JP2006247491A - Reaction apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reaction apparatus the power consumption of which is increased when the temperature of a reactor is raised and decreased when the reactor is operated at fixed temperature. <P>SOLUTION: The reaction apparatus 3 is provided with: a reactor main body 6 in which an internal space for reacting reactants is formed; a resistance pattern 13 patterned on the reactor main body 6; and a high-voltage contact and a low-voltage contact each of which is made to conduct electrically to the resistance pattern 13 so that the distance between the high-voltage contact 48 and the low-voltage contact 49 can be increased/decreased along the resistance pattern 13. When the temperature of the reactor 6 is raised, the distance between the high-voltage contact 48 and the low-voltage contact 49 is decreased to reduce the resistance between the high-voltage contact 48 and the low-voltage contact 49 and the power consumption of the resistance pattern 13 is increased so that the temperature of the reactor 6 is raised suddenly. When the reactor is operated at fixed temperature, the distance between the high-voltage contact 48 and the low-voltage contact 49 is increased to increase the resistance between the high-voltage contact 48 and the low-voltage contact 49 and the power consumption of the resistance pattern 13 is decreased. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a reaction apparatus.

In recent years, fuel cells using hydrogen as fuel as a clean power source with high energy conversion efficiency have begun to be applied to automobiles and portable devices.
A fuel cell is a device that directly extracts electric energy from chemical energy by electrochemically reacting fuel and oxygen in the atmosphere. The fuel used in the fuel cell includes hydrogen, but there is a problem in handling and storage due to being a gas at room temperature. If liquid fuels such as alcohols and gasoline are used, a reformer that takes out hydrogen necessary for power generation by reacting the liquid fuel with high-temperature steam is required.
In general, since the reformer needs to reform the fuel at a high temperature, a temperature adjusting means using a resistor pattern such as a metal is required (see, for example, Patent Document 1).

  FIG. 11 shows a conventional small reformer 100. As shown in FIG. 11, a chamber 101 is formed inside the reformer 100, a catalyst (not shown) and a resistor pattern 102 are provided in the chamber 101, and power is supplied by lead wires 103 and 104. The resistor pattern 102 is energized from the portion 105. In addition, the resistor temperature sensor 108 is disposed in the chamber 101, the wires 109 and 110 of the resistor temperature sensor 108 are connected to the temperature measuring unit 111, and the thermoelectric force is measured by the temperature measuring unit 111, thereby the chamber 101. The temperature inside is measured.

When power is supplied from the power supply unit 105 to the resistor pattern 102 through the lead wires 103 and 104, and the resistor pattern 102 generates heat, the fuel and water supplied through the supply pipe 106 are heated by the resistor pattern 102, and the fuel and water are heated. Water reacts with the catalyst to produce hydrogen. Further, since there is an appropriate temperature when the fuel and water react, a signal indicating the temperature measured by the temperature measuring unit 111 is input to the control unit 112, and the control unit 112 of the power supply unit 105 is based on the input signal. By controlling the electric power, the inside of the chamber 101 is kept at an appropriate temperature.
JP 2003-117409 A

  By the way, the present applicant has proposed that the resistor pattern for heating the reactor has a function of a temperature sensor.

  In order to raise the temperature of the reactor rapidly, it is preferable that the resistance value is low in order to increase the amount of heat generated by the resistor pattern. On the other hand, during the constant temperature operation of the reaction apparatus, the amount of heat generated by the resistor is small, so that the resistance value of the resistor pattern is preferably large in order to reduce power consumption. In order for the resistor pattern to function as a temperature sensor, it is preferable that the resistance value that is the basis of the resistor pattern is as high as possible in order to increase or decrease the resistance value of the resistor pattern due to temperature changes.

  An object of the present invention is to provide a reaction apparatus that satisfies the above-described requirements and can increase power consumption during a temperature rising operation of a reactor and reduce power consumption during a constant temperature operation.

  In order to solve the above problems, the invention according to claim 1 is a reactor main body in which an internal space for reacting a reactant is formed, a resistor pattern provided in the reactor main body, and the resistor pattern. A high voltage contact and a low voltage contact that are electrically connected to each other, and a distance between the high voltage contact and the low voltage contact along the resistor pattern is provided to be changeable. .

  According to the first aspect of the present invention, by shortening the distance between the high voltage contact and the low voltage contact during the temperature rising operation of the reactor, the resistance between the two contacts is reduced and the power consumption of the resistor pattern is increased. The reactor can be rapidly heated. On the other hand, by increasing the distance between the high-voltage contact and the low-voltage contact during the constant temperature operation of the reactor, the resistance between the two contacts can be increased and the power consumption of the resistor pattern can be reduced.

