JP2003045459A - Heating arrangement, reforming device and fuel cell system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance efficiency in used energy. SOLUTION: This micro-reforming reactor 90 has a junction structure formed by superimposing an upper base 91, a middle base 92, and a lower base 93 to join them. A zigzag micro-passage 95 is formed on the middle base 92. A reforming catalyst 96 is formed on the inner surface of the micro-passage 95. In addition, a cavity 94 having a U-shaped cross section is formed on the middle base 92 and the lower base 93 so as to surround the micro-passage 95 and so as to stay along the micro-passage 95. A thin film heater 97 is interposed between the micro-passage 95 and the cavity 94. While an evaporated raw material gas flows in the micro-passage 95, the raw material gas is heated by the thin film heater 97 and expedited by the reforming catalyst 96 to cause reforming. Thereby, a gas containing hydrogen is produced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heating device for heating a reforming raw material, a reforming device equipped with this heating device, and a fuel cell system.

[0002]

2. Description of the Related Art In recent years, various chemical batteries have been used in all fields of consumer use or industrial use. For example, primary batteries such as alkaline dry batteries or manganese dry batteries are widely used in watches, cameras, toys or portable audio equipment, etc. It is easy to obtain.

On the other hand, secondary batteries such as nickel-cadmium storage batteries, nickel-hydrogen storage batteries or lithium-ion batteries have been remarkably popularized in recent years, such as mobile phones, personal digital assistants (PDAs, etc.), digital video cameras, digital still cameras, etc. It is widely used in mobile devices and has the advantage of being economical because it can be repeatedly charged and discharged. Further, among secondary batteries, a lead storage battery is used as a power source for starting a vehicle or a ship, an emergency power source in industrial equipment or medical equipment, and the like.

By the way, in recent years, with the increasing concern about environmental problems or energy problems, the above-mentioned problems concerning disposal of chemical batteries after use and energy conversion efficiency have been highlighted. In particular, in the case of primary batteries, as mentioned above, the product price is low and it is easy to obtain, and many devices are used as power sources.
Basically, the battery capacity cannot be recovered once discharged, and it can be used only once (so-called disposable), so the annual displacement is several million tons.
Here, in the whole chemical battery, the rate of recovery by recycling is only about 20%, and there is also statistical data that the remaining 80% is dumped in the natural world or is landfilled. There is concern about environmental destruction due to heavy metals such as mercury and indium contained in uncollected batteries, and deterioration of aesthetics of the natural environment.

Further, when the above-mentioned chemical battery is verified from the viewpoint of the utilization efficiency of energy resources, the primary battery is produced by using approximately 300 times as much energy as the dischargeable energy, so that the energy utilization efficiency is 1%. Less than On the other hand, even with a secondary battery that can be repeatedly charged and discharged and is excellent in economic efficiency, a household power source (for example,
When the battery is charged from an outlet, etc., the energy use efficiency will drop to about 12% due to the power generation efficiency and transmission loss at the power plant, so it can be said that the effective use of energy resources is not always achieved. There wasn't.

Therefore, in recent years, a so-called fuel cell, which has little influence on the environment and can realize an extremely high energy utilization efficiency of about 30 to 40%, has been attracting attention, and is used as a drive power source for vehicles or household use. Research and development for practical use are being actively conducted for the purpose of applying the above to a cogeneration system or the like, or for the purpose of substituting the above-mentioned chemical battery.

A solid polymer type fuel cell comprises a polymer electrolyte membrane sandwiched between an anode and a cathode. Hydrogen is supplied to the anode and oxygen is supplied to the cathode to cause an electrochemical reaction to generate electricity. Has become. Also,
A fuel reformer is used as a hydrogen supply source of a fuel cell. This fuel reforming apparatus heats a liquid fuel such as an alcohol-based or gasoline fuel and water to evaporate it, and heats vapor and steam of the liquid fuel and accelerates the reaction by using a reforming catalyst. And a reformer that reforms and produces a reformed gas containing hydrogen. A fuel cell system is constituted by such a fuel cell and a fuel reformer.

[0008]

[Problems to be Solved by the Invention] However, in the future,
In order to reduce the size and weight of a fuel cell system using a fuel cell with high energy utilization efficiency and to apply it as a portable or portable portable power source, for example, as an alternative to the above-mentioned chemical battery, various problems are solved. There is a need to. That is, thermal energy is consumed in addition to heating the liquid fuel and water, or the vapor and steam of the liquid fuel, resulting in heat loss. Therefore, the energy use efficiency of the entire fuel cell system may deteriorate.

An object of the present invention is to improve energy utilization efficiency.

[0010]

In order to solve the above problems, the invention according to claim 1 uses a reforming raw material as shown in FIG. 5, FIG. 7, FIG. 8, FIG. 12 or FIG. In the heating device used in the reforming device for reforming (for example, the micro-evaporator 50, the micro-reforming reactor 51, the micro-reforming reactor 90, the micro-batch reactor 151 or the micro-continuous tank reactor 251), The first internal space where the reforming raw material exists (for example, the evaporation chamber 63, the micro flow channel 68,
A main body (for example, the middle substrate 56 and the lower substrate 5) provided with the microchannel 95, the reaction chamber 164, or the reaction chamber 264.
7, middle substrate 70 and lower substrate 71, middle substrate 92 and lower substrate 93, middle substrate 153 and lower substrate 154, or middle substrate 253 and lower substrate 154) and heating means for heating the first internal space ( For example, thin film heaters 58, 7
6, 97 or 157), and a second interior space (eg, cavity 60, 74, 94 or 162) is provided in the body in the vicinity of the first interior space. .

In the above-mentioned invention of claim 1, the reforming raw material and the main body are also heated by heating the first internal space by the heating means. Although the second internal space is provided in the vicinity of the first internal space, it is difficult for heat to be conducted from the first internal space through the second internal space. Therefore, the heat energy generated from the heating means is efficiently used to heat the reforming raw material. Therefore, in the heating device according to the present invention, heat loss of energy is suppressed and energy utilization efficiency is improved. The reforming raw material may be liquid or gas.

According to a second aspect of the present invention, as shown in FIG. 7, for example, in the heating device according to the first aspect, the main body has a first substrate (for example, an intermediate substrate) provided with the first internal space. 70) and a second substrate (for example, the lower substrate 71) provided with a recess (for example, the recess 71a),
The second substrate is bonded to the first substrate so as to cover the recess, and thus the recess becomes the second internal space.

In the invention according to claim 2 above, the reforming raw material and the first substrate are also heated by heating the first internal space by the heating means. Then, the second substrate is joined to the first substrate to form the second internal space by the recess, but since the second internal space exists, the heat of the first substrate passes through the second internal space. It is difficult to conduct to the second substrate. Therefore, the thermal energy generated from the heating means is efficiently used for heating the first internal space and the first substrate, and ultimately for heating the reforming raw material. Therefore, in the heating device according to the present invention, the utilization efficiency of energy is improved.

According to a third aspect of the present invention, in the heating device according to the second aspect, the thermal conductivity of the first substrate is higher than that of the second substrate.

In the invention described in claim 3 above, the heating material heats the first internal space to heat the reforming raw material and the first substrate, but the thermal conductivity of the first substrate is Since it is higher than the thermal conductivity of the two substrates, it is difficult for heat to be transferred from the first substrate to the second substrate. Therefore, the heat energy generated from the heating means is efficiently used for heating the first internal space, and ultimately for heating the reforming raw material. Therefore, in the heating device according to the present invention, the utilization efficiency of energy is improved.

According to a fourth aspect of the present invention, in the heating device according to any one of the first to third aspects, in the second internal space, a gas of a polyhalogenated derivative of methane or ethane containing fluorine, or air. Alternatively, it is characterized by being filled with carbon dioxide gas.

In the invention according to claim 4 above, since the gas of the polyhalogenated derivative of methane or ethane containing fluorine, air or carbon dioxide gas is filled in the second internal space, Very low thermal conductivity. Therefore, heat is not absorbed in the second internal space, and
It is difficult for heat to be conducted from the first internal space through the second internal space. Therefore, the heat of the heating means is efficiently used for heating the first internal space, and ultimately for heating the reforming raw material.

According to a fifth aspect of the present invention, in the heating apparatus according to any one of the first to third aspects, the second internal space is substantially vacuum.

In the above-mentioned invention of claim 5, since the second internal space is substantially vacuum, the thermal conductivity of the second internal space is very low. Therefore, heat is not absorbed in the second internal space, and it is difficult for heat to be conducted from the first internal space through the second internal space. Therefore, the heat of the heating means is efficiently used for heating the first internal space, and ultimately for heating the reforming raw material.

The invention according to claim 6 is, for example, as shown in FIG. 7, in the heating device according to any one of claims 1 to 5, a mirror surface (for example, vapor deposition) is formed on the inner surface forming the second internal space. A film 75) is formed.

In the invention according to the sixth aspect, the reforming raw material and the main body are also heated by heating the first internal space by the heating means. The heat of the main body in the portion surrounding the first internal space passes through the second internal space as electromagnetic waves and is radiated as heat, but since the mirror surface is formed on the inner surface of the second internal space, Electromagnetic waves are reflected to the main body in the portion surrounding the internal space of. Therefore, heat radiation is suppressed, and the heat energy generated from the heating means is efficiently used for heating the reforming raw material.

