JP2009007231A - Reactor, electricity generator, and electronic apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reactor, an electricity generator, and an electronic apparatus each of which can easily cope with even the case when a carbon monoxide removal apparatus is overheated by cooling the removal apparatus. <P>SOLUTION: The low-temperature reaction section 606 of a microreactor module 600 is provided with a combustion fuel feed passage 716 (reaction passage) in the inside of which reactants flow and react with each other, A fluid is allowed to pass through the combustion fuel passage 716, whereupon the passage 716 can serve also as a cooling passage for cooling the low-temperature reaction section 606. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a reaction device, a power generation device, and an electronic device.

In recent years, fuel cells using hydrogen as a fuel have begun to be applied to automobiles and mobile phones as a clean power source with high energy conversion efficiency. A fuel cell is a device that directly extracts electric energy from chemical energy by electrochemically reacting fuel and oxygen.
The fuel used in the fuel cell includes hydrogen, but if it is stored as it is at normal temperature and pressure, the amount of storage per unit volume is not sufficient and there is a problem in storage. Therefore, in order to reform hydrogen fuel such as alcohols and gasoline to produce hydrogen, a vaporizer that vaporizes the liquid fuel, or a reformer that extracts hydrogen necessary for power generation by reacting the liquid fuel with high-temperature steam. In some cases, a carbon monoxide remover or the like that removes carbon monoxide, which is a by-product of the reforming reaction, is used.
By the way, a reactor such as a carbon monoxide remover may generate an unexpected temperature rise. If such an abnormal temperature rise is detected, a large amount of water for reforming reaction is added. A technique for cooling with a heat exchanger is known (for example, see Patent Document 1).
JP 2004-115321 A

However, by providing a heat exchanger for cooling a reactor whose temperature has been raised as described in Patent Document 1 with a large amount of water for reforming reaction, the microreactor is enlarged, and the heat loss of the entire system is large. There is a problem that it does not become highly efficient.
The present invention has been made in view of the above circumstances, and provides a reaction apparatus, a power generation apparatus, and an electronic device that can be easily cooled even when the temperature of the reactor is higher than a desired temperature. It is aimed.

In order to solve the above problems, the invention of claim 1
A combustor that generates heat by burning;
A reaction part;
A flow path for selectively supplying a fuel for burning in the combustor and a refrigerant for cooling the reaction section;
It is characterized by providing.

Invention of Claim 2 is the reaction apparatus of Claim 1,
A plurality of the reaction parts are provided,
Of the plurality of reaction units, a first reaction unit that causes reaction of a reactant includes a reformer that reforms fuel,
The second reaction section that causes the reaction of the reactant at a temperature lower than the reaction temperature of the first reaction section includes a carbon monoxide remover that removes carbon monoxide contained in the product. .
Invention of Claim 3 is the reaction apparatus of Claim 2,
The channel is a heat exchanger that cools the second reaction section.
Invention of Claim 4 is the reaction apparatus of Claim 1,
When the reaction part is at a predetermined temperature or higher, the supply of fuel to the combustor is stopped, and the reaction part is cooled by flowing a refrigerant through the flow path,
When the reaction part is below a predetermined temperature, it is controlled to heat the reaction part by burning in the combustor by flowing fuel and air through the flow path.

The invention of claim 5
In a reactor equipped with a reaction part that causes reaction of reactants,
The reaction section includes a reaction flow path in which a reactant flows to cause a reaction,
In the reaction channel, at least one bent portion is formed at a location where a plurality of reactants are mixed.

Invention of Claim 6 is the reaction apparatus of Claim 5,
The bent portion is formed so as to change direction at approximately 90 degrees with respect to the flow direction of the reactant.
The invention according to claim 7 is the reaction apparatus according to claim 5 or 6,
A plurality of the reaction parts are provided,
Of the plurality of reaction units, a first reaction unit that causes reaction of a reactant includes a reformer that reforms fuel,
The second reaction section that causes the reaction of the reactant at a temperature lower than the reaction temperature of the first reaction section includes a carbon monoxide remover that removes carbon monoxide contained in the product. To do.
Invention of Claim 8 is the reaction apparatus of Claim 7,
The bent portion is formed immediately before the reaction flow path leading to the carbon monoxide remover.

The invention of claim 9 is the power generator,
It has a power generation cell which takes out electric power from the reformed gas generated by the reactor according to any one of claims 1 to 8 by an electrochemical reaction.
The invention of claim 10 is an electronic device,
The power generator according to claim 9 is provided as a power supply source.

  According to the present invention, it is possible to easily cope with the case where the reaction section is overheated by flowing a cooling fluid through the cooling flow path. In addition, the size can be reduced and heat loss can be reduced.

The best mode for carrying out the present invention will be described below with reference to the drawings. However, various technically preferable limitations for carrying out the present invention are given to the embodiments described below, but the scope of the invention is not limited to the embodiments and the illustrated examples.
FIG. 1 is a side view of the microreactor module 600. This microreactor module 600 is built in electronic devices such as notebook personal computers, PDAs, electronic notebooks, digital cameras, mobile phones, watches, registers, and projectors together with fuel cells, and reforms liquid fuel for use in fuel cells. It produces gas.

  As shown in FIG. 1, the microreactor module 600 includes a pipe group 602 in which reactants are supplied and products are discharged, a high-temperature reaction unit 604 in which a reforming reaction at a proper temperature required for operation occurs, The inflow or outflow of reactants or products between the low temperature reaction unit 606 where the selective oxidation reaction occurs at a temperature lower than the proper operation temperature of the high temperature reaction unit 604 and the high temperature reaction unit 604 and the low temperature reaction unit 606 occurs. And a connecting portion 608 for performing.

  FIG. 2 is a schematic side view when the microreactor module 600 is divided for each function. As shown in FIG. 2, the pipe group 602 is mainly provided with a carburetor 610 and a first combustor 612. The first combustor 612 includes a fuel that is at least partially vaporized (for example, hydrogen gas, methanol gas, and the like) and a gas that serves as an oxygen source such as air containing oxygen for burning the fuel. The fluids are supplied separately or as mixed fluids, and these fluids are burned by the catalyst in the first combustor 612 to generate heat. The vaporizer 610 is supplied with water and liquid fuel (for example, alcohols such as methanol and ethanol, ethers such as dimethyl ether, and fossil fuels such as gasoline) from the fuel container separately or mixed. The heat of combustion in the combustor 612 propagates into the vaporizer 610, whereby water and liquid fuel are vaporized in the vaporizer 610.

The high temperature reaction section 604 is mainly provided with a second combustor 614 and a reformer 400 provided on the second combustor 614. The second combustor 614 includes a fuel at least partially vaporized (for example, hydrogen gas, alcohols such as methanol and ethanol, ethers such as dimethyl ether, fossil fuels such as gasoline), and the like. A gas serving as an oxygen source such as air containing oxygen for burning the gas is supplied separately or as a mixed fluid, and heat is generated by catalytic combustion of the fluid.
In some cases, unreacted hydrogen gas may be included in the off-gas discharged from the fuel cell after the fuel cell has generated an electrochemical reaction with the hydrogen gas supplied from the microreactor module 600. At least one of the second combustor 614 may burn the unreacted hydrogen gas with a gas such as air containing oxygen to generate heat. Needless to say, at least one of the first combustor 612 and the second combustor 614 is configured so that liquid fuel (for example, methanol, ethanol, butane, dimethyl ether, gasoline, etc.) stored in the fuel container is supplied by another vaporizer. The vaporized fuel may be burned with a gas such as air containing oxygen.
Further, when the microreactor module 600 is started up, a heating wire 724 described later generates heat to vaporize liquid fuel in a liquid fuel introduction pipe 622 (vaporizer 610) described later, and in a steady state, The liquid fuel in the liquid fuel introduction pipe 622 may be continuously vaporized by burning the fuel. However, when the heating wire 724 is not provided, the liquid fuel stored in the fuel container is first stored when the microreactor module 600 is started. It is supplied into the combustor 612 and heated by preheating of a heating wire 720, which will be described later, and burned while being vaporized to vaporize the liquid fuel in the vaporizer 610, and the off-gas containing hydrogen is stably discharged from the fuel cell. Then, the supply of liquid fuel from the fuel container to the first combustor 612 is stopped, and off gas is supplied into the first combustor 612 to supply hydrogen. Tempering the liquid fuel in the vaporizer 610 may be vaporized.