  The invention according to claim 2 is the reaction apparatus according to claim 1, wherein the reactor has three or more terminals along the resistor pattern, and one end of the resistor pattern during a temperature rising operation of the reactor body. The odd-numbered terminals are connected to each other, the even-numbered terminals are connected to each other, one is connected to the high-voltage contact, and the other is connected to the low-voltage contact. The terminal on one end side is made conductive with the high voltage contact and the terminal on the other end side is made conductive with the low voltage contact.

  According to the second aspect of the present invention, the odd-numbered terminals are electrically connected to each other from one end of the resistor pattern during the temperature rising operation of the reactor main body, the even-numbered terminals are electrically connected to each other, and one of them is a high voltage contact. By making the other conductive with the low voltage contact, the resistors from the odd-numbered terminals to the even-numbered terminals are connected in parallel, and the resistance of the resistor pattern is reduced. Thereby, the power consumption of the resistor pattern when a voltage is applied can be increased, and the temperature of the reactor can be rapidly increased.

  On the other hand, the resistance of the resistor pattern is increased by setting the terminal on one end of the resistor pattern as a high voltage contact and the terminal on the other end as a low voltage contact during the constant temperature operation of the reactor. Thereby, the power consumption of the resistor pattern when a voltage is applied can be reduced.

  According to a third aspect of the present invention, in the reaction apparatus according to the first or second aspect, the resistance value of the resistor pattern changes according to the temperature change.

  According to the invention described in claim 3, since the resistance value of the resistor pattern changes depending on the temperature, the temperature of the reactor main body is measured by measuring the change in the resistance value of the resistor pattern. be able to. Further, since the resistance of the resistor pattern is increased during the constant temperature operation, a change in the resistance value depending on the temperature is increased, and the temperature measurement accuracy can be improved.

  The invention according to claim 4 includes a reactor main body in which an internal space for reacting reactants is formed, and a resistor pattern provided in the reactor main body and selectively connected in parallel and in series. It is the reaction apparatus characterized by these.

  According to the invention described in claim 4, by connecting in parallel, the internal resistance can be reduced to flow a large current, the power consumption can be increased, and heating can be quickly performed. It becomes possible to heat while suppressing power consumption.

  According to a fifth aspect of the present invention, in the reactor according to the fourth aspect, the resistor patterns are connected in parallel during a temperature raising operation, and are connected in series during a constant temperature operation.

  According to a sixth aspect of the present invention, in the reaction apparatus according to the fourth or fifth aspect, the resistance value of the resistor pattern changes according to a temperature change.

  ADVANTAGE OF THE INVENTION According to this invention, while increasing power consumption at the time of temperature rising operation, a reactor main body can be heated up rapidly, and the power consumption at the time of a constant temperature operation of a reactor main body can be reduced.

  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.

  FIG. 1 is a block diagram of the power generator 1. As shown in FIG. 1, the power generation apparatus 1 is generated by a fuel container 2 storing fuel and water, a reaction apparatus 3 that generates hydrogen from the fuel and water supplied from the fuel container 2, and the reaction apparatus 3. A fuel cell 4 that electrochemically reacts hydrogen to obtain electric energy.

  As the fuel stored in the fuel container 2, a compound containing hydrogen such as alcohols such as methanol and ethanol and gasoline can be applied. Fuel and water are stored in the fuel container 2 separately or in a mixed state. In this embodiment, methanol is used as the fuel, but other hydrogen-containing compounds may be used.

  The reaction apparatus 3 includes a vaporizer body 5, a reformer body 6, and a CO remover body 7. In the present embodiment, the present invention is applied to the reformer body 6, but the present invention may be applied to the vaporizer body 5 and the CO remover body 7.

  The vaporizer body 5 has a structure in which two substrates are joined, and a twisted microchannel is formed on the joining surface of one or both of these substrates. . On the outer wall surfaces of the two bonded substrates, a heater made of an electrothermal material such as a resistor pattern that generates heat when a voltage is applied and a heat generating semiconductor is formed. By this heater, the fuel and water supplied from the fuel container 2 to the micro flow path in the vaporizer body 5 are heated and evaporated.

The reformer body 6 reforms the fuel (methanol) and water mixture supplied from the vaporizer body 5 into hydrogen as shown in chemical reaction formulas (1) and (2) (reforming reaction). The CO remover body 7 oxidizes carbon monoxide in the gas mixture of the product produced by the reformer body 6 as shown in the chemical reaction formula (3) to remove the carbon monoxide.
CH ₃ OH + H ₂ O → 3H ₂ + CO ₂ (1)
2CH ₃ OH + H ₂ O → 5H ₂ + CO + CO ₂ (2)
2CO + O ₂ → 2CO ₂ (3)

  In the present embodiment, as will be described later, the reformer body 6 and the CO remover body 7 are integrated to form a microreactor 9.