The invention according to claim 7 is, for example, as shown in FIGS.
As shown in FIG. 2 or FIG. 13, the heating device according to any one of claims 1 to 6 (for example, the micro evaporator 50, the micro batch reactor 151, or the micro continuous tank reactor 25).
In 1), a supply means (for example, a fuel supply means 59, a first microvalve 155 or a fuel supply means 255) for supplying a liquid reforming raw material to the first internal space is provided,
It is characterized in that the supplied reforming raw material is heated by the heating means to be evaporated in the first internal space.

In the above-mentioned invention of claim 7, the liquid reforming raw material is supplied to the first internal space by the supplying means, but the liquid is reformed by heating the first internal space by the heating means. The reforming raw material is also heated, and the reforming raw material is evaporated in the first internal space. Since the second internal space is provided in the vicinity of the first internal space, the thermal energy generated by the heating means is efficiently used for heating the reforming raw material. Therefore, the liquid reforming raw material is efficiently evaporated.

A reformer according to an eighth aspect of the present invention is, for example, as shown in FIG. 12 or 13, a heating device according to the seventh aspect and a reforming catalyst (for example, a reformer) provided in the internal space. And a catalyst 167 or 267), and hydrogen is generated by reforming the evaporated reforming raw material in the internal space by the reforming catalyst.

In the invention described in claim 8 above, the vaporized reforming raw material is also heated by heating the first internal space by the heating means. The evaporated reforming raw material is promoted by the reforming catalyst to be reformed into hydrogen. Since the second internal space is provided in the vicinity of the first internal space, the thermal energy generated by the heating means is efficiently used to heat the evaporated reforming raw material. Therefore, the reaction rate for reforming is improved.

According to the ninth aspect of the present invention, there is provided a reforming apparatus according to the first aspect as shown in FIG. 4 and FIG.
To the heating device according to any one of 1 to 6, an evaporation unit that evaporates the liquid reforming raw material and communicates with the first internal space (for example, the microphone evaporator 50), and the heating device is provided in the first internal space. And a reforming catalyst (for example, the reforming catalyst 79 or the reforming catalyst 96) that is vaporized in the first internal space by the reforming catalyst. It is characterized by producing hydrogen.

In the above-mentioned invention according to claim 9, since the vaporizing section and the first internal space communicate with each other, when the reforming raw material is vaporized in the vaporizing section, the vaporized reforming raw material is transferred to the first internal space. Flowing. Further, since the heating means heats the first internal space, the evaporated reforming raw material is also heated. The evaporated reforming raw material is promoted by the reforming catalyst to be reformed into hydrogen. Since the second internal space is provided in the vicinity of the first internal space, the thermal energy generated by the heating means is efficiently used to heat the evaporated reforming raw material. Therefore, the reaction rate for reforming is improved.

A fuel cell system according to a tenth aspect of the present invention is, for example, as shown in FIG. 2, produced by a reformer (for example, a microreactor 5) according to the eighth or ninth aspect and oxygen and the reformer. And a fuel cell (for example, the main power generation section 6) that reacts with the generated hydrogen to generate power.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a heating device according to the present invention,
Specific aspects of the reformer and the fuel cell system will be described with reference to the drawings. However, the scope of the invention is not limited to the illustrated examples.

[First Embodiment] FIGS. 1A and 1B.
FIG. 1 shows an example of the appearance when the fuel cell system according to the present invention is applied to a cylindrical cell, and FIG. 1C shows the appearance when the chemical cell is applied to a general-purpose cylindrical cell. ing. Further, FIG. 2 is a functional block diagram showing the basic configuration of the fuel cell system according to the present invention.

As shown in FIGS. 1 (a), 1 (b) and 2, the fuel cell system 1 is roughly classified into a fuel pack 2 in which a mixed liquid containing a fuel (that is, a reforming raw material) is enclosed.
And a power generation module 3 for generating power based on the mixed liquid supplied from the fuel pack 2, and supplies power to an external load 34. It is removable.

The fuel pack 2 is a highly-sealed fuel storage container and is detachably connected to the power generation module 3. The fuel pack 2 may be integrally connected to the power generation module 3.

In this example, the fuel pack 2 is provided with the negative electrode 2a and the power generation module 3 is provided with the positive electrode 3a, but conversely, the fuel pack 2 is provided with the negative electrode and the power generation module 3 is provided with the positive electrode. It may be provided.

The fuel pack 2 is replaced by the power generation module 3
Outside dimensions (for example, length L
a, diameter Da) is approximately equal to the outer dimensions (for example, length Lp, diameter Dp) of a general-purpose chemical battery 100 (for example, AA type) standardized by the Japanese Industrial Standard (JIS).

First, the fuel pack 2 will be described in detail. Even if the fuel pack 2 is artificially heated or incinerated, or chemically or chemically treated, an organic chlorine compound (for example, dioxins; polychlorinated dibenzoparadioxin, polychlorinated dibenzofuran), chlorinated The fuel pack 2 is made of a material that produces less harmful substances such as hydrogen gas or heavy metals and environmental pollutants.
For example, the fuel pack 2 is made of biodegradable or photodegradable plastic, and specifically, a polymer material containing an aliphatic organic compound synthesized from petroleum-based raw materials, or corn or sugar cane. It is composed of a polymer material such as starch or polylactic acid extracted from plant-based raw materials such as.

In the fuel used in the fuel cell system 1, the fuel pack 2 in which the mixed liquid containing the fuel is enclosed is dumped or landfilled in the natural world, and the mixed liquid is placed in the atmosphere, soil or water. It is a fuel that does not become a pollutant to the natural environment even if it leaks. Further, the fuel used in the fuel cell system 1 is
It is a fuel that can generate electric energy with high energy conversion efficiency in a power generation module. Specifically, the fuel is alcohols such as methanol (CH ₃ OH) or ethanol (C ₂ H ₅ OH), or liquid fuel such as gasoline. In this embodiment, the fuel pack 2
In the case of methanol and water (H ₂ O), it is preferable that the mixed liquid enclosed in 1) be uniformly mixed at the same molar ratio, but the molar ratio of methanol may be high. In the fuel pack 2, a delivery pipe (not shown) for automatically delivering the enclosed mixed liquid to the sub power generation unit 4 and the microreactor 5 by a capillary phenomenon, and a by-product generated in the main power generation unit 6 described later. A recovery pipe (not shown) for recovering the water is provided.

According to the fuel pack 2 and the mixed liquid having such a structure, the fuel cell system 1 including the fuel pack 2 may be discarded in the natural world, landfilled, incinerated, or chemically treated. Even if there is, it is possible to significantly suppress the adverse effects on the natural environment, such as pollution of the atmosphere, soil, or water, on nature, as compared with a general-purpose chemical battery. Furthermore, it is possible to significantly suppress the adverse effects on the human body such as the production of environmental hormones.

When the fuel pack 2 is detachable from the power generation module 3 so that the remaining amount of the enclosed liquid mixture is exhausted or reduced, the fuel pack 2 is replenished with the liquid mixture. , Or a new fuel pack can be replaced. Therefore, the amount of waste of the fuel pack 2 and the power generation module 3 can be significantly reduced, and even if the used fuel pack 2 is discarded, the adverse effect on the natural environment is significantly reduced. It

Next, the power generation module 3 will be described. As shown in FIG. 2, the power generation module 3 reforms the mixed liquid supplied from the fuel pack 2 and the sub power generation unit 4 for generating electric energy that serves as an operating power source of each component of the power generation module 3. Of the microreactor 5, a main power generation unit 6 for generating electric energy as driving power using the fuel reformed by the microreactor 5, and supplying the power to the external load 34, and the main power generation unit 6. A starting detection unit 7 for detecting starting, a power detection unit 8 for detecting electric power generated by the main power generation unit 6, and a control unit 9 for controlling each component of the power generation module 3. Prepare

The sub-power generation unit 4 generates electric energy by an electrochemical reaction using the mixed liquid supplied from the fuel pack 2, and supplies it to other components of the power generation module 3 (for example, the control unit 9 and the microreactor 5). In addition to supplying power, standby power is supplied to the load 34 when the main function is off.

FIG. 3 shows an example of the sub power generation section 4. The sub power generation unit 4 is a polymer electrolyte fuel cell that employs a direct fuel supply system. That is, the sub-power generation unit 4 includes the fuel electrode 4 including carbon electrodes to which predetermined catalyst fine particles are attached.
1, an air electrode 42 formed of a carbon electrode to which a predetermined catalyst is attached, and an ionic conductive film 43 interposed between the fuel electrode 41 and the air electrode 42. The mixed liquid enclosed in the fuel pack 2 is directly supplied, and the air electrode 42 is supplied with oxygen gas (O ₂ ) in the atmosphere.

Specifically, when methanol (CH ₃ OH) and water (H ₂ O) contained in the mixed liquid are directly supplied to the fuel electrode 41, as shown in the following chemical reaction formula (1), Electrons (e ⁻ ) are separated by the catalytic reaction, and hydrogen ions (protons; H ⁺ ) are generated. Then, hydrogen ions pass to the side of the air electrode 42 through the ionic conductive film 43, and electrons (e ⁻ ) are taken out by the carbon electrode forming the fuel electrode 41, and the electrons are emitted to the control unit 9 and the microreactor 5. Supplied. CH ₃ OH + H ₂ O → 6H ⁺ + 6e ⁻ + CO ₂ (1)

On the other hand, when air is supplied to the air electrode 42, as shown in the following chemical reaction formula (2), electrons (e ⁻ ) and ionic conductivity are passed by the catalyst via the control unit 9 and the microreactor 5 and the like. Hydrogen ions (H ⁺ ) passing through the membrane 43 react with oxygen (O ₂ ) in the air to react with water (H
₂ O) is produced. 6H ⁺ + 3 / 2O ₂ + 6e ⁻ → 3H ₂ O (2) The produced water is recovered by a predetermined recovery means in the fuel pack 2 through the recovery pipe.

