JP2000351605A - Fuel-reforming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent a steam producing system from being frozen, and also to improve the efficiency of a fuel-reforming apparatus and to miniaturize the apparatus. SOLUTION: In this apparatus, an aqueous solution of hydrogen peroxide of 60 wt.% concentration is fed into an evaporator 30 made of a material activating the decomposition reaction of hydrogen peroxide. Hydrogen peroxide is resolved into water and oxygen within the evaporator 30 and also water in the aqueous solution is vaporized by the heat of decomposition, and consequently the evaporator 30 dispenses with an apparatus for vaporizing water. The quantity of methane fed to the evaporator 30 is made to correspond to the quantity of oxygen generated by the decomposition of the hydrogen peroxide and consequently an oxygen-containing gas need not be fed into the evaporator 30. Since the aqueous solution of hydrogen peroxide produces only water and oxygen, hydrogen concentration in an obtained fuel gas can be heightened in comparison with a gas obtained by introducing air as an oxygen- containing gas comprising a large amount of nitrogen and the like into the evaporator 30. Since the freezing point of the aqueous solution of hydrogen peroxide of 60 wt.% concentration is -55.4 deg.C, the freezing of a steam producing system can be prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel reformer, and more particularly, to a fuel reformer for reforming a hydrocarbon-based fuel into a hydrogen-rich fuel gas.

[0002]

2. Description of the Related Art Conventionally, as a fuel reformer of this type,
2. Description of the Related Art A fuel reforming apparatus that supplies methanol and water at a predetermined ratio and steam reforms methanol has been proposed (for example, JP-A-2-168802). In this device, methanol from a methanol tank and water from a water tank are mixed by a mixer so as to be mixed at a predetermined ratio, and the mixed liquid mixture is supplied to a reformer.

[0003]

However, in such a fuel reformer, since methanol and water are stored separately in tanks, the water, water-based pipes, pumps and the like in the tank are frozen in cold regions. However, there is a problem that the fuel reformer cannot be started immediately.

[0004] In response to such a problem, the applicant has proposed a fuel reforming apparatus in which methanol is mixed in a water tank and stored as an aqueous methanol solution, and this methanol aqueous solution is supplied to a reformer (Japanese Patent Application No. Hei 10-284). 6-248879
issue). In this apparatus, by storing as a methanol aqueous solution, its freezing point is lowered to prevent freezing of water, pipes, pumps and the like in the tank, thereby avoiding the adverse effects caused by freezing.

However, when methanol is used as a reforming raw material, freezing and the adverse effects caused by freezing can be avoided by the applicant's proposal, but when a hydrocarbon-based fuel other than methanol is used as the reforming raw material, The technique proposed by the applicant cannot be used, and freezing and the adverse effects caused by freezing can occur.

The purpose of the fuel reforming apparatus of the present invention is to avoid adverse effects caused by freezing of water in the tank, water-based pipes, pumps and the like even when a hydrocarbon-based fuel other than methanol is used as a reforming raw material. One. Another object of the fuel reformer of the present invention is to generate steam used for reforming in a compact configuration. Still another object of the fuel reforming apparatus of the present invention is to increase the concentration of hydrogen in the fuel gas obtained by reforming. Or,
An object of the fuel reformer of the present invention is to reform hydrocarbon-based fuel with a compact configuration. Another object of the fuel reformer of the present invention is to supply necessary steam even at the time of startup.

[0007]

Means for Solving the Problems and Their Functions and Effects The fuel reforming apparatus of the present invention employs the following means to achieve at least a part of the above objects.

A first fuel reforming apparatus of the present invention is a fuel reforming apparatus for reforming a hydrocarbon-based fuel into a hydrogen-rich fuel gas, and stores a hydrogen peroxide solution. Means, a steam generating means for receiving a supply of the aqueous hydrogen peroxide solution from the aqueous hydrogen peroxide storage means to generate steam, and reforming the hydrocarbon-based fuel into the fuel gas using the generated steam. And a reforming means.

In the first fuel reformer of the present invention, steam is generated from the aqueous hydrogen peroxide solution. The freezing point of the aqueous hydrogen peroxide solution varies depending on the concentration.
-32.8 ° C. at a concentration of -50.0 ° C. at a concentration of 50 wt% and -55.4 at a concentration of 60 wt%.
Since the temperature becomes ° C, freezing of the aqueous solution of hydrogen peroxide, piping and pumps of the aqueous solution, and adverse effects due to freezing can be avoided.

In the first fuel reforming apparatus of the present invention, a hydrogen peroxide storage means for storing hydrogen peroxide or a high-concentration aqueous hydrogen peroxide solution, and the stored hydrogen peroxide or high-concentration peroxide solution Hydrogen peroxide supply means capable of supplying a hydrogen aqueous solution to the hydrogen peroxide aqueous solution storage means may be provided. In this case, an aqueous solution of hydrogen peroxide having an arbitrary concentration can be obtained. In the first fuel reforming apparatus of this aspect of the present invention, the temperature of the outside air of the hydrogen peroxide solution storage means and / or the temperature of the hydrogen peroxide solution stored in the hydrogen peroxide solution storage means is detected. Temperature detection means, and supply amount control means for controlling the supply amount of hydrogen peroxide or a high-concentration aqueous hydrogen peroxide solution to the aqueous hydrogen peroxide solution storage means by the hydrogen peroxide supply means based on the detected temperature May be provided. In this case, the concentration of the aqueous hydrogen peroxide solution can be adjusted based on the temperature of the outside air and the temperature of the aqueous hydrogen peroxide solution. In this embodiment, the concentration of the aqueous hydrogen peroxide solution stored by the aqueous hydrogen peroxide solution storage means may be any concentration, and may be water containing no hydrogen peroxide at all. Further, in the first fuel reforming apparatus according to the aspect of the present invention, the supply amount control means may be configured such that the lower the temperature detected by the temperature detection means is, the more the peroxide stored in the hydrogen peroxide aqueous solution storage means is. Means may be a means for controlling the supply amount of hydrogen peroxide or a high-concentration hydrogen peroxide aqueous solution to the hydrogen peroxide aqueous solution storage means by the hydrogen peroxide supply means so that the concentration of the hydrogen aqueous solution becomes high. . In this case, freezing of the aqueous hydrogen peroxide solution can be avoided more reliably.