When the second combustor 614 burns off-gas discharged from the fuel cell, first, at startup, the reformer 400 is heated by a heating wire 722 to be described later to generate hydrogen, and the fuel cell to which this hydrogen is supplied. When the off-gas containing hydrogen is steadily discharged from the gas, the second combustor 614 burns the hydrogen in the off-gas and heats the reformer 400. When the second combustor 614 becomes the main heat source, the heating wire 722 lowers the applied voltage so as to switch to the auxiliary heat source.
The reformer 400 is supplied with a mixture of water and fuel from the vaporizer 610, and the reformer 400 is heated to an appropriate reaction temperature range by the second combustor 614. In the heated reformer 400, hydrogen gas or the like is generated from water and 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. 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 500. The carbon monoxide remover 500 is heated by the first combustor 612, supplied with a gas mixture containing hydrogen gas, carbon monoxide gas, and the like from the reformer 400, and further supplied with an oxygen source such as air. The In the carbon monoxide remover 500, carbon monoxide is selectively oxidized from the air-fuel mixture, whereby a chemical reaction such as the following formula (3) occurs, and carbon monoxide is removed.
CO + 1 / 2O ₂ → CO ₂ (3)
An air-fuel mixture mainly composed of hydrogen from which carbon monoxide has been removed is supplied to the fuel electrode of the fuel cell.
In the present invention, the fuel that has been supplied for the combustion reaction in the first combustor 612 when the carbon monoxide remover 500 is heated to a high temperature close to or within the upper limit of the appropriate reaction temperature range. In addition, the carbon monoxide remover 500 is cooled by stopping the heating by stopping the supply of the fuel among the air for burning the fuel and the like, and supplying only the air as the refrigerant. The air supplied to cool the carbon monoxide remover 500 flows into a combustion fuel supply channel 716 (see FIG. 7), to be described later, to which fuel and air are supplied for the combustion reaction, and the combustion fuel supply channel 716 is also used as a cooling channel. When the carbon monoxide remover 500 is sufficiently cooled to be below the appropriate reaction temperature range, the fuel supply is started again and the carbon monoxide remover 500 is heated by the combustion reaction.

A specific configuration of the microreactor module 600 will be described with reference to FIGS. 1 and 3 to 9. 3 is an exploded perspective view of the microreactor module 600, FIG. 4 is an exploded perspective view of the reformer 400, FIG. 5 is an exploded perspective view of the carbon monoxide remover 500, and FIG. FIG. 7 is a cross-sectional view taken along the line VI-VI in FIG. 1, and FIG. 7 is a sectional line VII in FIG. 1.
FIG. 8 is a cross-sectional view taken along the line VII-VII, FIG. 8 is a cross-sectional view taken along the line VIII-VIII in FIG. 1, and FIG. 9 is a cross-sectional view taken along the line IX-IX in FIG. 10 is a perspective view of the base plate 642. FIG.

  As shown in FIGS. 1, 3, and 6, the pipe group 602 surrounds the liquid fuel introduction pipe 622 made of Kovar (NiFeCo alloy) and the liquid fuel introduction pipe 622 at the upper end of the liquid fuel introduction pipe 622. Combustor plate 624 made of Kovar (NiFeCo alloy) provided and five pipes 626, 628, 630, 632, 634 made of Kovar (NiFeCo alloy) arranged around liquid fuel introduction pipe 622 To do. The combustor plate 624 is joined to the liquid fuel introduction pipe 622 and the low temperature reaction unit 606 by hard brazing, and the brazing agent includes the highest temperature among the temperatures of the fluid flowing through the liquid fuel introduction pipe 622 and the combustor plate 624. A gold wax containing silver, copper, zinc and cadmium in gold, a wax mainly composed of gold, silver, zinc and nickel, or gold having a melting point higher than that, preferably a melting point of 700 ° C. or more, Particularly preferred are waxes based on palladium and silver. The combustor plate 624 also functions as a flange for joining the liquid fuel introduction pipe 622 to the low temperature reaction unit 606.

  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 may be a material in which inorganic fibers or organic fibers are hardened with a binder, or a sintered inorganic powder or an inorganic powder. It may be solidified with or 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.

  A through hole is formed in the central portion 624A of the combustor plate 624, the liquid fuel introduction pipe 622 is fitted into the through hole 624A, and the liquid fuel introduction pipe 622 and the combustor plate 624 are joined. Further, a partition wall 624 </ b> B is provided on one surface of the combustor plate 624. A part of the partition wall 624 </ b> B is provided over the entire outer edge of the combustor plate 624, the other part is provided in 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. 1 and 3, the high temperature reaction unit 604, the low temperature reaction unit 606, and the connection unit 608 have a base plate 642 as a common base. A plate member 690, corrugated plates 420, 520, 540, a separate plate 550, and cup bodies 410, 510 are provided on one surface of the base plate 642, and thereby a reaction vessel such as a high temperature reaction unit 604, a low temperature reaction unit 606, and a connection unit 608. Is formed. An insulating plate 640 is provided on the other surface of the base plate 642 that forms the reaction vessel.

  The base plate 642 is made of Kovar (NiFeCo alloy), and includes a base portion 652 serving as a base of the low temperature reaction portion 606, a base portion 654 serving as a base of the high temperature reaction portion 604, and a connection base portion 656 serving as a base of the connection portion 608. Is provided. 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 insulating plate 640 includes a base portion 662 serving as a base of the low temperature reaction portion 606, a base portion 664 serving as a base of the high temperature reaction portion 604, and a connection base portion 666 serving as a base of the connection portion 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.

  Here, the linear expansion coefficient of the electrical insulator forming the insulating plate 640 is a metal material that forms a reaction vessel such as the cup bodies 410 and 510, the corrugated plates 420, 520, and 540, the separate plate 550, the plate material 690, and the base plate 642. The linear expansion coefficient is preferably 70 to 130%, more preferably 90 to 110%, and most preferably equal.

As a reaction vessel material to be the base plate 642 in contact with the electric insulator and the insulating plate 640, for example, mullite (3Al ₂
O ₃ · 2SiO ₂ , linear expansion coefficient 5.0 × 10 ⁻⁶ / ° C.) and Kovar (FeNiCo alloy, linear expansion coefficient 5.16 × 10 ⁻⁶ / ° C.) as a reaction vessel material may be mentioned. Not limited to this.

  As shown in FIGS. 3 and 7, 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. 1 and 3, the base portion 662 of the insulating plate 640 becomes a lower surface portion of the low temperature reaction portion 606, and pipes 626, 628, 630, 632, 634 and a liquid fuel introduction pipe 622 are formed on the lower surface of the low temperature reaction portion 606. Are joined at their flanges. 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. 3, 6, and 7, the combustor plate 624 is joined to the lower surface of the low-temperature reaction unit 606, and one end of the combustion flow path 625 of the combustor plate 624 is connected to the through hole 676. The other end of the combustion channel 625 communicates with the through hole 677.