Such a series of electrochemical reactions (equations (1) and (2)) proceed under a relatively low temperature environment of about room temperature. Therefore, the sub-power generation section 4 undergoes a chemical reaction without a heating means such as a heater, so that the fuel accumulated in the mounted fuel pack 2 is completely consumed or the fuel pack 2 is removed from the power generation module 3. Until removal, the fuel is continuously supplied by the capillary phenomenon regardless of whether the main power generation unit 6 is driven or not, and power is constantly generated during the period.

Next, the microreactor 5 will be described. As shown in FIG. 4, the microreactor 5 includes a micro-evaporator 50 that heats and evaporates a mixed liquid (that is, methanol and water), and hydrogen gas (H ₂ ) and carbon dioxide gas that heats methanol gas and steam. A micro-reforming reactor 51 for reforming to (CO ₂ ) and an aqueous shift for reducing the concentration of a small amount of carbon monoxide (CO) generated in the micro-reforming reactor 51 by an aqueous shift reaction. A reactor 52, a selective oxidation reactor 53 for chemically converting a small amount of carbon monoxide generated in the microreforming reactor 51 into a harmless substance by a selective oxidation reaction, and an aqueous shift reactor 52.
And a radiation fin 54 for radiating heat generated by each reaction of the selective oxidation reactor 53.

The micro-evaporator 50 is constructed as follows. FIG. 5 shows a cross section of the microevaporator 50. As shown in FIG.
The basic configuration includes an upper substrate 55, an intermediate substrate 56, a lower substrate 57, a thin film heater 58, and a fuel supply means 59. Upper substrate 55, middle substrate 56 and lower substrate 57
Have a laminated structure in which they are overlapped and bonded to each other to form the main body of the micro-evaporator 50.

The lower substrate 57 is a substrate made of glass, and its thermal conductivity is about 1.3 [W / m · K].
A recess 57a for forming the cavity 60 is formed on the upper surface of the lower substrate 57 by applying a semiconductor manufacturing technique (for example, etching). A film 65 of aluminum or silver is formed on the surface of the recess 57a by vapor deposition, and the surface of the recess 57a is a mirror surface by the film 65. A thin film heater 58 is provided on the upper surface of the lower substrate 57 so as to cover the recess 57a. Then, a cavity 60, which is an internal space surrounded by the lower substrate 57 and the thin film heater 58, is formed, and in addition to suppressing heat propagation to the lower substrate 57 in the cavity 60 in which a medium that propagates heat is small, The radiant heat of the film is reflected by the film 65 to suppress the heat diffusion to the lower substrate 57, and more efficiently the middle substrate 56 and the evaporation chamber 63.
It has a structure that heats the inner space to promote hydrogen production. The thin film heater 58 is an electric resistor (for example, TaS).
iO _x N or TaSiO _x NH), the thin film heater 58 is supplied with the electric power generated by the sub power generation section 4 through the wiring 61, and the thin film heater 58 generates heat by the electric power. Furthermore, on the thin film heater 58 and the wiring 61, silicon oxide (SiO _x ) or silicon nitride (Si _x
The insulating film 62 formed of N _y ) is coated.

The intermediate substrate 56 is a substrate made of single crystal silicon and has a thermal conductivity of about 105 [W / m.multidot.m].
K], and is composed of a member having a higher thermal conductivity than at least the lower substrate 57 and the upper substrate 55 described later. Medium board 5
The lower surface of 6 has a recess 56 a for forming the evaporation chamber 63.
Are formed by the sandblast method. Recess 56
The middle substrate 56 is bonded to the lower substrate 57 via the insulating film 62 so that a faces the thin film heater 58 and the cavity 60. As a result, the evaporation chamber 63 that is an internal space surrounded by the middle substrate 56 and the insulating film 62 is formed.

The upper substrate 55 is a substrate made of glass, and its thermal conductivity is about 1.3 [W / m · K].
On the lower surface of the upper substrate 55, a recess 55a for forming the cavity 64 is formed by applying a semiconductor manufacturing technique.
A vapor deposition film 66 of aluminum or silver is formed on the surface of the recess 57a, and the surface of the recess 57a is a mirror surface by the vapor deposition film 66. The upper substrate 55 is bonded to the middle substrate 56 so that the recess 57 a faces the evaporation chamber 63. As a result, a cavity 64 that is an internal space surrounded by the upper substrate 55 and the middle substrate 56 is formed.

Air (heat conductivity 0.036 [W / m · K]) or carbon dioxide (C
It is filled with a gas such as O ₂ and a thermal conductivity of 0.017 [W / m · K]). Instead of air or carbon dioxide gas, gaseous Freon (made by DuPont) is used in the cavities 60 and 6.
4 may be filled. Freon is a polyhalogenated derivative of methane or ethane containing fluorine, such as dichlorodifluoromethane (CCl ₂ F ₂ ,
Freon 12, thermal conductivity 0.010 [W / mK]) chlorodifluoromethane (CHClF ₂ , Freon 22,
The thermal conductivity is 0.011 [W / m · K]). Also,
The cavities 60 and 64 may be in a vacuum state in which the pressure is reduced from atmospheric pressure.

Further, the intermediate substrate 56 is provided with fuel supply means 59 for supplying the mixed liquid sealed in the fuel pack 2 into the evaporation chamber 63. This fuel supply means 59
Is a thermal jet type liquid droplet ejecting apparatus (for example, an inkjet head of a so-called printer is applied), which heats the nozzle to which the mixed liquid from the fuel pack 2 is supplied and the mixed liquid in the nozzle. It has a basic structure with a heating element. In the fuel supply means 59 configured as described above, when the electric power generated by the sub-power generation unit 4 is supplied to the heating element, the mixed liquid in the nozzle is heated by the heating element to become the mixed liquid in the nozzle. Bubbles are generated. As a result, the pressure inside the nozzle rises, and droplets of the mixed liquid are ejected toward the thin film heater 58 from the nozzle hole formed at the tip of the nozzle.

Further, the middle substrate 56 and the upper substrate 55 are formed with a discharge passage 67 which leads from the evaporation chamber 63 to the micro-reforming reactor 51.

The micro-evaporator 5 configured as described above
At 0, the fuel supply means 59 jets the liquid droplets of the mixed liquid toward the lower wall portion of the vapor chamber 63. And the thin film heater 5
When 8 heats the insulating film 62 and the droplet of the mixed liquid, the mixed liquid is evaporated (that is, vaporized). The pressure in the evaporation chamber 63 rises due to the vaporization of the mixed liquid, and the vaporized gas of the mixed liquid (a gas in which methanol gas and water vapor are mixed, hereinafter referred to as raw material gas) flows from the evaporation chamber 63 to the discharge path 67 due to the pressure. Flows.

As described above, the middle substrate 56 is the upper substrate 55.
Also, since it is formed of silicon having a higher thermal conductivity than the lower substrate 57, the thermal energy generated in the thin film heater 58 tends to be thermally conducted to the middle substrate 56. Therefore, the thermal energy generated in the thin film heater 58 is
It is mainly used for heating the evaporation chamber 63 and the mixed liquid in the evaporation chamber 63. Further, adjacent to the intermediate substrate 56, the cavity 6
Since 0 and the cavity 64 are formed, it becomes difficult for the heat energy conducted to the middle substrate 56 to be conducted to the upper substrate 55 and the lower substrate 57. In particular, when the gas filled in the cavities 60 and 64 is air, carbon dioxide gas or Freon,
The thermal conductivity of the gas is smaller than that of the medium substrate 56.
On the other hand, if the cavities 60 and 64 are vacuum-sealed, the amount of air, which is a medium for heat propagation, per unit volume is small, so that the cavities 60 and 64 have a thermal conductivity of gas or medium substrate. It is very small compared to 56. Therefore, the thermal energy generated in the thin film heater 58 is
There is almost no conduction to 0 and the cavity 64, and it is consumed for heating the intermediate substrate 56 and for heating and evaporating the mixed liquid in the evaporation chamber 63.

Electromagnetic waves generated by thermal energy are radiated from the thin film heater 58 or the middle substrate 56 to the lower substrate 57 through the cavity 60, and a mirror-like film 65 is formed on the surface of the cavity 60. Therefore, the electromagnetic wave is reflected by the film 65. Thereby, heat radiation from the middle substrate 56 to the lower substrate 57 is suppressed. Similarly, since the mirror-evaporated film 66 is formed on the surface of the cavity 64, heat radiation from the middle substrate 56 to the upper substrate 55 is suppressed.