Further, in the first fuel reformer of the present invention, the steam generating means may be a means for decomposing hydrogen peroxide in a hydrogen peroxide aqueous solution.
Since hydrogen peroxide is decomposed into water and oxygen, water and oxygen obtained by the decomposition can be used for reforming hydrocarbon fuel. In the first fuel reforming apparatus according to the aspect of the present invention, the steam generating means is means for generating steam from water generated by the decomposition of the hydrogen peroxide and / or water in the aqueous hydrogen peroxide solution. It can also be.

[0012] In the first fuel reforming apparatus of the present invention in which hydrogen peroxide is decomposed by the steam generating means, the steam generating means generates water by using heat generated by the decomposition of the hydrogen peroxide. It may be a means for vaporizing. In this case, the heat of decomposition can be effectively used, and the energy efficiency can be improved.

[0013] In the first fuel reforming apparatus of the present invention, wherein the hydrogen peroxide is decomposed by the steam generating means, the reforming means uses the oxygen generated by the decomposition of the hydrogen peroxide to produce the hydrocarbon. It may be a means for reforming the system fuel into the fuel gas. In this case, at least a part of the oxygen necessary for reforming the hydrocarbon fuel can be provided. In the first fuel reforming apparatus according to the aspect of the present invention, the reforming unit receives supply of the generated steam and oxygen generated by decomposition of the hydrogen peroxide from the steam generation unit, and supplies the oxygen. It may be a means for receiving the supply of the hydrocarbon-based fuel according to the supply amount and reforming the hydrocarbon-based fuel into the fuel gas. In this case, all of the oxygen necessary for reforming the hydrocarbon fuel can be covered by the oxygen generated by the decomposition of hydrogen peroxide. Therefore, it is not necessary to provide a means for supplying an oxygen-containing gas containing oxygen, for example, air to the reformer. When air is used as the oxygen-containing gas, for example, the fuel gas contains nitrogen in the air, and the hydrogen concentration in the fuel gas decreases by the amount of nitrogen introduced. Since only water vapor and oxygen are generated from the aqueous solution, the hydrogen concentration in the fuel gas can be increased as compared with the case where another oxygen-containing gas is supplied.

[0014] In the first fuel reforming apparatus of the present invention, the hydrogen peroxide solution storage means may be a means for storing a hydrogen peroxide solution adjusted to a concentration of about 60 wt%. In this case, the freezing point of the aqueous hydrogen peroxide solution can be set to −50.0 ° C. This 60w
The molar ratio of water to hydrogen peroxide in the t% aqueous hydrogen peroxide solution is 54:44. At this molar ratio, all of the water generated by the decomposition of hydrogen peroxide and the water in the aqueous hydrogen peroxide solution can be vaporized by the heat of decomposition of hydrogen peroxide.
There is no need to externally apply the heat required to generate steam, and there is no need to provide equipment for applying heat to the steam generating means. As a result, the device can be made simple and compact.

A second fuel reforming apparatus according to the present invention is a fuel reforming apparatus for reforming a hydrocarbon-based fuel into a hydrogen-rich fuel gas, and stores a hydrogen peroxide solution. Means for supplying hydrogen peroxide solution from the hydrogen peroxide aqueous solution storage means to decompose hydrogen peroxide in the hydrogen peroxide aqueous solution, and use heat generated by the decomposition to generate hydrogen peroxide in the aqueous hydrogen peroxide solution. Steam generating means for evaporating water of the above and water generated by the decomposition to produce steam, supplying steam supplied from the steam generating means and oxygen generated by decomposition of the hydrogen peroxide, and supplying the oxygen The fuel supply system further comprises a reforming unit that receives the supply of the hydrocarbon-based fuel according to the amount and reforms the hydrocarbon-based fuel into the fuel gas.

In the second fuel reforming apparatus of the present invention, since an aqueous hydrogen peroxide solution is used for generating steam, freezing of water, pipes, pumps, and the like in the tank in the steam generating system, and the freezing of these components are caused. Evil effects can be prevented. In addition, since water is vaporized using heat generated by the decomposition of hydrogen peroxide, the heat of decomposition can be used effectively,
Energy efficiency can be improved. Furthermore, since reforming is performed by supplying a hydrocarbon fuel in accordance with the supply amount of oxygen generated by the decomposition of hydrogen peroxide, all of the oxygen necessary for reforming the hydrocarbon fuel is replaced with hydrogen peroxide. Can be covered by the oxygen generated by the decomposition of Therefore,
There is no need to provide a means for supplying an oxygen-containing gas containing oxygen to the reformer, and the apparatus can be made simple and compact. Since the oxygen-containing gas is not used, the hydrogen concentration in the fuel gas can be increased.

In the second fuel reforming apparatus according to the present invention, the hydrogen peroxide aqueous solution storage means may include about 60 wt%
And a means for storing an aqueous solution of hydrogen peroxide adjusted to a concentration of 1.The steam generating means may be means for evaporating water using only heat generated by the decomposition of the hydrogen peroxide. it can. In this case, the molar ratio of water to hydrogen peroxide in the aqueous hydrogen peroxide solution can be set to 54:44. At this molar ratio, the heat generated by the decomposition of hydrogen peroxide vaporizes all of the water generated by the decomposition of hydrogen peroxide and the water in the aqueous hydrogen peroxide solution, so it is necessary to externally apply the heat necessary to generate water vapor. Therefore, there is no need to provide a device for applying heat to the steam generating means. As a result, the device can be made simple and compact.