Although not shown, the fuel cell 4 includes a fuel electrode carrying catalyst fine particles, an air electrode carrying catalyst fine particles, a film-like solid polymer electrolyte membrane interposed between the fuel electrode and the air electrode, It has. A mixture of products is supplied from the CO remover body 7 to the fuel electrode of the fuel cell 4, and air from the outside is supplied to the air electrode of the fuel cell 4. At the fuel electrode, as shown in the electrochemical reaction formula (4), hydrogen in the gas mixture is separated into hydrogen ions and electrons by the action of the catalyst particles of the fuel electrode. Hydrogen ions are conducted to the oxygen electrode through the solid polymer electrolyte membrane, and electrons are taken out by the fuel electrode. At the oxygen electrode, as shown in the electrochemical reaction formula (5), hydrogen ions that have passed through the solid polymer electrolyte membrane, electrons that have moved from the fuel electrode to the oxygen electrode through an external circuit, and oxygen in the air are Reaction produces water. The movement of electrons at this time becomes electric energy.
H ₂ → 2H ⁺ + 2e ⁻ (4)
2H ⁺ + 1 / 2O ₂ + 2e ⁻ → H ₂ O (5)

  The power generation device 1 is mounted on a digital camera, a mobile phone device, a notebook computer, a wristwatch, a PDA, an electronic calculator, or other electronic device main body. In particular, the vaporizer body 5, the reaction device 3, and the fuel cell 4 are built in the electronic device body, and the fuel container 2 is detachably attached to the electronic device body. When the fuel container 2 is mounted on the electronic device main body, the methanol and water in the fuel container 2 are supplied to the vaporizer main body 5 by a pump, and the methanol in the fuel container 2 is supplied to the vaporizer main body 5 of the reactor 3. It has become so.

  Next, the microreactor 9 in which the reformer body 6 and the CO remover body 7 are integrated will be described in more detail with reference to FIGS.

  FIG. 2 is a perspective view of the microreactor 9. As shown in FIG. 2, the microreactor 9 includes an upper substrate 10 and a lower substrate 11. Formed outside the upper substrate 10 is a reaction supply port 21 through which water and a compound containing hydrogen such as methanol to be reformed into hydrogen in the reformer body 6 and water. The vaporizer body 5 is connected to the reaction supply port 21, and vaporized methanol and water are supplied from the vaporizer body 5.

  3 is a cross-sectional view taken along the line III-III of FIG. 2 in the plane direction. FIG. 4 is a cross-sectional view of the upper substrate 10 along the line IV-IV of FIG. It is the cut | disconnected arrow sectional drawing. As shown in FIGS. 2 and 4, the lower substrate 11 is bonded to the lower portion of the upper substrate 10. Resistor patterns 13 and 14 are formed on the upper surface of the upper substrate 10 as shown in FIG. The resistor patterns 13 and 14 are formed at positions corresponding to the reforming reaction chamber 18 and the CO removal flow path 24, respectively.

  The upper substrate 10 and the lower substrate 11 are formed with heat insulating chambers 27 and heat insulating chambers 30 and 30 each having a through hole penetrating from the opposing surface to the other surface. Both the heat insulation chamber 27 and the heat insulation chambers 30 and 30 are provided with a radiation preventing film 28 that enhances the heat insulation effect. In order to make the drawing easier to see, the antireflection film 28 is not shown in FIG. The heat insulation chambers 27, 30, 30 of the upper substrate 10 and the heat insulation chambers 27, 30, 30 of the lower substrate 11 have the same shape and the same dimensions, and overlap at the same position when the upper substrate 10 and the lower substrate 11 are bonded together. It is provided to fit.

  As shown in FIG. 3, the upper substrate 10 has a reaction supply port 21, a reforming reaction chamber 18 that is the reformer body 6, a communication channel 22, an oxygen auxiliary supply port on a surface facing the lower substrate 11. 23, a CO removal passage 24 which is the CO remover body 7, and a reaction outlet 26 for discharging carbon dioxide and water produced by the reforming catalyst reaction and the CO removal catalyst reaction are formed. The reaction supply port 21, the reforming reaction chamber 18, the communication channel 22, the oxygen auxiliary supply port 23, the CO removal channel 24, and the reaction discharge port 26 constitute a channel as an integral groove. Between the reaction chamber 18 and the CO removal flow path 24, an oxygen auxiliary supply port 23 for supplying oxygen that oxidizes carbon monoxide to the CO removal flow path 24 is provided, and the reforming reaction chamber 18 and the CO removal flow are further provided. A communication channel 22 that communicates with the channel 24 is formed. The reaction supply port 21, the oxygen auxiliary supply port 23, and the reaction discharge port 26 are opened at the peripheral edge of the upper substrate 10. The oxygen auxiliary supply port 23 delivers oxygen from the outside of the microreactor 9 by a pump (not shown). At this time, since the fluid delivery direction of the pump is one direction, the mixture gas from the reforming reaction chamber 18 and the CO removal flow path 24 are used. Is not discharged from the oxygen auxiliary supply port 23 to the outside of the microreactor 9.