Therefore, the thermal energy generated by the thin film heater 58 is mainly used for heating the intermediate substrate 56, and ultimately for heating and evaporating the mixed liquid in the evaporation chamber 63. Since the cavities 60 and the cavities 64 are formed in the vicinity of the evaporation chamber 63 as described above, the loss of thermal energy of the thin film heater 58 can be suppressed. Since the heat energy loss of the thin film heater 58 is suppressed,
It is possible to suppress the consumption of electric power for the thin film heater 58 to generate heat, in other words, the consumption of the mixed liquid consumed in the sub power generation unit 4.

In the micro-evaporator 50, the evaporation chamber 63, the cavity 60 and the cavity 64 are provided on three substrates, but the evaporation chamber 63, the cavity 60 and the cavity 64 are provided on one substrate. And the cavity 60 or the cavity 6
Similarly, even when the thin film heater 58 is provided between the thin film heater 58 and the evaporation chamber 63, the heat energy loss of the thin film heater 58 can be suppressed.

Next, regarding the micro reforming reactor 51,
This will be described with reference to FIG. As shown in FIG. 6, the micro-reforming reactor 51 has a micro flow path 68 with a zigzag shape.
Is provided. FIG. 7 shows an AA cross section of FIG. As shown in FIG. 7, the micro-reforming reactor 51
Includes an upper substrate 69, a middle substrate 70, and a lower substrate 71. The upper substrate 69, the middle substrate 70, and the lower substrate 71 have a laminated structure in which the upper substrate 69, the middle substrate 70, and the lower substrate 71 are overlapped and bonded to each other to form the main body of the microreforming reactor 51. The lower substrate 71 is a substrate made of glass. A recess 71 a for forming the cavity 74 is formed on the upper surface of the lower substrate 71. Recess 71a
A vapor deposition film 75 of aluminum, silver, or the like is formed on the surface of the substrate by vapor deposition, and the surface of the recess 71a is a mirror surface due to the vapor deposition film 75. A thin film heater 76 is provided on the upper surface of the lower substrate 71 so as to cover the recess 71a. As a result, a cavity 74 that is a space surrounded by the lower substrate 71 and the thin film heater 76 is formed. Thin film heater 7
6 is an electrical resistance (for example, TaSiO _x N or TaS)
iO _x NH), and the thin film heater 76 is supplied with the electric power generated by the sub power generation unit 4 through the wiring 77, and the thin film heater 76 is heated by the electric power.
Further, an insulating film 78 made of silicon oxide or silicon nitride is coated on the thin film heater 76 and the wiring 77.

The middle substrate 70 is a substrate formed of single crystal silicon, and is composed of a member having a higher thermal conductivity than at least the upper substrate 69 and the lower substrate 71. On the lower surface of the intermediate substrate 70, a groove 70a for forming the microchannel 68 is formed by a sandblast method using a photoresist mask, and the groove 70a is formed in a zigzag shape. A reforming catalyst 79 is formed on the surface of the groove 70a. The reforming catalyst 79 has a function of promoting a chemical reaction with respect to methanol and water, and has a function of generating hydrogen and carbon dioxide from methanol and water.

The middle substrate 70 is bonded to the lower substrate 71 via the insulating film 78 so that the groove 70a faces the thin film heater 76 and the cavity 74. As a result, the micro flow path 68 is formed by the groove 70a. The micro channel 68 is a space surrounded by the middle substrate 70 and the insulating film 78. Further, one end of the micro channel 68 communicates with the discharge channel 67 of the micro evaporator 50, and the other end of the micro channel 68 communicates with the aqueous shift reactor 52. The cross-sectional width W of the micro flow channel 68 (that is, the groove 70a) is preferably 100 [μm] or less when the reforming catalyst 79 is coated, and the cross sectional depth D of the micro flow channel 68 is It is desirable that it is 500 [μm] or less when the catalyst 79 is coated. The micro channel 68 is heated by the thin film heater 76 generating heat.

The upper substrate 69 is a substrate made of glass. A recess 69a for forming the cavity 72 is formed on the lower surface of the upper substrate 69. A vapor deposition film 73 of aluminum or silver is formed on the surface of the recess 69a, and the surface of the recess 69a is a mirror surface by the vapor deposition film 73. The upper substrate 69 is bonded to the middle substrate 70 so that the recesses 69 a face the microchannels 68. This allows
Cavity 7 serving as a space surrounded by the upper substrate 69 and the middle substrate 70
2 is formed.

The cavities 72 and 74 are filled with air or a gas such as carbon dioxide. Note that the cavities 72 and 74 may be filled with gaseous freon instead of air or carbon dioxide gas. The cavities 72 and 74 may be vacuum-sealed.

In the micro-reforming reactor 51 having the above-mentioned structure, the source gas (ie, methanol gas and water vapor) vaporized in the micro-evaporator 50 is discharged through the discharge passage 67.
(Illustrated in FIG. 5) and then flows into the micro flow channel 68. Then, while the raw material gas is flowing through the micro flow channel 68, the raw material gas undergoes a steam reforming reaction as shown in the following chemical reaction formula (3), and hydrogen gas and carbon dioxide gas are discharged into the micro flow channel 68. Is generated in.

CH ₃ OH + H ₂ O → 3H ₂ + CO ₂ (3) The steam reforming reaction is an endothermic reaction and is promoted by heating the raw material gas by the thin film heater 76 and by the reforming catalyst 79. It

It should be noted that not all the raw material gases undergo the above reaction, but a small amount of the raw material gas has the following chemical reaction formula (4).
A carbon monoxide gas is produced in a small amount though the reaction shown in FIG. 2CH ₃ OH + H ₂ O → 5H ₂ + CO + CO ₂ (4)

The produced gases (ie hydrogen gas, carbon dioxide, carbon monoxide, etc.) are discharged to the aqueous shift reactor 52.

As described above, the middle substrate 70 is the upper substrate 69.
Also, since it is formed of silicon having a higher thermal conductivity than the lower substrate 71, the thermal energy generated in the thin film heater 76 tends to be thermally conducted to the intermediate substrate 70. Therefore, the thermal energy generated in the thin film heater 76 is
It is used to heat the micro channel 68 and the source gas in the micro channel 68. Further, since the cavity 72 and the cavity 74 are formed adjacent to the middle substrate 70, the heat energy conducted to the middle substrate 70 is hard to be conducted to the upper substrate 69 and the lower substrate 71. Therefore, the thermal energy generated by the thin film heater 76 is mainly used for heating the intermediate substrate 70, that is, for heating and reforming the raw material gas in the microchannel 68. Therefore, the reaction speed related to the reforming can be improved, and the loss of thermal energy of the thin film heater 76 can be suppressed.

The electromagnetic wave emitted from the thin film heater 76 or the intermediate substrate 70 is emitted toward the cavity 74.
Electromagnetic waves are reflected by the vapor deposition film 66. Therefore, heat radiation from the thin film heater 76 or the middle substrate 70 to the lower substrate 71 is suppressed. Similarly, a mirror-evaporated film 66 is formed on the surface of the cavity 64.
The heat radiation from the middle substrate 70 to the upper substrate 69 is suppressed due to the formation. Therefore, the thermal energy generated by the thin film heater 76 is mainly consumed for heating the intermediate substrate 70, that is, for heating and reforming the raw material gas in the microchannel 68. Therefore, the loss of heat energy of the thin film heater 76 can be suppressed.

A micro reforming reactor 90 as shown in FIG. 8 may be used in place of the micro reforming reactor 51 as shown in FIG. The same effect as the quality reactor 51 is obtained.

As shown in FIG. 8, the micro-reforming reactor 9
0 includes an upper substrate 91, a middle substrate 92, and a lower substrate 93. The upper substrate 91, the middle substrate 92, and the lower substrate 93 have a laminated structure in which they are overlapped and bonded to each other.
It is the main body of 0. The lower substrate 93 is a substrate made of glass. On the upper surface of the lower substrate 93, a concave portion 93a for forming the cavity 94 is formed.

The middle substrate 92 is a substrate made of single crystal silicon, and is composed of a member having a higher thermal conductivity than at least the upper substrate 91 and the lower substrate 93. A groove 92c for forming a folded microchannel 95 is formed in the middle substrate 92. The groove 92c vertically penetrates the middle substrate 92. A thin film heater 9 is provided on the lower surface of the middle substrate 92.
7 is provided. The thin film heater 97 is provided along the groove 92c and closes the lower portion of the groove 92c. The reforming catalyst 96 is formed on the inner surface of the groove 92c and the upper surface of the thin film heater 97. The reforming catalyst 96 has a function of promoting a chemical reaction with respect to methanol and water, and has a function of generating hydrogen gas and carbon dioxide gas from methanol and water. The cross-sectional width of the micro channel 95 is preferably 100 [μm] or less when the reforming catalyst 96 is coated, and the cross-sectional depth of the micro channel 95 is when the reforming catalyst 96 is coated. It is preferably 500 [μm] or less.

On both sides of the groove 92c, recesses 92a and 92b are formed on the lower surface of the intermediate substrate 92 along the groove 92c. Then, the thin film heater 97 is provided in the recess 93a of the lower substrate 93
The middle substrate 92 is bonded to the lower substrate 93 so as to face the bottom surface of the substrate and the thin-film heater 97 extends along the recess 93a. As a result, the U-shaped cavity 94 in cross section is formed in the middle substrate 92 and the lower substrate 93 so as to be along the groove 92c and surround the groove 92c.