A third fuel reforming apparatus of the present invention is a fuel reforming apparatus for reforming a hydrocarbon-based fuel into a hydrogen-rich fuel gas, and receives a supply of water or an aqueous solution of another substance. Steam generating means for generating the steam, reforming means for reforming the hydrocarbon-based fuel into the fuel gas using the generated steam, and peroxide for storing hydrogen peroxide or an aqueous solution of hydrogen peroxide Hydrogen storage means, hydrogen peroxide supply means capable of supplying the stored hydrogen peroxide or aqueous hydrogen peroxide solution to the steam generation means, and steam supply for detecting a supply state of steam supplied to the reforming means The gist of the present invention includes a state detection unit and a hydrogen peroxide supply control unit that controls the hydrogen peroxide supply unit based on the detected supply state of steam.

In the third fuel reforming apparatus according to the present invention, hydrogen peroxide or an aqueous solution of hydrogen peroxide can be supplied to the steam generating means based on the supply state of the steam supplied to the reforming means. The hydrogen peroxide supplied to the steam generating means is decomposed into water and oxygen, and the water generated by the decomposition is used to vaporize the water, so that the generation of steam in the steam generating means can be promoted. Therefore, by adjusting the supply of hydrogen peroxide or an aqueous solution of hydrogen peroxide,
The generation of steam, that is, the amount of steam supplied to the reforming means can be adjusted.

[0020] In the third fuel reforming apparatus of the present invention, the hydrogen peroxide supply control means may determine whether the supply of steam to the reforming section is insufficient by the steam supply state detection means. The hydrogen peroxide supply means may be a means for controlling the hydrogen peroxide supply means so that an aqueous solution of hydrogen or hydrogen peroxide is supplied to the steam generation means.
With this configuration, when the supply amount of steam to the reforming unit is insufficient, for example, even when starting the fuel reformer, the supply amount of steam to the reforming unit can be increased to perform more appropriate operation. Can be.

[0021] In any one of the first to third fuel reformers of the present invention including various aspects, the steam generating means has at least a part formed of a material active in a decomposition reaction of hydrogen peroxide. It can also be. In the fuel reforming apparatus according to any one of the first to third aspects of the present invention, the steam generating means includes copper or an alloy of copper, ordinary steel, titanium, a noble metal as a material active in the decomposition reaction of the hydrogen peroxide. At least a part of the inside may be formed of heavy metal such as.

[0022]

Next, embodiments of the present invention will be described with reference to examples. FIG. 1 is a configuration diagram schematically showing the configuration of a fuel reforming apparatus 20 according to one embodiment of the present invention. As shown in the figure, the fuel reformer 20 of the embodiment includes an evaporator 30 that receives supply of methane and an aqueous hydrogen peroxide solution, heats them to a predetermined temperature, and generates water vapor. A reforming section 32 for reforming heated methane to a hydrogen-rich reformed gas using steam, and oxidizing carbon monoxide in the reformed gas in preference to hydrogen to have an extremely low carbon monoxide concentration CO selective oxidizing unit 36 as fuel gas
And an electronic control unit 40 for controlling the entire apparatus.
And

The evaporating section 30 is formed at least partially of a material that is active against the decomposition reaction of hydrogen peroxide, for example, heavy metals such as copper and copper alloys, ordinary steel, titanium, and noble metals. Methane tank 22 for storing methane and hydrogen peroxide solution as hydrogen-based fuel
Further, the water is supplied from a hydrogen peroxide aqueous solution tank 24 by a methane supply pump 23 and an aqueous solution supply pump 25. In the embodiment, the entire inside is made of titanium.

The aqueous hydrogen peroxide solution stored in the aqueous hydrogen peroxide solution tank 24 is adjusted to a concentration of about 60 wt% and a molar ratio of water to hydrogen peroxide of 54:44. Since the freezing point of this 60 wt% aqueous hydrogen peroxide solution is -55.4 ° C., even if the fuel reformer 20 is used in cold and cold regions, the hydrogen peroxide is maintained until the outside air reaches a temperature below this freezing point. Aqueous solution tank 24 and aqueous solution supply pump 25
Do not freeze.

The hydrogen peroxide in the aqueous hydrogen peroxide solution is decomposed into water and oxygen by a decomposition reaction represented by the following equation (1) inside the evaporating section 30. On the other hand, the heat of evaporation of water is 44 kJ / mol as shown in the following equation (2).

H ₂ O ₂ (liq.) → H ₂ O (gas.) + (１ ／) O ₂ +54.3 kJ (1) H ₂ O (liq.) → H ₂ O (gas.)-44 kJ (2)

Here, paying attention to the reaction heat of the equations (1) and (2) and considering the heat balance, the molar ratio of water and hydrogen peroxide supplied to the evaporator 30 is 54:44. If adjusted so that all the water can be evaporated by the heat of decomposition of hydrogen peroxide. That is, in the embodiment, the aqueous hydrogen peroxide solution prepared so that the molar ratio of water to hydrogen peroxide is 54:44 is stored in the aqueous hydrogen peroxide tank 24 and supplied to the evaporating section 30. By
Decomposes hydrogen peroxide in the supplied hydrogen peroxide aqueous solution,
Water in the aqueous hydrogen peroxide solution is vaporized by the heat generated by the decomposition. As a result, the evaporator 3 of the embodiment
At 0, steam can be obtained without external heat supply. In the embodiment, the hydrogen peroxide solution is supplied so as to be sprayed into the evaporating unit 30 so that the hydrogen peroxide in the hydrogen peroxide solution is easily decomposed.

The reforming section 32 receives the mixed gas of methane, steam and oxygen from the evaporating section 30 and reforms methane by the reaction of the following formulas (3) to (5) to reform the methane. Get. Although not shown, the reforming unit 32 converts the reforming reaction of Formulas (3) and (4) and a part of carbon monoxide into Formula (5)
And a shift reaction unit which is arranged at the subsequent stage and mainly performs the shift reaction of the formula (5). The reason why the reforming section 32 is configured in two stages is to prevent oxygen from reacting with the generated hydrogen and to make the shift reaction of the equation (5) a reaction of the equations (3) and (4). This is because the reaction rate is lower than that of the reforming reaction. The reforming reaction section is filled with a reforming catalyst such as a noble metal catalyst such as a nickel catalyst or platinum or ruthenium rhodium palladium, and the shift reaction section is, for example, a copper or copper-zinc catalyst or an iron-chromium catalyst. Is filled.