  A reforming catalyst 19 for catalyzing a reforming reaction is provided on the inner wall surface of the reforming reaction chamber 18. The reforming catalyst 19 is heated by heat generated from the resistor pattern 13 in order to promote the reforming reaction.

  The heat generated by the resistor pattern 13 is conducted to the reformer main body 6, but the heat insulating chamber 27 and the heat insulating chamber 30 having extremely low heat propagation properties are interposed between the reformer main body 6 and the CO remover main body 7. Since it is interposed, heat is not easily propagated to the CO remover body 7, and the temperature difference is set between the CO remover body 7 and the reformer body 6.

  In the inside of the CO removal channel 24, hydrogen monoxide generated by the reforming catalyst 19 and a small amount of carbon monoxide generated in addition to water are supplied by oxygen supplied from the oxygen auxiliary supply port 23 of the communication channel 22. A CO removal catalyst 25 that is oxidized to remove carbon monoxide is provided. The CO removal catalyst 25 is heated by heat generated from the resistor pattern 14 in order to promote the oxidation reaction of carbon monoxide.

  The reforming catalyst 19 is a copper / lead oxide-based catalyst, and alumina / carrier is supported on copper / lead oxide. Further, the CO removal catalyst 25 is a platinum-based catalyst, in which platinum or platinum and ruthenium are supported on alumina.

  Further, the inside of the heat insulating chambers 27 and 30 can be filled with a gas having a heat insulating effect such as a rare gas such as argon or helium, in addition to reducing the pressure to 1 Pa or less. The material of the radiation preventing film 28 is a metal such as aluminum.

  Here, the resistor patterns 13 and 14 according to the present invention will be described. As shown in FIG. 2, the resistor patterns 13 and 14 are formed at positions corresponding to the reformer body 6 and the CO remover body 7 on the upper surface of the upper substrate 10.

  FIG. 5 is a longitudinal sectional view showing an outline of the structure of the resistor patterns 13 and 14. The resistor patterns 13 and 14 are composed of three layers of heat generation layers 13a and 14a, diffusion prevention layers 13b and 14b, and adhesion layers 13c and 14c, and adhesion layers 13c and 14c and diffusion prevention layer from the surface of the lower substrate 11. 13b and 14b and the heat generating layers 13a and 14a are formed in this order.

  The heat generating layers 13a and 14a are materials having the lowest resistivity among the three layers. When a voltage is applied to the resistor patterns 13 and 14, current flows intensively and heat is generated. 6. Heat the CO remover body 7. The diffusion prevention layers 13b and 14b are made of a material that can maintain a dense bonded state even at high temperatures so that the heat generating layers 13a and 14a do not thermally diffuse in a temperature range that causes a chemical reaction of the reformer body 6 and the CO remover body 7. Has been. The adhesion layers 13c and 14c are made of a material having excellent adhesion interposed between the diffusion preventing layers 13b and 14b and the lower substrate 11 when the adhesion is not excellent.

Further, the resistor patterns 13 and 14 change their resistance values depending on their temperatures, and also function as temperature sensors that read changes in temperature from changes in resistance values.
FIG. 6 is a graph showing the relationship between the electrical resistance of a general metal and the temperature change. The horizontal axis of FIG. 6 represents the temperature of the metal, and the vertical axis represents the electric resistance R (T) of each metal at the temperature T.

  In a general metal, for example, due to impurities or lattice defects in each metal, the electrical resistance is caused by a region D1 in which the electrical resistance does not change due to a temperature change and thermal vibration of atoms in each metal. There is a region D2 in which changes in proportion to the temperature. In the following description, the electrical resistance in the D1 region is referred to as residual resistance R (0).

In the D1 region, R (0) and R (T) have substantially the same value, and in the D2 region, R (T) / R (0) = α (T−T ₀ ) (6)
Is established. Here, α is the rate of change of electric resistance (temperature coefficient) with temperature change, T ₀ is the boundary temperature between the D1 region and D2 region, and R (T ₀ ) = R (0).
As described above, the residual resistance R (0) and the temperature coefficient α of each metal are obtained in advance, and the electric resistance R (T) is measured by the measuring device in the D2 region, thereby calculating the temperature T of the microchannel. Can do.

  Au is preferably used as the material constituting the heat generating layers 13a and 14a. Since Au has a characteristic that the temperature coefficient is large, a measurement error of the temperature T can be suppressed.