A vapor deposition film 98 is formed on the surface of the cavity 94 (mainly the surface facing the groove 92c), and the surface of the cavity 94 is a mirror surface due to the vapor deposition film 98. The cavity 94 is filled with air or a gas such as carbon dioxide. Instead of air or carbon dioxide gas, gaseous freon may be filled in the cavity 94. In addition, the cavity 94 is
It may be vacuum-sealed.

The upper substrate 91 is a substrate made of glass. Then, by joining the upper substrate 91 to the middle substrate 92, the upper portion of the groove 92 c is closed by the upper substrate 91.
As a result, the micro channel 95 is formed by the groove 92c. The inside of the micro flow channel 95 is heated by the heat generated by the thin film heater 97.

Since the U-shaped cavity 94 is formed so as to surround the micro flow channel 95 in a sectional view, the thin film heater 9 is formed.
The thermal energy generated in 7 becomes difficult to be conducted to other than the micro flow channel 95. Therefore, the loss of heat energy of the thin film heater 97 is further suppressed.

In the micro-reforming reactor 90 configured as described above, the raw material gas (ie, methanol gas and water vapor) vaporized in the micro-evaporator 50 is discharged through the discharge path 67.
(Illustrated in FIG. 5) and then flows into the microchannel 95. While the raw material gas is flowing through the micro flow channel 95, the raw material gas is heated by the thin film heater 97, and is promoted by the reforming catalyst 96, so that the chemical reaction formula (3) and the chemical reaction are performed. The reaction shown in formula (4) is performed. As a result, the raw material gas is reformed into hydrogen gas and carbon dioxide gas, and also becomes a trace amount of carbon monoxide gas.

Next, the aqueous shift reactor 52 and the selective oxidation reactor 53 will be described with reference to the sectional view shown in FIG. Aqueous shift reactor 52 and selective oxidation reactor 5
3, a micro flow path 80 having a folded shape is provided. Further, the aqueous shift reactor 52 and the selective oxidation reactor 53 are integrated, and are specifically configured as follows.

That is, the aqueous shift reactor 52 and the selective oxidation reactor 53 have a laminated structure in which the upper substrate 81 and the lower substrate 82 are stacked and joined. Grooves 81 a for forming the micro flow channel 80 are formed in the upper substrate 81.
By joining the lower substrate 82 to the upper substrate 81, the micro channel 80 is formed by the groove 81a. The end of the micro flow channel 80 on the side of the aqueous shift reactor 52 communicates with the other end of the micro flow channel 68 of the micro reforming reactor 51. Then, the gas generated in the micro reforming reactor 51 (that is, hydrogen, carbon monoxide, carbon dioxide, etc.)
Flow into the micro flow channel 80. The other end of the micro flow channel 80 communicates with a fuel electrode 31 (shown in FIG. 10) of the main power generation unit 6 described later, and the gas generated in the micro reforming reactor 51 is in the micro flow channel. It flows through 80 and flows to the fuel electrode 31. Further, the upper substrate 81 is provided with heat radiation fins 54 so that the heat generated by the chemical reaction of carbon monoxide in the micro flow channel 80 is radiated by the heat radiation fins 54.

An aqueous shift reaction catalyst 83 is formed in the groove 81a of the aqueous shift reactor 52, and a selective oxidation reaction catalyst 84 is formed in the groove 81a of the selective oxidation reactor 53. The aqueous shift reaction catalyst 83 has a function of promoting a chemical reaction with respect to carbon monoxide and water, and has a function of generating hydrogen and carbon dioxide from carbon monoxide and water. The selective oxidation reaction catalyst 84 has a function of preferentially oxidizing carbon monoxide over hydrogen under hydrogen excess conditions. The cross-sectional width w of the micro flow channel 80 (that is, the groove 81a) is equal to
3 and 10 with the selective participation reaction catalyst 84 coated
It is desirable that the thickness is 0 [μm] or less, and the microchannel 80
The cross-sectional depth d is preferably 500 [μm] or less when the aqueous shift reaction catalyst 83 and the selective oxidation reaction catalyst 84 are coated.

The operation of the aqueous shift reactor 52 and the selective oxidation reactor 53 configured as above will be described. The gas generated in the micro reforming reactor 51 is the micro flow channel 80.
In the aqueous shift reactor 52 while passing through
Carbon monoxide is promoted by the aqueous shift reaction catalyst 83 to cause an aqueous shift reaction as shown in the following chemical reaction formula (5). CO + H ₂ O → CO ₂ + H ₂ (5) The unreacted water in the microreforming reactor 51 is used as water in the aqueous shift reaction.

In the selective oxidation reactor 53, the carbon monoxide contained in the gas passing through the micro flow channel 80 is selected by the selective oxidation reaction catalyst 84, and the carbon monoxide is converted into the following chemical reaction formula (6). The selective oxidation reaction as shown is performed.
Further, since the selective oxidation reaction catalyst 84 is formed in the micro flow channel 80, hydrogen contained in the gas is hardly oxidized. 2CO + O ₂ → 2CO ₂ (6) Note that oxygen in the atmosphere is used as oxygen in the selective oxidation reaction.

As described above, according to the microreactor 5 comprising the microevaporator 50, the microreforming reactor 51, the aqueous shift reactor 52 and the selective oxidation reactor 53, the microreforming reactor 51 has a very small amount. Although carbon monoxide is generated, carbon monoxide is hardly generated because carbon monoxide is converted into hydrogen and carbon dioxide in the aqueous shift reactor 52 and the selective oxidation reactor 53. The respective one flow paths of the aqueous shift reactor 52 and the selective oxidation reactor 53 were connected in series with each other. It may be connected to the flow path on the outlet side of the reforming reactor 51.
One flow path of the aqueous shift reactor 52 and one flow path of the selective oxidation reactor 53 may be connected in parallel to the flow path on the outlet side of the.

Next, the main power generation section 6 will be described with reference to FIG. The main power generation unit 6 is a polymer electrolyte fuel cell that employs a fuel reforming method. That is, the main power generation unit 6 includes a fuel electrode (that is, a cathode) 31 including a carbon electrode to which catalyst fine particles such as platinum or platinum / ruthenium are attached, and an air electrode (that is, a cathode) including a carbon electrode to which catalyst fine particles such as platinum are attached (that is, a cathode). , An anode) 32, and a film-like ionic conductive film (that is, an exchange film) 33 interposed between the fuel electrode 31 and the air electrode 32. The fuel electrode 31 is connected to the negative electrode 2a shown in FIG.
2 is connected to the positive electrode 3a shown in FIG.

Here, the hydrogen gas produced in the microreactor 5 is supplied to the fuel electrode 31, while the oxygen gas (O ₂ ) in the atmosphere is supplied to the air electrode 32, whereby A predetermined electric energy is generated (ie, power generation) by an electrochemical reaction in the power generation unit 6,
Drive power (ie voltage, current and electrical energy) for the load 34 is generated.

Specifically, when hydrogen gas is supplied to the fuel electrode 31, hydrogen ions separated from electrons are generated by the catalyst attached to the fuel electrode 31, as shown in the following chemical reaction formula (7). Hydrogen ions pass through the ion conductive film 33 toward the air electrode 32, and at the same time, electrons are taken out by the carbon electrode forming the fuel electrode 31 and supplied to the load 34. _{^{3H 2 → 6H + + 6e -}} ... (7)

On the other hand, when oxygen gas is supplied to the air electrode 32, as shown in the above chemical reaction formula (2), electrons are passed through the load 34 by the catalyst, hydrogen ions are passed through the ion conductive film 33, and in the air. The water generated by the reaction with the oxygen gas of 10 is recovered by a predetermined recovery means in the fuel pack 2 through the recovery pipe.

The electrochemical reaction in the main power generation section 6 is approximately 6
Since it proceeds under a relatively low temperature condition of 0 to 80 ° C., even if a slight amount of carbon monoxide is supplied to the fuel electrode 31, the fuel electrode 31 is easily poisoned by adsorption and its activity is likely to decrease. Since the generated gas contains almost no carbon monoxide, the fuel electrode 31 is not adsorbed and poisoned.
Therefore, even if the fuel cell system 1 is used for a long time, the driving power generated by the main power generation unit 6 is not reduced.

Next, the start-up detector 7, the power detector 8 and the controller 9 will be described. Start detection unit 7, power detection unit 8
The control unit 9 and the control unit 9 are formed into microchips on the order of several microns by applying existing semiconductor manufacturing technology.

The start-up detection section 7 detects that the main power generation section 6 is to be started, and specifically, a sensor (for example, a fuel cell) that detects that the load 34 is connected to the main power generation section 6. A position sensor or the like for detecting the position of the load 34 with respect to the system 1) or a sensor for detecting a change in potential due to a change in the capacity of the load when a user presses an operation button or the like of the load 34. Then, the activation detection unit 7 outputs a signal indicating the detection to the control unit 9 when the detection is performed.

The power detection unit 8 detects the value of the drive power generated in the main power generation unit 6, and specifically, an ammeter that detects the value of the current flowing from the main power generation unit 6 to the load 34. Alternatively, it is a voltmeter or the like for detecting the value of the voltage applied to the load 34 from the main power generation unit 6. Then, the power detection unit 8 outputs a signal indicating the value of the drive power generated in the main power generation unit 6 to the control unit 9.