CH ₄ + (１ ／) O ₂ → 2H ₂ + CO + 35.7 kJ (3) CH ₄ + H ₂ O → 3H ₂ + CO−206.2 kJ (4) CO + H ₂ O → H ₂ + CO ₂ +41.2 kJ ( 5)

In the embodiment, the supply of methane from the methane tank 22 to the evaporator 30 is adjusted so that the molar ratio of oxygen to methane is 1: 2. Thus, the molar ratio of methane to water vapor is about 1: 1. In order to make the reactions of the formulas (3) to (5) efficient under these conditions, that is, to shift the chemical equilibrium to the right, in the reforming section 32 of the embodiment, the temperature of the reforming reaction section is increased. About 800 ° C,
The temperature of the shift reaction section is adjusted to 300 ° C. for baking. The hydrogen peroxide solution and methane evaporator 30
The control of the supply amount to the heater and the temperature control of the reforming section 32 are performed by an electronic control unit 40.

The CO selective oxidizing section 36 is filled with a selective oxidizing catalyst for oxidizing carbon monoxide in the reformed gas in preference to hydrogen, for example, a noble metal catalyst such as platinum, ruthenium, rhodium and palladium. The temperature is adjusted to about 150 ° C. so that this reaction can be performed well. An oxygen-containing gas (air in the embodiment) containing oxygen for oxidizing carbon monoxide is introduced by a blower 34 into a supply pipe for supplying a reformed gas to the CO selective oxidizing unit 36. The electronic control unit 40 also controls the temperature of the CO selective oxidizing unit 36 and the drive control of the blower 34.

The electronic control unit 40 is constructed as a one-chip microprocessor composed mainly of a CPU 42, and has a ROM 4 storing a processing program.
4, a RAM 46 for temporarily storing data, and an input / output port (not shown). The electronic control unit 40 has an input port for the temperature of each section from a reforming reaction section and a shift reaction section of the evaporating section 30 and the reforming section 32, a temperature sensor (not shown) attached to the CO selective oxidizing section 36, and the like. Have been entered through. Further, a drive signal to the methane supply pump 23 and the aqueous solution supply pump 25, a drive signal to the blower 34, and the like are output from the electronic control unit 40 through output ports.

As described above, the fuel reformer 20 of the embodiment is controlled by the electronic control unit 40 so that the methane stored in the methane tank 22 is adjusted to a concentration of about 60 wt% and the hydrogen peroxide solution tank 24 The stored aqueous hydrogen peroxide solution is supplied to the evaporator 30 so that the molar ratio of oxygen peroxide to methane in the aqueous hydrogen peroxide solution is 1: 1. Hydrogen is decomposed and water is vaporized by the heat generated by this decomposition. In the reforming section 32, the mixed gas supplied from the evaporating section 30 is slightly carbon monoxide by the reaction of the above-mentioned equations (3) to (5). And the CO selective oxidation unit 36 reduces carbon monoxide in the reformed gas to obtain a fuel gas as a final product.

According to the fuel reforming apparatus 20 of the embodiment described above, an aqueous solution of hydrogen peroxide having a concentration of about 60 wt% is stored, and steam necessary for the reforming reaction is generated from the aqueous solution of hydrogen peroxide. It is possible to prevent the water vapor generation system such as the aqueous hydrogen peroxide solution tank 24 and the aqueous solution supply pump 25 from being frozen and the problems caused by the freezing, such as the deterioration of the startability and the damage of the device. Further, according to the fuel reforming apparatus 20 of the embodiment, the concentration of the aqueous hydrogen peroxide solution is set to about 60 wt%, and the hydrogen peroxide is decomposed in the evaporator 30, so that only the heat generated by the decomposition of the hydrogen peroxide is obtained. Can vaporize all the water. As a result, there is no need to apply heat for evaporating water to the evaporator 30.

According to the fuel reformer 20 of the embodiment, methane is supplied to the evaporator 30 according to the amount of oxygen generated by the decomposition of the hydrogen peroxide supplied to the evaporator 30. The oxygen required for the reaction (3) can be entirely covered by the amount of oxygen resulting from the decomposition of hydrogen peroxide. As a result, there is no need to provide a device for introducing an oxygen-containing gas (for example, air) containing oxygen into the evaporating unit 30 or the reforming unit 32 for the reaction of the formula (3). It can be. In addition, hydrogen peroxide produces only water and oxygen by decomposition, and this oxygen is used in the reaction of the formula (3). The hydrogen concentration can be increased. That is, if air is used as another oxygen-containing gas,
Nitrogen in the air will be included in the resulting fuel gas, and this nitrogen will reduce the hydrogen concentration in the fuel gas,
In an embodiment using only oxygen from the decomposition of hydrogen peroxide,
Since nitrogen other than that introduced by the blower 34 is not contained, the hydrogen concentration in the fuel gas can be increased.

In the fuel reformer 20 of the embodiment, a hydrogen peroxide aqueous solution having a concentration of about 60% is stored in the hydrogen peroxide aqueous solution tank 24 and supplied to the evaporating section 30. For example, a hydrogen peroxide solution having a concentration of 35 wt% or 50 wt% or any other concentration may be stored and supplied to the evaporating section 30. The freezing point of the aqueous hydrogen peroxide solution is −32.8 ° C. when the concentration is 35 wt%, and −5 when the concentration is 50 wt%.
0.0 ° C. Therefore, from the viewpoint of preventing freezing, an aqueous hydrogen peroxide solution having a concentration that does not freeze in relation to the outside air may be used in consideration of the area. In this case, since all the water cannot be vaporized only by the heat generated by the decomposition of hydrogen peroxide in the evaporating section 30, the evaporating section 30
It is necessary to provide a heating device for evaporating water.
However, the heating device may be any device that can supply heat that is insufficient by the heat generated by the decomposition of hydrogen peroxide, and therefore has a smaller capacity than when water is supplied to the evaporator 30. be able to. Therefore, 60 wt%
Even in a device that stores an aqueous solution of hydrogen peroxide having a lower concentration and supplies the same to the evaporating unit 30, the entire device can be downsized as compared with a device that stores water and supplies water to the evaporating unit.