  As a constituent material of the diffusion preventing layers 13b and 14b, it is preferable to use a material having a relatively high melting point and a low reactivity. An example of a material that satisfies such a condition is W. Here, the diffusion preventing layers 13b and 14b made of W have low reactivity, and there is a possibility that the adhesion with the lower substrate 11 having high reactivity may be lowered. Therefore, the diffusion preventing layers 13b and 14b and the lower substrate 11 are not provided. It is preferable to provide the adhesion layers 13c and 14c.

  It is preferable that at least one of Ta, Mo, Ti, and Cr is included as a substance constituting the adhesion layers 13c and 14c. This is because Ta, Mo, Ti, and Cr have a reactivity closer to that of the lower substrate 11 than W and can maintain adhesion to the lower substrate 11.

  FIG. 7 is a graph showing the relationship between the temperature of the resistor patterns 13 and 14 and R (T) / R (0). The resistor patterns 13 and 14 are formed by forming adhesion layers 13c and 14c made of Ti having a thickness of 50 nm on the surface of the lower substrate 11, and forming diffusion preventing layers 13b and 14b made of W having a thickness of 50 nm thereon. On top of this, heating layers 13a and 14a made of 200 nm thick Au are formed.

Here, since the rate of change α of the electric resistance R (T) / residual resistance R (0) when the temperature T changes by a unit amount is constant, the electric resistance R decreases as the value of the residual resistance R (0) decreases. The rate of change of (T) increases.
For example, when R (T) / R (0) varies from 1.4 to 1.6, when R (0) = 10 (Ω), R (T) is from 14 (Ω) to 16 (Ω) However, when R (0) = 20 (Ω), R (T) changes 4 (Ω) from 28 (Ω) to 32 (Ω). Therefore, as the residual resistance R (0) is larger, the electric resistance R (T) is more greatly displaced by the change in the temperature T. In other words, if the resistor patterns 13 and 14 are formed of a material having a large residual resistance R (0), even if the temperature change ΔT is slight, the temperature resistance change ΔR that changes with the temperature change ΔT is sufficiently large. Therefore, it is possible to easily measure the temperature finely and with a small error.
The layer thickness of the heat generating layers 13a and 14a can be arbitrarily changed according to the required resistance value, and the resistance increases as the layer thickness decreases.

  The resistor pattern 13 for the reformer body 6 includes a resistor body 15, terminals 15a, 15b, 15c, and a lead wire 15d. As shown in FIG. 2, the terminals 15 a and 15 b are integrally provided at both ends of the resistor main body 15. The terminal 15c is provided in the vicinity of the terminals 15a and 15b, and the lead wire 15d connects the central portion of the resistor main body 15 and the terminal 15c. The resistance value between the terminals 15a and 15b is larger than the resistance value between the terminals 15a and 15c and the resistance value between the terminals 15b and 15c.

  The terminals 15a, 15b, and 15c are connected to the switch device 50 (see FIGS. 8 and 9), and two lead wires 48 and 49 (see FIGS. 8 and 9) are connected to the switch device 50. The lead wire 48 is a high voltage contact connected to the output terminal on the high voltage side of the power supply unit 60, and the lead wire 49 is a low voltage contact connected to the output terminal on the low voltage side of the power supply unit 60. The lead wire 48 is connected to the terminal 15a and to one end of the switch 42. The other end of the switch 42 is connected to the terminal 15b. The lead wire 49 is connected to one end of the switch 42, and the switch 43 selectively connects the other end to only one of the terminal 15b and the terminal 15c. The wiring resistance from any one of the switches 42 and 43 and the lead wires 48 and 49 to any one of the terminals 15a, 15b, and 15c and the internal resistance of the switches 42 and 43 are negligible compared to the resistance of the resistor body 15. small.

  The switch device 50 switches the connection between the terminals 15a, 15b, 15c and the lead wires 48, 49 between the temperature raising operation and the constant temperature operation of the reformer body 6. When the reaction apparatus 3 is started, the temperature is rapidly increased so that the reformer 6 and the CO remover 7 reach the proper reforming reaction temperature and the proper CO removal reaction temperature, respectively. During such a temperature raising operation, as shown in FIG. 8A, the switch 42 is closed and the terminal 15b is electrically connected to the lead wire 48, and the switch 43 is electrically connected to the terminal 15c and the lead wire 49. During the constant temperature operation, as shown in FIG. 8B, the switch 42 is opened to make the lead wire 48 and the terminal 15b non-conductive, and the switch 43 makes the terminal 15b and the lead wire conductive. That is, the switch device 50 divides the resistor main body 15 into a plurality of parts in parallel during the temperature raising operation, and makes the resistor main body 15 electrically in series during the low temperature operation.