The control unit 9 uses a dedicated logic circuit or CP
An arithmetic processing unit having a U (central processing unit) and the like, and detects a potential that is displaced along with the shift of the load 34 from the standby state to the state in which the main function is activated, via the positive electrode 3a and the negative electrode 2a of the fuel pack 2. Based on the signal input from the activation detection unit 7, it is determined that the main power generation unit 6 is activated, and when it is determined that the main power generation unit 6 is activated, a signal instructing the microreactor 5 to operate is output. Has become. Specifically, the controller 9 outputs an operation signal for instructing the fuel supply means 59 provided in the microreactor 5 to operate.
As a result, the fuel supply means 59 injects the mixed liquid (that is,
Supply), hydrogen gas begins to be generated in the microreactor 5, the main power generation unit 6 starts, and the main power generation unit 6 starts.
Drive power is generated from the. On the other hand, the control unit 9 controls the positive electrode 3a and the negative electrode 2 of the fuel pack 2 to have a potential that changes with the shift from the state where the main function is driven to the standby state.
When it is determined that the main power generation unit 6 is stopped based on the signal input from the activation detection unit 7 detected via a, a stop signal that instructs the microreactor 5 to stop is output. Specifically, the control unit 9 outputs a stop signal for instructing the fuel supply unit 59 provided in the microreactor 5 to stop. As a result, the fuel supply means 59 injects (ie, supplies) the mixed liquid.
However, since the hydrogen gas is not generated in the microreactor 5, the main power generation unit 6 stops and the driving power is not generated from the main power generation unit 6.

Furthermore, when the main power generation section 6 is activated,
The control unit 9 determines the value of the drive power of the main power generation unit 6 based on the signal input from the power detection unit 8 and controls the microreactor 5 based on the determined drive power value. . As a result, the amount of hydrogen gas produced from the microreactor 5 is adjusted. That is, the controller 9 controls the fuel supply means 5 provided in the microreactor 5.
Control 9 Thereby, the supply amount of the mixed liquid injected from the fuel supply unit 59 (that is, the injection amount per unit time, for example, the interval at which the fuel supply unit 59 injects fuel) is controlled by the control unit 9, and the microreactor 5 is operated. The amount of generated hydrogen gas is adjusted, and as a result, the drive power (that is, voltage, potential, and electric energy) generated from the main power generation unit 6 is adjusted. Specifically, the control unit 9 determines the time interval from when the fuel supply means 59 injects the mixed liquid once and injects the mixed liquid again next time.
The amount of hydrogen gas produced is adjusted by controlling the. Further, the control unit 9 controls the drive power and the like generated from the main power generation unit 6 to be constant based on the signal input from the power detection unit 8 (for example, the voltage applied to the load 34 is constant 1.5 [V]), fuel supply means 5
9 is controlled.

That is, in the above fuel cell system 1, the fuel supply means 59 is provided, and the fuel supply means 5 is provided.
By adjusting the supply amount of the mixed liquid injected from 9 by the control unit 9, the production amount of hydrogen gas can be easily controlled. Further, the mixed liquid is injected from the fuel supply unit 59 and electric power is generated from the main power generation unit 6 only when the activation detection unit 7 detects the electric power. The liquid mixture is not injected (when not connected to the system 1). Therefore,
The waste of the mixed liquid by the main power generation unit 6 can be suppressed.

Next, the method of use and operation of the fuel cell system 1 will be described. First, the fuel pack 2 filled with the mixed liquid is attached to the power generation module 3. next,
The fuel cell system 1 with the fuel pack 2 attached is connected to the load 34. Then, when the activation detection unit 7 detects the activation state of the load 34, hydrogen gas is generated in the microreactor 5 and drive power is generated in the main power generation unit 6. As a result, drive power is supplied to the load
Supplied to. At this time, the control unit 9 adjusts the amount of hydrogen gas generated from the microreactor 5 to adjust the electric power generated in the main power generation unit 6.

In the fuel cell system 1 as described above, heat energy loss is suppressed in the micro-evaporator 50 and the micro-reforming reactor 51, so that the consumed heat energy for evaporating the mixed liquid and for reforming the mixed liquid is reduced. It can be suppressed. Therefore, in the entire fuel cell system 1, the energy conversion efficiency into electric energy is very good, and the fuel cell system 1 having high energy utilization efficiency is provided.

[Second Embodiment] The fuel cell system according to the second embodiment has almost the same structure as the fuel cell system 1 according to the first embodiment, but the structure of the microreactor is different. Is different. Therefore,
The configuration of the fuel cell system according to the second embodiment is the same as that of the fuel cell system 1 according to the first embodiment.
The configuration different from that will be mainly described.

In the second embodiment, as shown in FIG. 11, the microreactor 5 in the second embodiment is used.
Is a micro-evaporator 50 and a micro-reforming reactor 51.
Instead of (as shown in FIG. 4 etc.), a microbatch reaction for heating and evaporating the mixed liquid and reforming methanol gas and water vapor into hydrogen gas (H ₂ ) and carbon dioxide gas (CO ₂ ). The container 151 is provided.

The microbatch reactor 151 has the fuel heating device and the fuel reforming device according to the present invention applied thereto. As shown in FIG. 12, the microbatch reactor 151
Has a basic configuration including an upper substrate 152 and an intermediate substrate 153.
A lower substrate 154, a first microvalve 155, a second microvalve 156, and a thin film heater 157. The upper substrate 152, the middle substrate 153, and the lower substrate 154 have a laminated structure in which they are overlapped and bonded to each other to form a main body of the microbatch reactor 151.

The lower substrate 154 is a substrate made of glass. A recess 154a for forming the cavity 162 is formed on the upper surface of the lower substrate 154, and the lower substrate 154 serves as a wall portion of the recess 154a. A vapor deposition film 160 of aluminum or silver is formed on the surface of the recess 154a, and the surface of the recess 154a is a mirror surface due to the vapor deposition film 160. The thin film heater 157 is formed so as to cover the recess 154a.
Are provided on the upper surface of the lower substrate 154. This allows
A cavity 162 which is a space surrounded by the lower substrate 154 and the thin film heater 157 is formed. The thin-film heater 157 is composed of an electric resistance, and the thin-film heater 157 includes a sub power generation unit 4
The electric power generated at is supplied through the wiring 158, and the thin film heater 157 generates heat by the electric power. Further, an insulating film 159 made of silicon oxide or silicon nitride is coated on the thin film heater 157 and the wiring 158.

The middle substrate 153 is a substrate formed of single crystal silicon, and at least the upper substrate 152 and the lower substrate 1
It is composed of a member having a higher thermal conductivity than 54. Medium board 1
On the lower surface of 53, the recess 1 for forming the reaction chamber 164.
53a is formed. A reforming catalyst 167 is formed on the surface of the recess 153a. The reforming catalyst 167 has a function of promoting a chemical reaction with respect to methanol and water, and has a function of generating hydrogen gas and carbon dioxide gas from methanol and water.

With the recess 153a facing the thin film heater 157 and the cavity 162, the intermediate substrate 56 is covered with the insulating film 15.
It is joined to the lower substrate 154 via 9. As a result, a reaction chamber 164 which is a space surrounded by the middle substrate 153 and the insulating film 159 is formed.

The upper substrate 152 is a substrate made of glass. On the lower surface of the upper substrate 152, a recess 152a for forming the cavity 163 is formed. A vapor deposition film 161 of aluminum or silver is formed on the surface of the recess 152a, and the surface of the recess 152a is a mirror surface due to the vapor deposition film 161. The upper substrate 152 is bonded to the middle substrate 153 so that the recess 152 a faces the reaction chamber 164. As a result, a cavity 163 serving as a space surrounded by the upper substrate 152 and the middle substrate 153 is formed.

The cavities 162 and 163 may be filled with a gas such as air, carbon dioxide, or gaseous freon. Further, the cavity 162 and the cavity may be vacuum-sealed.

Further, the intermediate substrate 153 is provided with a suction passage 165 which leads from the fuel pack 2 to the reaction chamber 164. In addition, the middle substrate 153 and the upper substrate 152 are provided with a discharge passage 166 that leads from the reaction chamber 164 to the micro flow passage 80 of the aqueous shift reactor 52. Inhalation channel 165
Is provided with a first micro valve 155, and the discharge passage 166 is provided with a second micro valve 156. The first microvalve 155 is for opening and closing the suction passage 165, and the second microvalve 156 is for discharging the discharge passage 16.
6 is opened and closed. The first microvalve 155 and the second microvalve 156 are configured to be opened / closed by the electric power generated by the sub power generation unit 4, and the opening / closing operation is controlled by the control unit 9.

Next, the operation of the micro batch reactor 151 will be described. First, the control unit 9 controls the second microvalve 156 so that the second microvalve 1
56 is closed, and the discharge path 166 is closed. And
The first microvalve 155 is opened by the control unit 9 controlling the first microvalve 155. By opening the first microvalve 155, the mixed liquid is supplied from the fuel pack 2 into the reaction chamber 164. When a predetermined amount of the mixed liquid is supplied into the reaction chamber 164 (or after a predetermined time elapses), the control unit 9 controls the first microvalve 155 to close the first microvalve 155.