Even when an aqueous solution of hydrogen peroxide having a concentration other than 60 wt% is used, if methane is supplied to the evaporating section 30 in accordance with the amount of oxygen generated by the decomposition of hydrogen peroxide, the reaction represented by the formula (3) Can be supplied by oxygen generated by decomposition of hydrogen peroxide. For example, 3
If a 5 wt% aqueous solution of hydrogen peroxide is used and the molar ratio of oxygen to methane is 1: 2, the ratio of steam to methane will be 2.3: 1, and the chemical equilibrium for shifting the chemical equilibrium to the right. The temperature of the reforming reaction section of the reforming section 32 is about 700 ° C. Also, if a 50 wt% aqueous solution of hydrogen peroxide is used and the molar ratio of oxygen to methane is 1: 2, the ratio of water vapor to methane is 1.4: 1, and the chemical equilibrium is shifted to the right. The temperature of the reforming reaction section of the reforming section 32 for shifting is about 750.
° C. As a result, the effect of supplying oxygen required for the reaction of the formula (3) with oxygen generated by the decomposition of hydrogen peroxide, that is, there is no need to provide a device for supplying an oxygen-containing gas, and the device can be downsized. An effect can also be achieved.

In the fuel reformer 20 of the embodiment, the methane corresponding to the amount of oxygen generated by the decomposition of hydrogen peroxide is evaporated.
However, the oxygen-containing gas is supplied to the evaporating section 30.
The apparatus may be provided with a device for supplying oxygen to the fuel cell to compensate for insufficient oxygen due to decomposition of hydrogen peroxide. This way,
The molar ratio between the amount of water vapor and methane can be freely designed.

Next, a fuel reformer 20B according to a second embodiment of the present invention will be described. FIG. 2 is a configuration diagram schematically showing the configuration of the fuel reforming apparatus 20B of the second embodiment. The configuration of the fuel reforming apparatus 20B of the second embodiment is, as shown in the drawing, provided with a blower 21B for supplying air as an oxygen-containing gas to the evaporating section 30B, and a water tank 24B instead of the hydrogen peroxide aqueous solution tank 24. , A hydrogen peroxide tank 28B that stores hydrogen peroxide capable of supplying hydrogen peroxide to the water tank 24B, a point that the evaporator 30B includes a combustor 31B, and an outside air temperature sensor that detects the temperature of outside air. It has the same configuration as the configuration of the fuel reforming apparatus 20 of the first embodiment except that the fuel reforming apparatus 50 is provided. Therefore, the first of the configurations of the fuel reformer 20B of the second embodiment
The same components as those of the fuel reforming apparatus 20 of the embodiment are denoted by the same reference numerals, and description thereof will be omitted.

In the fuel reformer 20B of the second embodiment, water stored in a water tank 24B is supplied to an evaporator 30B by a water supply pump 25B. Also,
A temperature sensor 26 for detecting the temperature of the internal water is attached to the water tank 24B. Further, the fuel reforming apparatus 20B of the second embodiment includes a hydrogen peroxide tank 28B for storing hydrogen peroxide, and the hydrogen peroxide can be supplied to the water tank 24B by a hydrogen peroxide supply pump 29B. . The water supply pump 25 </ b> B and the hydrogen peroxide supply pump 29 </ b> B are connected to the electronic control unit 40 by a signal line, and are controlled by the electronic control unit 40.

The evaporator 30B includes a combustor 31B for supplying heat necessary to burn a part of the supplied methane and vaporize water. The operation of the combustor 31B is controlled by the electronic control unit 40 based on the supply amount of water, the temperature of the evaporator 30B, and the like.

In the fuel reformer 20B of the second embodiment, the supply amounts of methane, water, and air to the evaporator 30B are, for example, a molar ratio of oxygen to methane of 1: 2 and a molar ratio of methane to water. Is controlled to be 1: 2 by the electronic control unit 40 for the blower 21B, the methane supply pump 23, and the water supply pump 25B.

Next, the operation of the fuel reforming apparatus 20B according to the second embodiment, particularly the operation relating to the prevention of freezing, will be described. FIG. 3 shows a fuel reformer 20 according to the second embodiment.
FIG. 4 is a flowchart showing an example of a freeze prevention processing routine during stop processing executed by the electronic control unit 40 when the operation of B is stopped. FIG. 4 shows a state in which the operation of the fuel reforming apparatus 20B of the second embodiment is stopped. 9 is a flowchart showing an example of a stop-time anti-freezing process routine repeatedly executed by the electronic control unit 40 at predetermined time intervals (for example, every 10 minutes). First, the freeze prevention process during stop processing illustrated in FIG. 3 will be described, and then the freeze prevention process during stop illustrated in FIG. 4 will be described.

As described above, the freeze prevention processing routine during stop processing of FIG. 3 is performed by the fuel reforming apparatus 20B of the second embodiment.
Is executed when the operation of the electronic control unit 40 is stopped.
42, first reads the outside air temperature To detected by the outside air temperature sensor 50 (step S100), and executes a process of comparing the read outside air temperature To with the threshold Tr1 (step S102). Here, the threshold Tr1 is provided to prevent freezing of water, and its freezing point, that is, 0
It is set to a temperature slightly higher than ° C.