  As shown in FIGS. 7 and 10, the base plate 642 has a reformed fuel supply channel 702, a communication channel 704, an air supply channel 706, a mixing channel 708, and carbon monoxide on one surface. Combustion fuel supply flow path 716 also used as a cooling flow path used when cooling remover 500, combustion chamber 712 serving as second combustor 614, exhaust gas flow path 714, combustion fuel supply flow path 710, exhaust gas A stage 641 and a stage 643 that are one step higher than these grooves are provided in the base portion 652 and the base portion 654 so that grooves serving as the chamber 718 are formed.

  The reformed fuel supply channel 702 is formed so as to extend from the through hole 678 of the low temperature reaction unit 606 to the corner of the base unit 654 of the high temperature reaction unit 604 through the connection base unit 656 of the connection unit 608.

In the base portion 652 of the low temperature reaction portion 606, the mixing channel 708 includes two straight portions 708a and 708b extending in the short direction of the base portion 652, and end portions 707A of the straight portions 708a and 708b facing each other. 709A and a bent portion 708c that is bent in a substantially C-shape and is connected to each of 709A. The two straight portions 708a and 798b are arranged on the same straight line. The bent portion 708c includes three bent portions 708d, 708e, and 708f. The bent portion 708d is bent at approximately 90 degrees to the right with respect to the linear direction of the straight portion 708a at one end portion 707A of one straight portion 708a. Yes. The bent portion 708e is bent approximately 90 degrees twice to the left with respect to the bent portion 708d, and the bent portion 708f is bent approximately 90 degrees to the right with respect to the bent portion 708e, so that one end portion of the other straight portion 708b. 709A is formed continuously. Then, the other end portion 707 B of one straight line portion 708 a reaches the air supply flow path 706, and the other end portion 709 B of the other straight line portion 708 b extends to the corner portion 652 a of the base portion 652 to the introduction port 532. Communicates.
Thus, by forming the mixing channel 708 from the two straight portions 708a, 708b and the three bent portions 708d, 708e, 708f, the reformed gas and air flowing through the mixing channel 708 are bent at the bent portion 708c. Since the direction is changed several times by about 90 degrees with respect to the flow direction, mixing of the reformed gas and air can be promoted, and the reformed gas and air are mixed before flowing into the carbon monoxide remover 500. Can be completed.

Here, the effect when the bent portions 708d, 708e, and 708f are provided in the mixing channel 708 as compared with the case where the mixing channel 708 has only a linear shape will be described.
FIG. 11 (a) is an oxygen concentration distribution diagram in the mixing flow path 708 having the bent portions 708d, 708e, and 708f, and FIG. 11 (b) is a linear mixed flow having no bent portions 708d, 708e, and 708f. 5 is an oxygen concentration distribution diagram in a path 708. FIG. In FIG. 11, the oxygen concentration of the oxygen concentration in the range of code A is 6.050mol / m ^3, an oxygen concentration of B is 0 mol / m ^3, C oxygen concentration of 3.025mol / m ^3, D is 0.353mol / m ³ , the oxygen concentration of E is 0.908 mol / m ³ , the oxygen concentration of F is 1.513 mol / m ³ , and the oxygen concentration of G is 1.210 mol / m ³ .
As is apparent from the results of FIG. 11, by providing the bent portions 708d, 708e, and 708f as in the present embodiment, the reformed gas and air are substantially mixed in the vicinity of the first bent portion 708d, and thereafter oxygen It can be seen that the concentration is uniform.
The mixing channel 708 has three bent portions 708d, 708e, and 708f, but it is sufficient to provide at least one bent portion, and the number is not limited to three. Further, the bending angle is not limited to approximately 90 degrees, and is not limited to the C-shape described above, and may be formed in an arc shape or a mountain shape as long as it can be mixed with a plurality of types of fluids. It can be changed as appropriate, such as an M shape, an N shape, an S shape, a V shape, and the like.

  The communication channel 704 is formed so as to reach from the corner of the base portion 654 of the high temperature reaction section 604 to the mixing channel 708 through the connection base portion 656. The air supply channel 706 is formed so as to extend from the through hole 675 of the low temperature reaction unit 606 to the mixing channel 708.

  The combustion chamber 712 is formed by a C-shaped bottom surface 711 at the center of the base portion 654. On the wall surface of the combustion chamber 712 including the lower surface of the plate material 690 and the upper surface of the bottom plate 711, a combustion catalyst for burning the combustion mixture is supported.

  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 flow path 716 also serving as the cooling flow path is disposed inside the air supply flow path 706 in the base portion 652 and is formed to meander from the through hole 674 to the through hole 676. The exhaust chamber 718 is formed as a rectangular recess that is one step lower than the stage 641 in the base portion 652, and a through hole 671 communicates with a corner of the exhaust chamber 718.

  A reformer 400 is provided on the base portion 654. As shown in FIGS. 4, 8, and 9, the reformer 400 includes a cup body 410 that is open on the lower surface, a corrugated plate 420 that is accommodated in the cup body 410, and a lower opening of the cup body 410. And a closed bottom plate 430.

  The cup body 410 includes a top plate 412 having a square shape or a rectangular shape, and a pair of side plates 414 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 and 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. Thus, the bottom face opening of the cup body 410 is closed by the bottom plate 430, whereby a parallelepiped box having a hollow is formed.

  The corrugated plate 420 is made of Kovar (NiFeCo alloy) meandering in a corrugated shape. A pair of reinforcing portions 422, 422 facing each other on both ends of the plate, a plurality of partitioning portions 424, 424,... Facing the reinforcing portion 422 between the two reinforcing portions 422, 422, and four partitioning portions 424 Among the sides, a plurality of folded portions 426, 426,... Connected between the adjacent partition portion 424 and the partition portion 424 or between the adjacent partition portion 424 and the reinforcing portion 422 are provided.

The corrugated plate 420 is accommodated in the cup body 410 so that the wave height direction is parallel to the side plate 414, and the reinforcing portion 422 of the corrugated plate 420 contacts the side plate 414, and preferably the reinforcing portion 422 contacts the side plate 414. Joined by brazing. Therefore, the reinforcing portion 422 functions as a reinforcing member that reinforces the side plate 414 of the cup body 410. For this reason, even if stress is generated in the side plate 414, the structure is not easily deformed.
The folded portion 426 of the corrugated plate 420 abuts on the side plate 416 so that the folded portion 426 is preferably joined to the side plate 416 by brazing. Accordingly, each folded portion 426 functions as a reinforcing member that reinforces the side plate 416 of the cup body 410. For this reason, even if stress is generated in the side plate 416, the structure is difficult to be easily deformed.

  The upper side portion of the folded portion 426 and the upper side portion of the reinforcing portion 422 are in contact with the top plate 412 of the cup body 410, and are preferably joined by brazing. The lower side portion of the folded portion 426 and the lower side portion of the reinforcing portion 422 are in contact with the bottom plate 430, and are preferably joined by brazing.

  Thus, since the corrugated plate 420 is accommodated in the cup body 410, the hollow formed by the cup body 410 and the bottom plate 430 is partitioned 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 at one end in the wave height direction of each partition 424, and adjacent spaces 418 and 418 communicate with each other through the through holes 428 and 428. Therefore, a hollow formed by the cup body 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 has a meandering shape.

  As shown in FIGS. 1 and 3, the bottom plate 430 of the reformer 400 is joined to a stage 643 positioned on 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 400, a reforming catalyst (for example, a Cu / ZnO-based catalyst or a Pd / ZnO-based catalyst) is supported on the inner surface of the cup body 410 and the bottom plate 430 and the corrugated plate 420.

  A carbon monoxide remover 500 is provided on the base portion 652. The carbon monoxide remover 500 includes a cup body 510 that is open on the lower surface, a separation plate 550 that is accommodated in the cup body 510 and partitions the space in the cup body 510 up and down, and a lower opening of the cup body 410. A closed bottom plate 530, a corrugated plate 520 accommodated in the upper space of the two spaces partitioned by the separate plate 550, and a corrugated plate 540 accommodated in the lower space are provided.