  For example, in the reformer 6, the reforming reaction chamber 18 must be heated to 300 ° C. at the time of startup, and the connection between the terminals 15a, 15b, 15c and the lead wires 48, 49 by the switch device 50 is shown in FIG. ), The resistance between the terminal 15a and the terminal 15c and the resistance between the terminal 15b and the terminal 15c are connected in parallel. When the resistance value R (0) 1 between the terminal 15a and the terminal 15c and the resistance value R (0) 2 between the terminal 15b and the terminal 15c are 14Ω at room temperature, respectively, the resistance value R (0) 1 and the resistance The parallel combined resistance value R (0) P of the value R (0) 2 is 7Ω. Since the resistance of the Au / W / Ti resistor pattern 13 at 300 ° C. is about 1.75 times the normal temperature, the resistance between the terminal 15a and the terminal 15c when the temperature is raised to 300 ° C. Resistance value R (300) 1 and the resistance value R (300) 2 between the terminal 15b and the terminal 15c are 24.5Ω respectively, and the resistance value R (300) 1 and the resistance value R (300) 2 are The parallel combined resistance value R (300) P is about 12.3Ω. That is, in the reformer 6, the resistance at the time of temperature rise changes from 7Ω to 12.3Ω.

  When using three lithium ion secondary batteries (single cell voltage 3.7V) connected in series as a power source for supplying power to the resistor pattern 13, the output voltage E = 11.1V, When the temperature is raised to a constant voltage output during the state of FIG. 8A, approximately 17.6 (W) is consumed at room temperature and approximately 10 (W) is consumed at 300 ° C. As described above, since the power consumption applied to the resistor pattern 13 is large and the resistance is lower than that in series, a large current flows, so that the temperature of the reforming reaction chamber 18 can be rapidly increased during the temperature raising operation.

On the other hand, during the constant temperature operation, the temperature of the reforming reaction chamber 18 is maintained at a set temperature of 250 to 320 ° C. For example, if the set temperature is 300 ° C. and the connection of the switch device 50 is in the state of FIG. 8B, the resistance value R (300) 1 and the resistance value R (300) 2 are 24.5Ω, respectively. The series combined resistance value R (300) S of (300) 1 and the resistance value R (300) is about 49Ω. The power is 2.51 (W). That is, since the amount of heat generated during the constant temperature operation is not required as in the temperature increasing operation, the power consumption can be suppressed by connecting the switch device 50 to the state shown in FIG.
Further, the residual resistance value R (300) S of the combined resistance between the lead wires 48 and 49 when the connection of the switch device 50 is in the state of FIG. 8B is 49Ω, and the residual resistance value R (0) is increased. By doing so, the change in the electric resistance R (T) is large even with a minute temperature change, so that temperature detection with a small error becomes possible.

  The connection switching by the switch device 50 may be controlled by the control unit 70 described later.

  The resistor pattern 14 for the CO remover body 7 is composed of a resistor body 16 and terminals 16a and 16b. The terminals 16a and 16b are integrally provided at both ends of the resistor body 16. One lead wire 51 (high voltage contact) and 52 (low voltage contact) (see FIG. 9) is connected to each of the terminals 16a and 16b. The resistor pattern 13 is supplied with power from a power supply unit (not shown) via lead wires 48 and 49 and the switch device 50, and the resistor pattern 14 is supplied with power from a power supply unit (not shown) via lead wires 51 and 52. . Since the set temperature during the constant temperature operation of the CO removal / removal channel 24 is 160 ° C. to 180 ° C., the resistor pattern 14 does not require as much power as the resistor pattern 13 during the temperature rising operation.

  Here, an electric system for supplying power to the resistor patterns 13 and 14 will be described with reference to FIG. The resistor pattern 13 is connected to the electrode of the power supply unit 60 through the switch device 50, the lead wire 48, and the lead wire 49. The power supply unit 60 is connected to the resistor pattern 13 through the switch device 50 and the lead wires 48 and 49. It supplies power. The resistor pattern 14 is connected to the electrode of the power supply unit 60 via the lead wire 51 and the lead wire 52 without going through the switch device 50, and the power supply unit 60 is connected to the resistor pattern 14 through the lead wires 51 and 52. Supply power.

  The power supply unit 60 supplies appropriate power to the resistor patterns 13 and 14, and the power supply unit 60 measures at least one of a voltage applied to the resistor patterns 13 and 14 and a current passed through the resistor patterns 13 and 14. can do. As a power source of the power supply unit 60, for example, a lithium ion secondary battery or the like can be used. The power source can also function as an output buffer that stabilizes the output of the fuel cell 4.

  The power supply unit 60 outputs at least one of current and voltage measurement signals to the control unit 70. The controller 70 can detect the electrical resistance of the resistor patterns 13 and 14 based on this measurement signal. That is, since the electrical resistance of the resistor patterns 13 and 14 depends on the temperature, the temperature of the resistor patterns 13 and 14 can be calculated from the electrical characteristics measured by the power supply unit 60. As a result, the reformer body 6 and the temperature of the CO remover body 7 can be calculated.