When the outside temperature To is equal to or higher than the threshold Tr1,
It is determined that freezing of the water tank 24B, the water supply pump 25B, and the like does not occur, the value 0 is set to the anti-freezing processing flag F (step S104), and this routine ends. The anti-freezing processing flag F is a flag having as a value whether or not anti-freezing processing has been performed. Since the anti-freezing processing has not been performed in step S104, a value of 0 is set to that effect. On the other hand, when the outside air temperature To is less than the threshold value Tr1, it is determined that the anti-freezing process is necessary, and the amount of hydrogen peroxide Q is set based on the outside air temperature To (step S
106), the set amount Q of hydrogen peroxide is set in the water tank 2
4B (step S108), the value 1 is set to the anti-freezing processing flag F (step S110), and this routine ends. When the hydrogen peroxide is charged into the water tank 24B, the aqueous hydrogen peroxide solution is stored in the aqueous hydrogen peroxide tank 24, and the freezing point of the hydrogen peroxide solution is increased as described in the fuel reformer 20 of the first embodiment. , The freezing can be prevented. In the embodiment, the input amount Q of hydrogen peroxide is set based on the outside air temperature To. However, the setting may be such that the input amount Q is increased as the outside air temperature To becomes lower. May be set. Further, the input amount Q may be set based on the amount of water stored in the water tank 24B.

When the hydrogen peroxide is charged into the water tank 24B as described above, when the fuel reformer 20B of the second embodiment is started next, the aqueous hydrogen peroxide solution is supplied to the evaporator 30B. In other words, as described in the fuel reformer 20 of the first embodiment, by forming the inside of the evaporating section 30B with a material such as titanium which is active against the decomposition reaction of hydrogen peroxide, Hydrogen can be decomposed to generate steam well, and methane can be reformed well. Since the decomposition of hydrogen peroxide, the generation of water vapor thereby, and the heat balance thereof have been described above, the description is omitted here.

Next, the stop-time freezing prevention process of FIG. 4 executed while the operation of the fuel reformer 20B of the second embodiment is stopped will be described. When the stop-time anti-freezing processing routine of FIG. 4 is executed, the CPU 4 of the electronic control unit 40
2. First, the anti-freezing processing flag F is read (step S200), and a process of determining the value is executed (step S202). When the anti-freezing processing flag F has the value 1, it is determined that the anti-freezing processing has already been performed, and this routine ends.

On the other hand, when the anti-freezing flag F is 0, the water temperature Tw of the water tank 24B is read (step S204), and the read water temperature Tw is compared with a threshold value Tr2 (step S206). Here, the threshold Tr2 is for determining the possibility of freezing of water in the water tank 24B, and is set to a freezing point of water, that is, 0 ° C. or a temperature slightly higher than this. When the water temperature Tw is equal to or higher than the threshold Tr2, it is determined that the anti-freezing processing is not required, and this routine is terminated. When the water temperature Tw is lower than the threshold Tr2, it is determined that the anti-freezing processing is required, and the amount of hydrogen peroxide is determined. A predetermined value Qset is set to Q (step S208), hydrogen peroxide having the set input amount Q is input to the water tank 24B (step S210), and a value 1 is set to the anti-freezing flag F (step S212). ), End this routine. In the embodiment, the input amount Q of hydrogen peroxide is set to a predetermined value Qse
Although set to t, it may be set based on the amount of water stored in the water tank 24B.

The fuel reformer 2 of the second embodiment described above
According to 0B, hydrogen peroxide is charged into the water tank 24B as needed, so that the water tank 24B and the water supply pump 25
It is possible to prevent freezing of water systems such as B and the adverse effects caused by freezing. In addition, since hydrogen peroxide is supplied based on the outside air temperature To and the water temperature Tw of the water tank 24B, freezing can be prevented more reliably.

In the fuel reforming apparatus 20B of the second embodiment, water is stored in the water tank 24B and supplied to the evaporating section 30B. However, an aqueous hydrogen peroxide solution is stored in the water tank 24B. May be supplied to the evaporator.
In this case, the temperature at which the aqueous solution of hydrogen peroxide having a predetermined concentration freezes or a temperature slightly higher than the threshold is set to the threshold Tr1 or the threshold T.
r2, and the necessity of the freeze prevention process may be determined using the thresholds Tr1 and Tr2.

In the fuel reformer 20B of the second embodiment, while the operation is stopped, the water temperature Tw of the water tank 24B is maintained.
The need for anti-freezing treatment was determined by the
It may be determined by the following.

In the fuel reforming apparatus 20B of the second embodiment, the input amount of hydrogen peroxide is set based on the outside air temperature To. However, when the aqueous hydrogen peroxide solution is stored in the water tank 24B, When water is turned into an aqueous hydrogen peroxide solution by adding hydrogen peroxide, the concentration of hydrogen peroxide in the aqueous hydrogen peroxide solution is detected, and the concentration may be set based on this concentration and the outside air temperature To. Good. This makes it possible to more reliably prevent freezing and prevent excessive injection of hydrogen peroxide.

In the fuel reforming apparatus 20B of the second embodiment, hydrogen peroxide is stored and charged into the water tank 24B. However, a high-concentration aqueous hydrogen peroxide solution is stored in the water tank 24B. 24B.

Next, a description will be given of a fuel reformer 20C according to a third embodiment of the present invention. FIG. 5 is a configuration diagram schematically illustrating a configuration of a fuel reforming apparatus 20C of the third embodiment. The configuration of the fuel reforming apparatus 20C of the third embodiment is, as shown, provided with a blower 21C for supplying air as an oxygen-containing gas to the evaporating section 30C, and a water tank 24C instead of the hydrogen peroxide aqueous solution tank 24. Evaporating unit 3
The configuration is the same as that of the fuel reformer 20 of the first embodiment except that a hydrogen peroxide tank 28C that stores hydrogen peroxide capable of supplying hydrogen peroxide to 0C is provided. Therefore, among the configurations of the fuel reforming apparatus 20C of the third embodiment, the same components as those of the fuel reforming apparatus 20 of the first embodiment are denoted by the same reference numerals, and description thereof will be omitted.

In the fuel reformer 20C of the third embodiment, the water stored in the water tank 24C is supplied to the evaporator 30C by the water supply pump 25C.
The hydrogen peroxide stored in the hydrogen peroxide tank 28C is supplied to the evaporator 30C by a hydrogen peroxide supply pump 29C. The water supply pump 25C and the hydrogen peroxide supply pump 29C are connected to the electronic control unit 40 by a signal line, and are driven and controlled by the electronic control unit 40.