  The cup bodies 410, 510, the corrugated plates 420, 520, 540 and the bottom plates 430, 530 are preferably made of Kovar (NiFeCo alloy), and have a linear expansion coefficient of 70 to 130 of an electric insulator forming an insulating plate 640 described later. % Is preferable, and 90 to 110% is more preferable.

  The cup body 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 and 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, thereby forming a parallelepiped box having a hollow. The separate plate 550 is accommodated in the cup body 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 middle portions of the side plates 514, 514, 516 and 516.

  The corrugated plate 520 includes a plate made of Kovar (NiFeCo alloy) meandering in a corrugated shape, and a pair of reinforcing portions 522 and 522 facing each other on both ends of the plate, and a reinforcing portion 522 between the two reinforcing portions 522 and 522. Between the plurality of partitioning parts 524, 524,. A plurality of folded portions 526, 526,... Connected in between.

  Similarly to the corrugated plate 520, the corrugated plate 540 has the same material and substantially the same shape, and includes a pair of reinforcing portions 542, 542, a plurality of partition portions 544, 544,..., And a plurality of folded portions 546, 546. ...

The corrugated plate 520 is accommodated in a space between the separation plate 550 and the top plate 512 so that the wave height direction is parallel to the side plate 514, and the reinforcing portion 522 of the corrugated plate 520 contacts the side plate 514, preferably The reinforcing portion 522 is joined to the side plate 514 by brazing. Therefore, the reinforcing portion 522 functions as a reinforcing member that reinforces the side plate 514 of the cup body 510. For this reason, even if stress is generated in the side plate 514, the structure is difficult to be easily deformed.
Further, the folded portion 526 of the corrugated plate 520 contacts the side plate 516 and preferably the folded portion 526 is joined to the side plate 516 by brazing. Accordingly, each folded portion 526 functions as a reinforcing member that reinforces the side plate 516 of the cup body 510. For this reason, even if stress is generated in the side plate 516, the structure is not easily deformed.

  The upper side portion of the folded portion 526 and the upper side portion of the reinforcing portion 522 are in contact with the top plate 512 of the cup body 510, and are preferably joined by brazing. The lower side portion of the folded portion 526 and the lower side portion of the reinforcing portion 522 are in contact with the separate plate 550 and are preferably joined by brazing.

  A corrugated plate 520 is accommodated in a space between the top plate 512 and the separate plate 550 in the cup body 510, and the space is partitioned into a plurality of spaces 518, 518,.

  The corrugated 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 side plate 514, and the reinforcing portion 542 of the corrugated plate 540 contacts the side plate 514, Preferably, the reinforcing portion 542 is joined to the side plate 514 by brazing. Further, the folded portion 546 of the corrugated plate 540 contacts the side plate 516 in a facing state, and preferably the folded portion 546 is joined to the side plate 516 by brazing.

  The upper side portion of the folded portion 546 and the upper side portion of the reinforcing portion 542 are in contact with the separate plate 550 of the cup body 510, and are preferably joined by brazing. The lower side portion of the folded portion 546 and the lower side portion of the reinforcing portion 542 are in contact with the bottom plate 530 and are preferably joined by brazing.

  A corrugated plate 540 is accommodated in a space between the bottom plate 530 and the separate plate 550 in the cup body 510, and the space is partitioned into a plurality of spaces 519, 519,. The lower corrugated plate 540 overlaps the upper corrugated plate 520 with the separate plate 550 interposed therebetween, and the upper space 518 is partitioned by the separate plate 550 into the lower space 519.

  A through hole 528 is formed in each partition 524, and adjacent spaces 518 and 518 communicate with each other through the through hole 528. Similarly, a through hole 548 is formed in each 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. These spaces 518, 518,... And spaces 519, 519,... Constitute a predetermined series of 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.

  As shown in FIGS. 1 and 3, the bottom plate 530 of the carbon monoxide remover 500 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 channel 708, the combustion fuel supply channel 716 that also serves as the cooling channel, and the exhaust chamber 718 are covered. The inlet 532 formed in the bottom plate 530 is positioned on the other end of the straight portion 708 b of the mixing channel 708, and the outlet 534 formed in the bottom plate 530 is positioned on the corner 719 of the exhaust chamber 718. ing.

  In the carbon monoxide remover 500, a carbon monoxide selective oxidation catalyst (for example, platinum or the like) is supported on the inner surface of the cup body 510 and the bottom plate 530, the corrugated plate 520, the corrugated plate 540, and the separate plate 550.

  As shown in FIG. 3, the bottom plate 430 of the reformer 400 and the bottom plate 530 of the carbon monoxide remover 500 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 portion 608. In this connection portion 608, 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, and a part of the communication channel 704 are connected to each other. Covered by 680.

  As shown in FIG. 1 and the like, the outer shape of the connecting portion 608 is a prismatic shape, the width of the connecting portion 608 is narrower than the width of the high temperature reaction portion 604 and the width of the low temperature reaction portion 606, and the height of the connecting portion 608 is also high temperature reaction. It is lower than the height of the part 604 and the low temperature reaction part 606. Therefore, the difference between the appropriate temperature of the high-temperature reaction unit 604 and the appropriate temperature of the low-temperature reaction unit 606 can be maintained, heat loss of the high-temperature reaction unit 604 can be suppressed, and the temperature of the low-temperature reaction unit 606 is raised to a set temperature or higher. It can also be suppressed. The connecting portion 608 is installed between the high temperature reaction portion 604 and the low temperature reaction portion 606. The connection portion 608 is connected to the high temperature reaction portion 604 at the center in the width direction of the high temperature reaction portion 604 and at a low temperature. The reaction unit 606 is connected to the low temperature reaction unit 606 at the center in the width direction. Therefore, the stress to the connection part 608 based on the difference in thermal expansion caused by the difference between the appropriate temperature of the high temperature reaction part 604 and the appropriate temperature of the low temperature reaction part 606 is minimized, and fluid leakage from the connection part 608 is prevented. it can. However, since the connecting portion 608 is small in this way, it does not have a sufficiently strong rigidity against stress.

  As described above, the connecting portion 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.

  The paths of the flow paths provided inside the pipe group 602, the high temperature reaction unit 604, the low temperature reaction unit 606, and the connection unit 608 are as shown in FIGS. Here, the correspondence between FIGS. 12, 13 and 2 will be described. The liquid fuel introduction pipe 622 corresponds to the carburetor 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. 3, the lower surface of the low temperature reaction unit 606, that is, the lower surface of the insulating plate 640 is patterned in such a manner that the heating wire 720 meanders. 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, and 724 on the insulating film or insulating plate 640, the voltage to be applied is hardly applied to the base plate 642 made of metal material, the liquid fuel introduction pipe 622, the combustor plate 624, and the like. The heating efficiency of the heating wires 720, 722, 724 can be improved because the heating wires 720, 722, 724 are supplied.
The heating wires 720, 722, and 724 are laminated in the order of the adhesion layer, the diffusion prevention layer, and the heat generation layer from the insulating plate 640 side. 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. For the diffusion prevention layer, it is preferable to use a substance (for example, W) having a relatively high melting point and low reactivity so that the material of the heat generation layer does not diffuse into the diffusion prevention layer or the adhesion layer. The adhesion layer is used when the diffusion prevention layer does not have excellent adhesion to the insulating plate 640, and is a material having excellent adhesion to the diffusion prevention layer and the insulation plate 640 (for example, , Ta, Mo, Ti, Cr). The heating wire 720 heats the low-temperature reaction unit 606 at the start-up, the heating wire 722 heats the high-temperature reaction unit 604 and the connection unit 608 at the start-up, and the heating wire 724 includes the vaporizer 502 and the first combustion of the pipe group 602. The vessel 612 is heated. Thereafter, off-gas containing hydrogen remaining without being used in the electrochemical reaction is exhausted from the fuel cell that generates power using the hydrogen gas discharged from the microreactor module 600. When this off gas is introduced into the second combustor 614 and combusted, the heating wire 722 heats the high temperature reaction unit 604 and the connection unit 608 as an auxiliary to the second combustor 614. Similarly, when off-gas containing hydrogen from the fuel cell is burned in the first combustor 612, the heating wire 720 and the heating wire 724 heat the low-temperature reaction unit 606 and the pipe group 602 as assistance of the first combustor 612. .
In addition, since the electric resistances of the heating wires 720, 722, and 724 change according to a change in temperature, they also function as a temperature sensor that can read the temperature from a resistance value with respect to a predetermined applied voltage or current. 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. 1, the heating wires 720, 722, and 724 and the lead wires 731 to 736 are not shown in order to make the drawing easy to see.

