2 , wherein the folded portion of the partition plate is in surface contact with an inner surface of the box.   The reaction device according to claim 3, wherein the folded portion is joined to the inner surface of the box body by either welding or brazing. The reaction device according to any one of claims 1 to 4, wherein an edge portion of the partition plate is in contact with an inner surface of the box.   6. The reaction apparatus according to claim 5, wherein an edge portion of the partition plate is joined to the inner surface of the box body by either welding or brazing. The through hole for flowing the said reaction material between each said partition part is formed in the wave height direction one end part side of each said partition part, It is any one of Claim 1 to 6 characterized by the above-mentioned. Reactor. The box has a bottom plate, a rectangular top plate, and four side plates connected in a state of being vertically connected to four sides of the top plate, and accommodates the partition plate, and an opening is formed in the side plate. A box-shaped member joined and closed to the bottom plate,
The reaction apparatus according to any one of claims 1 to 7, wherein the partition plate is accommodated such that a wave height direction is parallel to the top plate. A separate plate that is housed in the box and partitions the space in the box;
The partition plate is accommodated in a space partitioned by the separate plate,
The reaction apparatus according to any one of claims 1 to 8, wherein an edge portion of the partition plate is in contact with the separate plate.   The reaction apparatus according to claim 9, wherein an edge portion of the partition plate is joined to the separate plate.   The reaction apparatus according to any one of claims 1 to 10, further comprising a heat-insulating container that covers the whole of the reactor and that has a vacuum pressure inside. The reactor is
A first reaction section set at a first temperature and causing a reaction of the reactants;
A second reaction part set to a second temperature lower than the first temperature and causing a reaction of the reactant;
A connecting pipe for sending reactants and products between the first reaction part and the second reaction part,
The first reaction portion and at least one of the second reaction portion, the reaction apparatus according to any one of claims 1 to 10, characterized in that it comprises the reactor.   The said reaction apparatus is further equipped with the heat insulation container which covers the whole said 1st reaction part, said 2nd reaction part, and the said connection pipe, and the inside is made into vacuum pressure. Reactor. The first reaction part is supplied with a first reactant to produce a first product, and the second reaction part is supplied with the first product to produce a second product. Produce things,
The first reactant is an air-fuel mixture in which water and hydrocarbon liquid fuel are vaporized, and the first reaction section is a reformer that causes a reforming reaction of the first reactant. The first product includes hydrogen and carbon monoxide;
The reaction apparatus according to claim 12 or 13 , wherein the second reaction unit is a carbon monoxide remover that removes carbon monoxide contained in the first product by selective oxidation.

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