The evaporator 30C includes a combustor 31C for supplying a heat necessary to burn a part of the supplied methane and vaporize water. The operation of the combustor 31C is controlled by the electronic control unit 40 based on the water supply amount, the temperature of the evaporator 30C, and the like, as in the second embodiment.

In the fuel reforming apparatus 20C of the third embodiment, similarly to the fuel reforming apparatus 20B of the second embodiment, the evaporating section 30C
The supply amounts of methane, water, and air to the blower 21C, the methane supply pump 23, and the water are set so that, for example, the molar ratio of oxygen to methane is 1: 2 and the molar ratio of methane to water is 1: 2. The drive of the supply pump 25C is controlled by the electronic control unit 40.

Next, the operation of the fuel reforming apparatus 20C according to the third embodiment configured as described above, particularly when the steam generated in the evaporating section 30C runs short, such as when starting the fuel reforming apparatus 20C. Will be described. FIG. 6 is a flowchart illustrating an example of a hydrogen peroxide input processing routine executed by the electronic control unit 40 of the fuel reforming apparatus 20C of the third embodiment. This routine is executed at predetermined time intervals (for example, one time) from the start of the fuel reformer 20C of the third embodiment.
(Every minute).

When the hydrogen peroxide input processing routine is executed, the CPU 42 of the electronic control unit 40 firstly determines the state of the evaporator 30C and the reformer 32, for example, the operating temperature of the evaporator 30C and the reforming of the reformer 32. The temperature of the quality reaction section and the shift reaction section, the amount of steam supply from the evaporating section 30C to the reforming section 32, and the like are read (step S300), and it is determined whether the apparatus is in a steady operation state (step S302). In the steady operation state, if hydrogen peroxide has been charged, the charging is stopped (step S304), and this routine ends. On the other hand, when the apparatus is not in the steady operation state, it is determined whether the steam supplied to the reforming section 32 is insufficient (step S306). This determination is made by the reforming unit 3
2 is performed based on the flow rate of the mixed gas supplied to the fuel cell 2 and the temperature of the evaporating section 30C. For example, when the evaporating unit 30C is not at the steady operation temperature, it can be determined that there is a possibility of insufficient supply of steam. When the flow rate of the mixed gas supplied to the reforming unit 32 is less than the steady flow rate, it is possible to determine that It can be determined that the supply is insufficient.

When it is determined that the supply of water vapor is insufficient,
The injection of hydrogen peroxide is executed (step S308), and this routine is terminated. When it is determined that the supply of steam is sufficient, this routine is terminated without doing anything. The charging of the hydrogen peroxide into the evaporating unit 30C is performed by decomposing the hydrogen peroxide in the evaporating unit 30C to generate water vapor, and also vaporizes the water that has been supplied by the decomposition heat but has not been vaporized. Can be increased. It should be noted that the amount of hydrogen peroxide to be charged may be a predetermined amount, or may be set based on the shortage of water vapor supply obtained.

The fuel reformer 2 of the third embodiment described above
According to 0C, when the supply amount of steam to the reforming unit 32 is temporarily insufficient, hydrogen peroxide is supplied to the evaporating unit 30C, thereby making it possible to eliminate the insufficient supply of steam. As a result, the device can be quickly brought into a steady operation state, and a decrease in the methane reforming rate due to a shortage of steam supply can be prevented.

In the fuel reformer 20C of the third embodiment, water is stored and supplied to the evaporator 30C.
The hydrogen peroxide water container may be stored, and the aqueous hydrogen peroxide solution may be supplied to the evaporating unit 30C. In this case, about 60
If an aqueous solution of hydrogen peroxide having a concentration of wt% is supplied, the evaporator 30C does not need to include the combustor 31C.
Further, if methane is supplied in accordance with the amount of oxygen generated by the decomposition of hydrogen peroxide, it is not necessary to introduce air into the evaporating section 30C, so that the blower 21 can be omitted.

In the fuel reforming apparatus 20C of the third embodiment, hydrogen peroxide is stored and supplied to the evaporating section 30C. However, a high-concentration aqueous hydrogen peroxide solution is stored and this is evaporated. It is good also as what is thrown into 30C.

The fuel reformer 2 of the first to third embodiments
In 0, 20B, and 20C, methane was used as a hydrocarbon fuel, but other hydrocarbon fuels, such as saturated hydrocarbons such as ethane, unsaturated hydrocarbons such as ethylene and acetylene, and alcohols such as methanol It is also possible to use such as.

The embodiments of the present invention have been described with reference to the embodiments. However, the present invention is not limited to these embodiments, and various embodiments may be made without departing from the scope of the present invention. Of course, it can be carried out.

[Brief description of the drawings]

FIG. 1 is a configuration diagram schematically showing the configuration of a fuel reforming apparatus 20 according to one embodiment of the present invention.

FIG. 2 is a configuration diagram schematically illustrating a configuration of a fuel reforming apparatus 20B according to a second embodiment.

FIG. 3 is a flowchart illustrating an example of a stop prevention freeze prevention routine executed by an electronic control unit 40 when the operation of the fuel reformer 20B of the second embodiment is stopped.

FIG. 4 is a flowchart of a stop-time anti-freezing routine that is repeatedly executed by the electronic control unit 40 at predetermined time intervals (eg, every 10 minutes) while the operation of the fuel reformer 20B of the second embodiment is stopped. It is a flowchart which shows an example.

FIG. 5 is a configuration diagram schematically illustrating a configuration of a fuel reforming apparatus 20C according to a third embodiment.

FIG. 6 is a flowchart illustrating an example of a hydrogen peroxide input processing routine executed by an electronic control unit 40 of a fuel reforming apparatus 20C according to a third embodiment.