  The control unit 70 basically adjusts the power of the power supply unit 60 based on the electrical signal measured by the power supply unit 60, but includes a general-purpose CPU (central processing unit) or the like. , Which has a dedicated logic circuit, processes a signal from the power supply unit 60 to control the power supply unit 60. Further, the control unit 70 performs a process of calculating the electrical resistance of the resistor patterns 13 and 14 from the fed back measurement signal according to the electrical law, and further, from the electrical resistance of the resistor patterns 13 and 14, the resistor pattern 13, The process of calculating the temperature of 14 is performed. If the resistor patterns 13, 14, the reforming reactant 18, and the CO removal channel 24 are in thermal equilibrium, the resistor pattern 13 is at the temperature in the reforming reaction chamber 18, and the temperature of the resistor pattern 14 is at CO. It is equal to the temperature in the removal flow path 24.

  Next, the operation of the microreactor 9 will be described. First, the reformer body 6 is heated to the set temperature by the resistor pattern 13. At this time, the switch device 50 is set to the state shown in FIG. 8A, and during this state, a constant voltage is output to reduce the electrical resistance between the lead wires 48 and 49, and a large amount of power is consumed in a short time. The temperature of the mass device body 6 is rapidly increased. Further, the temperature of the CO remover body 7 is raised to a set temperature by the resistor pattern 14.

  During this time, the power supply unit 60 measures current and voltage, and current and voltage measurement signals are output to the control unit 70. In the control unit 70 to which the measurement signal is input, the electrical resistances of the resistor patterns 13 and 14 are calculated, and as a result, the temperatures of the respective resistor patterns 13 and 14 are calculated in the control unit 70.

  When the temperature of the reformer body 6 rises above the lower threshold temperature, the switch device 50 is brought into the state shown in FIG. Switching of the switch device 50 is performed electromagnetically by the control unit 70.

  Then, in accordance with the measurement signal, the control unit 70 appropriately feeds back the control signal to the power supply unit 60 so that the reformer body 6 and the CO remover body 7 are each stabilized at a predetermined temperature. For example, when the temperature of the resistor patterns 13 and 14 becomes higher than the upper threshold temperature, the control unit 70 causes the power supply unit to reduce the power supplied from the power supply unit 60 to the resistor patterns 13 and 14 from the current power. 60, when the temperature of the resistor patterns 13 and 14 is lower than the lower threshold temperature (but not higher than the upper threshold temperature), the resistor patterns 13 and 14 are supplied from the power supply 60 to the resistor patterns 13 and 14. The control unit 70 controls the power supply unit 60 so that the power becomes larger than the current power. The power supplied from the power supply unit 60 to the resistor patterns 13 and 14 is adjusted by the control unit 70, so that the temperature of the resistor pattern 13 is kept between the lower threshold temperature and the upper threshold temperature.

  The control unit 70 performs such control separately on the reformer body 6 and the CO remover body 7. That is, in the case of the reformer body 6, the temperature at which the reaction rate of the chemical reaction formulas (1) and (2) is the fastest is between the upper threshold temperature and the lower threshold temperature. The upper threshold temperature and the lower threshold temperature are set in the control unit 70. In the case of the CO remover body 7, the upper threshold temperature and the lower threshold temperature are such that the temperature at which the reaction rate of the chemical reaction formula (3) is the fastest is between the upper threshold temperature and the lower threshold temperature. A threshold temperature is set in the control unit 70.

  At this time, since the switch device 50 is in the state shown in FIG. 8B, the electrical resistance between the lead wires 48 and 49 is increased, resulting in low power consumption. Further, by increasing the residual resistance R (0), it becomes easier to detect a change in the electrical resistance R (T) of the resistor pattern 13 due to a temperature change, and the measurement accuracy of the temperature T of the reformer body 6 is improved. be able to.

  Next, methanol and water in a liquid state supplied from the fuel container 2 are vaporized in the vaporizer body 5, and the vaporized methanol and water are transferred from the reaction supply port 21 of the reformer body 6 to the reforming reaction chamber 18. Let it flow. In the reforming reaction chamber 18, vaporized methanol and water cause the reforming reaction of the chemical reaction formulas (1) and (2) by the reforming catalyst 19 to generate hydrogen, carbon dioxide, and carbon monoxide. The generated hydrogen, carbon dioxide, and carbon monoxide are transferred from the reforming reaction chamber 18 to the CO removal channel 24 via the communication channel 22. Of these, carbon monoxide is mixed with oxygen flowing from the oxygen auxiliary supply port 23 of the communication channel 22, and the reaction of the chemical reaction formula (3) is caused by the CO removal catalyst 17 to become carbon dioxide. Then, hydrogen and carbon dioxide in the CO removal channel 24 are discharged from the reaction discharge port 26. Of these, hydrogen causes reactions of electrochemical reaction formulas (4) and (5) in the fuel cell 4. Power is output from the fuel cell 4 as described above.