Then, the thin film heater 157 which is generating heat.
However, when the mixed liquid supplied to the insulating film 159 and the reaction chamber 164 is heated, the mixed liquid is vaporized and becomes a gas. Then, the raw material gas (that is, methanol gas and steam) is heated by the thin film heater 157 and is promoted by the reforming catalyst 167, so that the raw material gas becomes the chemical reaction formula (3) and the chemical reaction formula. The reaction shown in (4) occurs. In this way, the raw material gas is reformed to generate hydrogen gas, carbon dioxide gas and a trace amount of carbon monoxide gas. Further, the pressure in the reaction chamber 164 rises due to vaporization of the mixed liquid or generation of hydrogen gas, carbon dioxide gas, and carbon monoxide gas from the raw material gas.

Then, after a lapse of a predetermined time from the closing operation of the first micro valve 155, the control unit 9 controls the second micro valve 156 to open the second micro valve 156. When the second micro valve 156 is opened, the generated gas flows to the discharge passage 166 due to the pressure in the reaction chamber 164 and then to the micro flow passage 80 of the aqueous shift reactor 52.

Thereafter, similarly, the first micro valve 155
By repeating the opening and closing operations of the second microvalve 156 and the second microvalve 156, the product gas is intermittently generated in the aqueous shift reactor 52.
Flow into the micro channel 80.

In the above micro batch reactor 151, since the middle substrate 153 is made of silicon having a higher thermal conductivity than the upper substrate 152 and the lower substrate 154, the thermal energy generated by the thin film heater 157 is Heat tends to be conducted to the substrate 153. Furthermore, adjacent to the middle substrate 153,
Since the cavities 163 and 162 are formed, it is difficult for the thermal energy conducted to the middle substrate 153 to be conducted to the upper substrate 152 and the lower substrate 154. Therefore, the thin film heater 1
The thermal energy generated in 57 is mainly used for heating the intermediate substrate 153, that is, for heating and evaporating the mixed liquid in the reaction chamber 164 and for heating and reforming the source gas. Become. Therefore, the heat energy loss of the thin film heater 157 can be suppressed. Thin film heater 1
Since the heat energy loss of 57 is suppressed, it is possible to suppress the consumption of electric power for the thin film heater 157 to generate heat, in other words, the consumption of the mixed liquid consumed in the sub power generation unit 4.

Further, the thin film heater 157 or the intermediate substrate 15
Although the electromagnetic wave emitted from No. 3 is emitted toward the cavity 162, the electromagnetic wave is reflected by the vapor deposition film 160. for that reason,
Thin film heater 157 or middle substrate 153 to lower substrate 154
The heat radiation to the is suppressed. Similarly, since the mirror-finished vapor deposition film 161 is formed on the surface of the cavity 163, the intermediate substrate 15
The heat radiation from 3 to the upper substrate 152 is suppressed. Therefore,
The thermal energy generated by the thin film heater 157 is generated by the intermediate substrate 7
It is consumed for heating 0, heating and evaporating the mixed solution in the reaction chamber 164, and heating and reforming the raw material gas in the reaction chamber 164. Therefore, the thin film heater 15
It is possible to suppress the loss of heat energy in No. 7 and to suppress the consumption of the mixed liquid consumed in the sub power generation unit 4.

[Third Embodiment] The fuel cell system according to the third embodiment has substantially the same configuration as the fuel cell system 1 according to the first or second embodiment, but the microreactor is used. The configurations are different.
Therefore, regarding the configuration of the fuel cell system in the third embodiment, the configuration different from the fuel cell system 1 in the first or second embodiment will be mainly described.

In the third embodiment, the microreactor 5 is replaced by the microbatch reactor 151 shown in FIG. 12, and a micro continuous tank reactor 251 as shown in FIG.
Is equipped with. The micro continuous tank reactor 251 heats and evaporates the mixed liquid, and reforms methanol gas and water vapor into hydrogen gas (H ₂ ) and carbon dioxide gas (CO ₂ ). In the following, regarding the micro continuous tank reactor 251, the same components as those of the micro batch reactor 151 are denoted by the same reference numerals, and detailed description thereof will be omitted.

The micro continuous tank reactor 251 is one to which the fuel heating device and the fuel reforming device according to the present invention are applied, and as a basic configuration, an upper substrate 152 and an intermediate substrate 253.
, A lower substrate 154, a thin film heater 157, and a fuel supply unit 255.

The lower substrate 154 is a substrate made of glass. As in the case of the second embodiment, this lower substrate 1
The cavity 162 is formed by providing the thin film heater 157 on the upper surface of 54.

The intermediate substrate 253 is a substrate formed of single crystal silicon, and at least the upper substrate 152 and the lower substrate 1
It is composed of a member having a higher thermal conductivity than 54. Medium board 2
The lower surface of 53 is provided with a recess 2 for forming a reaction chamber 264.
53a is formed. A reforming catalyst 267 is formed on the surface of the recess 253a. The reforming catalyst 267 has an action of promoting a chemical reaction with respect to methanol and water, and has a function of generating hydrogen gas and carbon dioxide gas from methanol and water.

The concave portion 253a is made to face the thin film heater 157 and the cavity 162 so that the intermediate substrate 253 becomes the insulating film 1.
It is bonded to the lower substrate 154 via 59. As a result, a reaction chamber 264 which is a space surrounded by the middle substrate 253 and the lower substrate 154 is formed.

The upper substrate 152 is a substrate made of glass. Similar to the case of the second embodiment, the upper substrate 152
Is bonded to the middle substrate 253, so that the recess 152a
A cavity 163 is formed. The cavities 162 and 163 may be filled with a gas such as air, carbon dioxide, or gaseous freon. Further, the cavity 162 and the cavity may be vacuum-sealed.

Further, the intermediate substrate 253 is provided with fuel supply means 255 for supplying the mixed liquid sealed in the fuel pack 2 into the reaction chamber 264. The fuel supply means 255 is a thermal jet type liquid droplet ejecting apparatus (for example, a so-called inkjet head of a printer is applied), and the nozzle to which the mixed liquid from the fuel pack 2 is supplied and the inside of the nozzle. The basic configuration is a heating element for heating the mixed liquid of. In the fuel supply unit 255 configured as described above, when the electric power generated by the sub-power generation unit 4 is supplied to the heating element, the mixed liquid in the nozzle is heated by the heating element to become the mixed liquid in the nozzle. Bubbles are generated.
As a result, the pressure inside the nozzle rises, and the liquid droplets of the mixed liquid are discharged from the nozzle hole formed at the tip of the nozzle into the thin film heater 15.
It is injected toward 7.

Further, the upper substrate 152 and the middle substrate 253 are provided with a discharge passage 266 which leads from the reaction chamber 264 to the micro flow passage 80 of the aqueous shift reactor 52.

The operation of the micro continuous tank reactor 251 will be described below. First, the fuel supply unit 255 sprays the liquid droplets of the mixed liquid toward the lower wall of the reaction chamber 264. Then, when the thin film heater 157, which is generating heat, heats the droplets of the mixed liquid, the mixed liquid is vaporized and becomes a gas. The raw material gas (that is, methanol gas and water vapor) is the thin film heater 15.
By being heated by 7 and being promoted by the reforming catalyst 267, the reactions shown in the chemical reaction formulas (3) and (4) are performed. In this way, the raw material gas is reformed to generate hydrogen gas, carbon dioxide gas and carbon monoxide gas. The generated gas (that is, hydrogen gas, carbon dioxide gas, and carbon monoxide gas) diffuses into the exhaust passage 266 by mass diffusion and convection. In addition, the pressure in the reaction chamber 264 rises due to vaporization of the mixed liquid or reforming of the source gas into hydrogen gas, carbon dioxide gas, and carbon monoxide gas. As a result, the generated gas is discharged to the aqueous shift reactor 52 through the discharge passage 266 by the atmospheric pressure in the reaction chamber 264.

As described above, the middle substrate 253 is the upper substrate 1
Since it is formed of silicon having a higher thermal conductivity than the lower substrate 52 and the lower substrate 154, the heat energy generated in the thin film heater 157 tends to be conducted to the middle substrate 253. Therefore, the thermal energy generated in the thin film heater 157 is mainly consumed for heating the intermediate substrate 253, the reaction chamber 264, the mixed liquid in the reaction chamber 264, and the source gas.

Further, the cavity 16 is provided adjacent to the intermediate substrate 253.
2 and the cavity 163 are formed, the middle substrate 253 is formed.
The thermal energy conducted to the upper substrate 152 and the lower substrate 15
It is difficult to conduct heat to 4. That is, since the cavities 162 and 163 are filled with air, freon, or carbon dioxide gas, or the cavities 162 and 163 are vacuum-filled, the thermal energy generated in the thin film heater 157 or the intermediate substrate 253. The conducted thermal energy is hard to be conducted to the cavity 162 or the cavity 163, and the cavity 162 or the cavity 1
It is difficult to conduct to the upper substrate 152 or the lower substrate 154 via 63. Therefore, the thermal energy generated in the thin film heater 157 is mainly consumed for heating the intermediate substrate 253, the reaction chamber 264, the mixed liquid in the reaction chamber 264, and the source gas.

Further, the thin film heater 157 or the intermediate substrate 25
Although the electromagnetic wave emitted from No. 3 is emitted toward the cavity 162, the electromagnetic wave is reflected by the vapor deposition film 160. for that reason,
Thin film heater 157 or middle substrate 253 to lower substrate 154
The heat radiation to the is suppressed. Similarly, since the mirror-finished vapor deposition film 161 is formed on the surface of the cavity 163, the intermediate substrate 25
The heat radiation from 3 to the upper substrate 152 is suppressed. Therefore,
The thermal energy generated by the thin film heater 157 is generated by the intermediate substrate 2
Mainly consumed for heating 53 (that is, the reaction chamber 264), after all, for heating and evaporating the mixed liquid in the reaction chamber 264 and for heating and reforming the raw material gas.