As shown in FIG. 14, the microreactor module 600 includes a heat insulation package 791, and the high temperature reaction portion 604, the low temperature reaction portion 606, and the connection portion 608 are accommodated in the heat insulation package 791. The heat insulation package 791 is composed of a rectangular 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 an alloy plate such as stainless steel (SUS304). The heat insulation package 791 suppresses propagation of heat radiation from the pipe group 602, the high temperature reaction portion 604, the low temperature reaction portion 606 and the connection portion 608 to the outside of the heat insulation package 791. The internal space between the heat insulating package 791 and the microreactor module 600 is exhausted under reduced pressure so that the internal pressure becomes 1 Pa or less. A pipe 634 serving as a hydrogen gas discharge path of the pipe group 602 is exposed from the heat insulation package 791 and connected to a fuel electrode of a power generation cell 808 described later, and the liquid fuel introduction pipe 622 is connected to the fuel via the flow rate control unit 806. It is connected to the container 804.
A part of the wiring group 739 including the lead wires 732, 731, 733, 734, 736, 735, 737, 738 is exposed from the heat insulating package 791. In the liquid fuel introduction pipe 622 and the lead wires 732, 731, 733, 734, 736, 735, 737, and 738, outside air enters the heat insulation package 791 from the portions exposed from the heat insulation package 791, and the internal pressure rises. The liquid fuel introduction pipe 622 and the lead wires 732, 731, 733, 734, 736, 735, 737, and 738 are joined to the base plate 793 of the heat insulation package 791 with metal wax, glass material, or insulating sealing material so that no gap is generated. Has been. Since the heat insulating package 791 is metallic, it exhibits conductivity. However, since the lead wires 732, 731, 733, 734, 736, 735, 737, 738 are covered with a high melting point insulator, the lead wires 732, 731, 733 734, 736, 735, 737, and 738 are not electrically connected to the heat insulating package 791, respectively. Since the internal pressure of the internal space of the heat insulation package 791 can be kept low, the medium that propagates the heat generated by the microreactor module 600 becomes dilute, and heat convection in the internal space is suppressed, so that the heat retention effect of the microreactor module 600 is increased.
In the space sealed with the heat insulation package 791, a connection portion 608 having a predetermined distance is interposed between the high temperature reaction portion 604 and the low temperature reaction portion 606 of the microreactor module 600. The volume of the connection portion 608 is as follows. Since the volume of the high temperature reaction unit 604 and the low temperature reaction unit 606 is extremely small, propagation of heat from the high temperature reaction unit 604 to the low temperature reaction unit 606 by the connecting unit 608 is suppressed, and the high temperature reaction unit 604 and the low temperature reaction unit 606 In the meantime, the temperature gradient necessary for the reaction can be maintained, the temperature in the high temperature reaction unit 604 can be easily equalized, and the temperature in the low temperature reaction unit 606 can be equalized easily.

  On the surface of the low-temperature reaction part 606, a fluid that may leak from the microreactor module 600 over time, a fluid generated from the microreactor module 600 over time, and sufficient vacuum exhaust cannot be performed when the case 792 and the base plate 793 are joined. A getter material 728 is provided to remove from the internal space of the heat insulation package 791 by adsorbing a factor that increases the pressure in the internal space of the heat insulation package 791, such as a part of the remaining outside air and the outside air that enters the heat insulation package 791 over time. The getter material 728 is provided with a heater such as an electric heating material, and a wiring 730 is connected to the heater. Both ends of the wiring 730 are positioned on the lower surface of the base plate 28 around the combustor plate 624, and lead wires 737 and 738 are connected to both ends of the wiring 730, respectively. The getter material 728 is activated by heating and has an adsorption action. Examples of the material of the getter material 728 include an alloy containing zirconium, barium, titanium, or vanadium as a main component. The lead wires 737 and 738 are partially exposed from the heat insulation package 791, and the lead wire 737 does not generate a gap that causes the outside air to enter the heat insulation package 791 from the exposed portion to increase the internal pressure. , 738 are joined to the base plate 793 of the heat insulating package 791 by a metal, glass material or insulating sealing material. The wiring group 739 is desirably spaced apart so that the intervals between the lead wires are equal, and is preferably disposed around the liquid fuel introduction pipe 622. Further, the thickness of the heat insulation package 791 (case 792 and plate 793) is 0.1 mm to 0.2 mm, and has a metal-specific flexibility with respect to stress applied to each surface of the heat insulation package 791.

  In this way, the plurality of through holes 795 pass 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 795. The through hole 795 is sealed with a metal or glass material. Although the internal space of the heat insulation package 791 is sealed, since the internal space is decompressed, the heat insulation effect is high. Therefore, heat loss can be suppressed.

  The pipe materials 626, 628, 630, 632, 634 and the liquid fuel introduction pipe 622 are in a state of protruding both inside and outside 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 part 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 part 608 are separated from the inner surface of the heat insulation package 791.

In addition, the liquid fuel introduction pipe 622 is preferably connected to the lower surface of the low temperature reaction unit 606 at the center of gravity of the high temperature reaction unit 604, the low temperature reaction unit 606, and the connection unit 608 in plan view.
If the liquid fuel introduction pipe 622, the pipe group 602, and the wiring group 739 are provided in the high temperature reaction section 604, the high temperature reaction section 604 needs to be kept at a high temperature during operation, so the liquid fuel introduction pipe 622, the pipe group 602 and the wiring group 739 reach a high temperature, and the amount of heat transferred from the liquid fuel introduction pipe 622, the pipe group 602, and the wiring group 739 to the heat insulation package 200 is increased, but the liquid fuel introduction pipe 622 and the pipe group 602 and the wiring group 739 are provided in the low-temperature reaction unit 606. Therefore, the amount of heat transferred from the liquid fuel introduction pipe 622, the pipe group 602, and the wiring group 739 to the heat insulation package 791 is small, and the liquid fuel introduction pipe 622 and the pipe In the group 602 and the wiring group 739, the amount of heat radiated from the portion exposed to the outside of the heat insulation package 791 is also small. See, quickly high-temperature reaction unit 604, can heat the low temperature reaction unit 606, and it is easy to stably hold the heating temperature.

  Note that although the getter material 728 is provided on the surface of the low temperature reaction portion 606, the position of 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. As a result, factors that increase the pressure of gas or the like in the heat insulation package 791 are adsorbed by the getter material 728, the degree of decompression in the heat insulation package 791 increases, and the heat insulation efficiency increases.

  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 part 604, the low temperature reaction part 606, and the connection part 608 are made of a metal material, heat conduction between them is easy. Note that the current and voltage of the heating wires 720, 722, and 724 are measured by a control device (for example, a control unit 826 of a power generation unit 801 described later), whereby the liquid fuel introduction pipe 622, the high temperature reaction unit 604, and the low temperature reaction unit. 606 is measured, the measured temperature is fed back to the control device, and the voltage of the heating wires 720, 722, 724 is controlled by the control device, whereby the liquid fuel introduction pipe 622, the high temperature reaction unit 604 and the low temperature reaction unit 606 are controlled. Temperature control is performed.