[Explanation of symbols]

20, 20B, 20C Fuel reformer, 21B, 21C
Blower, 22 methane tank, 23 methane supply pump, 24 hydrogen peroxide aqueous solution tank, 24B, 24C
Water tank, 25 aqueous solution supply pump, 25B, 25C
Water supply pump, 26 temperature sensor, 28B, 28C hydrogen peroxide tank, 29B, 29C Hydrogen peroxide supply pump, 30, 30B, 30C Evaporator, 31B, 31C
Combustor, 32 reforming unit, 34 blower, 36 CO selective oxidation unit, 40 electronic control unit, 42 CPU, 44
ROM, 46 RAM, 50 outside temperature sensor.

Claims (16)

[Claims] 1. A fuel reformer for reforming a hydrocarbon-based fuel into a hydrogen-rich fuel gas, comprising: a hydrogen peroxide solution storage means for storing a hydrogen peroxide solution; and a hydrogen peroxide solution storage means. And a reforming means for reforming the hydrocarbon-based fuel into the fuel gas by using the generated steam. Quality equipment. 2. The fuel reforming apparatus according to claim 1, wherein the hydrogen peroxide or high-concentration hydrogen peroxide aqueous solution is stored, and the stored hydrogen peroxide or high-concentration hydrogen peroxide is stored. A fuel reformer comprising: a hydrogen peroxide supply unit capable of supplying an aqueous hydrogen peroxide solution to the hydrogen peroxide aqueous solution storage unit. 3. The fuel reformer according to claim 2, wherein the temperature of the outside air of the hydrogen peroxide solution storage means and / or the temperature of the hydrogen peroxide solution stored in the hydrogen peroxide solution storage means. Temperature detecting means for detecting the temperature, and supplying the hydrogen peroxide supplying means for controlling the supply amount of the hydrogen peroxide or high-concentration aqueous hydrogen peroxide solution to the aqueous hydrogen peroxide solution storing means based on the detected temperature. A fuel reformer comprising: a quantity control unit. 4. The supply amount control means is configured to increase the concentration of the aqueous hydrogen peroxide solution stored by the aqueous hydrogen peroxide storage means as the temperature detected by the temperature detection means decreases. 4. The fuel reformer according to claim 3, wherein the amount of the hydrogen peroxide or the high-concentration aqueous hydrogen peroxide solution supplied by the supply means to the hydrogen peroxide solution storage means is controlled. 5. The fuel reformer according to claim 1, wherein said steam generating means is means for decomposing hydrogen peroxide in an aqueous hydrogen peroxide solution. 6. The fuel reformer according to claim 5, wherein said steam generating means is means for generating steam from water generated by decomposition of said hydrogen peroxide and / or water in said aqueous hydrogen peroxide solution. 7. The fuel reformer according to claim 5, wherein the steam generating means is means for vaporizing water using heat generated by the decomposition of the hydrogen peroxide. 8. The fuel according to claim 5, wherein the reforming means is means for reforming the hydrocarbon-based fuel into the fuel gas using oxygen generated by the decomposition of the hydrogen peroxide. Reformer. 9. The reforming means receives supply of the generated steam and oxygen generated by the decomposition of the hydrogen peroxide from the steam generation means, and adjusts the amount of the hydrocarbon based on the supply amount of the oxygen. 9. The fuel reformer according to claim 8, wherein the fuel reformer is a means for reforming the hydrocarbon-based fuel into the fuel gas by receiving a supply of the fuel. 10. The fuel reforming apparatus according to claim 1, wherein said hydrogen peroxide solution storage means is means for storing a hydrogen peroxide solution adjusted to a concentration of about 60 wt%. 11. A fuel reformer for reforming a hydrocarbon-based fuel into a hydrogen-rich fuel gas, comprising: a hydrogen peroxide solution storing means for storing a hydrogen peroxide solution; and a hydrogen peroxide solution storing means. From the aqueous hydrogen peroxide solution to decompose the hydrogen peroxide in the aqueous hydrogen peroxide solution, and use the heat generated by the decomposition to separate the water in the aqueous hydrogen peroxide solution and the water generated by the decomposition. A steam generating means for vaporizing into steam, the hydrocarbon-based fuel receiving supply of steam generated from the steam generating means and oxygen generated by decomposition of the hydrogen peroxide, and according to a supply amount of the oxygen; And a reforming means for reforming the hydrocarbon-based fuel into the fuel gas by receiving the fuel gas. 12. The fuel reformer according to claim 11, wherein the hydrogen peroxide aqueous solution storing means is a means for storing a hydrogen peroxide aqueous solution adjusted to a concentration of about 60 wt%, and wherein the steam generation is performed. The means is a means for vaporizing water using only heat generated by the decomposition of the hydrogen peroxide. 13. A fuel reforming apparatus for reforming a hydrocarbon-based fuel into a hydrogen-rich fuel gas, comprising: a steam generating means for receiving water or an aqueous solution of another substance to generate steam; Reforming means for reforming the hydrocarbon-based fuel into the fuel gas using the generated water vapor; hydrogen peroxide storage means for storing hydrogen peroxide or an aqueous solution of hydrogen peroxide; and the stored peroxide. A hydrogen peroxide supply unit capable of supplying hydrogen or hydrogen peroxide aqueous solution to the steam generation unit; a steam supply state detection unit for detecting a supply state of steam supplied to the reforming unit; A fuel reformer comprising: a hydrogen peroxide supply controller that controls the hydrogen peroxide supplier based on a supply state. 14. The hydrogen peroxide supply control means, when the steam supply state detection means detects insufficient supply of steam to the reforming section, converts the hydrogen peroxide or the aqueous hydrogen peroxide solution into the steam generation means. 14. The fuel reformer according to claim 13, wherein the means for controlling the hydrogen peroxide supply means is supplied to the fuel reformer. 15. The fuel reforming apparatus according to claim 1, wherein said steam generating means has at least a part formed of a material active in a decomposition reaction of hydrogen peroxide. 16. The steam generating means is formed by forming at least a part of the inside thereof from a heavy metal such as copper or an alloy of copper, ordinary steel, titanium or a noble metal as a material active in the decomposition reaction of the hydrogen peroxide. Item 16. The fuel reformer according to Item 15.