The present invention is not limited to the above embodiment, and various improvements and design changes may be made without departing from the spirit of the present invention.
For example, in the above embodiment, the terminals 15a, 15b, and 15c are provided at both ends and the center of the resistor body 15 of the resistor pattern 13, and the terminals 15a and 15b are connected to the lead wire 48 during the temperature raising operation of the reformer body 6. The terminal 15c is electrically connected to the lead wire 49, but a plurality of terminals 151, 152,..., (150 + 2n) may be provided on the resistor body 15, as shown in FIG.

  10 (a), the odd-numbered terminals 151, 153,..., (150 + 2n-1) are connected to the lead wire 48 and the even-numbered terminals 152, 154 from one end of the resistor body 15 during the temperature raising operation. ,..., (150 + 2n) are electrically connected to the lead wire 49, thereby greatly reducing the resistance value between the lead wires 48 and 49, increasing the power consumption by the resistor pattern 13, and rapidly changing the reformer body 6 The temperature can be raised. During constant temperature operation, as shown in FIG. 10B, the terminal 151 at one end of the resistor body 15 is electrically connected to the lead wire 48 and the terminal (150 + 2n) at the other end is electrically connected to the lead wire 49. The electrical resistance can be increased, the power consumption can be reduced, and the temperature measurement accuracy can be improved. The number of terminals may be an even number or an odd number.

In the above embodiment, the present invention is applied only to the reformer main body 6, but may be applied to the vaporizer main body 5 and the CO remover main body 7, or may be applied to the fuel cell 4. . Further, the reformer body 6 and the CO remover body 7 may be integrated, or may be provided on separate substrates.
In the above embodiment, the high voltage contact 48 is connected to one end of the switch 42 and the low voltage contact 49 is connected to either the terminal 15b or the terminal 15c. The low voltage contact 49 may be connected to one end of the switch 42, and the high voltage contact 48 may be connected to either the terminal 15b or the terminal 15c.

It is a block diagram which shows the electric power generating apparatus 1 to which the reaction apparatus 3 which concerns on this invention is applied. 1 is a perspective view showing a microreactor 9. FIG. It is sectional drawing of the surface along the III-III line of FIG. It is sectional drawing of the surface along the IV-IV line of FIG. FIG. 6 is a cross-sectional view showing the structure of resistor patterns 13 and 14. It is a graph which shows the relationship between the electrical resistance of a general metal, and a temperature change. It is a graph which shows the relationship between the electrical resistance of the resistor patterns 13 and 14, and a temperature change. (A) is a circuit diagram of the switch device 50 during a temperature raising operation of the reformer body 6, and (b) is a circuit diagram of the switch device 50 during a constant temperature operation of the reformer body 6. It is the block diagram which showed the reaction apparatus in this embodiment. (A) is a circuit diagram of the switch device during the temperature raising operation of the reformer body 6, and (b) is a circuit diagram of the switch device during the constant temperature operation of the reformer body 6. 1 is a diagram illustrating a conventional reformer.

Explanation of symbols

3 Reactor 6 Reformer 7 CO Remover 13, 14 Resistor Patterns 15a, 15b, 15c, 16a, 16b Terminals 48, 51 Lead Wire (High Voltage Terminal)
49, 52 Lead wire (low voltage terminal)

Claims (6)

A reactor body in which an internal space for reacting reactants is formed;
A resistor pattern provided in the reactor body;
A high voltage contact and a low voltage contact conducted to the resistor pattern;
A reaction apparatus, wherein a distance between the high-voltage contact and the low-voltage contact along the resistor pattern is changeable. Having three or more terminals along the resistor pattern;
Conducting the odd-numbered terminals from one end of the resistor pattern during the temperature rising operation of the reactor main body, conducting the even-numbered terminals to each other, conducting one to the high voltage contact and the other to the low voltage contact Conducting,
2. The reaction apparatus according to claim 1, wherein a terminal on one end of the resistor pattern is electrically connected to a high voltage contact and a terminal on the other end is electrically connected to a low voltage contact during a constant temperature operation of the reactor main body. .   The reaction device according to claim 1 or 2, wherein the resistance value of the resistor pattern changes according to a temperature change. A reactor body in which an internal space for reacting reactants is formed;
A resistor pattern provided in the reactor body and selectively connected in parallel and in series;
A reaction apparatus comprising:   The reactor according to claim 4, wherein the resistor patterns are connected in parallel during a temperature raising operation and connected in series during a constant temperature operation.   6. The reaction apparatus according to claim 4, wherein the resistance value of the resistor pattern changes according to a change in temperature.

Images