  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 is heated and vaporized in the liquid absorbing material 623, and the mixture of fuel and water evaporates from the liquid absorbing material. The porous liquid absorbing material 623 is vaporized from a large number of fine liquid surfaces partitioned by fine holes. For this reason, since each hole has only a small amount of liquid mixture, even if an excessive amount of heat is applied, it can be vaporized quantitatively and stably without bumping.

  Then, the air-fuel mixture evaporated from the liquid absorbing material 623 flows into the reformer 400 through the through hole 678, the reformed fuel supply channel 702, and the introduction port 432. Thereafter, when the air-fuel mixture flows in the reformer 400, 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 400 flows into the mixing channel 708 through the outlet 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 channel 708 through the through hole 675 and the air supply channel 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 into the carbon monoxide remover 500 from the mixing channel 708 through the inlet 532. When the air-fuel mixture flows through the carbon monoxide remover 500, 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, but the liquid mixture is continuously supplied to the liquid fuel introduction pipe 622 after that. Then, oxygen (may be 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 also serving as a cooling channel, and the through hole 676, and the combustion mixture flows into the combustion channel. At 625, catalytic combustion occurs. As a result, combustion heat is generated. However, since the combustion flow path 625 circulates around the liquid fuel introduction pipe 622 below the low temperature reaction section 606, the liquid fuel introduction pipe 622, that is, the vaporizer 610 is heated by the combustion heat. At the same time, the low temperature reaction part 606 is heated. Therefore, the power consumption of the heating wires 720 and 724 can be reduced, and the energy utilization efficiency is increased.
The combustion fuel supply channel 716 is located in the lower part of the carbon monoxide remover 500, and the fluid introduced into the combustor plate 624 is a combustion fuel between the through hole 674 and the through hole 676 before being introduced. Passing through the supply channel 716, heat exchange with the carbon monoxide remover 500 is performed. In particular, when the fluid is at room temperature such as the atmosphere, the carbon monoxide remover 500 is cooled. If the heat-exchanged fluid is a combustion mixture to be combusted, it becomes easier to burn by being heated.

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 channel 710, and the combustion mixture is catalytically combusted in the combustion chamber 712. As a result, combustion heat is generated, but the reformer 400 is heated by the combustion heat. Therefore, the power consumption of the heating wire 722 can be reduced, and the energy utilization efficiency is increased.
Here, since the high temperature reaction unit 604 must be kept at a higher temperature than the low temperature reaction unit 606, the hydrogen supply amount of off-gas per unit time in the second combustor 614 is set to be per unit time in the first combustor 612. The supply amount per unit time of oxygen (air) serving as a refrigerant in the first combustor 612 is set to be larger than the hydrogen supply amount of the off-gas of the first gas. You may make it more than quantity.

  The liquid fuel stored in the fuel container 804 may be vaporized, and the vaporized fuel / air combustion mixture may be supplied to the pipes 628 and 632.

In a 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 with the heating wires 720, 722 and 724, While controlling the applied voltage of the heat 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. Here, it is preferable to control the temperature so that the high temperature reaction part 604 is 375 ° C. and the low temperature reaction part 606 is 150 ° C. to 180 ° C.
In particular, when the temperature of the carbon monoxide remover 500 at the low-temperature reaction unit 606 is equal to or higher than the upper limit of the appropriate reaction temperature range or a predetermined temperature near the upper limit (for example, 180 ° C. or higher), the control device is In order to cool the carbon oxide remover 500 to within an appropriate reaction temperature range, mixing of air and off-gas higher than room temperature discharged from the fuel cell is stopped, and only the room temperature air taken from the atmosphere is used as the tube material 632. The air is supplied to the cooling flow path, that is, the combustion fuel supply flow path 716. When the temperature of the carbon monoxide remover 500 falls below a predetermined temperature within an appropriate reaction temperature range (for example, 150 ° C. or less), the control device again mixes off-gas and oxygen, and this combustion mixture Is supplied to the pipe 632. In this manner, the carbon monoxide remover 500 is controlled to be at a predetermined temperature while suppressing the carbon monoxide remover 500 from reaching a predetermined temperature or higher. Therefore, during operation, the carbon monoxide remover 500 does not last below 150 ° C. for a long time, so that the upper part of the vaporizer 610 can also maintain the temperature at which the liquid fuel is vaporized.
As described above, the fluid taken in from the pipe 632 is not directly supplied to the combustion channel 625 but is exchanged with the carbon monoxide remover 500 via the combustion fuel supply channel 716, so that In addition, the carbon monoxide remover 500 can be cooled.

  At this time, if the difference between the linear expansion coefficient of the insulating plate 640 and the linear expansion coefficients of the reaction vessels such as the cup bodies 410, 510, the corrugated plates 420, 520, 540, the separation plate 550, the plate material 690, the base plate 642 is large, As the temperature of the reaction part 604 and the low-temperature reaction part 606 rises, there is a possibility that a thermal stress acts on the bonded part of both, causing deformation such as warping toward a lower linear expansion coefficient. In particular, since the insulating plate 640 is directly provided with the heating wires 720, 722, 724 and the combustor plate 624 as heat sources, the insulating plate 640 is likely to have a high temperature and easily generate thermal stress. In the present embodiment, the materials are selected so that the linear expansion coefficients of the reaction vessel and the insulating plate 640 are approximated.

Next, the power generation unit 801 assembled with the microreactor module 600 will be described. FIG. 15 is a perspective view of the power generation unit 801.
The power generation unit 801 includes 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 fuel pump, a water pump, a flow rate sensor, a valve, and the like, and a heat insulation package 791. 16, a power generation cell 808 having a fuel cell, a humidifier, a recovery device, and the like, an air pump 810, a secondary battery 828, a DC-DC converter 830, and a control unit shown in FIG. And a power supply unit 812 having 826 and the like. 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, hydrogen gas is generated as described above, and the hydrogen gas is supplied to the fuel cell of the power generation cell 808. The generated electricity is stored in the secondary battery 828 of the power supply unit 812.

Next, FIG. 16 shows a system block diagram of the power generation unit 801, and the power generation unit 801 will be described in detail from the functional aspect.
As shown in FIG. 16, the power generation unit 801 includes a fuel tank 804a for storing fuel, a fuel container 804 having a water tank 804b for storing water, a microreactor module 600, a power generation cell 808, a microreactor module 600, and power generation. An air pump 810 for supplying air to the cell 808 is provided.
The water tank 804b is connected with a water pump P2 for delivery, and an ON-OFF valve V2 is provided downstream thereof. The ON-OFF valve V2 branches into two flow paths L1 and L2, and one of the flow paths L1 is connected to a merging valve 814 via a control valve V3. A flow rate sensor S2 is provided between the control valve V3 and the junction valve 814. Further, the other one flow path L2 further branches into two flow paths L3 and L4, and the respective flow paths L3 and L4 are connected to the oxygen electrode input port 808A and the power generation cell 808 of the power generation cell 808 via the humidifiers 816 and 818, respectively. Are connected to the input port 808B of the fuel electrode.

  A fuel pump P1 for delivery is connected to the fuel tank 804a, and an ON-OFF valve V1 is provided downstream thereof. A junction valve 814 is connected to the downstream side of the ON-OFF valve V1. A flow rate sensor S1 is provided between the ON-OFF valve V1 and the junction valve 814.