Therefore, the loss of heat energy of the thin film heater 157 can be suppressed. Therefore, the thin film heater 1
It is possible to suppress the amount of electric power consumed for heating 57, in other words, the amount of mixed liquid consumed in the sub power generation unit 4.

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

For example, in each of the above embodiments, the outer shape of the fuel cell system 1 is not limited to the cylindrical shape as shown in FIG. 1, and may be, for example, a circular shape such as a button type or a coin type, or a special type. It may be a non-circular type such as a shape type, a square type, or a flat type.

Further, in the first or third embodiment, the fuel supply means 59 and the fuel supply means 255 are of the thermal jet type, but a piezo type liquid droplet ejecting apparatus (so-called piezo type ink jet). A head to which a head is applied.) Or an electrostatic droplet ejecting device (a so-called electrostatic inkjet head is applied).
May be applied. The piezo-type inkjet head includes a nozzle to which the mixed liquid is supplied from the fuel pack 2 and a piezo element that deforms when a voltage is applied.
Then, when a voltage is applied to the piezo element by the electric power generated by the sub power generation unit 4, droplets of the mixed liquid are ejected from the nozzle hole formed at the tip of the nozzle, and the mixed liquid is supplied thereby. .

Further, the electrostatic ink jet head is provided with a nozzle, a vibration plate which is a part of the nozzle, and a counter electrode which is arranged so as to face the vibration plate. And
In the electrostatic inkjet, when a voltage is applied between the diaphragm and the counter electrode, the diaphragm is bent toward the counter electrode by the Coulomb force. After that, when the voltage between the diaphragm and the counter electrode disappears, the diaphragm is restored. This allows
A droplet of the mixed liquid is ejected from a nozzle hole formed at the tip of the nozzle, whereby the mixed liquid is supplied.

Further, instead of the thin film heaters 58, 76, 97 or 157, for example, a heating means for emitting heat from a heat fluid or the like for heating may be used.

In each of the above embodiments, the evaporation chamber 6
3, microchannel 68, reaction chamber 164 or reaction chamber 26
Although a cavity is formed above and below 4, the cavity may be further formed in front of, behind, left, or right of the evaporation chamber 63, the micro flow channel 68, the reaction chamber 164, or the reaction chamber 264. good. In each of the above embodiments, single crystal silicon having high thermal conductivity is used as the intermediate substrate to promote the reaction, but the thermal conductivity is higher than that of the upper substrate and / or the lower substrate, and the workability is excellent. If it is a material that is not limited to this,
For example, aluminum or its alloy may be used. Further, as long as sufficient sealing is possible, a two-layer structure of an upper substrate and a middle substrate having a cavity or a two-layer structure of a lower substrate having a middle substrate and a cavity may be used. Further, in each of the above embodiments, methanol was used as the fuel, but any other liquefied fuel may be used as long as it produces hydrogen by an endothermic reaction, and it is more preferable if it is a fuel that vaporizes at normal temperature and pressure such as butane. .
In addition, in each of the above-described embodiments, the heat insulating structure related to the heater of each element of the fuel cell has been described, but the present invention is not limited to this, and a microminiature reaction for chemically reacting a predetermined substance such as identification and synthesis of a gene such as DNA. It is also possible to apply the above-mentioned heat insulation structure to the plant.

[0131]

As described above, according to the present invention, the reforming raw material and the main body are also heated by heating the first internal space by the heating means. Although the second internal space is formed in the vicinity of the first internal space, it is difficult for heat to be conducted from the first internal space through the second internal space. Therefore, the heat energy generated from the heating means is efficiently used to heat the reforming raw material. Therefore, in the heating device according to the present invention,
The heat loss of energy is suppressed, and the energy utilization efficiency is improved.

[Brief description of drawings]

FIG. 1 is a perspective view showing outer shapes of a fuel cell system according to the present invention and a conventional chemical cell.

FIG. 2 is a diagram showing a functional block diagram of the fuel cell system.

FIG. 3 is a diagram schematically showing a configuration example of a fuel cell provided in the fuel cell system.

FIG. 4 is a diagram showing a configuration example of a microreactor provided in the fuel cell system.

FIG. 5 is a cross-sectional view showing a micro evaporator provided in the micro reactor.

FIG. 6 is a perspective view showing a micro-reforming reactor provided in the micro-reactor.

FIG. 7 is a cross-sectional view showing the micro-reforming reactor.

FIG. 8 is a cross-sectional view showing a micro-reforming reactor which is another example than the micro-reforming reactor.

FIG. 9 is a cross-sectional view showing an aqueous shift reactor and a selective oxidation reactor provided in the microreactor.

FIG. 10 is a diagram schematically showing a configuration of a fuel cell provided in the fuel cell system.

FIG. 11 is a drawing showing a configuration example of a microreactor which is another example than the microreactor.

FIG. 12 is a cross-sectional view showing a micro batch reactor provided in the micro reactor of the another example.

FIG. 13 is a cross-sectional view showing a micro continuous tank reactor provided in the micro reactor of the another example, instead of the micro batch reactor.

[Explanation of symbols]

1 Fuel Cell System 5 Micro Reactor (Reforming Device) 6 Main Power Generation Unit (Fuel Cell) 50 Micro Evaporator (Heating Device, Evaporating Unit) 51 Micro Reforming Reactor (Heating Device) 55 Upper Substrate (Main Body, Second Substrate) 55a recess 56 middle substrate (main body, first substrate) 57 lower substrate (main body, second substrate) 57a recess 58 thin film heater (heating means) 59 fuel supply means (supply means) 60 cavity (second internal space) 63 evaporation Chamber (first internal space) 64 Cavity (second internal space) 65 Film (mirror surface) 66 Evaporated film (mirror surface) 68 Micro channel (first internal space) 69 Upper substrate (main body, second substrate) 69a Recessed portion 70 Medium substrate (main body, first substrate) 71 Lower substrate (main body, second substrate) 71a Recessed portion 72 Cavity (second inner space) 73 Evaporated film (mirror surface) 74 Cavity (second inner space) 75 Evaporated film (mirror ) 76 thin film heater (heating means) 90 micro reforming reactor (heating device, reforming device) 91 upper substrate (main body) 92 middle substrate (main body) 93 lower substrate (main body) 94 cavity (second internal space) 95 Micro flow path (first internal space) 96 Reforming catalyst 97 Thin film heater (heating means) 98 Evaporated film (mirror surface) 151 Micro batch reactor (heating device, reforming device) 152 Upper substrate (main body, second substrate) 152a recess 153 middle substrate (main body, first substrate) 154 lower substrate (main body, second substrate) 154a recess 155 first microvalve (supplying means) 157 thin film heater (heating means) 160 vapor deposition film (mirror surface) 161 vapor deposition film ( Mirror surface 162 Cavity (second internal space) 163 Cavity (second internal space) 164 Reaction chamber (first internal space) 167 Reforming catalyst 251 Micro continuous tank reactor ( Thermal device, reformer) 253 in the substrate (body, first substrate) 255 Fuel supply unit (supply means) 264 reaction chamber (first internal space) 267 reforming catalyst

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Claims (10)

[Claims] 1. A heating device used in a reforming device for reforming a reforming raw material, wherein a main body provided with a first internal space in which the reforming raw material is present, and the first internal space are heated. A heating means, wherein a second internal space is provided in the main body in the vicinity of the first internal space. 2. The heating device according to claim 1, wherein the main body includes a first substrate provided with the first internal space and a second substrate provided with a recess, and the recess covers the first substrate. The heating device, wherein the second substrate is bonded to the first substrate in such a manner that the concave portion becomes the second internal space. 3. The heating device according to claim 2, wherein the thermal conductivity of the first substrate is higher than the thermal conductivity of the second substrate. 4. The heating device according to claim 1, wherein the second internal space is filled with a gas of a polyhalogenated derivative of methane or ethane containing fluorine, air, or carbon dioxide gas. A heating device characterized by being. 5. The heating device according to claim 1, wherein the second internal space is substantially vacuum. 6. The heating device according to any one of claims 1 to 5, wherein a mirror surface is formed on an inner surface forming the second internal space. 7. The heating device according to claim 1, further comprising a supply means for supplying a liquid reforming raw material to the first internal space, wherein the supplied reforming raw material is the heating means. A heating device, wherein the heating device evaporates in the first internal space by heating. 8. The heating device according to claim 7, and a reforming catalyst provided in the first internal space, wherein the evaporated reforming raw material is reformed in the first internal space by the reforming catalyst. A reformer characterized by producing hydrogen by qualifying. 9. The heating device according to claim 1, an evaporation portion that evaporates a liquid reforming raw material and communicates with the first internal space, and the evaporation device is provided in the first internal space. And a reforming catalyst for generating hydrogen by reforming the reforming raw material vaporized in the vaporizing section in the first internal space by the reforming catalyst. 10. A fuel cell system comprising: the reformer according to claim 8 or 9, and a fuel cell for reacting oxygen with hydrogen produced by the reformer to generate electricity.