  The microreactor module 600 includes a vaporizer 610 for vaporizing water and fuel supplied via the ON-OFF valves V1 and V2 as described above, and vaporization by the vaporizer 610 as shown in the chemical reaction formula (1). The hydrogen gas that is not used for power generation supplied from the reformer 400 that reforms the gas containing hydrogen by heating the water and the fuel, and the output port 808C of the fuel electrode of the power generation cell 808 And the first combustor 612 for heating the vaporizer 610 and the carbon monoxide remover 500 based on the air supplied from the air pump 810, the second combustor 614 for heating the reformer 400, and the chemical reaction formula (1 ), The carbon monoxide produced in a trace amount by the chemical reaction formula (2) that occurs sequentially, as shown in the chemical reaction formula (3), and the gas supplied from the reformer 400 and Carbon monoxide remover 500 to extract the hydrogen gas is removed by oxidation based on the air supplied from the air pump 810, it is provided. The exhaust gas discharged from the first and second combustors 612 and 614 is exhausted through the ON-OFF valve V4.

  Air is sucked into the air pump 810 through the air filter 820. The air pump 810 branches to five flow paths L5, L6, L7, L8, and L9, and one of the flow paths L5 is connected to the second combustor 614 via the air control valve V5. The other one flow path L6 is connected to the inlet of the carbon monoxide remover 500 via the air control valve V6. The other flow path L7 is connected to the oxygen electrode input port 808A of the power generation cell 808 via the air ON-OFF valve V7. Since the flow path L3 is connected to the flow path L7, the steam output from the humidifier 816 is added to the air passing through the flow path L7 and humidified. The other flow path L8 is connected to the first combustor 612 (combustor plate 624) via the air control valve V9. Furthermore, the other one flow path L9 is connected to the surplus off-gas combustor 822 via the air control valve V10. Flow rate sensors S3 to S7 are connected to the flow paths L5 to L9, respectively.

The power generation cell 808 supplies the hydrogen gas supplied from the carbon monoxide remover 500, humidified by the humidifier 818, and supplied to the fuel electrode input port 808B to the catalyst of the fuel electrode as shown in the electrochemical reaction formula (4). It separates into hydrogen ions and electrons by the action of fine particles. Hydrogen ions are conducted to the oxygen electrode through the solid polymer electrolyte membrane, and electrons are taken out as electric energy (generated power) by the fuel electrode. On the other hand, the air supplied from the air pump 810 and humidified by the humidifier 816 is supplied to the oxygen electrode input port 808A, as shown in the electrochemical reaction equation (5). The oxygen therein reacts with hydrogen ions that have passed through the solid polymer electrolyte membrane to produce water. Then, the off-gas containing surplus hydrogen gas that is not used for power generation is sent from the fuel electrode output port 808C of the power generation cell 808 to the first combustor 612 and the second combustor 614 via the off-gas flow control valves V11 and V12. It is sent and used for combustion of the first combustor 612 and the second combustor 614. Further, surplus hydrogen gas other than hydrogen gas supplied to the first combustor 612 and the second combustor 614 is sent to the off-gas combustor 822. At this time, when the temperature of the carbon monoxide remover 500 is equal to or higher than a predetermined temperature, the supply of hydrogen gas to the first combustor 612 and the heat generation of the heater heating wire 720 are stopped, and the first combustor 612 only with air. The surplus hydrogen gas is sent to the off-gas combustor 822. The hydrogen gas sent to the off-gas combustor 822 is mixed with the air sent from the air pump 810 to the off-gas combustor 822 via the air control valve V10 and burned.
The exhaust gas discharged from the output port 808D of the oxygen electrode of the power generation cell 808 lowers the exhaust temperature via the separator 824, returns the liquid water to the flow path L2, and the steam is turned on and off. Exhaust is performed through the valve V8.
H ₂ → 2H ⁺ + 2e ⁻ (4)
2H ⁺ + 1 / 2O ₂ + 2e ⁻ → H ₂ O (5)

The control unit 826 includes, for example, a general-purpose (Central Processing Unit), a RAM (Random Access).
Memory), ROM (Read Only Memory), and the like. The control unit 826 is electrically connected to a fuel pump P1, a water pump P2, and an air pump 810 through a driver (not shown), and each pumping operation of the fuel pump P1, the water pump P2, and the air pump 810 is performed. (Including adjusting the delivery amount).
Further, the control unit 826 is electrically connected to the ON-OFF valves V1 and V2 and the flow rate control valves V3 to V12 via a driver (not shown), and the flow rate sensors S1 to S7 are also electrically connected. Further, the control unit 826 can recognize the flow rate of air in response to the measurement results of the flow rate sensors S1 to S7, and opens and closes the ON-OFF valves V1 and V2 and the flow rate control valves V3 to V12 (including adjustment of the opening amount). Is controlling.
Then, the control unit 826 is configured such that the heating wires (heaters) 720, 722, and 724 for heating the vaporizer 610, the reformer 400, the first combustor 612, the second combustor 614, and the carbon monoxide remover 500 are drivers. The control unit 826 controls the amount of heat generated by the heating wires 720, 722, and 724 and the stop thereof, and measures the resistance value of the heating wires 720, 722, 724 that changes depending on the temperature. Thus, the temperature of each reactor of the vaporizer 610, the reformer 400, the first combustor 612, the second combustor 614, and the carbon monoxide remover 500 can be detected. The heating wires 720, 722, and 724 heat the vaporizer 610, the reformer 400, the first combustor 612, the second combustor 614, and the carbon monoxide remover 500 to appropriate temperatures when the microreactor module 600 is started up. When the first and second combustors 612 and 614 start combustion and can be heated stably, they are stopped or the amount of heat is reduced.
Further, the control unit 826 detects the temperature of the carbon monoxide remover 500 by measuring the resistance value of the heating wires 720 and 724 that heat the carbon monoxide remover 500, and the detected temperature detected is an appropriate reaction temperature. In order to cool the carbon monoxide remover 500 if the temperature is equal to or higher than a first predetermined temperature (for example, about 180 ° C.) at or near the upper limit of the range, the power generation cell 808 supplying the first combustor 612 The supply of the generated hydrogen gas is stopped, only air is supplied to the first combustor 612, and the detected temperature of the carbon monoxide remover 500 is within a proper reaction temperature range lower than the first predetermined temperature. When the temperature falls below a predetermined temperature (for example, about 150 ° C.), the supply of hydrogen gas to the first combustor 612 is started again.

FIG. 17 is a system block diagram focusing on the first combustor 612, the second combustor 614, the power generation cell 808, and the control unit 826 in the system block diagram of FIG. Is shown. FIG. 18 is a flowchart showing a cooling operation process of the carbon monoxide remover 500 by the control unit 826.
As shown in FIGS. 17 and 18, the control unit 826 has a first predetermined temperature (for example, about 180 ° C.) at or near the upper limit of the appropriate reaction temperature range in the steady state operation. It is determined whether or not the above is true (step S1). If the carbon monoxide remover 500 is lower than the first predetermined temperature, the state of steady operation is maintained, and if it is equal to or higher than the first predetermined temperature, the offgas control valve V11 leading to the first combustor 612 is closed. Then, the supply of the off gas to the first combustor 612 is stopped, the air control valve V9 is opened, and the air is allowed to flow excessively (step S2). Then, the off gas originally supplied to the first combustor 612 is supplied to the off gas combustor 822. Also, an amount of air that can burn all of the hydrogen contained in the offgas supplied to the offgas combustor 822 is sent to the offgas combustor 822 via the air control valve V10. At this time, since the second combustor 614 that heats the reformer 400 operates in the same manner as in the steady operation state, the off-gas control valve V12 and the air control valve V5 have the same amount as in the steady operation. Adjust the off-gas and air flow rates. In this way, the carbon monoxide remover 500 is cooled by supplying a large amount of room temperature air to the first combustor 612.
Then, it is determined whether or not the carbon monoxide remover 500 has become equal to or lower than a second predetermined temperature (for example, about 150 ° C.) within an appropriate reaction temperature range lower than the first predetermined temperature (step S3). If the carbon monoxide remover 500 is equal to or higher than the second predetermined temperature, the supply of off-gas to the first combustor 612 is stopped as described above, and a large amount of air is continuously supplied. When the carbon monoxide remover 500 becomes equal to or lower than the second predetermined temperature, each valve is returned to the same state as in the steady operation. That is, the off-gas control valve V11 is opened to start the supply of off-gas to the first combustor 612, and the air control valve V9 flows the same amount of air as in steady operation.
As described above, the control unit 628 constantly monitors the temperature of the carbon monoxide remover 500 and periodically executes the flow of FIG.

  FIG. 19 shows a simulation in which, when the carbon monoxide remover 500 exceeds 180 ° C. (202 ° C.), air of 20 ° C. and 150 ml / min is circulated through the combustion fuel supply channel 716 that is also used as a cooling channel. It is a result. From this result, by supplying a large amount of air only when the temperature of the carbon monoxide remover 500 is increased, the temperature of the carbon monoxide remover 500 is reduced by about 50 ° C., and the steam reforming which is the high temperature reaction unit 604 is improved. It can be seen that the temperature change of the mass device 400 and the heat insulation package 791 is small, and the influence on the surroundings due to cooling is suppressed.

  FIG. 20 is a perspective view of an electronic device 900 using the power generation unit 801 as a power source. As shown in FIG. 20, the electronic device 900 is a portable electronic device, and particularly a notebook personal computer. The electronic device 900 includes a lower casing 902 that includes a calculation processing circuit including a CPU, a RAM, a ROM, and other electronic components and includes a keyboard 901, and an upper casing 904 that includes a liquid crystal display 903. Prepare. The lower casing 902 and the upper casing 904 are hinge-coupled, and can be folded with the upper casing 904 overlapped with the lower casing 902 and the liquid crystal display 903 facing the keyboard 901. . A mounting portion 906 for mounting the power generation unit 801 is recessed from the right side surface to the bottom surface of the lower housing 902. When the power generation unit 801 is mounted on the mounting portion 906, the electronic device 900 operates by electricity of the power generation unit 801. .

  As described above, according to the embodiment of the present invention, the combustion fuel supply channel 716 is also used as a cooling channel, and the temperature of the carbon monoxide remover 500 is increased to a predetermined temperature or higher. In this case, in order to cool the carbon monoxide remover 500, the combustion of the off gas discharged from the fuel cell and oxygen (air) is stopped, and only the air in the atmosphere is supplied to the pipe 632, Air is cooled by flowing through the cooling flow path (combustion fuel supply flow path 716). Then, when the temperature of the carbon monoxide remover 500 becomes equal to or lower than a predetermined temperature, the off-gas and air are mixed again, and this combustion mixture is supplied to the tube material 632. In this way, the combustion fuel supply channel 716 is also used as a cooling channel, and it is possible to easily cope with the temperature rise of the carbon monoxide remover 500 simply by changing the fluid flowing through the combustion fuel supply channel 716. The size can be reduced without changing the number of input / output pipes for cooling, and as a result, heat loss can also be reduced.

In addition, this invention is not limited to the said embodiment, You may perform a various improvement and design change in the range which does not deviate from the summary.
For example, although the gas that flows when the carbon monoxide remover 500 is cooled is air, the air may be room temperature air or air cooled to room temperature or lower.

2 is a side view of a microreactor module 600. FIG. It is a schematic side view at the time of dividing the micro reactor module 600 for every function. 4 is an exploded perspective view of a microreactor module 600. FIG. 2 is an exploded perspective view of a reformer 400. FIG. 2 is an exploded perspective view of a carbon monoxide remover 500. FIG. It is arrow sectional drawing of the surface along the cutting line VI-VI of FIG. It is arrow sectional drawing of the surface along the cutting line VII-VII of FIG. It is arrow sectional drawing of the surface along the cutting line VIII-VIII of FIG. It is arrow sectional drawing of the surface along the cutting line IX-IX of FIG. It is a perspective view of the base plate 642. FIG. (a) is an oxygen concentration distribution diagram in the mixing channel 708 having the bent portion 708c, and (b) is an oxygen concentration distribution diagram in the linear mixing channel 708 having no bent portion 708c. It is drawing which showed the path | route until a water etc. which are a product are discharged | emitted after a combustion air-fuel mixture is supplied. It is drawing which showed the path | route after supplying liquid fuel and water until the hydrogen gas which is a product is discharged | emitted. It is a perspective view of the state which the heat insulation package 791 decomposed | disassembled. 3 is a perspective view of a power generation unit 801. FIG. 2 is a system block diagram of a power generation unit 801. FIG. In the system block diagram in FIG. 16, the first combustor 612, the second combustor 614, the power generation cell 808, and the control unit 826 are system block diagrams. 7 is a flowchart showing a cooling operation process of the carbon monoxide remover 500 by a control unit 826. It is the simulation result which distribute | circulated 20 degreeC and 150 ml / min air to the carbon monoxide remover 500. FIG. 1 is a perspective view of an electronic device 900.

Explanation of symbols

400 reformer 500 carbon monoxide remover 600 microreactor module (reactor)
604 High temperature reaction unit 606 Low temperature reaction unit 612 First combustor 614 Second combustor 708 Mixing channel (reaction channel)
708a, 798b Straight portions 708d, 708e, 708f Curved portion 716 Combustion fuel supply flow path, cooling flow path (reaction flow path)
801 Power generation unit (power generation device)
808 Power generation cell 900 Electronic device

Claims (10)

A combustor that generates heat by burning;
A reaction part;
A flow path for selectively supplying a fuel for burning in the combustor and a refrigerant for cooling the reaction section;
A reaction apparatus comprising: A plurality of the reaction parts are provided,
Of the plurality of reaction units, a first reaction unit that causes reaction of a reactant includes a reformer that reforms fuel,
The second reaction section that causes the reaction of the reactant at a temperature lower than the reaction temperature of the first reaction section includes a carbon monoxide remover that removes carbon monoxide contained in the product. The reaction apparatus according to claim 1.   The reaction apparatus according to claim 2, wherein the flow path is a heat exchanger that cools the second reaction section. When the reaction part is at a predetermined temperature or higher, the supply of fuel to the combustor is stopped, and the reaction part is cooled by flowing a refrigerant through the flow path,
2. The control according to claim 1, wherein when the reaction part is below a predetermined temperature, the reaction part is controlled to be heated by burning in the combustor by flowing fuel and air through the flow path. The reactor described. In a reactor equipped with a reaction part that causes reaction of reactants,
The reaction section includes a reaction flow path in which a reactant flows to cause a reaction,
In the reaction channel, at least one bent portion is formed at a location where a plurality of reactants are mixed.   The reaction apparatus according to claim 5, wherein the bent portion is formed so as to change direction at approximately 90 degrees with respect to a flow direction of the reactant. A plurality of the reaction parts are provided,
Of the plurality of reaction units, a first reaction unit that causes reaction of a reactant includes a reformer that reforms fuel,
The second reaction section that causes the reaction of the reactant at a temperature lower than the reaction temperature of the first reaction section includes a carbon monoxide remover that removes carbon monoxide contained in the product. The reaction apparatus according to claim 5 or 6.   The reaction apparatus according to claim 7, wherein the bent portion is formed immediately before the reaction flow path leading to the carbon monoxide remover.   A power generation device comprising a power generation cell that extracts electric power from the reformed gas generated by the reaction device according to any one of claims 1 to 8 by an electrochemical reaction.   An electronic apparatus comprising the power generation device according to claim 9 as a power supply source.

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